DE2633036A1 - Three dimensional recording system - uses energy-selective physical chemical reactions in layers of medium - Google Patents

Abstract

A three dimensional image record is produced by selective illumination of the subject and by selective physical-chemical changes in the layers of the recording medium. The changes a*e proportional to the energy levels of the transmitted illumination, and hence indicate the density variation of the subject. A large variety of illumination sources and corresponding receptors can be used, depending on what information is to be recorded. A first radiation condition can comprise a frequency simultaneously absorbing two photons from the signal sufficient to raise electrons from a lower to a higher state with an intensity insufficient to produce the structure.

Description

J) rei-I) iiimsional systems

The invention relates to the controlled arrangement of inhomogeneities in material-empty spaces through the use of directed changes of energy levels, through the new image-wise use of many-photon excitation techniques be evoked. Such inhomogeneities are used for various purposes, underneath are: amplifier functions using consecutive Photoreactions with single photons for the production of three-dimensional products, such as three-dimensional display devices, three-dimensional optical products, and three-dimensional optical storage systems for computers. In alternative manufacturing methods the products according to the invention are directly as the controlled arranged inhomogeneities obtained, which by excitation mechanisms with many photons, as well as with a Combination of single-photon and multi-photon mechanisms can be obtained, which Cause changes in energy levels when they are in different order be applied.

The invention provides new means of producing the useful three-dimensional products, which were first described in US-PA 165 042 (W.K. Swainson) are described in which similarly usable inhomogeneities through the use can be obtained from one-photon reactions in various combinations, especially certain media with two-stage photoreactions are used. The invention shows means by which conventional, on single photons reactive materials are used as two-stage radiation-sensitive materials when deployed within new systems that can be selected from Facilities for radiation energy states and reactive materials exist. Two important new products brought about by the invention are variable refractive index optical components and optical storage systems for computers that program and to be read.

U.S. Patents 3,123,711, 3,397,316, 3,474,248, 2,604,607, and 3,829,838 describe light emitting pattern generators for display purposes which are used for manufacture of the remanent three-dimensional, structured inhomogeneities according to the invention are unsuitable.

US-PA 165 042 and Japanese application 48 395/68, both from the year 1968, showed as the first means of generating three-dimensional, remanent Inhomogeneities in volume using photosensitive materials, that responded to radiation states. Section by section, these are named patents registration as GB-PS 1 243 043 and 1 243 044 published. In U.S. Patents 3,636,250 and also in one embodiment of US Pat. No. 3,829,838, remanent three-dimensional ones Arrangements described by bundled Heat effects in thermally sensitive materials were generated. In U.S. Patent 3,609,707 describes the creation of a remanent arrangement in a volume which is photoohromisches Contains material that can be selectively colored by a beam and then that is deleted in selected parts to leave a remanent, colored sub-image. US Pat. No. 3,689,264 describes the production of light-conducting structures by means of movement the focal point of a lens or a hologram through the inside of a photo-polymerizable Plastic described. Finally, in U.S. Patent No. 3,828,087, one arrangement is disclosed static bit elements are described, which are in a crystalline matrix by a into the interior of the same bundled light beam is formed, the resulting Product is used as memory for a computer. All facilities listed above to create a remanent pattern in conventional photoreactive materials use one-photon reactions or a series of one-photon reactions and conventional ones Photochemistry. These previously known methods for creating three-dimensional products differ from the invention in that these earlier systems comply with Stark-Einstein's law obey the photochemical equivalent (e.g. that the amount of radiation absorbed is limited to one quantum per molecule involved), while the invention Systems do not obey this law. The older systems are described in US-PA 165 042 divided into Class 1 or Class II systems, or mixtures of both. Class 1 systems generally use a medium that is photoreactive Contains components that are activated by different radiation states.

Class II systems use a medium with a photoreactive Component which, after being exposed to a first radiation state, a second, different from the first component is generated, which in a second Radiation state is active.

The dependence of both of these systems on multiple, interacting ones Radiation states allow physico-chemical changes to be made inside, by coordinated interaction taking place within a volume.

Although they are not photo-chemical reactions in the ordinary Literally, the Sinai processes (Applied Option, January 1971, Vol. 10, 5, 99) and Geller (US Pat. No. 3,654,626), in which, respectively Neutron radiation or high-intensity electromagnetic radiation are used, to destroy glass structures or the structure of crystalline material to optical Causing changes, which as optical components and as volume storage can be used. The first goal is also through ion diffusion at high levels Reached temperatures as described by Hamblen in US Pat. No. 3,486,808 and by Pearson et. al. (Applied Physios Bettes, Vol. 15, 15 July 1969, p. 76) as using Metal salts and variously shaped glass blanks performed has been described. These mentioned methods to achieve optical inhomogeneities in a particular Area suffer from a multitude of problems, including structural weaknesses, limited size and defects in the crystal matrices and those already present Limitations in resolution are when using a single focus beam will. Of course, the ion diffusion techniques cannot have any index structures at all generate which stand freely inside the volumes. A similar defect in the control of the arrangements characterizes the interpolymerization technique, which by R.S. Moore in U.S. Patent 3,718,383 wherein monomers of various Index can be placed in different areas of a shape, and then overall are polymerized. While the possibility of influencing the arrangements, in the techniques given by Chandross and Gell, he opposed those given above represent an improvement they are through materials and technology limited to changed areas of practically microscopic size: e.g. analog Formed into optical fibers and bit elements, which, however, are undesirably in of one dimension, because of the use of a single, focused one Beam of electromagnetic energy connected physical limit.

Simultaneously with the development of the invention occurred in the past Years of intense interest on the part of theoretical opticians such as Duncan Moore (Journ. Optical Soc.

of America, Vol. 61, No. 7, pp. 886-894), Lüneburg, Sands and others to simplify and improve the structure of common optical systems on what the possibility would result in accurate and reliable changes of the refractive index in substantial parts of lenticular components. So far the best way to get closer to these theoretical materials has been the Ion diffusion technology. The invention encompasses methods of making these inhomogeneous ones optical components as good as others, while maintaining the symmetry properties, can fully control the property change rates and boundary conditions. This range of design options is ion diffusion or other known ones Methods far superior, and in addition, the invention allows real-time monitoring and feedback is used to simplify the manufacturing process.

The invention leads as a novel means of controlled arrangement of inhomogeneities within volumes of matter interaction systems between selected radiation states and materials that react to them, up to now only in the recently discovered two-photon spectroscopic analysis and have been used in laser-induced selective photochemical reactions. Going beyond the teaching of US Pat. No. 168,042, the invention describes additional ones Subdivisions of the known systems according to class 1 (hereafter as class 1 group 1 systems) and the systems according to class II (here later as class II Group 1 systems). While these previously known systems are based on usual One-photon reactions were based either simultaneously or sequentially in a matrix is used by the new, structure-forming system Class 1 Group 2 the phenomenon of simultaneous many-photon absorption only excitable kind with excitation of radiation states of the same energy. The new structure-forming mechanism of class 1 group 3 uses the phenomenon the simultaneous many-photon absorption of a single excitable species when excited of radiation states of different energies. The new structure-building system Class II Group 2 uses stepwise or sequential many-photon excitation of a single excitable kind in the excitation of states with different energies, where the inter-stage condition is restricted to the excited state. That new structure-forming system of class II group 3 uses the gradual or sequential many-photon excitation of a single excitable species, with at least one of the intermediate step conditions is a ground state. These structured materials in the excited state serve either directly or through subsequent interaction with components of the medium to produce the structured products of the invention.

In various notable modifications of the invention the medium is transparent to individually occurring excitation radiation, which allows remarkable effects with simple photo reactions according to Grotthus-Draper cannot be achieved.

It is the object of the invention to provide a device whereby a large group of conventional photosensitive materials in systems using selected radiation states can be used, so that the usual one-photon-one-state behavior the photosensitivity can be converted into a two-state behavior, how it is needed to build a three-dimensional structure.

It is a further object of the invention to provide inhomogeneous optical elements to create in which the inhomogeneities out of control of the symmetry properties, the rates of change and the boundary conditions can be precisely arranged.

It is also an object of the invention to create superstructures, whereby inhomogeneous optical elements are monitored during the creation process that automatic feedback and production control are possible.

Another object of the invention is to provide improved devices for the production of three-dimensional objects by produced by photoresist To create differences in solubility and volatility.

It is another object of the invention to provide improved devices to create volume holograms, correction plates and zero correctors.

Another object is to provide improved means of manufacture to create optical switching devices and blocking elements for computers, which can be assembled with such an optical switching device.

Another goal is reinforcement and awareness systems to increase the range of materials used in the present invention Systems can be used.

The invention further provides the two-photon structure formation system, in connection with various one-photon photoreactions and with itself to produce the products according to the invention.

1. "Radiation state" is called a special condition of an electromagnetic one or partial radiation defined by a unique and complete A distinction is made between a number of parameters which describe: A. the wavelength, the intensity, polarization and direction of propagation, if it is an electromagnetic radiation, and the B./deBroglie wavelength, the Particle current density, the type of excitation and / or ionization (if available), the polarization and the direction of propagation if it is a partial radiation acts.

2. "The active area" is defined as the structured distribution location within a volume of a medium in which at the end of a sequence directed photochemical Reactions including simultaneous or sequential two-photon reactions, Reinforcement reactions etc., the desired physico-chemical according to the invention Inhomogeneity developed.

In the schemes and the figures, the aLitive area is represented by the Symbol "X" denotes.

3. The presence of an active area symbolized by X "can be characterized by the presence of radicals, ions, color structures, energy transfer media, physico-chemical changes."X'l can also represent additional states of excitation if more than two photons Mechanisms can be used. For example, a sequence of reactions is shown on page 33: where "X" additional excited states and formed parts such as

as described on page 39.

4. hv1 is a primary ray, hv2 is a secondary ray, A shows an atom or a molecule in the ground state, 1AV / r shows an excited species in a higher one Vibration / rotation level of a variety of ground states, 1A * shows an excited one Species in a variety full of singlets, 1A ** shows an excited species in a higher one Singlet state of a variety, 3A * shows an excited species in a variety of an excited triplet, Figure 3A ** shows an excited species in a higher excited one Triplet state from a variety.

Many-photon absorption processes, which in the simultaneous many-photon absorption method of the invention (class 1 group 2 systems with the same photons or class 1 group 3 systems with photons of different energies) are detailed in more recent literature in e.g. the book Organic Photochemistry by Robert 0. Kan, Mc Graw-Hill, New Kork, 1966, Chapter 1. A particularly useful review article by Wm.Martin McOlain in Accounts of Chemical Research, Volume 7, Number, May 1974, pages 129 to 135 describes methods for obtaining two-photon spectrograms, which may be useful for the invention to generally define the wavelengths and Predict energy parameters for useful radiation sources. Other useful Reviews were given by W.L.

Petic ~ olas in Annual Reviews Phys.Ohem., Vol. 18, 1967 and H. Mahr, Physios of Color Centers, H.B. Fowloer, ed., Academic Press, N.X. 1968, and J.M. Warlock, Laser Handbook, F.T. Arrechi ed. North Holland Pub. Co., published in 1972. Another article by H.Mahr appears in Treatise in Quantum Electronics, ed. C.L. Tang and H. Rabin, Academic Press, N.Y. 1974.

The first published description of a selected two-step or consequent excitation of materials, which are used here in a novel way is used to create structured three-dimensional structures (class II, groups 2 and 3) appeared in an article by R.V. Ambartzumian and V.S. Letokhov in Applied Option, Vol. 11, Number 2, February 1972, pages 354-58. But it should also mentioned again the above-mentioned articles by McClain and Mahr and attention should be directed to a growing literature dealing with selected Excitation processes in selected chemical reactions and with isotope separation using laser radiation. Useful mechanisms including Two-step photoionization, two-step photo-disassociation, and photo-predissociation were discussed in early papers by C. Bradley Moore (ans. Rev. Phys.Chem. Vol. 22, 1971, p. 387 and t nn Rev. Ohem.Phys. Vol. 23, 5. 41, 1973 and Accounts Chem. Research, Sd. 6, 1973, pp. 323-328), while more recent publications e.g. at A.M. Ronn (Spectroscopy Letters, 8 (5), 1975, pp. 303-328; see also reference 1 of this essay, there is a list of summarizing articles, and see Reference 2 of this article, where the laser "catalyzed" photochemicals are discussed) can be found. C.T. Lin has a means described the effectiveness of magnifying processes that lead to reduction of the resonance energy transition mechanisms are based on the direct excitation of a triplet state from a ground state, taking advantage of the fact that for a resonance transition from a triplet state a forbidden spinflip transition to a singlet state transition) is necessary. Very valuable calculations on the use of self-ionization resonances in the reduction of the required power are detailed in the article by V.F.Letokhov (Spektroscopy Letters, 8 (9), 1975, pp. 697-709), and a simple one Quantification formula for photopolymerization and other processes involved in the invention used appears in U.S. Patent 3,829,838 from column 12, line 28 to column 13, line 20. These notes are included here to reflect the state of the art in to show the laser-induced photochemistry that the invention uses to create structured To form inhomogeneities with physicochemical behavior.

The combinations of materials described in the following pages and processes were selected to illustrate particular systems; it was it is not intended to create the impression that any particular material can only be used in a particular system described, and not in one of the alternative systems described below. The above-mentioned and other objects of the invention are achieved by the controlled introduction of selected ones Changes in energy levels within matter-filled volumes, the Matter is selected in such a way that it follows the chain of laws simultaneously or step by step Subject to energy absorption. In a preferred embodiment of the invention an increase in the energy level within the volume of matter by achieves the joint effect of at least two sources of a certain radiation, which is electromagnetic radiation, and where the sources are characterized by a unique and complete set of parameters, which the wavelength, the intensity, the polarization and the direction of propagation describe in such a way that at the selected points usable levels are simultaneous Multi-photon absorption or gradual multi-photon absorption occur, while at the same time the radiation sources and the material in their properties are coordinated so that a selected response to the one-photon processes the usual photochemistry can be avoided.

The material chosen for the reaction can be liquid, e.g. a photopolymerizable monomer, a mixture of monomers, a mixture of Monomers and polymers or it can be one viscous polymer that is still another Photoreaction is capable. The reaction material can, however, also be in the solid state, e.g. a gel-like polymer, a frozen monomer, a reactive ingredient within a matrix made of plastic, a glass or a crystalline material.

The energy sources can be lasers, arc lamps or particle beams from charged particles or atomic radiation with certain types of amplification of the invention. The structuring state is preferably the generation of inhomogeneities with the use of narrow-band light emitters, such as lasers or filtered Arc lamps, in the ultraviolet, visible, or infrared regions of the spectrum executed. The special combinations of the radiation states are determined according to the Requirements of the simultaneous or step-wise multiphotonic excitation processes selected to be used.

It does not matter whether the systems used belong to class 1, group 3 or belong to class II, groups 2 or 3, the preferred agents, the desired ones Raising energy levels to achieve in selected locations are common Effect of at least two rays of light emanating from the outside into the volume of matter projected so that their intersection creates the desired structure. details about the light sources, the beam guidance and control and the structure of the structures can be found in US Pat. No. 165,042 and US Pat. No. 3,829,838.

The control and guiding apparatus described in these documents is light adapt for the invention. When using a system according to class 1, group 2 (identical photons with simultaneous absorption) it is useful in some cases to to use a beam bundling effect, and this can be done by using either a lens array or a holographic lens can be achieved. The ability holographic lens multi-point focal ranges and those of various shapes is particularly useful in certain applications, such as the production of optical switching devices and memory memories for computers. This ability of holographic imaging was first described by Swainson (see US-PA 165 042) and was further acquired by J.M. Moran in Applied Optics, Vol. 10, Feb. 1971, 5.412 and T.J. Othara in IBM Technical Disclosure Bulletin, Brd. 11, 5, 1168, Feb. 1969.

The amount of power required varies widely because of the quantitative change in the product obtained, e.g. in the trace amounts of the constituent produced by energy transfer compared to the polymer Mass in the case of chemically precipitable images. In example 42 there is one List of critical parameters and a formula for calculating the samples. In the Selection of the system to be used become the structures of the energy levels and help to select the arrangement of the intermediate states in a certain material, which of the systems described and which light source should be used. In terms of quantum yield, results are as low as 10 5 or 10 6 im The case of simultaneous two-photon absorption is quite practical, especially where it is the product in a reinforcement process as described several times in this application is, participates.

Far higher quantum yields can be achieved by getting cheap - Intermediate levels combined with large cross-sections, connecting the dimension the cut areas are small. It can have values on the order of 10 5 ° or 10 48 cm2 / watt / cm2 can be achieved.

Processes with relatively low yields are most satisfactory in connection with effective systems, e.g.

the polymerization initiated by methylene blue, with a concentration of methylene blue in the order of magnitude of 10 6 mol / liter can be effective. In in this case the polymerization yield can be of the order of 106 at any excitation can be polymerized molecules, while some similar systems up go to 108 molecules produced per excitation. The most effective systems can be expected from processes with similar polymerisation yields, which at the same time allow a photon yield in the size of 1/10.

Really simultaneous because of the relatively low probability Three-photon absorptin wrist such a system is not very practical. The usage of many-photons and in particular of three-photon absorptions in series or mixed in series and at the same time is very practical and has special Advantages, including e.g. high contrast.

It should also be noted that in this application only simple systems being represented. The permutation of such simple systems in connection with one another e.g. a three-photon system that consists of the simultaneous absorption of two photons with subsequent absorption of a third photon) is in the sense of this Invention.

Such systems can be developed using many-photon absorption by the presence of resonating or nearly resonating Intermediate states in the system is made possible. In such cases. will be the difference blurred between simultaneous and successive processes, and they are useful when both contrast and yield need to be maximized. Comes. the first photon in such a system is closer and closer to an absorption state and finally within the line width of this state, so becomes the second Photo resonate from the first level of excitation to the second level. From the point of view The effectiveness and contrast are those systems that are in resonance or have near-resonant intermediate states, in many cases preferable.

When using a system with successive excitation states, in which a photon with the wavelength A1 produces the excited state As with the lifetime Y, where Y is very large compared to #! is, it is for the case that the excited state is a second photon with # 2 to bring about a further excited state As * of the lifetime absorbs, obviously that if the photon densities in the two photon processes are the same, that process has a much higher probability of occurrence. The probability of getting A ** is directly related to the lifetime Y.

If the process just described is carried out with a further step Generation / A * K repeats, whereby the active area according to the invention is generated, then it becomes possible to measure the volume of matter with photons of three different wavelengths to be scanned in a fan-shaped manner along lines perpendicular to the respective scanning direction stand. So an input in the form of the usual Cartesian coordinates x, y and z given and the scanning happened one-dimensional. This and the lower required Performance liners such gradual stimulation are beneficial, plus the additional It is preferable that a background reaction that is not related to the image to be generated stems from, is reduced.

The following are examples of the many-photon simultaneous absorption systems of class 1, groups 2 and 3 are discussed.

The simplest example of a Class 1, Group 2 system is shown as follows; As shown in scheme (1), two identical photons, labeled bvl, are absorbed by a photoreactive material in a ground state (usually a ground state, but the reaction can also be part of a more complex series where A represents an intermediate state of excitation) , whereby this changes into the excitation state k, from which the material changes to the product state X. This product state can either be a distribution that represents an end structure, or it can take part in a further reaction, catalysis or amplification, etc.

As a general rule in the practical application of the invention should be be assumed that the selection of the respective System from the starting point of a given material with known photoreactive properties that relate to Bin-photon processes relate, proceeds, although it is just as possible, from the Knowledge of available light sources and the photoreactive material this directly or through the use of sensitizers with suitable absorption properties adapt. In order for simultaneous two-photon absorption to occur, the wavelength should of the photons hv1 are selected so that the energy difference between the States A and A * equal to or less than twice the energy of the photon hv1, but greater than the energy of the photon hv1: hv1 <E S 2hv1.

With many materials it is possible to use the various aspects of their Predict behavior in two-photon absorption if their behavior in one-photon photoreactions is known; in other cases it may be the simplest to use a simple experimental one Apparatus to set up for an attempt, while again in other cases it is desirable can be to set up the full two-photon spectrogram, as it was in earlier McClain et al.

Typically, Class 1, Group 2 systems are most effective used where the image resolution does not have to have the highest achievable value, and where it is more convenient to use the focus of a single beam rather than separately controlled beams. Some optical components can be convenient with this System. The use of two intersecting rays with identical energy value is less than satisfactory where the contrast between Image and background play an important role, as the productivity of area X proportional to the square of the used light intensity. Under such conditions obviously increase the use of a focused beam the contrast is very strong.

Because of their generally greater usefulness, the following Design and operation of Class I modifications in which photons of different Energy and wavelength used are described in more detail. The following will be a few examples of Class I, Group 2 systems are described in the Photons of the same energy are used.

1) A frozen jar made of monomeric styrene in a Pyrex cell is made a focused, high-intensity, pulsed ruby laser beam with a peak power exposed to about 3 x 105 watts. The focus is slowly going through the center of the materials moves and leaves behind a trace of poinerized material.

There can be-even-single-individual-rays, within-the-material to the.

Cutting, with the result of reduced effectiveness. And reduced contrast. Other monomers, such as ap-isopropylstyrene or chlorine-substituted ones Styrene derivatives give higher yields of polymers, and the addition of a difunctional one monomers such as divenylbenzene set the solubility of the polymerized structure down.

2) A solution of 8 'allyl-6'nitro-1,3,3-trimethylspiro- (2' N-1-benzopyran -2'-2-indoline) in benzene becomes intersecting, synchronized pulsed rubinase rays (4 J output, free laser mode, pulse length 3 * 10-4 sec) with UV filter exposed. A color point is formed in the area of the beam intersection, which is approximately Fades for 10 sec. The same experiment - kaun wiede, rholt.wer.den in one Plastic (polymethyl methacrylate) dissolved spiropyran, in which case the fading time the color extends over a few minutes. the Fading speed can be controlled by changing the temperature. Other photochromes can be the same Way to be used.

3) A transparent matrix containing Beuko-azur A creates a red color when as described above, with rays of high intensity, pulsed Light from a ruby laser is illuminated. Other variations are possible, though those described in the article by Oster, J. American Chemical Society, Vol. 81, pp. 5100 Materials are used. Other color producing compounds such as photochromes of the 2,4-dinitrophenylpyridine type can be used to create moving image displays. The speed of fading can be controlled within a 105-fold range by changing the pH of the system will.

See Journ. American Chemical Society, Vol. 84, p. 3658.

4) A viscous solution containing 10 2 mol eosin Y, 10 3 p-toluenesulfonic acid, 30 56 acrylamide, 5 56 methylene biacrylamide in ethylene glycol is a group of high intensity, exposed to intersecting rays from a ruby laser. In the area of A polymer as a material overlaps with one of its surroundings different refractive index, with both materials showing transparency.

Class 1, group 3 systems follow.

The simplest example of such a system using the simultaneous absorption of two unequal photons is: In such systems, the frequencies, and thus the energy values, of hv1 and hv2 are preferably different and selected so that they meet the following conditions: E (hv1) + 2) (hv1)> (hv2), and E> 2 (hv2 ).

Under these conditions a very intense jet is left Low energy photons (hv2) with a low intensity beam but with Cut higher energy photons (hv1). It is more common to use this system than the one above Similar to the Group 2 system described, except that where Group 2 two Photons of normally half the energy needed to be used the one-photon process of photoreaction with the given photoreactive material carry out, in the existing system of group 3, the sum of the unequal photons considered as an energy value, equal to the sum of the two identical photons, as an energy value considered is.

Such a system is shown in FIG. One sees atif the left side shows the typical absorption curve of a pilot-reactive material in a usual one-photon process, while on the right an approximately congruent one Two-photon absorption spectrogram is drawn by the method according to McClain was received. When using the group 2 process with two identical Photons would be an intense beam of a wavelength within the range of the Two photon absorption spectrogram can be used to initiate the reaction. In the preferred group 3 type, which uses unequal photons, at least the high-intensity (hv2) beam especially from the region of two-photon absorption be excluded. In Fig.

23 is hv2 as from a pulsed ruby laser and hv1 as from a pulsed argon laser originating shown. The procedure for the systems according to group 3, Class 1 can be understood from the description that follows.

As described above, the radiation sources are in the following, complementary relationships to each other: 1. The laser R has a low Energy per photon and a high beam intensity.

2. The laser G has a high energy per photon and a low one Beam intensity. (Note that the amount of energy per photon, for example is not confused with the energy per pulse length). The permissible, necessary and forbidden values for the photoactive absorption spectrum in the two-photon mechanism are provided by the wavelengths of these two radiation sources.

Photoactive absorption cannot extend into a range in which the wavelengths are longer than those of laser R (the high-intensity radiation source), nor can it form an active range if the wavelength is shorter than the wavelength A x in: Should the selected photoreactive material (or the sensitizing material or the energy transfer agent) have an absorption curve that extends into the longer wave range, then two photons from the radiation source with higher energy will be sufficient to drive the reaction on the entire radiation path of this radiation source should the absorption spectrum on be limited to a range that is shorter than the wavelength XX, then the active region according to the invention will not be generated because of the insufficient energy at the intersection.

At least part of the absorption spectrum must be in the range between these two boundaries extend in so that the necessary conditions are fulfilled. As previously stated, if a given material, a given photoreactive Component and a number of energy sources successful are to be used, the other components must be selected in such a way that that spurious absorption by non-reactive substances, thermal reactivity and unwanted side reactions are excluded. Such precautionary measures include to the area of responsibility of the specialist in the field of photochemistry. Such professionals are aware of the fact that, although the generalized description given above the limitations in the relationship between absorption structures and radiation sources in general, structures of the photoactive spectrum are useful are available that allow in the materials / modifications. The absorption spectrum of a material is not always identical to the photoactive absorption spectrum. For example, the photoactive absorption spectrum with the wavelength of a Radiation source coincide, and this would become an excludable condition form, which amounts to the fact that spurious images are formed by common one-photon reactions along the radiation path. On the other hand, this absorption cannot be of be photoactive in nature, and then the main problem is that of effectiveness of the process would be weakened or lost entirely due to unnecessary absorption and that there might be problems with the heating of the material. Some other considerations which are important to the invention are given below briefly touched on for clarification, although based on professionals are not new to the field of photochemistry and two-photon spectroscopy.

If a system of the type of simultaneous two-photon reaction is designed, cross-sectional factors that are greater are generally avoided than about 10 5 ° to 10 48, except for systems that are close to the resonance range play, where the upper feasibility limit is substantially the same as that in successive operations. The effectiveness of photon absorption, which at successive absorption can be achieved with simultaneous two-photon absorption processes, which take place in the vicinity of the resonance, approximately reached.

In general, systems with resonance transitions are preferred when high yield is desired. The probability of a two-photon transition is inversely proportional to the distance from the resonance state (e.g. from a one-photon transition) of the intermediate state compared to the photon energies. Ideally, it disappears this distance to the vicinity of the agreement (with complete agreement it is a follow-up process) exactly at the top of the absorption line, and reduced thus the energy denominator in the absorption cross-section for two-photon processes like this as far as possible.

The special value of systems in which resonance or Fas resonance occurs lies in the efficiency and high yield which they allow. In the expression <o1} is proportional to the one-photon absorption coefficient to an intermediate level, and <9> means a second one-photon transition from the intermediate state to the final state.

- @ tv represents the energy level difference between the photon hv1 and the intermediate energy state. It can be seen that the probability of these two photon transitions is the product of the two absorption coefficients <0 / µ / 1> and <4 / / 2> is proportional, divided by the energy gap between the intermediate level and the photon energy hv1. If the distance is at the mean value the photon energy is low, then the energy denominator is small and the probability (and the productivity) very large. If the distance = zero, then we have not more of a simultaneous system according to class 1, but a follow-up system according to class II. So becomes an intermediate state in order to obtain a strong transition and a high productivity or intermediate states are used in which a one-photon transition is very possible and has a high energy value and at which there is an intermediate energy level which is only slightly higher than the energy of hv1.

As far as the yield is considered, so is the selection of Materials particularly important, which reasonable lifetimes of the excited states own for this particular purpose. For example, a long-lived excited State result in an energy transfer to neighboring molecules, which occurs so often If the dissolution becomes worse, so do the dissolution and the productivity not compatible with each other.

In general it can be said that species have an extremely short lifespan produce a lower yield than species with lifetimes of the order of magnitude from 10 5 to 10 9 sec.

Obviously, systems that are used in high-speed computer operations must be excluded from this be owned.

It is also important to refer to the lifetimes of the excited states to consider the energy balance of a given process. For example will it in a follow-up system that uses a continuous wave laser as a radiation source and a pulsed second radiation source is operated, be desirable, to have an excited state that lasts long enough to keep enough Absorb photons from the weaker radiation source. Few continuous wave radiation sources are, even if they are focused, it is energetic enough to operate simultaneously without extraordinarily large waste of energy operated together with a pulsed laser to become. For this reason, in most systems that operate simultaneously, both Laser pulsed synchronously.

An alternative mechanism for direct excitation of a molecule in the ground state to a triplet excitation state has been described by CT Lin (Spectr.Lettr., 8 (9), 1975, pp. 901-915): Because of the longer lifespan of the triplet state compared to the singlet state, and because no energy is lost through the resonance-energy transition (for a resonance transition from the triplet to the singlet state, a forbidden spin change transition is necessary), this mechanism is more productive estimated to be the stimulus to a singlet state.

Because the preparation of a full two-photon spectrogram is very often a tedious and boring process, some general ones should now be considered Principles are established, which often the selection of suitable radiations and radiation sources to allow practical work with the invention, if only the one-photon absorption spectrum and the molecular properties, such as symmetry properties, Location of the various energy levels characteristic of the photoreactive material are known. This information will enable those skilled in the art to Spectroscopy and two-photon spectroscopy, very often predicting energy levels which allow two-photon transitions, as well as the approximate strength of these transitions to predict. For example it will almost always when an absorption peak of a two-photon transition does not occur at a point twice the wavelength corresponds to the one-photon absorption peak, at a slightly higher energy level such a transition must be present. In general, the lowest energy transition will be be the allowed one-photon transition, and it can just as well be the allowed two-photon transition but it is unlikely that the lowest transition is the allowed two-photon transition is, and that the one-photon transition is forbidden.

The materials for which the prediction of the one-photon spectrum gram suggests that they are not in agreement with the two-photon spectrogram those with strong molecular symmetry, a property that the investigator finds will be known.

The following measures are given as a general rule for examples, where symmetry properties and vibration disturbances allow the assumption, that the one-photon and the two-photon transitions, as described above, from each other depend. In general, it is possible from well-known, published experimental To determine data relating to the one-photon behavior of photorealftive material, which two-photon transitions will be allowed and which will be forbidden. Such predictions based on theoretical principles are less useful when the energy values of the transitions should be determined, or, if it should be said whether or whether not a certain energy state with a certain symmetry at a certain one Energy occurs.

Since the field of two-photon spectroscopy is fairly new, is such information is generally not readily available in the literature, and in some interesting systems one will experiment with two-photon spectroscopy methods need to apply. However, it won't always be laboriously necessary Two-photon spectrogram complete to set up the for to obtain the information required for the invention. If that's under observation standing medium can be recorded directly in order to record useful reactions (e.g. through fluorescence emission or through a change in the refractive index or in the absorption behavior), A simple series of tests will often suffice. Such a shortened process is connected to a tunable radiation emitter (e.g.

a tunable Lasse0, which shows the probable range which covers the energy values, as well as another radiation source (e.g. for systems Class 1, Group 3 a source with lower photon energy, but higher Intensity), which is simultaneously directed at the sample -, and with an observation system, to track the desired responses while they are changing the first radiation source occur. If radiation is emitted during the process Earth, one will advantageously use a photodetector system for detection. If a change in the refractive index or a polymerization is to be achieved, the display value of the sample can be recorded if one is not photochemically emits and measures active beam.

The following is indicative of the operation required given a photoreactive material, its two-photon response spectrum is known or estimated and the required lasers should be selected.

To simplify the case, assume that the material consists of only one type, for example a monomer capable of polymerizing, and that precautions have been taken to avoid non-selective thermal decomposition. If the operating mode according to class 1, group 3 is to be used, a first laser must first be selected, usually a commercially available ruby laser with high power output, which emits at 694 nm. If the known or estimated two-photon absorption, which causes photopolymerization of the monomer, is to be used, one can refer to Table 10, which has been calculated for the case where a ruby laser is used. Column 1 of the table shows a range of photoalftive absorption wavelengths from ultraviolet to visible light, which is adapted to the two-photon absorption properties of the selected medium. Using the formula given by Kan in the above mentioned paper: we can derive the energy required to initiate the photoreaction in relation to the specific laser wavelength in kcal / mol. In the present case the emission wavelength of the ruby is> = 694 nm and the required power derived therefrom for a specific absorption range is shown in column + er table 10.

Depending on the optical density and the size of the medium, a selected activation wavelength can be used in the region of the peak absorption, or for large volumes in the slope region or near the base of the absorption region. In most cases it will be best to use energy sources that are focus value in the area of interest. Since the laser wavelength of the one beam is now fixed at 694 nm and an absorption range at, for example, 380 nm, one can use the formula determine the frequency which is given to the second laser and which is given in the third column of table 10 in this case with b = 846 nm or shorter.

Examples of systems of class 1, group 3 with two-photon absorption using different frequencies are given below: 5. One cell filled with diphenylcyclopentadiene solution becomes intersecting Illuminated bundles of rays which have the 'wavelengths' 9.431 cm and 18.862 cm 1 (hv1 and hv2). A single laser can be used if desired, uni forming the first beam path through the medium, and unabsorbed radiation from the back can be through a KPD crystal to generate the second harmonic passed through (to form hv2) and through a filter (to excrete hv1), and then directed back onto an optical path that puts the beam back in allows the medium to enter from a new entry point so that it follows the original ray path cuts. In this example, fluorescence known in the prior art occurs and each fluorescent structure is not one of the examples of the structures of the invention that do not emit radiation. To these materials according to the invention to use it is necessary to add an additional component to the mixture, which reacts to the internal fluorescence emission in such a way that it has a secondary area and provides the non-radiant product of the invention.

6. ChroSzarbonyl is dissolved in methyl methacrylate and azolesobutyl nitrile and heated to 50 G until the polymerization is complete. - penetrate this Medium two each other intersecting rays as described above, this results in a two-photon absorption, which causes an intense yellow color, which is stable at 770 K, but fades in a few hours at room temperature.

7. Barium acrylate is dissolved in a hot gelatin solution which Contains methylene blue and p-toluenesulfonic acid. The solution is cooled until forms a gel. Two photon absorption, as described above, is generated at the intersection of the rays Radil.ale, which polymerize the barium acrylate, with an opaque, light-scattering image from polymers is created.

8. A frozen glass made of acrylonitrile in which a larger amount of compounds such as benzoin or azo-isobutyl nitrile were dissolved, which light-activated Forming radicals is illuminated in a similar way. Two-photon absorption of the The catalyst generates radicals that form light-scattering, insoluble polymers.

9. A solution of a photo-crosslinking agent, e.g.

2-methylanthraquinone or 1-chloroanthraquinone in a suitable one Monomer such as vinyl acetate, styrene, methyl acrylate, etc., which is a photopolymerization catalyst contains, the absorption spectrum of which is similar to that of the crosslinking agent frozen and exposed to two intense beams of light.

At the point of intersection, the monomer is polymerized and crosslinked.

After exposure, the glass is melted and the illuminated Areas are separated from the matrix with or without the use of solvents.

10. Gels can be used for lighting instead of frozen glass will. A heat activated polymerization catalyst can be added in Example 8 will. the Solution is then heated until it gels and then ' as described above, illuminated. A catalyst like azotsobutyl nitrile would work for this system should be suitable as it is activated by both heat and light will.

Solvents are used to separate the image from the matrix.

11. A photo-crosslinkable, photosensitive polymer with or without the use of sensitizers and additional crosslinking agents, as described in FIG. 9, exposed to two intense bundles of light so that at the point of intersection the bundle of two-photon absorption occurs.

The crosslinked polymer is then made using solvents separated from the matrix. Examples of polymers that are suitable for this system are: polyvinyl tinamate, polyvinylbenzophenol, polymers containing diethyldithiocarbamate contain, anthracene, azides, acrylic azides, sulphonyl azide, acrylic diazide, a-diazoketones, Furylacryl and allyl groups, stilbene, azidocinnamates, polyacetylenes, and polymers, in which the light-sensitive group by means of isocyanate compounds is a polymer Scaffold is connected, and the urethanes form, certain olefin polymers with sensitizing Halogen compounds and polyesters derived from tin amylid ~ enmalonic acids and related mixtures were formed. Other photosensitive polymers that use a photodimerization mechanism, or those as a result of photolysis a photolabile group that is linked to either the polymer chain or can be separated from it, can be substituted and used in the same way will.

12. A color containing lactoflavin or a similar-acting color thiolated gelatin is illuminated as described in Example 10. The thiol groups network in the overlap area, which gives an insoluble picture.

13. A gel crosslinked by mercury chloride, which is a light reducible Contains color, is as described in Example 10, illuminated. In the area of the ray intersection the mercury ion is reduced, which breaks the crosslinking of the gel. Here is a negative working system that is used to create a hollow shape can be.

14. A clear matrix that has a high percentage of a halogenated Resin and, if necessary, other halogenated compounds and zinc acetate or a Contains another chemical compound which, in the presence of a halogen, produces a Friedel CraSiF catalyst forms, is illuminated as described above. At the intersection of two more intense The catalyst is formed and caused by a beam of suitable frequency Degeneracy of the polymer and colored compounds.

These images can be intensified using heat.

15. Examples 1 through 4 on pages 18 and 19 become two intersecting If exposed to beams of suitable frequency and intensity, go arise the superior results described there.

The systems presented here according to Class II, Group 2 and Group 3 using multi-photon stepwise absorption were made up of mechanisms the gradual two-photon excitation developed, which has recently been considered analytical and chemical processing techniques were used. An important system of this Art arose from the gradual process first introduced by, Ambartzumian and LetoMlov 1972 was described. The systems according to class II, group 2 differentiate themselves of those according to class II, group 3 in that the former are only excited intermediate states usually have singlet or triplet states, while the latter use at least one basic state in between.

The higher excited state or its precursors can be a higher one Vibrational state, a higher rotational state and / or a higher electronic one Be state. The transition from the precursor to the desired excited state must take place before or before the Rejattaton of the vibrational or electronic state occurs the excitation energy can be passed on to neighboring molecules. In some In some cases, this condition requires the use of high-intensity or pulsed laser light sources.

There are three basic types of reactions that fall under the classification of successive two-photon excited states via intermediate reactions.

In the above mechanism is the performance requirement for the Condition 1Av / r is relatively low, and it follows that it is convenient to have a Use wavelengths in the lower or infrared energy range for hv1. Examples such reactions are described in the article by V.S. Letokhov (Science, vol. 180, 1973, pp. 451-458).

The second type of sequential two-photon reactions with intermediate excited states can be represented as follows: 16) An example of such a reaction sequence occurs when an azulene solution is illuminated by a primary beam of wavelength 530 nm and a secondary beam of wavelength 1060 nm. The primary beam lifts the azulol molecules along its path into an excited oscillation state of the lowest singlet S10. If they are not further excited, these molecules return to the ground state without fluorescence. In the area of overlap in which the two beams act one after the other, the molecules in the excited state S1 are raised to the state by the secondary beam, and fluorescence radiation is emitted.

Although there is little theoretical understanding of the underlying processes, a third sequential reaction with two-photon excitation is described as follows: In this case, a molecule that can absorb energy of an appropriate wavelength forms an excited singlet state, which then transitions outside of the system to form a triplet state. These triplets cannot form radicals or produce images through realizations and soon decay into the ground state if they are not further excited. However, when exposed to radiation of an appropriate frequency, they can form triplet excited states which are highly reactive and can initiate the various desired reactions.

Using this system, the primary beam creates triplet states along its path and the secondary ray rises the triplet states to excited triplet states at the points of intersection.

The great advantage of systems that use at least two different laser wavelengths combined - use opposite systems that rely on the effect of the intense flow of photons based on a single wavelength lies in the significantly lower power requirements and the flexibility of the wavelength in the high energy laser that enables when used in conjunction with a tunable, low power light source is used. The power requirement can be 1/1000 of that for a single Wavelength is required and there in the case with two wavelengths the radiation power at the selection step is small, and the oscillation / rotation lines of the molecular absorption not widened significantly, it becomes much easier to identify particular components of the medium to activate.

To operate a system according to scheme (3) with minimal power, the excitation according to Ao will normally be done by a tunable laser, whose wavelength is selected in such a way that it excites the lower vibration levels, the absorption cross-sections being relatively large.

To compensate for the molecular inharmony, the wavelength can be gradual be carried away via the appropriate lines of the lower excited states in order to to keep the suggestion in resonance, and thereby the performance requirements at the Occupy the first vibration levels to keep them low.

The high-power laser is then used to set the level to be driven with generally smaller absorption cross-sections, the less require exact wavelength selection.

In many cases, the greatest effect will be the energy used achieved by striking the radiation in successive pulses lets that the photons hv1 be followed by the photons hv2, and that the time from the beginning of the hv1 pulse to the end of the hv2 pulse much shorter than the lifetime of the first excited intermediate state.

Radiation sources suitable for the radiation beam can be divided into two General groups can be divided: The first group is made up of lasers with moderate Power and variable wavelength in the infrared for selected excitation of Molecular vibrations, and in the visible range for electron excitation of atoms and olecules are formed. Such lasers include the spin change class used in generally covers the area between 5 µm and 15 mm, or the high-pressure gas laser, in which the lines of rotation overlap and very broad reinforcement bands form the range between 2.5 em to 12J & m with a high level of performance cover, or Raman lasers, in which t'td glass is pumped, which the area cover from 1.2 µm to 2.5 µm, or laser with organic colors with frequency control, which cover the range from 0.4 / in to 1.2fim. Other sources of radiation with adequate Control of the output quality can of course also be used.

The second type of useful laser has a high power output in the ultraviolet, it does not need to have wavelength tuning, but it provides a power density (E2) to such an extent that or where # phd and # phi mean the photodissociation and photoionization cross-sections. Ruby laser (with a second harmonic of 3.6 eV) and Nd glass laser (third and fourth harmonics with 3.5 eV and 4.7 eV, respectively) and nitrogen laser with wavelengths of 337.1 nm (3.7 eV) can also be used, such as the hydrogen laser (160 nm to 110 nm) or the Xe laser at around 170 nm. From the standpoint of energy consumption and efficiency, the recently developed noble gas halogen lasers are in the range from 250 to 350 nm is particularly attractive. These last-mentioned lasers, for example complex xenon and chlorine lasers, result in a high degree of efficiency (ie the yield of photons per unit of electrical energy can be several orders of magnitude better than with argon-ion lasers). Such sources of radiation with high photon energy are particularly valuable when free radicals are desired in the active region, since they can be reached even by smaller molecules. A number of properties are shown by the structured results of the following examples: 17. Tetramethylphenol dianine in an EPA matrix at 77 K forms a wonderfully blue colored structure when it is moved towards an intersection of beams of 340 nm and 400 nm. The color results from the formation of a TMPD radical cation, which can also be used to catalyze polymerization. The color also forms in methane or propylene carbonate solutions, and similar systems can be prepared using triphenyl, 3,4-benzopyrene or diphenyl in boric acid glasses.

18. Beta-Naphthol, which is in a Polæmlethylmethacrylat-Ixiatric two Rays exposed to the singlet band and the triplet band of absorption are matched, form a semi-stable yellow radical at the intersection of the two Bundle of rays.

19. Naphthalene - in a solution of a monomer, a difunlitional Monomers (to create crosslinking) and ethyl iodide are exposed to two beams of light, one of 313 nm and one of ray in the visible range - of a wavelength, which is absorbed by the triplet of naphthalene. That arises; lde stimulated Triplet generates radicals which, directly or indirectly, polymerize the monomer and network. Other compounds that can be used instead of naphthalene to generate similar radicals are akridan, 9-phenylakridan, toluene, naphthol, Etriflavine, and acridine.

20. Orotinic acid and similar compounds also form excited ones Triplets in two-photon processes. These triplets can be from suitable donors Stripping hydrogen atoms, forming radicals in the process, which are an effective catalyst for polymerization and possible crosslinking processes.

21. Benzoyl and oxalyl chloride and benzophenol, in one polymer dissolved, forming an excited state that crosslinks the polymer and becomes insoluble makes, whereby a similar Z-photon mechanism is effective.

In the new systems according to class II, group 2 described above the absorption of the secondary beam happened by a molecule in an excited state, and a distinction was made between singlet and triplet excited states.

In the case of the systems to be discussed according to group 3, this distinction is made not important because the secondary beam from a molecule or atom in the ground state is absorbed, and in the following section the pontic can be im excited State can be either a singlet or a triplet.

The intermediate systems of group 3 which are in their basic state can be prepared in such a way that one or both of the reactions is irreversible. An example of this is the scheme (7) 22. Such a system is prepared using a polymethine-cyanine dye which, upon irradiation with (hvl), produces a mono-Ois isomer which reacts upon irradiation with (hv2) to give a colored di-cis isomer . In a similar system, rose bengal is present and is converted to a de-iodinated derivative by (hv1) which in turn is converted to fluorescein by (hv2), giving a colored fluorescent compound and a catalyst for polymerization. However, these non-reversible systems can only be used for a limited group of simple figures.

In the next scheme (8) a more useful reversible sequential two-phase reaction is shown: In this case, the absorption of the (hv1) photon by the component (A) causes the conversion to the component (B). The absorption of the secondary photon (hv2) by B creates a radical or a colored compound, or an energy transfer agent, etc., as previously described.

In the areas in which (hv2) did not take effect, the Compound B back to compound A. This decay can be caused by absorption of light - or Thermal energy can be generated, and it can be achieved by suitable irradiation accelerated if the desired speed and occurrence cannot be reached with the existing ambient light and heat. Examples of such systems are discussed below: 23. O-methyl and O-benzophenone, which reversibly photo-enolize upon absorption of ultraviolet light suitable materials. When exposed to radiation, these enols react with a blue (hv2) photon with the formation of semi-stable cyclic compounds of yellow color.

24. Similar Rcalttionen can when using 2-Benzhydryl-3-Benzoylchromon and its analogs can be obtained.

The dihydrobenzofurans can also take advantage of the photochemical Ring opening can be used in conjunction with photocyclization. The relatives Furilchromones also make a photochemical rearrangement between non-fluorescent ones and fluorescent isomers by what they are specific, in the following example makes the purposes described most useful. Additional information can be obtained from Huffman et.al., J.Amer.Chem.Soc., Vol. 92, 1970, p. 599 and Zweig, J. Pure and Applied Chem., Bd 33, 1973, St 394 can be obtained.

25. Another such system uses isooxazoles, which are different when exposed to radiation with the first photonthv1) convert into azirenes by irradiation with (hv2) in isooçazolc and by irradiation with (hv3) oxazole from the intermediate state Azirine surrendered. These and similar materials are particularly interesting for the invention, since only one of the forms (oxazole) fluoresces. In this way The structured surface of Oxazole can be used as a reinforcing link or especially as the active part in a storage system for computers, in which the bit information is in the form of an arrangement of digits in a three-dimensional Volume is present, which fluoresce or a stimulated emission capable are.

26. Other reversible systems according to group 3 can be prepared, by using C-nitrose compounds, which are stable dimers in aqueous or form organic solutions.

These dimers can be broken down into monomers using either heat or ultraviolet light. See also scheme (9).

In this system, the life of the monomer depends on the particular Nitrose compound, as well as the selected solvent and the temperature. Compared to the dilzer, the monomer has an absorption band in the visible red. The light absorbed by this band photolyzes the monomer and generates radials. Certain dinitrose compounds, e.g.

1,4-dichloro-1,4-dinitrose-cyclohexane can be used in the same manner will.

With a change in the method, colored compounds can be obtained when the radicals are added by color-forming compounds that the mediiu: i have been captured.

Another modification of the invention uses photochromic materials, which are usually only switched back and forth between two states as shown in scheme (10): Scheme (10) shows the straight line one-photon process used in US Pat. No. 165,042 and US Pat. No. 3,609,707 to produce colored number images with a photochromic matrix. In the practice of the invention, instead of using a write and erase combination of hv1 with hv2 as shown therein, a colored image can be obtained by applying the right combination of radiations to produce two-photon transitions and coloring in the selected areas. This mechanism is much more flexible and makes a more useful technique for complex patterns. It can be shown as follows: Of course, the many-photon excitation systems used can be any of those described in this application, or combinations thereof.

27. Suitable photochromic materials are also the 6,6 | dietithioindigo colors and their derivatives, the optical influences between the Gis and Trans states Can be switched if two wavelengths hv1 and hv2 are used fourth. the two isomers have different colors and properties including the fact that only the trans isomer fluoresces. An advantage of these materials is a very high increased quantum yield at high temperatures (90 ° at some Epoxy resins), which gives stability at low temperatures after a picture was formed at a higher temperature.

28. Also for this process are those described in US Pat. No. 3,329,502 To use epoxy. These connections are thermally stable and can be between colorless or light yellow and red-colored states can be switched.

29. In the same way gives N, N'-diacetylindigo, which in xylene and molten polyvinyl acetate was dissolved, after cooling a very stiff one polymeric solution which, upon exposure to blue (458 µm) light, changes into the fiicnrote Trans-configuration transformed. Like the switchable indigo color derivatives of the Example 27, the diacetylindigo color derivatives fluoresce only in the trans form, so that they can be used in both memory designs that rely on light emission based, as well as those based on different light transmittance.

Additional details, the properties of the polymethyn paints (ex. 22, 5. 39) in the field of excitation emission, plus the description the use of optically structured inhomogeneities in laser structures, which can be generated three-dimensionally by this invention are at Nelishchuk (Spectroscopy Bett. 8 (9), 1975, p. 669). For more information about these properties for the oxazoles (see example 25 on page 40/41) are at Abukumov et.al., Spectrosc. Lett., 83 (9) 1975, pp. 651-667, to find as well as Andrejeschtschew, Baroni, Kovyrzina, Rozman, Shoiiiia in Akademy Nauk, 5. 64-66, Adrova, Koton, Ranov and Florinskii in Akademy Nauk, 5. 59-41 (the last both give information about scintillation in English translation to be used where the excitation radiation is particle radiation instead of electromagnetic radiation Radiation is). The memory processes and the reinforcement processes can activate by two-photon or one-photon systems (see US-PA 165 042).

More information about these materials can be found in an article by A. Zweig, J. Pure and Appl. Chem., Vol. 33, 1973 pp. 389-410 and those named there References 21, 22 and 23 can be found. There is also information in an essay by A. Zweig, W.A. Henderson jr. and K.R. Hoffmann to find that of the American Cyanamid Co., Chem. Res. Div., Stamford Connecticut, under the heading "Intensity Dependent Photoimaging Systems was preprinted. We also recommend: G.R. Bird, Symposium III, Unconventional Photographic Systems, October 20-23 1971, SPSE Abstracts p. 79 and by the same author in Photographic Science and Engineering, Vol. 17, No. 3, May / June 1973, pp. 261 to 267.

An important modification of the invention involves the use of additional Components that are added to the medium and sensitize it for various purposes can. Such sensitizers are generally capable of absorbing such radiation energy, to which other components do not respond, and absorb enough energy in the Process of training the structured product distribution to a recipient transferred to.

For example, the use of sensitizers can reduce the formation of spuriously excited triplets in the primary beam path. These undesirable excitations can occur when there is an overlap between the band of the ground-state singlet absorption and that of the triplet-triplet absorption (this is rare, however, since in general there is a much higher energy with the transition from the ground-state singlet to the state of the first excited singlet is connected than corresponds to the lowest triplet-triplet band). A more common overlap could be of type T1 T4: The use of sensitizers can also reduce the attenuation of the primary rays as they can be used in lower concentrations. They can also be used to increase the yield of triplets.

It gives a few examples of sensitization reactions specified in systems of class 1 and also class II; however, it should be note that the number of possible combinations is very large, and how in the case of the other examples in this document, they are only intended as an illustration.

The following schemes indicate some class 1 awareness mechanisms.

Scheme (13) shows the absorption of two dissimilar photons by a sensitizer using the singlet-singlet interaction or fluorescence. The following schemes (14) and (15) show singlet and triplet reactions with sensitization.

The following schemes and examples show sensitization mechanisms of class II. In one group of such sensitized reactions, the sensitizer absorbs the primary beam, and the energy is transferred to a molecule in the ground state: In both of the above systems, sensitization occurs through a singlet-singlet interaction or through the absorption of fluorescent radiation. Although there is little theoretical knowledge of the details of these energy transfer mechanisms, the knowledge from practical experience that it is only necessary that the emission spectrum of the donor and the absorption spectrum of the acceptor overlap is sufficient for present purposes. The light used need only be of the wavelength that is absorbed by the sensitizer; the acceptor can be completely transparent.

Scheme (18) shows a triplet-triplet sensitization in which, as above, the energy is transferred to a molecule in the ground state.

30. An example according to the scheme (18) can be prepared if one adds benzophenone as a sensitizer to that in Example 19 (page? ^) and then changes the length of the primary beam to 365 nm. This wavelength becomes not absorbed by pure naphthalene.

In the following systems (schemes (19) and (20)) the secondary beam is absorbed by the sensitizer and the energy is converted to the product of the primary beam. In scheme (19) the sensitizer transfers its energy to an excited singlet, while in scheme (20) the energy is supplied to an excited triplet.

In another significant variation of the invention, the structured distribution of product X is used as an intermediate step in producing the final product. In a variant of this variation, X is an energy transfer medium that can absorb energy in the form of electromagnetic or particle radiation below the excitation energy. In a simple case, the distributed product X can be a distribution of fluorescent molecules which generally do not fluoresce in any of the radiations used to generate the structures, but which begin to fluoresce under selected radiation conditions and thus transfer energy to other previously inactive photosensitive mechanisms, such as a polymerization process. The advantage is that a single fluorescent molecule can transfer thousands of photons per second to an acceptor system. In this way, the original structure-generating process of Class 1 or Class II is subjected to a large amplification, whereby a considerable amount of the end product is produced at the same time when the concentration of X is low. This is particularly advantageous when X is obtained from relatively ineffective two-photon absorption processes. This process can be shown schematically as follows, where L denotes the receptor system: Depending on the demands placed on the resolution, a second component which is capable of absorbing transferred energy, as described in the previous section, will generally have to have a higher absorption coefficient or higher reactivity to the energy transfer mechanism and also a higher concentration in the medium, if the The demands on the resolution are increasing. It is quite common to develop concentration tables for specific materials which give the minimum value of the molar absorption coefficient against the value of the desired resolution. This same consideration is also applicable to the various mechanisms of energy transfer, such as fluorescence, emission / absorption, the Förster mechanism of energy transfer, and other types of energy transfer which do not depend on 1 and which function primarily through molecular contact and which are generally recognized by the skilled person as different forms of intramolecularity radiationless transitions are known, applicable.

Examples of such awareness and reinforcement systems will be given below.

31. A color precursor in a clear matrix is exposed to two intersecting beams of light of adequate energy so that two photon absorption processes, as described earlier, result in a pattern of selected distributed colors. The color (see below) is determined by its ability / to sensitize the decay of the color precursor via a photon reaction (T + T energy transfer), which results from the absorption of the long many lengths of the scanning beam or a separate development beam. This is shown in scheme (22): (here A is the color precursor and 3 is the color) Such a system can be prepared in a transparent matrix which contains amines such as diphenylamine or N-vinylcarbazole together with an organic halogen such as iodoform or carbon tetrabromide. The halogens and amines combine to form a complex that, when exposed to a focused ruby laser beam, creates a small amount of color that can be magnified by exposure to red light. See also Fotland, J.Photogr. Sc., Vol. 18, 1970, p. 33, Hazy gC Petro, Laser Focus, Vol. 8, 1972, p. 32.

32. Stable fluorescors can also have simultaneous two-photon absorption systems when using the fluorszor precursors described in Zweig (J.Pure and Äpplied Chem ^, Vol. 33, pp. 389-440) are described. Among the useful reactions there are oxidative cyclization, dedimerization, tautornerization, rearrangement, Elimination, oxidation, substitution and reduction. The preferred materials are in greater detail in the section on fluorescence emission memories discussed at the end of this document and they include the use of split of photodimers by light into fluorescent monomers (Salmon and Chandross, Änalytical Chemistry, Vol. 45, Dec. 7973, 5. 21S46), the photochemical generation of fluorescent Cyclohexa-1,3-diene by ultraviolet light of a wavelength less than that than 300 lim when using rays with a longer wavelength and two-photon absorption according to US-PS 3,899,678, and the transition from cis to fluorescent trans isomers in the indigo color series (J. Phys. Chem. Vol. 72, No. 8, Aug. 1968, 5. 2817).

George R. Bird has an important group of new energy transfer systems and means in Phot. Sc. and Engineering, Vol. 17, No. 3, May / June 1973, pp. 261-267 described. Bird describes other direct intramolecular energy transfer systems in his U.S. Patents 3,622,316 and 3,622,317.

In another variation of the above, the product Cx) can be a photocatalytic agent. A photocatalysis agent differs from an energy transfer agent in the fact that it is consumed in the formation reactions of the following scheme. These are shown schematically and followed by examples: (Sensitive object produced by irradiating E with low-energy radiation) 33. A compound CA), which can form a polymerization catalyst (B) by means of a photoreaction, is dissolved in a suitable monomer or in a crosslinkable polymer. Two-photon absorption with intersecting beams is used to create the active photocatalyst (B) in the desired structure. The matrix is then exposed to a type of radiation that activates the catalyst (R) but not CA). The compound CA) can also be a polymerization catalyst which has been chemically modified or transformed into a complex in such a way that the inactivation can be canceled by two-photon absorption and the original properties can be restored.

34. This process is also useful when using certain colors that can only initiate polymerization if they are attached to macromolecular Substrates are bound.

A gel containing crystalline purple leuconitrile, a monomer a contains difunctional monomer, a mild reducing agent and polymethylacrylic acid, is exposed as in Example 4 on page 19. The one created by two-photon absorption Color cation bonds with the polymer. The gel is then exposed to radiation in the absorption band exposed to the color below the excitation energy. The color is reduced and generates radicals to polymerize the monomer. This way the ineffectiveness becomes the two-photon absorption process overcome by a light "development" of the faint image is used. This reinforcement effect is an additional one Advantage in the case of unfocused areas of overlap, or if the rays join a diffuse geometry instead of being focused, thin rays. For example, if three planes of light are used to define the active area create a single point at their intersection, which is an active one Area includes, form.

The examples described above contain quite a few where the inhomogeneous product encloses inhomogeneities of the refractive index. Among them are Example 4, page 19, Example 7, page 30 (if sodium acrylate or acrylamide is substituted for the barium compound), Examples 9, 1Q, 11, page 30 and 31, example 12, page 31/32, example 17, page 37, examples 19, 20, 21, page 38/39. To this and related inhomogeneities of the refractive index for optical purposes To use it is necessary to arrange and design the areas according to certain To influence the rules that are set out in the following: The ones for the production Optical elements of various types usable materials can be widely used Meaning to be described as photochemically active materials that differ from one another State with a refractive index in at least one different state with different refractive index from those in US-PA 165 042 or in the preceding Let parts of this application bring mechanisms shown. In certain cases, as in the manufacture of apodization screens are distributions that allow passage of light, valuable.

A group of suitable materials are the glasses and crystalline Materials such as those from Crow et. inal. (Applied Optics Vol. 14 March 1975, 5.580 and in the / Applied Optics series of articles by Thaxter (April 1974, 5. 913), Staebler and Phillips (April 1974, 5. 788) and Micheron, Mayeux and Trotier (April 1974, 5. 784) described v Jurden. These materials include: Strontion-Bariwn-lSiobat, Lithium niobate and lead lantane titanium zirconate ceramics (PLZT). Some of these materials can also be sensitized for use as described earlier (Phillips et.al. RCA Rev. 33 (1972) pp. 94; and Ishida et al. Applied Phys. Let. Vol. 21, (1972) P. 192).

When optical elements of considerable size are required, so plastic materials are preferred which are reliable without imperfections can be produced, and which a wide range of photochemical processes can be subjected to the differences in the refractive index and the permeability result. An important group of plastic materials is disclosed in U.S. Patent 3,726 588 (J.R. Rust). The plastic materials used in this document can be subjected to photochemical changes in two different ways, one of which gives an addition polymer and the other a condensation polymer. These different products have certain different indices of refraction and can be perturbed in a useful way to avoid the inhomogeneous optical components of this invention.

Likewise useful material is shown in U.S. Patent 3,615,454 (Cescon et.al.).

Another useful group of materials are those based on photochemical path from one state of polymerization to another, different one Polymerization state can be transferred. Materials for which a complex Polymer is brought into simpler polymeric states by photochemical means, are described, for example, in U.S. Patents 2,892,712 and 3,884,696 in which Connections are broken by light energy in the range from 170 to 400 nm. A larger group is characterized by reactions in which light excitation Making connections rather than making simpler products; it's here too mention US-PS 2,610,120 and 2,670,287 (polyvinyl-2innglat with light sensitizers, such as nitro compounds and diaminoaryl compounds), US Pat. No. 2,756,143 (benzal and zinnelal-arvinylacetophenone polymers), U.S. Patent 2,861,058 (alkali-soluble Succinic acid or phthalic esters of partially esterified polyvinyl alcohol, where the esterifying agent is cinnamic acid or its derivatives) U.S. Patent No. 2,702 243 (diazo compounds and polyirlides); U.S. Patents 3,143,416 and 3,143,417 (diazo compounds and special polyamides), US Pat. No. 3,189,451 (aldehydes and a diazo compound of a Arylamins), and U.S. Patent 2,927,022 (cellulosic derivatives and an ethylene compound as an addition polymerization compound). The ones compiled in this paragraph Materials can be brought about through the practical application of this invention that they can be used for controlled conversion from a monomer to a polymer or transform from polymers to addition and crosslinked polymers what by Processes of condensation, Addition or networking in a controlled and happens in areas expiring manner.

An important group of materials has been described in the literature, to record spatial holograms, and some of these materials are commercially available e.g. from DuPont Corporation, Newport Research Corporation, Hughes Aircraft Corporation and others. Accessible technical information that some of these materials concerns, shows that they often lead to a widely differing refractive index change and that they are particularly useful when there are significant changes in the index of refraction is required.

(See also plate 12).

One group of such holographic material was published by Chambers and Jenney (U.S. Patent 4,479,185, J.Opt. Soc. Am. Vol. 60, 1970, p. 1155 and Vol. 61, 1971, p. 5. 1116). These materials are liquid at first and shrink when exposed. They can be used in protection cells for the present purposes, and also, as other materials pertaining to use in this invention Experiencing volume changes, it may be necessary to reduce them by grinding and polishing post-treatment after the creation of the internal refraction inhorlogeneity. if Such materials are used, these are subsequent molding and finishing operations Part of the invention.

An example of amine other group of materials are those in one Article by Tomlinson, Chandross, and others in Appl.

Opt., Vol. 15, Feb. 1976, 5,534 and U.S. Patent 3,809,732 photopolymer Syster.ze-made up of many components in which photochemical processes Changes in chemical Composition with very large differences cause in the refractive index. The mechanisms that cause these differences have not yet been clarified, but obviously the materials can be used to create effective light guides within a volume that is the fiber optic are analogous to that produced by the methods described in this invention. Optical inhomogeneities in considerable volumes can be generated if the Diffusion requirements of the materials will be charged, and if the individual components are selectively excited with appropriate radiation mechanisms, which differ slightly in other ways than the respective polymerization rate (as described by Chandross and Tomlinson).

Other materials that cause a gradation in the refractive index can, were made by J.D. Margerum in his final report from July 1973 @ "Chemistry of Photopolynter Light Sensitive Systems "described as Report No. AD770068 is available from the Air Force Office of Scientific Research.

That of h'.J. Boden and others in Appl. Optics Vol. 1), No. 1, Jan. 1974, p. 112 described, specially prepared polymethyliaethacrylate has the disadvantage that the change in the refractive index takes place delayed, but can nevertheless in some Cases are used. This material was provided by Tomlinson and Chandross and another used to form optical waveguides by placing a focused beam of light and conventional photochemistry have been used (U.S. Patents 3,689,264 and 3,809,686) similar to it is described in US-PA 165,042.

Other media for recording holographs with considerable ability to Changing the index of refraction is disclosed in U.S. Patent 3,547,509 (R.G. Brandes), 3,926 637 (Bartolini and Bloom), US-PA 403 377/1973 (Ross) and by Booth in Appl.Opt. Vol. 11, No. 12, 1973, p. 2994. Ross's, Bartolini's and Bloom described the material is particularly interesting as a lot of castable polymeric matrix substances can be used to absorb the photoactive diketones, and Items of considerable size can easily be manufactured. More like that Material is found in U.S. Patent 3,707,371 (Files) and by D.S. Lo (Appl. Opt. Vol. 13, No. 4, April 1974, p. 861) and S. Maslowski (Appl.Opt. Vol. 13, No. 4, April 1974, p. 857). Files are made from a combination of color, styrene and peroxide, Eo uses a salicylide eneaniline and Maslowski uses a spyropyran derivative. Other materials used for recording hologram shells were obtained from M.R.B.

Forshaw in Optics and Laser Technology, Feb. 1974, p. 28 and by Bowden et al. In Polymer Engineering and Science, July 1974, Vol. 14, p. 494.

Of considerable value in the construction of computer memories and active optical switching systems are those of R.L. Fork et al.

in Appl.Phys.Lett., Vol. 20 of February 1972, S: 139 and von Kogelnik and Shank (Appl. Phys. Lett. Vol. 18, Feb. 1971, p. 152). Storage elements that use materials capable of excited emission, have the advantage over simple fluorescence systems that the emission direction can be determined by the direction of the stimulating radiation. This allows one increased efficiency when the memory is used in channel mode WLrd, and it results in better selectivity when reading out the bits. Mention should also be made Auxiliaries and the FixierungstechnSx, whereby after the formation of a distribution with changed refractive index.

the material for such wavelengths that were used in the construction, insensitivity can be made. An example such mechanisms using Aci anions can be found in U.S. Patents 3,531,281 and 3,531,282 will.

It should be remembered that in some applications, e.g. with correction plates, the size range of the refractive index change is not very large needs. For example, very small differences in / instruments are useful, where the beams are at a small angle, e.g. with lenses with a long Focal length, converge. Larger differences at the second and third decimal places are necessary for instruments with a less high refractive power in which the rays fall in wide angles.

A useful example in the middle range was calculated from Sinai, and it comprises a plano-convex lens where ii 1.477, R = 152 mm and 2h = 30 1m is. In this example, the variation in the refractive cortex as a function of Height of incidence (h): #n = K (n-1) h2 / f2, where h is the height of incidence in centimeters and K is the aberration coefficient. -: let this lens in the wrong direction is rotated, the greatest necessary change in the refractive index is dn = 0.005, as shown: = -2.28 x 10-3h2.

If, on the other hand, the lens is rotated in the favorable direction, then: = -0.61 x 10-3h2, and the largest required change in the index of refraction is only 0.0014. These changes are well in line with what is available Materials achievable changes (Table 12).

More examples can be found in the following sections, and in the table 9 are various combinations of the focal length (f), the refractive index range lT1 with the index differences (AN) for different values of the lens radii (r) for compiled a basic refractive index of No = 1,450. It is to be noted that with every single composition there are focal lengths that are one Require change in index of refraction of less than 0.07.

The correction for chromatic aberrations in optical systems is achieved primarily through the use of apochromats, in which the focal points, which correspond to two or three different wavelengths must coincide, whereupon the primary residual of the chromatic aberration is corrected. To this To achieve the goal it is unfortunately necessary to apply large amounts of curvatures to fall back on refractive surfaces, creating again geometric aborinations of a high order in the case of spherical lenses. Hence this draws the disadvantage of being limited to your opening angle. In the case of the invention Lenses with variable refractive index it becomes possible for the first time to deal with such to reconcile large amounts of curvatures of refracting surfaces with corrected geometric and chror: atic aberration.

While many of the. useful optical elements of the invention those with controlled distribution of the change in the refractive index are included some elements, and especially those in terms of refractive errors are corrected, different permeability distributions. A difunctional monomer, which is contained in the system described in example 1, calls such a different Permeability.

It is also possible for beams intersecting one another to be electronically magnetic Radiation including X-rays and gamma rays used in glass or plastic are, uri such less permeable places in the as apodization screen known optical elericent. Such screens correct mistakes, resulting from diffraction. An aperture which the -; [inner opening of the effective The beam of rays limited to the entrance pupil creates diffraction rings around the true Point that forms the image of a point. It is said that the diffraction figure is a contains middle or main maximum, in which most of the light energy is concentrated, as well as subsidiary or secondary maxima at which the light energy is considerably lower. A diffraction error becomes evident when an optical Image is created with two neighboring images with a large brightness difference: The image of the weaker element tends to be aligned with the diffraction rings of the brighter one Element to mix, and in addition, the subsidiary intensities of the Diffraction image to reduce the contrasts of the images of distant objects.

The distributed impermissions created by the inventive Apodization screens are generated, allow the reduction of the subsidiary intensities or secondary maxima by dividing the distribution of the amplitude of the light oscillations in through through continuously variable permeability none. This permeability is distributed in front of the opening of the entrance pupil and changes continuously from one point on the other hand; it is a function F Cx, y each Point of the screen. Such screens generally have a permeability which decreases from the central axis to the outer areas. Conversely, in a related application uses the opposite distribution to create a screen form, which sharpens the middle point of diffraction and thus the resolving power of the optical system with respect to point sources increased. An important application Apodized optical components exist in the field of laser optics and especially in the case of the laser components used in the energy systems for mergers with the use of Laser optics can be used.

The invention is illustrated below, for example, with reference to the drawing described; 1 shows the axial shape of an optical element with Symmetry properties, Fig. 2 the spherical shape of an element with symmetry properties, Fig. 3 shows the cylindrical shape of an element with symmetry properties, Fig. 4 and 5 each an element with a specific change in property, FIG. 6 an element with boundary properties, FIG. 7 shows a prism with optical inhomogeneity in terms of time instead of in spatial terms, 8 shows a single lens with a spherical Correction, using a higher refractive index in the middle range than at the outer edges, Fig. 9 a spherically corrected single lens with a lower Refractive index in the middle range, Fig. 10 the classic inhomogeneous Wood's Lens ", Fig. 11 a device for producing simple inhomogeneous lenses with radial gradient distribution, FIG. 12 shows the path of an axial light beam in a "Wood's lens 11, which is partially spherically corrected, FIG. 13 a UGl lens with even index distribution; Areas with the same index value are planes perpendicular to the optical axis, Fig. 14, a nse with a radial gradient of the type such as it is used in the generalized "Wood's lens", Fig. 15 a complex one optical element that has an aplanatic Telescope objective shows, Fig. 16 a refractive index distribution through a A device not in accordance with this invention, Figure 17 is a Refractive index distribution with radial gradient, obtained by modifying the example 36 was generated, this modification being part of the invention and is described in Example 37, Figure 18 is an automated system used for Real-time inspection and generation of inhomogeneous optics in accordance with this invention Fig. 19 is a f / 6.3 single lens with a cylindrical distribution of the refractive index, 20 shows an internal analog of an optical fiber optic constructed according to the invention, FIG. 21 a graphical representation of two-photon processes using ruby and Nd-Yag lasers in systems according to class 1, group 3, FIG. 22 shows a graph Representation of two-photon processes using argon and ruby lasers in systems of class 1, group 3, where the laser is of low intensity is tuned by a range of wavelengths, Fig. 23 shows an application of these Invention for computing purposes.

The refractive index distributions obtained by using this invention can be classified according to three properties: 1. Symmetry properties, 2. type of property change, and 3. boundary properties.

Each of these groups can be further subdivided.

Fig. 1 shows the axial shape of an element with symmetry properties. Such an axial gradient exists where the gradient always is parallel to the optical axis. The area + constant indices of refraction N are planes sank right to the axis. In Fig. 1, the dashed lines show planes constant Indexes within a plan-plan element, and the index function has the following polynomial form: N (X) = N0 + N1X + N2X2 + N3X3 :::; where N0, N1, N2 ... constants and X means the distance from a surface.

Fig. 2 shows the spherical shape of an element with symmetry properties. The index here becomes a function of the perpendicular distance from the surface or a function of radial distance from the center of curvature; the areas with constant refractive index are spherical surfaces. The form of the index function is in this Case: N (r) = N0 + N1r2 + N2r4 + N3r6 where No, N1, N2 ... are constants, and r is the radial distance from the center of curvature.

Fig. 3 shows a cylindrical shape of an element with symmetry properties. Cylindrical distributions result from continuous index changes in one Direction perpendicular to the optical axis. The area of a constant refractive index are therefore cylinders whose axes coincide with the optical axis. There the gradient of the refractive index is perpendicular to the optical axis, is also the The term 'radial gradient' is used to describe a cylindrical index distribution.

The form of the index function is: NCR) = No + N1R2 + N2R4 + N3R6 where Nos N1, N2 are constants and R is the vertical distance from the optical axis is.

Obviously, many other symmetries can be in this group as well with symmetry properties are presented.

Figures 4 and 5 show elements with index change properties Fig. 4 shows a linear axial gradient where N = 1.5 + 0.01 X while Figure 5 shows a polynomial axial gradient where N = 1.5 + 0.01 x2.

The description is: a) polynomial in a variable if X the distance along the optical axis is, N = No + N1X + N2X2 b) polynomial in more as a variable coordinate, e.g.

N (x1, R) = No + N1 (X) R2 + N2 (X) R4 Figure 6 shows a Element with interface properties.

The group with interface properties can be divided into two basic groups be subdivided.

a) Those in which the interface of the inhomogeneous distribution of indes at the same time is the interface of the material itself, b) those where a or several interfaces of the inhomogeneous media different from material interfaces are themselves, e.g. in Fig. 6, where a plan-plan element; t with a range with constant Index and two certain inhomogeneous areas. It should be noted that the Interface between the areas can be flat, spherical, or arbitrary.

The invention also leads to the production of apochromatic ones by itself Elements, especially because of their ability to have two regions with different refractive indices in a single volume. The refractive index of most optical Materials change with wavelength, and that is why the ray paths are of rays of different wavelengths through a lens different. Theory the chromatic aberration for inhomogeneous lenses was published by P. Sands in J.Opt.

Soc. Am., Vol. 61, 1971, p. 777.

It is also possible to see optical inhomogeneities as a function of the To create time instead of space. Fig. 7 shows a prism from that of Tomlinson described material in which the refractive index is due to a photochromic Effect is changed. Such a prism can be used in a solid-state scanner or, if the prism is turned into a lens, will pass through it Mechanism to change the focal length. The deflection of the angle B is given by the formula: Bi = dA given.

For a value AN = 0.01, a deflection of 1% from the wedge angle can be achieved d of the prism. With a wedge angle of 300 and a change in the index of refraction of 0.01 the deflection is approximately 1/2 °. Fig. 8 shows a HmP lens in the. the spherical aberration has been corrected by increasing the refractive index of the original cast or milled lens so that it has a gradient towards the center towards the lens (regions with the same refractive index are cylinders).

The focus of the central rays now coincides with the focus of the marginal rays together. In Fig. 9 the reverse process is shown, where the invention was used to let the refractive index decrease towards the edge, by which process the spherical aberration was corrected by the fact that the Edge rays now coincide with the focal point of the dead rays.

In general, radial gradients are far more effective at correcting of aberrations as axial gradients and they are part of the design of lenses of greater value. An important advantage of using even index distributions is the fact that manufacturing tolerances are considerable while maintaining good effectiveness can be facilitated. The radial distribution is most effective at altering the refractive power of a shaped lens (diopter change). When calculating this radial gradients, the refractive index is determined by a series expansion of the even-numbered ones Powers of the radial distance r from the optical axis in a cylindrical coordinate system developed: N (r) = No + N1r2 + ...

Then if t is the thickness of the lens, then it becomes the refractive power of the lens changed by the amount - 2N1t. For example, results in an eyeglass lens with a diameter of 40 mm and a thickness of 5 mm have a radial index gradient of N1 = - 0.000025 a change in refractive power of +1.00 diopters. It is over the total area of the Lens requires a refractive index change of only 0.01. Table 1 shows an example this relationship between refractive power and aperture. An important use case the invention lies in the possibility of the necessary supply of spectacle lenses different refractive power can be reduced by placing the blanks in the glasses desired refractive power, and even bifocal properties by locally brings limited change in the refractive index.

35. The classic inhomogeneous optical element is that first in the book by R.W. Wood's "Physical Optics" described so-called "Woodt lens". This Woodlsche Lens consists of a plane-parallel, plate-shaped optical element in which the refractive index changes outwards from the optical axis. A bigger one Refractive index on the optical axis compared to the border areas gives a convergent lens, while the reverse property gives a divergent lens.

With such a lens, the condition is that an image can be formed NCR) = No + N1R2, where R is the perpendicular distance from the optical axis (rotational symmetry axis). When the thickness of the plate is t and is much smaller than 1, then is the focal length of such a lens More general equations for the focal length f and the back focal length Bf for a Woodt lens are: A Wood1 lens is shown in FIG. 10, and Tables 2 and 9 give values for various combinations of focal lengths, N1 and thicknesses.

Although in the preferred form of this invention the required Change of energy levels through the combined action of at least two each other intersecting rays of light is caused to the internal arrangement for the The classic i'Joodt lens can create optical inhomogeneity Example (and the optical elements in Fig. 3, 8, 9 and 14) effectively a modified procedure be prepared, which is also at the production of correction plates of irregular shape or Schmidt plates can be applied.

In a variation of this alternative technique, what the Woodl's lens is to be inserted into an apparatus as shown in FIG. On the left is a source of actinic radiation, in the middle a screen that you can see completely can close 'to block the actinic radiation completely, and that continuously in the form of a growing circle from the center outwards to the interfaces of the optical element to be formed can be opened, and on the right is the workpiece displayed.

This workpiece is usually a cell made up of two flat Glass or quartz glass panels are made, depending on the actinic radiation that is used will. The construction of a suitable cell is described in Example 1 of US Pat. No. 3,732,097, whereby the distance can be changed as required.

The operation of this modified device depends on the particular one Composition of the medium, which is an energy transfer medium, such as a contains stable fluorescent, as it did earlier in a similar function was discussed. It should be noted that the change now described is very important because of their simplicity and usefulness, if otherwise each other intersecting bundles of rays are required to create special inner boundaries and the like to produce inhomogeneous optical elements according to this invention. This method offers a superior option for previously known inhomogeneous optical elements to get that so far only through the tedious Ion exchange process or the Sinai process could be obtained.

To the advantage of this veined procedure compared to the known To make the prior art clear, the following example 36 is given, which is not belongs to the examples of the invention. Example 37 is a modified one Form of Example 36 and is an example of the invention.

36. Not an example of the present invention.

1. In an arrangement according to Figure 11, the cell is in the darkroom filled with the following solution made at 400 C: gelatine 15% acrylamide 5% Dimedon 1.6 x 10 3 mol thionine 4.0 x 10 5 mol water to make up to 100%, adjusted pH 5.7.

2. Cool until there is a light blue, clear sheet of gelatin in the Cell has formed.

3. Close the shutter, switch on the red light source and that of the light source expose the facing side of the cell for a period of 10 to 20 minutes while the shutter is continuously opened so that it is full at the end of the exposure time is open. Cap the cell to prevent drainage from the gel.

16 shows the result of the experiment in a side sectional view the cell. It has an approximately conical area made of colorless polymeric copolymer Material formed, that on all sides except one of an area made of unpolymerized material is still surrounded by a light blue color. The process has also been treated mathematically by Tomlinson, Appl.Opt. Vol. 11, April 1971. In simple terms, the process is such that the absorption is at the front of the cell causing polymerization, the level of radiation on the back so reduced that the polymerization limit advances in the manner indicated. This effect occurs least clearly in photoreactions with increasing transparency it is clearest when the transparency remains the same or increases.

37. Step 1 of example 36 is repeated, but the solution a small amount of one of the energy transfer agents discussed earlier is added. For example, if the energy transfer medium is a fluorescent, then you will turn it off Pick the water-soluble fluorescers to meet the following requirements correspond to.

1. The fluorescent is caused by light from such a wavelength range activated, which is not the same as that absorbed by the activating color is activated and this is activated.

For example in the case of thionin one will use a fluorescent which is activated by blue light of about 450 nm or by ultraviolet.

2. The fluorescence emission should be in a range for which the The color to be activated is sensitive and in which it is activated. For example, in the case of thionine, the fluorescence should be in the red.

3. The fluorescent should not activate the polymerization itself.

Another difference to example 36 is the red light source replaced by a high intensity source of blue or ultraviolet light. In in the case of Example 36, the light intensity and the irradiation time were easier Way associated with the depth of penetration. In the present case, the provision is an intense light source is important for the success of the invention. The intensity the light source should be so large that a large excess of the number of photons per cm3 is present in the medium versus the number of molecules of the absorbent Energy transfer agent.

The exposure is carried out as described in Example 36, however a completely different result, as shown in FIG. 17, is obtained. In this In this case, the desired radially directed gradient is obtained and a real Woodsian one Lens is created in the cell.

The explanation for this difference is simply that the big one Excess of photons over the entire thickness of the cell from the front up to its back an approximately equal supply of photons to the fluorescent results.

It follows that along the entire path of light from the front approximately the same number of fluorescent molecules on the rear side, approximately the same Generate numbers of activating red photons, which in turn have approximately equal amounts activate a red-absorbing blue catalyst for the polymerization. An improved resolution (smaller free path for the red fluorescence photons before capture) can be achieved by increasing the proportion of energy transfer agent will.

The method described above for making the very desirable Inhomogeneous optical elements can easily use a variety of different energy transfer media or catalysts can be adapted if the three requirements discussed above get noticed. It is obvious that in the presence of other components in the volume, e.g., acid anion releasing components, around the generated element to fix, the wavelengths and the absorbing means are selected must so that such acid anions or other components are not activated unintentionally will.

While the automated device with feedback according to FIG is ideally suited to manufacture highly specialized inhomogeneous optical elements in this way, it is also possible to achieve the desired properties in some cases in a more satisfactory manner Way to get approximated, in the calculated amounts of radiation at carefully compound preparations are used. It should be noted that, though Generally light radiation sources are used, it is also possible to use materials to use what energy when using ionizing radiation as excitation energy transfer.

Such materials have been reported by Sangster and Irvine in J. of Chem. Phys., Vol. 24, 1956, 5. 670 compiled. An obvious advantage of such materials lies in the fact that they do not have to be fixed by a separate process, to prevent unwanted activation by light radiation that occurs during their Use as an optical element passes through it, but simply in front of the special ionization radiation are to be protected. As in the case of the light activated Materials can be seen as the variation in activating radiation across the surface of the optical element can be achieved by making a timed exposure, such as described above, applies, or an attenuator for the radiation can be made will, in which the attenuation profile is calculated as a function of the radiation law it is determined which one should be applied to the continuous change of the refractive index after the distance from the axis (in the case of the inhomogeneous optical elements with rotational symmetry around the axis).

It is also often advantageous when using the device with feedback be, by calculation, the approximate behavior of the medium among the particular ones To determine radiation flux conditions. In the case of a rotationally symmetrical element, in which the spherical aberration is to be corrected, this includes that the index correction to be carried out at each point of the lenses as a function of the axis distance is calculated, and that the radiation flux is also calculated, which at each of the Points must arrive in order to get the desired correction. An example of one such a calculation is given in example 42.

38. The mixing process according to step 1 in example 36 is repeated, whereby the thionin is replaced by eosin Y at a concentration of lo 2 mol Generation of the structured optical inhomogeneity becomes a controlled focus of a ruby laser according to the mechanism described in Class I Group 2. Alternatively, two intersecting laser beams with corresponding energy properties can be used (see Table 10), using the mechanisms of class 1 group 3, or combinations of lasers with fixed and tunable Wavelength according to the rules discussed in the mechanisms of Class II Group 2 have been selected.

Unlike the method of Example 37, these allow as well as controlled systems / an inner limit function such as a radial index distribution structure.

39. Two solutions A and B are prepared as follows: A. 14 g Polyacrylamide, 2.38 g of sodium p-toluenesulfinate dihydrate, 10 2 mol of eosin Y in 100 ml of water. Heat at 60 to 800, stirring, until the mixture is clear blue, viscous and is free of bubbles.

B. 50 weight percent sodium acrylate.

In the dark room, two room parts of solution A become two room parts the solution B mixed and half a volume of 37 0 / iger formaldehyde solution, with Acidified acrylic acid, added. The cell is filled as in Example 36 and exposed as in Example 38. After exposure - you get a tough, transparent one Gel with structured optical inhomogeneity that fixes completely and no longer is sensitive to light.

40. A cell is prepared in the dark room as in Example 36, using sodium m-nitrophenyl acetate with a minimum concentration of 10 2 mol in 100 ml of water 20% acrylamide, 0.5% methylene-bis-acrylamide and sufficient Gelatin for solidification. An exposure as in Fig. 38 gives a similar product. The acetate can also be replaced by eosin Y and dimidol or p-toluenesulfinate.

While it is not difficult, the optical behavior of the Woodtschen Lens control that of a simple convex single lens or symmetrical aspherical Devices equivalent is like by pressing the bezel controls according to the time described above, or, as it is equally easy, simple ones Rotational symmetries in optical elements due to regular movement of the focal point or to generate the beam intersection with respect to the body of the medium more complex optical elements preferably prepared using a device, the computer-controlled exposure allows. Combinations are preferred for this purpose from media that have little or no time delay to the radiation states react, and which remain stable after this reaction, used and that happens this together with an automatic feedback control (e.g. simultaneous Monitoring and inhomogeneity generation), but it is also possible to use materials that require subsequent aging or that of physical conversion are subjected to (e.g. the Jenny materials), in which after the generation of the Inhomogeneities and aging bring the optical element to its final state through the usual Finishing and polishing can be brought in.

Many test systems for optically inhomogeneous materials appear in the literature and can simply for the desired control feedback process be modified. A first example is the control feedback system, such as it in US-PS 3,587,195 under the title "Optical Surface Generating Method and Apparatus1, this application being briefly referred to in US Pat. No. 3,658,528 is described. Although this contraption was designed around the surface design Monitoring and guiding an optical element is what it is for the present slightly different purpose directly applicable. Other surveillance techniques that m the Manufacturing apparatus of US Pat. No. 3,829,838 can be connected and useful for the purpose described herein have been published by Wyant, O'Neill, and MacGovern in Appl.Opt. Vol. 13, 1974, 5. 1549 and also by Nadov (loc. Cit. 5. 1551). Other useful systems have been found by Tomlinson and Aumiller in Appl.Opt. Vol. 14, 1975, 5. 1100 and by Hunter and Schreiber Appl.Opt. Vol. 14, 1975, p. 25. Another such system is described by Brodnar and Ratajczyk in Appl.Opt. Vol. 4, 1965, 5. 181 described. Another technique that is a double exposure holography is used by Küpper and van Dijk in Rev.Sci.Instr. Vol. 43, 1972, p. 1492 described.

The combination of the test systems described in the previous paragraph with suitable beam steering devices as described in U.S. Patent 3,658,528 or other control systems is a trivial task for professionals the field of elementary optics and electronic control. The following brief description defines the basic elements of such a system for control, feedback and structuring.

In FIG. 18, a volume of a medium 1 is indicated which is caused by radiation states can perform evoked energy level changes, as they are referred to as combined Effect of the two laser beams 3 and 4 at point 2 are displayed. The lasers are equipped with beam intensity control and deflection devices 5 and 6, which can be built in many ways (see US-PS 3,829,838, there are construction and operational details). 7 is a pattern generator and 8 is a receiving device, can input the received signals in digital form to a computer 9, which also contains information, which relate to the desired optical property of the volume 1, contains.

The computer 9 controls either directly or through additional computers and Control functions the control and deflection devices 5 and 6 in the correct Way to adjust the properties of the optical element in the desired manner (see the above-mentioned patent for details on the computer parts).

41. The image produced by a "Woodtian lens" is not free of image errors. To get an axial image free of spherical aberrations the third To generate order, the coefficient of the next expression N2 is needed for N (R), so that: N (R) = N0 - N1 i N N2 Should still be the fifth order of the spherical deviation corrected, a coefficient N3 is necessary and the expression is called: N (R) = N0 - N1R2 - N2R4 -N3R6.

In Fig. 19 is a "generalized Wood's lens" with a light beam seen moving from an axial object point to an axial image point. D. Moore describes in J. Opt. Soc. At the. Vol. 61, 1971, 5. 886 the index distribution for such a lens. This data appears here as Table 3 and contains the Results of a calculation of N1 and N2 in such a way that the system does the prescribed Has a back focal length and corrects the spherical aberration of the third order is. The special value of the optical elements with a radial gradient of the Inhomogeneity is denoted by the size of N1: It is very easy to a generalized Wood's lens1, with a back focal length of 10 cm and a Make a radius of 2 cm In this case, coma, astigmatism, Image curvature and distortion not corrected. The fact that in this "generalizedE Woodt's lens, the spherical aberration of the third order is practically zero has been reduced, is particularly important and can with a normal lens, whose Curvature of a minimal spherical aberration could not be achieved.

42. D.Moore has computationally in the J. Opt.Soc.Am. Vol. 61, 1971, 5. 886 to 894 the effect of a planar index distribution on the control of the Aberration shown. It has been found that the contribution of an inhomogeneous Surface is most effective in controlling spherical aberration and therefore has the same effect as an aspherical surface. It surrenders also that the contribution of the passage is small and therefore a change in the Strength has little effect in correcting third order aberrations.

It is well known that when astigmatism and Petzval curvature are in a lens are present, a stop exists for which the disturbance is the same Is zero. Using a flat index distribution, two spherical surfaces and a stopping point so it is possible the third order spherical aberration, that Correct coma and aberration. Fig. 13 shows such a lens, Table 4 gives the construction data.

A corrected lens of this type can be made using the device 17, using an energy transfer means such as it is described in Example 37. However, the device with feedback after Fig. 18 is not used, then the possible accuracy is due to discrepancies in the composition and the like. not the greatest. With careful control it can however, such an approximation is useful for non-critical optical components be. The following calculations are used to determine the basic requirements to be determined by the medium and the radiation quality.

A. Calculation assuming an external radiation state it and an inner radiation state transmitted by an energy transfer medium.

For a simple case it is assumed that the excess of photons over the number of energy-transferring molecules in the medium at least 100: 1 per cm3 of the medium volume means that the maximum thickness of the medium is a few Millimeters and that the energy transfer has the effect of polymerization and to increase the refractive index, then the refractive index is an increasing one Function of the total radiation received.

This function can generally be expressed by the following formula recover: n = flj + b / (24) where ni is the initial refractive index of the medium The beginning of the radiation is g is the total recorded at a distance h from the axis Is the amount of radiation and b is a constant.

The expression: describes the principal spherical aberration of a thin lens, where r is the lens radius, f is the focal length and A is a constant. By comparing this expression to the change in focal length resulting from a change in the convergence of the lens from the center to the edge, we get the formula: We now turn to the classical optical relationship, which connects the relative change in index with the relative change in focal length and is written: and compare these two formulas (26) and (27), then we get: where A is a constant and the formula expresses the change in the index of refraction that can be achieved at point M of the lens which is h from the axis in order to force a focal length variation which corrects for the principal spherical aberration resulting from that point .

A comparison of the above equations (24) and (28) results in the further calculation formula: zXn = nn = -ah2 = n. + Bn n0, where n0 means the refractive index on the axis, where h = 0, n = n0> = 6o is, and # means the total amount of radiation received on the axis, and therefore: O = nl + b0 - n0 and B Calculation assuming external radiation states that interact within the medium. In this operating mode, the important relationships are similar to those previously described, except that here the structure can be influenced at discrete depths, which means that interfaces can be attached in a controlled manner of this kind, it is necessary to consider the overlap size and quantum yield factor, which are similar for other types of structures but are described here in such a way that they apply to the case where inhomogeneities in the refractive index result from direct processes. There is then a direct connection between the cessation of the polymerization (and therefore the increase in the refractive index) and the decline from an excited state, which was achieved by an excitation process of at least two steps the structured optical inhomogeneity coincide. In this case the degree of polymerization will be a function of the efficiency of the polymerization through free radials, which in turn will be a function of the efficiency of the reactioxide process which will be stimulated by the disintegration of the last excited state of the structuring process. All of these can best be related to one another, and the final production of the optical inhomogeneities in a given area of the medium will then be a function of the following expression: where N is the density of the excitable type of molecule, V is the volume of the beam intersection, 112 and 123 are the average beam intensities, B12 and 325 are the Einstein absorption coefficients for transitions between a first and a second excited state or from a second to one third excited state, respectively durch.hv1 and hv2, and t 51 is the quantum yield of the polymerization per transition from the third excited state to the lowest state, N is the number of R times per second addressed locations and it was assumed that in each of the R times, at which a location was addressed, a pumping process was initiated by a single pair of temporally separated pulses, which enter in the order hv1 followed by hv2 so that the side from the beginning of the hv1 pulse to the end of the hv2 pulse is much shorter than the lifetime of the second excited state. Obviously, for maximum effect, it is desirable to make the term B12.B23.31 as large as possible.

45. While in example 35 the benefit of a distribution with radial Gradient that replaced the aspherical curvature is shown in the present If the radial gradient shown in FIG. 14 is used, namely in a single lens with a radial gradient like that in Wood's generalized Lens was used: N (R) = N0 + N1R2 + N2R4.

In this case, the construction data are given in Table 5.

It can be seen that three aberrations (the spherical, the coma and the Astigmatism) through an adapted choice of curvatures, strengths and values of N1 and N2 were corrected, while the distortion by changing the Halt point has been corrected. The Petzval field curvature remains uncorrected. These Lens is of all third order deviations except for the Petzval curvature free.

The focal length of a single lens with a radial gradient is given by the formula: given, where the upper expressions apply to N1 4 0 and the lower ones to N1> °, f is the focal length, CO is the first surface curvature, C1 is the second surface curvature, t is the mean thickness, the function of the refractive index is the same and For values (kt) 24 <1, this equation can be approximated by whereby is.

44. A more complex optical element is shown in FIG.

Here are two elements of equal thickness and with cylindrical faces with the same refractive index connected to one another to form an aplanar telescope lens to accomplish. While an equivalent lens could be created by two Wood t cal lenses, which can be made according to the GRIN or Sinai method this double telescope lens directly through within a single block of matter the present invention can be created. A similar element but with one Air gap, was described by Matsumara in US Pat. No. 3,637,295 using the GRIN technique was used to obtain two elements with radial gradients.

The two aberrations that have been corrected are the spherical Deviation and the coma. The design data for this corrected lens is compiled in table 6.

45. A lens with an aperture ratio of f / 6.3 is shown in FIG. It is a single lens with a cylindrical Index distribution. It has approximately the same spherical aberration, the same Coma, the same tangential and arrow field curvatures as a homogeneous photographic one Single lens with the ratio f / 1 1.

The half-field angle is 25 °, the aberrations are larger overall than of the third order. This lens has a difference in refractive index from -0.008 between the center and the edge of the lens. Table 7 gives the design data of this lens. A second lens with f / 1 1, its aberrations overall largely compared to a homogeneous photographic single lens f / 1 1 is listed in Table 8.

Various attempts have been made to determine the possibility to research training a volume calculator storage. One of these attempts used holography and was originally developed by van Heerden in Appl.Opt. Vol. 2, 1963, 5. 393 described. The infamation is stored as an interference pattern that extends through the entire volume of a room hologram. On one such attempt a control of the attachment is not possible and an information coding is found does not take place therein (e.g. the gradations in the optical density or in the refractive index develop through randomly placed patterns of interference fringes, where During the readout process with coherent light, the information is obtained through interaction with the entire supply of stored rings is resurrected). Such a memory is "page-organized" and right from the start for exchanging information with one Digital computer poorly suited.

Some researchers have described three-dimensional storage systems, in which areas with a special composition within the volume of a memory content can be created in which each bit is a positive or negative information bit represented according to its state and its place of arrangement. Two researchers have used thermal effects to write bits in volume memory, e.g. In US Pat. No. 3,715,734, a method is developed to convert carbon domains into one to create a three-dimensional arrangement from plastic, and an improved system US Pat. No. 3,820,087 uses melted areas of crystalline material to represent a negative bit incapable of harmonic generation and results in increased readout selectivity.

A number of researchers have described systems that allow the lightweight Access to two-photon absorption processes take advantage of them in our system according to class 1, groups 2 and 3 are present, but they have the value of these processes in the selective activation of real photochemicals Conversions not recognized. Instead, the energy supply was used to provide a To put material into an excited state condition that is artificially created via a can be sustained for a certain period of time. This excited state condition of Electrons in a crystalline matrix are not stable (see e.g. US-PS 5 466 616, 5 654 626 and 5 940 748), so that the memory is both under the normal Light and temperature conditions as well as when reading is inconsistent. The US PS 3 508 208 (Duguay and Rentzepis), in which materials capable of fluorescence (anthracene, Pyrene and 3,4-Benzopyrene) are frozen to programmed bits in the excited Maintain state before emitting a radiation and then by detecting the emitted Reading fluorescence on return to the ground state show a clear difference to the present invention, in which these same materials in an entirely used in any other way.

According to the Duguay and Rentzepis method, a greater volume will be made of a material such as anthracene used as a bipolar storage matrix in the the two states are the ground state and an excited state. After reading (in the absence of special reprogramming through feedback) that is Material, in turn, is a homogeneous volume of anthracene in the ground state. In the present Invention is programmed by placing the anthracene molecules between the two stable ground states of the monomers and dimers using the systems change to class 1 or class II (see also US-PA 544 480, there are for the same purpose applicable single-photon processes are listed) how already described earlier (see pages 40 to 43 and on pages -50 to 52 examples given.

It was noticed that the same transitions using other, two-photon systems described here can be carried out) have this Materials have different properties, such as ability to fluoresce or the lack of ability. In this way you can e.g. Determine the type of a programmed bit by bringing it into radiation states, which cause fluorescence reactions in the programmed bit, but this in the unprogrammed bit do not do. It should be noted that in this case none Extension of the excited state is necessary, and that after reading the fluorescent Bit returns to a stable ground state, which is different from the other stable Ground state of the molecule before programming.

It should be noted that these new systems make use of a whole A number of new storage materials are allowed instead of the special crystalline materials or the cryogenic methods of the prior art. Virtually any photochemical Conversion at selected points required for bit storage bring about differences in the absorption behavior at these programmed points, which by the in U.S. Patents 3,715,734 3,654,626 or 3,940,748 can be (see also the report by Geller and Taylor "Thre-e-Dimensional Information Storage in Alkali Halides by Two-Photon-Absorption "from January 4th, 1971, available from the Naval Electronics Laboratory Center under number NELC / TR 1749 is). Similarly, bit elements that can be distinguished by excited emission and by fluorescence are, advantageously with the detection system as described in U.S. Patent 3,508,208 is'or can be read similarly. Unlike crystalline materials, perfect Memory arrays of any size made with amorphous plastic materials with highly qualified optical properties.

Probably the biggest advantage of the storage systems presented here lies in the possibility of very rapid electronic transition processes, such as absorption and internal conversion (between 10 9 and 10 15 sec) instead of the proportional one slow mechanisms of fluorescence emission or the like (10 5 to 10 9 sec). Many photochromic processes are also very fast. To find out about these operations and to inform their application, see earlier, from Sylvania Corporation available report from Lewis C. Clapp entitled High Speed Optical Computers and Quantum Transition Memory Devices ". These and similar schemes (US-PS 3,341,825) are of the two-dimensional mode of operation according to the method of this invention expanded to a three-dimensional space storage system. You can do the same from say other two-dimensional storage systems based on photochemical transitions are based, e.g.

that of S. Maslowski in Appl.Opt. Vol. 13, 1974, p. 857, which produce opaque spots detected by the method of U.S. Patent No. 3,715,734 / can be. A method was also discussed in an earlier section of this application for In-Place Made Fiber Optics ". There are in the literature a large number of optical computer schemes which require manual fiber optic Use procedure. It is obvious that using combinations of radiation states and memory matrix compilations it is possible to have such integrated Build systems only through optical devices and rely on the methods of three-dimensional To expand volume storage. (See Burt et al. In Apl. Opt.

Vol. 12, 1973, p. 1213).

Although the bits themselves are preferably stored, there is also nor the possibility of the principles according to the invention for generating a holographic To use volume storage.

An important aspect of the effectiveness of some designs where Light emission takes place or light conduction is required to store radiation in To place, there are various devices for determining and controlling vectors. For example, it is done by optically isolating areas where there is fluorescence occurs, it is possible to treat these areas separately and perform parallel operations to perform in different parts of the store. As a general term for Devices for the optical isolation of sections of a three-dimensional volume the word "hodoscopy" is used; there are many different types, e.g. the Hinterberger and Winston instruments in Rev. Sci. Inst. March 1968 5.419 or Gottschalk (Rev.Sci.Inst. Jan. 1969, 5. 22) or the analogies of the scintography process, as described by Schmitz and Feuerhake (in Phys.Med. Biol. Vol. 15, 1970, pp. 649 to 656) useful mathematical treatment methods are also given.

The ability to generate it on the spot should also be mentioned Fiber optics, selected distribution or subdivision of storage by direction (where they lead) and by filtering out certain wavelengths (the she could forward to allow. Adaptable to optical isolation Facilities are described by M.Oda in the book "Small Rocket Instrumentation Technology1,1 published by North-Holland Verlag, Amsterdam in 1966, pp. 176 ff.

and by the same author in Appl.Opt. Vol. 4, 1965, p. 143.

Another way of dividing memory, alone or in Connection with the above can be applied is the temporal instead of spatial subdivision.

Modern electronic processes allow millions of events per second are checked individually over time and that they are differentiated from one another will. For example, Keene and others in Rev.Sci. Instr. Vol. 40, No. 9, 1969, 5. 1199 examples of such a device. In another essay, use yuan and post fast electronic procedures to locate an emission event in space, the device being adapted to a position determination according to the coordinates x, y and z can be (see Rev.Sci.

Instr. Vol. 23 No. 10, 1952, 5.553 and Jenes, Je Scientific Instr. Vol. 37, 1960, pp. 318 to 323).

Above was the filtering ability of waveguides generated in place and a variety of other properties of integrated optical systems can be included in advantageous embodiments according to the invention. Basic Claims to such circles were made by Marcatelli in Bell Syst.

Techn. J. Vol. 48, 5. 2071 ff. -And von Goell, in Bell Syst.Techn.J.

Vol. 48, p. 2133 described. Filters, directional couplers, and even laser devices (see the previous example with polymethol paints) can be prepared. While the Use of individually controlled (directed or converted, e.g.) Radiation states of a beam are generally preferred means to bring about change in the energy level according to the invention should still holographic patterns, e.g. point arrangements in one or in several planes, the projected by a hologram lens may be mentioned as an alternative. Such projected real holographic images as means, three-dimensional patterns of a physical chemical nature were first introduced by Swainson in his Danish Patent application dated July 12, 1967, and this process is part of US-PA 165 042. In some versions, the intersecting beams are focused Using radiation, such holographic patterns can be of particular value, e.g. in that they can simultaneously provide beams which are multiple Have high energy foci.

As in the other applications of the present invention, e.g.

three-dimensional color pattern images, fade-resistant pattern image for manufacturing purposes, structures with variable refractive index, etc. it will often be possible to start from known single-photon absorption data, if Storage systems are designed. A useful compilation of data, one-photon energy requirements Concerning a large group of changeable materials, Tufte and Chen in IEEE Spectrum, Vol. 10, 1973, p. 26. This literature passage and the one in it cited provide information useful for the purposes of the invention on both changeable materials, as well as matrix materials> the former with preservation their changeability / can be included.

Because of the sensitivity of the instrumentation to light emission uses a preferred embodiment of the invention Storage structures, which are read by processes that programmed such light emissions Cause bit positions, or the changeable properties of such a light emission E.g. in the wavelength, use it as a bit memory. Examples 25, 27, 29 and 32 describe preferred materials for this purpose. The properties more suitable Materials are well described, e.g. those of dimers (see Tomlinson et al. In Appl.Opt. Vol. 11, 1972, 5. 533) and Birks and Christophorou in Nature, Vol. 197, 1963, 5. 1064 and the quotations in the addendum to "Scintillation CountinU, page 631 and the essay by Salmon and Chandross in Anal.Chem. Vol. 45, 1973, p. 2446, which valuable information about the matrix and details of the absorption and reactivity structures of n-amyl anthroate. The laser properties of restored dimers are von Fork, German and Chandross in Appl.Phys.

Lett. Vol. 20, 1972, p. 139. Others particularly well-known and useful materials were found in Example 32 page 51 and in earlier examples mentioned, including in particular the isomazoles (5th example 25, as well as Ullman and Singh in J.Amer.

Chem. Sol., Vol. 88, 1966, 5th 1844, Singh et al. In the same journal Vol. 94, 1972, p. 1199). Similar properties of light emission and stability in a plastic matrix make the materials described in US Pat. No. 3,899,687 especially interesting.

A final group of preferred materials are the indigo color derivatives , here especially the thioindigo and diacetylindigo materials used by Blanc and Ross in J. of Phys. Chem., Vol. 72, 1968, p. 2817 and Rogers et al. in J. of Amer. Chem. Soc. Vol. 79, 1957, p. 2464. These materials were used in the experiments No. 27 and 29 on page 3 of this application. Table 11 shows some Examples of areas of one-photon reactivity some of these Materials effective in converting non-fluorescent to fluorescent forms they show the one-photon radiation that causes fluorescence and the emission range of fluorescence. The materials that make reversible cis-trans isomeric transitions (see Plate 11 and the citation from Zweig in Example 32) Particularly useful for reprogrammable, light-emitting memories. A number of useful mechanisms to effectively change the cis / trans ratio, are discussed by Kan (Organic Photochemistry, pp. 20-23), including are the optical pumping "and the use of sensitizers that selectively do one thing or make the other isomer predominate (see also the quote above from Kan, 5. 22-23).

While the preferred structuring mechanisms of the invention are light radiation combinations with other types of radiation are also possible. A big Group of inorganic Phösphat glasses, which under irradiation with short-wave UV or become fluorescent with particle irradiation have been reported by J.H. Schulman in one Overview "Survey of Luminescence Dosimetry" in the by F.H. Attix, at the US Atomic Energy Commision, Division of Technical Information, Oak Ridge, Tenn. Issued in 1967 Book luminescence dosimetry ". It can be clearly seen that a great Part of the materials with special dosimetry in the manufacture of fluorescent products were used, including on the energy equivalents of two-photon energy react with short-wave ultraviolet radiation, and used for the invention can be. Similar dosimetry materials, which change in coloration or in the transmission of light have been reported by A. Charlesby in "Atomic Radiation and Polymers ", Pergamon Press, N.X., 1960, pp. 101-107.

While many of the materials used in the invention are bipolar a ground state or an excited state S, it is for very fast Memory operations possible, the bipolarity of the excitation states of the upper levels to use. For example, vibrational cascade mechanisms work at times in of the order of 10-9 to 10-12 sec., and internal transition mechanisms work with times of the order of 10 13 to 10 14 seconds compared to fluorescence processes, the times in the order of 10 5 to 10 9 seconds. Details are in the citation by Lewis C. Clapp and in US-P53,341,825.

As with the other products according to the invention with structured Inhomogeneity is the case, memories with different of the many-photon systemx can also be used operate.

The examples are intended to explain the systems and how to use a particular material is not necessarily specific to the particular class or group of an example.

The use of the same rays both in reading and in Writing is of particular value in storage systems because of the increased accuracy, with which a bit can be located and reattached, since the effect of the small optical imperfections compensate for each other when used for different processes the same optics are used.

When different beams or combinations of different system groups are used, comparison bits with a known arrangement can be used will.

Fig. 23 shows a preferred embodiment of the invention in which the matrix is a non-crystalline, homogeneous material is this programmed and read by many-photon I-mechanisms of class 1 or II and can be programmed again. In this case, the bit information in Saved form of a bistable material that is between fluorescent and non-fluorescent States controlled back and forth by a many-photon absorption mechanism can be. Different combinations of lasers, choosing between the different ones Class 1, Groups 1, 2 and 3 and Class II, Groups 1, 2 and 3 systems, the choice between storage properties, such as color, polarization, permeability for particular wavelengths, fluorescence and excited-emission, the range of Reversible and non-reversible storage materials - all of this literally results Thousands of combinations that are used for the first time in the basic application described how they are in the unique access to and controlled structure a three-dimensional.

sional storage using many-photon absorption mechanisms and controlled and focused radiation.

An embodiment of the invention is shown in FIG.

There is a source of high intensity radiation seen at 27 and one tunable laser light source at 25. The memory is created by one of the mechanisms Class 1 Group 3 or Class II saved by intersecting each other Rays 32 and 34 at the interface 23 the formation of a fluorescent, for example Cause isomers. The memory is read by using the high intensity beam a retuned beam of high energy is cut that is so adjusted are that they follow the two-photon absorption band to achieve a fluorescence emission correspond. In this simple case, the Photodetector 31 to detect radiation emission depending on the state of the arrangement of the bit or not to capture. With a given two-photon structure, a ruby laser is used, which is provided with a tuning range of 400 µm to 600 nm in 25 nm interval areas is and S creates two-photon absorption energies to the activation structure of the material. When using a Nd-YAG laser and when tuning between 550 µm and 900 µm one obtains 15 other frequencies (Fig. 21), namely (ruby) 506 µm, 525 nm, 544 nm, 562 µm, 580 nm, 595 nm, 611 nm, 626 nm, 642 µm and (Nd-YAG) 724 µm, 744 µm, 764 nm, 784 nm, 804 µm, 822 µm, 841 µm, 860 µm, 878 nm, 894 nm, 910 nm, 926 nm, 942 µm, 958 nm and 972 µm. Continuous color matching of the Lasers using diffraction gratings, dispersion prisms, tunable etalons, birefringent filters and the like allows selective concentration in Ribbons that are only 1 nm wide and staggered tuning elements result in ribbons of 0.01 or less µm. This allows systems to be designed that, although only two beams are used, are highly selective, and multiple operations, such as e.g. the generation of fiber optic circular components, programming and reading out of memories and the other operations described above in a single matrix allow. The use of sensitizers when a particular material does not have any possesses appropriate two-photon absorption, the magnified, as previously described, the Possibilities> to design systems a lot and also the use of bundled radiation states gives further possibilities.

It is apparent that the photodetector 31 in Fig. 23 by a Replaced a large number of direction-sensitive detectors can be, as previously described in order to achieve separate areas of the memory can be operated independently of each other, and thus the capacity is increased. It also became the time division process using fast electronics described, which allows events according to the time in direct analogy to the similar technology in other areas. It was also mentioned that vector control of the radiation emitted by the vector of the exciting radiation when stimulated Emission processes can be determined, and polymethine inks have been described, which according to the invention can be used in internal laser elements. It was Reference is made to US Pat. No. 3,829,838, which contains a wealth of information on energy sources, Contains beam controls and mechanisms for the precise application that along with the other citations shows that the state of the art in these areas makes their description in this application unnecessary.

- Claims - TABLE 1 Refractive power versus aperture P = refractive power [diopters] = 1 - 2 N1d [N1] = m [d] = m Example: d = 5 mm = 5 x P = - 2N1 (5x10-3) = 1 m -1 = N1r2 = - 10-4 [mm-2] r2 Aperture r index (in mm) change 1 -10-4 10-0.01 25 1 -0.06 100 -1.0 The table on the left shows the change in the refractive index required for a change in the refractive power of one diopter at different aperture values.

Table 2 Different combinations of focal lengths f, refractive index coefficients N1 and strengths t with a basic refractive index No = 1.500 f / N1 / # N at r = 10 / t = 1 10 -0.0050 -0.5 20 -0.0025 -0.25 40 -0.00125 -0.125 80 -0.00063 -0.063 160 -0.00032 -0.032 t = 2 10 0 -0.0025 - 0.25 20 -0.00125 -0.125 40 -0.00063 -0.063 80 -0.00032 -0.032 160 -0.00016 -0.016 t = 3 10 -0.00167 -0.167 20 -0.00085 -0.085 40 -0.00427 -0.0427 80 -0.00021 -0.021 160 -0.00011 -0.011 TÄFBI, 3 index distribution for a "generalized Wood lens object image thickness N0 N1 N2 width width # -100 1.00 1.5000 .005011 0 # -10 1.00 1.5000 .051131 -.000176 # 100 1.00 1.5000 -.004989 0 -8.00 10 1.00 1.5000 .016700 -.000218 8.00 10 1.00 1.5000 -.111058 .000455 # 10 .10 1.5000 -.498881 .001607 # 10 .25 1.5000 -.198894 .000635 # 10 .50 1.5000 -.098899 .000311 # 10 1.00 1.5000 -.048908 .000149 # 10 2.00 1.5000 -.023927 .000069 Table 4 A) Flat index distribution N0 = 1.650 W1 = 0.065522 B) Radii r1 = 5.928 r2 = 419.71 C) Thickness t = 0.923 D) Properties of the lens EF = 10.00 BP = 9.40 EP = -0.79 ß = 17 ° Table 5 A) Cylindrical index distribution No = 1.522 N1 = 0.003932 N2 = 0.000052 B) Radii r1 = 16.667 r2 = -9.484 C) Thickness t = 8.75 D) Properties of the lens EF = 50 EF = 50.6 EP = -9.95 ß = 17 ° Table 6 A) Cylindrical index distribution, 1st area No = 1.6200 W1 = 0.032309 N2 = 0.003826 B) Cylindrical index distribution, 2nd area No = 1.620 N1 = 0.032309 N2 = -0.0040 08 C) Radii of the interfaces r1 = # r2 = Co r3 = D) Thickness between the interfaces t1 = 0.787 t2 = 0.787 E) Properties of the lens EF = 10.00 BP = 9.51 = 0.00 17 Table 7 A) Cylindrical index distribution No = 1.5215 N1 = 0.0036 N2 = 0.0 B) Radii r1 = 2.778 r2 = 5.416 C) Thickness t = 0.45 D) Properties of the lens EF = 10 BP = 9.44 EP = -3.70 ß = 26 ° opening: f / 6, table 8 A) Cylindrical index distribution No = 1.5215 N1 = 0.0044 N2 = -0.004 B) Radii r1 = 2.222 r2 = 3.615 C) Thickness t = 0.31 D) Properties of the lens EF = 10.00 BF = 9.45 EP = -3.40 ß = 26 ° aperture: 11 Table 9 List of different combinations of focal length (f), refractive index coefficient N1 and thickness ( t) with a basic index N0 = 1.450.

#N is the total index change based on values of the lens radius R.

t = 1 / f / N1 / approximately) / N1 (exactly) / # N for R = 2/10 0.050000 0.050568 0.20 20 0.025000 0.025148 0.10 40 0.012500 0.012536 0.07 80 0.006250 0.0062592 0.025 160 0.003125 0.0031273 0.013 t = 2 / f / N1 (approximate) / N1 (exact) / #N for R = 3/10 0.025000 0.025591 0.23 20 0.012500 0.012648 0.11 40 0.006250 0.0062865 0.056 80 0.003125 0.0031341 0.028 160 0.0015625 0.0015648 0.014 t = 5 / f f / N1 (approximate) / N1 (exact) / #N for R = 4/10 0.010000 0.0106362 0.27 20 0.005000 0.0051513 0.13 40 0.002500 0.0025374 0.063 80 0.001250 0.0012591 0.031 160 0.000625 0.0006273 0.016 t = 5 f / N1 (approximate) / N1 (exact) / #N for R = 12/250 0.000400 0.0004009 0.059 500 0.000200 0.0002002 0.029 750 0.000100 0.0001000 0.014 1000 0.000050 0.0000500 0.0072 t = 5 / f / N1 (approximate) / N1 (exact) / #N for R = 25/1000 0.000050 0.000050 0.032 2000 0.000025 0.000025 0.016 4000 o.0000125 o.0000125 o.0078 blackboard 10 systems according to class I group 3 table of energy requirements and wavelength of the 2nd laser if the first laser is a ruby laser (694 nm).

2-photon absorption - E keal / mol 2nd laser wave 400 nm 143 281 nm (or shorter) 440 130 322 480 119 - 368 520 110 416 560 102 470 600 95 532 640 89 598 680 84 668 720 79 757 760 75 846 800 72 929 840 68 1068 880 65 1202 920 62 1376 960 60 1536 1000 57 1811 1040 55 2074 1080 53 2426 1120 51 2921 T a f e 1 11 Excitable type of molecule converting h fluorescence emitting and result # generating hv tes hv 1. n-amyl anthroate * 300 nm 386 nm visible dimer # monomer 2. 5,5-Diphenyl-Iso- 254 nm 300 nm 389 nm oxazole # 2,5-Diphenyl-Oxazole 3. Thioindigo * 470 nm 542 nm 620 nm (cis # trans) 4. N, N-diazetylindigo * 440 nm 562 nm 620 nm (cis # trans) 5. 6,6-diethoxythio- 420 nm 546 nm 580 nm indigo (cis * 6. polyarylic Bicyclo-200-500 nm 300-400 nm visible heptan-7-one # Zyclohexa-1,3-diene 7. Bengal red # Fluores- (hv1 # hv2) 440-520 nm 518 nm zein 8. 3-Acryl-2-furyl * UV 430 nm 540 nm chromone acroleine * The materials marked in this way are photochromic and by the same wavelengths that they absorb in the non-fluorescent ones State traceable. As in conventional two-dimensional photochromic memories the light intensities are controlled in such a way that undesired extinction is avoided and reprogramming is possible. Wavelength specifications are approximate values and normally apply in styrene matrix. There are shifts in other matrices on.

n-Amylanthroate is particularly useful for a class of materials representative (see Tomlinson et al., Appl.Opt. Vol. 11, 1972, p. 533).

Table 12 Material (Xundstelle) Differential Refractive Index Efficiency Change of multicomponent polymer (1) 100% 1.5% Photochromic dedimerization 102 to 10 of crystals (2) 10-1-2 to 10-5-3 of a polymeric matrix (2) 10 4 up to 10-5 photopolymers (3) 1.415 - 1.5 photopolymers (4) 98% to 100% 5 # 3 X 10-3 Gelatin (5) 90% polymers (5) 10-3 to 10-4 polymethyl methacrylate (6) 5.1 x 10 to 3 x 10 polymer (7) 80% 2 # 5 x 10-3 to 3 # 5 x 10-3 polymer (8) .001 Organic Substance (9) 70% polymer (10) 46% polymer (11) 30% 1) Tomlinson, Applied Optics, Vol. 15, Feb. 1976, p. 534.

2) Tomlinson, Applied Optics, Vol. 11, March. 1972, p. 533.

3 Van Renesse, Optics & Laser Technology, Feb. 1972, p. 24.

4) Victor Files, U.S. Patent 3,707,371.

5) M.R.B. Forshaw, Optics & Laser Technology, Feb. 1974, p. 28.

6 Bowden et. al., Applied Optics, Vol. 13, Jan. 1974, p. 112.

7 Booth, Applied Optics, Vol. 11, Dec. 1972, p. 2994.

8 R.G. Brandes, U.S. Patent 3,547,509.

9) Bloom et. al., Appl. Physicy Letters, Vol. 24, June 15, 1974, pp. 612.

10) Colburn & Haines, Applied Optics, Vol. 10, July 1071, p. 1636.

(11) Bartolini & Bloom, U.S. Patent 3,926,637.

L e r s e i t e

Claims (23)

Claims 1. Device for generating no radiation emitting t) rei-dimensional basic state structure of a matter, thereby g e k e n n n n e i c h n e t that a. there is a volume of material that is in a multitude of different physico-chemical behavioral states exist and depending on a change in the energy level within the volume itself can undergo a change in the physical-chemical behavior, b. Guiding devices are present in order to change the energy level within the volume to produce, c. Control devices with the material volume and the guide devices cooperatively connected to the change in energy level within the volume distribute to selected locations, and d. at least one of the physico-chemical Behavioral states are caused by a photochemical process in which The primary absorption process is the absorption of at least two photons per an the type of response involved. 2 device for generating a three-dimensional structure according to Claim 1, g e k e n n n z e i c h n e t by a. a volume of a material that one undergoes a change in his physical-chemical state of aging can that it shows at least two recognizable different states, and on one radiation reacts to at least two specific radiation states possesses to bring about the change in physico-chemical behavior, b. one Device for generating at least two radiations, each one of the radiation states own. c. Control devices to control the radiations in front of the radiation device to lead into the material volume, whereby the material is clamped, under the effect of the two radiation states at selected locations between the two to change recognizable different states. 3. A structure generator according to claim 2, characterized in that g e k e n n -z e i c h n e t that the two radiations are two rays of a single beam and that the two different radiation states are two different port planting vectors of the two respective beams, and that there are means for the to focus individual bundles of rays at the selected locations. 4. A structure generator according to claim 1, characterized in that g e k e n n -z e i c h n e t that the different states states of differential polymerization lock in. 5. A structure generator according to claim 1, characterized in that g e k e n n -z e i c h n e t that the different states visibly different optical Include properties. 6. A structure generator according to claim 1, characterized in that g e k e n n -z e i c h n e t that the different states states of different indices of refraction lock in. 7. Device for generating an optical element, g e -k e n n z e i c h n e t by a. a volume of a material that is distinguishable in a multitude Refractive index states exist and undergo a change in the refractive index state in response to changes in energy level within the volume, b. Guide devices of at least one cooperative radiation state and an energy transfer means for the local generation of the energy level change, and c. Control devices, with the material volume and the control facilities are cooperatively connected to the change to distribute in the refractive index within the volume at certain points. 8. Device for generating an optical element, g e -k e n n z e i c h n e t by a. a volume of a material that is distinguishable in a multitude Refractive index states exist and undergo a change in the refractive index state in response to changes in energy level within the volume, b. Control devices for at least two cooperative radiation states in order to change the energy level to be attached, and c. Control devices that deal with the material volume and the guiding devices are cooperatively connected to the change in the refractive index within the volume to be distributed to selected positions. 9. An inhomogeneous optical element as produced in claim 1 was indicated by the fact that the structure has a controlled distribution the change in the refractive index. 10. A structure generator according to claim 1, characterized in that g e -k e n n z It is true that the various states can be separated. 11. A structure generator according to claim 2, characterized in that g e k e n n -z e i c h n e t that a. the first radiation state comprises a signal with one such Frequency that simultaneous absorption of two photons from the first signal by the material is sufficient to excite electrons from the lower to the higher state, and with an intensity which is insufficient to produce the structure, and that b. the second radiation state comprises a second signal with such a frequency, that the simultaneous absorption of two photons from the second signal is not sufficient, to excite electrons from the lower to the higher energy state, and with of a sufficiently large frequency and intensity to produce a structure through the mechanism to generate the simultaneous two-photon absorption in that section of the medium, in which the first and second signals overlap each other simultaneously, whereby the Material is forced to pass from the lower to the higher energy state. 12. A structure generator according to claim 2, characterized in that g e k e n n -z e i c h n e t that a. the first radiation state with a signal of such a frequency that the simultaneous absorption of two photons from the first signal through the material is enough to get electrons from the lower one in the higher state, and with an intensity that is not enough to stimulate to allow the transitions to occur to create a structure, and that b. the second Radiation state includes a signal with a frequency such that simultaneous Absorption of two photons from the second signal by the material is enough to To excite electrons from the lower to the higher state, and with an intensity which is not sufficient to allow the transitions to occur to create a structure, and that c. the first and second signals by the means for generating a Structure are forced to cooperate within the material in order to be selected Imagine creating a cooperative signal whose intensity is sufficient to make the transitions to allow a structure to occur. 13. A structure generator according to claim 2, characterized in that g e k e n n -z e i 0 h n e t that the material is in a lower state and in a multitude of higher ones States can exist, bad that the first radiation has an energy that the transition of the material from the lower state to at least a higher excited state State corresponds, and that an intermediate state of the medium is present and one second radiation has an energy that allows the transition of the material in the medium in the intermediate state corresponds to a further excited state that is not is the same as the first higher excited state. 14. A structure generator according to claim 1, characterized in that: g e -k e n n z e i n e t that the material used in a variety of physico-chemical Behavioral states may exist, including one type of molecule, the photochemical Stimulation is capable of increased energy levels and is called a sensitizer is, and that a second molecular component is present, the at least one Part of the energy can be obtained from the sensitizer, but that alone is the radiation to that which stimulates the sensitizer, is insensitive. 15. A structure generator according to claim 1, characterized in that it is g e -k e n n z e i c h n e t that the structure has energy from an outside of the volume Source can receive, thus generating a response to another change in the physico-chemical state of behavior of the medium. 16. A generator for producing a molded product according to claim 10, due to the fact that the interface between areas of matter, which can be separated is determined by the location of points making up the area interacting radiation states affected, and that after the structure formation Matter in a vector direction from the location of points from physico-chemical properties shows that are different from the properties of matter in the opposite Vector direction from the location of points. 17. A three-dimensional volume calculator memory, manufactured according to the method of claim 1, characterized in that the various Physico-chemical behavioral states at least a binary distribution that is distinguishable Include states that represent bit information. 18. A three-dimensional volume calculator memory, manufactured according to the method of claim 1, characterized in that the various physicochemical states include storage information of the analog type. 19. A reprogrammable memory according to claim 15, characterized in it is not stated that the binary states are caused by photochemical processes are interchangeable, which is selectively induced by interacting radiation states will. 20. A three-dimensional volume computer storage system, in the prograinin function in that a. a volume of storage medium a Contains programmable molecular species that are photochemical in response to energy level changes converted into a second, different basic state condition within the volume can be. b. Guiding devices are present to the inside the volume Generate changes in energy levels. c. Computers and control devices are in place to process input data record that indicate the position of at least one point within the volume, and to calculate the control signals therefrom, the control devices responding to the control signals react to cause the changes in energy levels to occur within the Material volume cooperate at at least one point therein in order to, accordingly the position of this point determined by the control signal there the programmable molecular type of the medium in the storage volume at that point To bring transformation into the different basic state condition, and that in the Memory read functionality included are: d. Recording computers and controllers of the input data that designate the location of the at least one point and for Calculating the control signals therefrom, and e. Guiding devices that refer to those in section d) of this claim, indicating the location of the at least one point Control signals respond to a change in energy level within the point enclosing volume, and f. detection devices to detect the different Response of the programmable molecular species at the point to that described in section -e) Change of energy level from the reaction of any other material at this point to distinguish. 21. A computer storage system according to claim 20, wherein g e -k e n It should be noted that the different reaction when reading out is a property of light emission is. 22. A computer storage system according to claim 20, characterized in that g e -k e n Do not note that the different reaction due to the difference of the Absorption structure between a Bese point, which is a first radiation state which it has absorbed, causing a change in the excited state compared to a Bese point which is not the first radiation state was exposed, the difference being in the absorbent structure by a second selected radiation condition is detected at such a time penetrates the point that it is possible to distinguish the excited state through the different To detect absorption of the second selected radiation state. 23. An inhomogeneous optical element, produced according to claim 8, thereby it is noted that the structure has a controlled distribution of refractive index variations is.