WO1998046799A1 - Method for photolytic liquid phase synthesis of group iv nanocrystalline materials - Google Patents
Method for photolytic liquid phase synthesis of group iv nanocrystalline materials Download PDFInfo
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- WO1998046799A1 WO1998046799A1 PCT/US1998/007175 US9807175W WO9846799A1 WO 1998046799 A1 WO1998046799 A1 WO 1998046799A1 US 9807175 W US9807175 W US 9807175W WO 9846799 A1 WO9846799 A1 WO 9846799A1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical class CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B41/00—Obtaining germanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24909—Free metal or mineral containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
Definitions
- the invention relates to novel dispersions of Group IV elements having nanocrystalline sized domains and a method for the liquid phase synthesis thereof.
- Germanium and tin are advantageous over comparable alternative materials because the well established processing techniques associated with silicon are amenable to use with these other Group IV elements. Investigation of the quantum size effect in the Group IV elements silicon, germanium and tin have been hampered by the inability to produce macroscopic quantities of such particles.
- the desired samples consist of particles that are: monodisperse; of tunable domain size on the dimensional scale wherein quantum size effects are observed, typically from 1 to 20 nanometers; amenable to variations in the surface passivating functionalities, which serve to prevent agglomeration and formation of bulk domains; produced in macroscopic quantities; dispersible in a gaseous or liquid carrier, thereby facilitating isolated particle behavior; and amenable to doping with various ions and molecular dyes common to the art.
- the metathesis reactions used to produce nanocrystals of Group II- VI semiconductors are inoperative.
- a nanocrystal is defined as a crystalline particle having cross sectional dimensions ranging from about 1 to 100 nanometers (hereafter nanometers are designated as "nm"). Metathesis reactions become increasingly difficult as the polarity of the resulting bond decreases. While Group II- VI nanocrystal materials such as CdS are readily produced from molecular precursors in an aqueous liquid phase solution ( M.L. Steigerwald et al., J. Am. Chem. Soc. 110, 3046 (1988); D. j. Norris, A. Scara, C.B. Murray, and M.G. Bawendi, Phys. Rev. Let. 72, 2612 (1994; H.J. Watzke and J.H. Fendler, J.
- Polycrystalline silicon and nanocrystalline silicon have been produced by a variety of well known techniques such as evaporation (S. Ijima, Jap. J. Appl. Phys.26, 357 (1987)), gas phase pyrolysis (K.A Littau, P.J. Szajowski, AJ. Muller, A.R. Kortan, L.E. Brus, J. Phys. Chem. 97, 1224(1993)), gas phase photolysis (J.M. Jasinski and F.K. LeGoues, Chem. Mater. 3, 989 (1991);), electrochemical etching (V. Petrova-Koch et al., Appl. Phys. Lett.
- evaporation S. Ijima, Jap. J. Appl. Phys.26, 357 (1987)
- gas phase pyrolysis K.A Littau, P.J. Szajowski, AJ. Muller, A.R. Kortan, L.E
- Such stabilizing agents have illustratively included soaps and detergents of fatty acids, resins, polyphosphates, organic polymers, chemically bonded small organic molecules of molecular weight less than about 500 and containing a nonfacile heteroatom such as O, N, S, P and the like, which serves to adsorb the molecule to the particle; clays and biopolymers such as albumin.
- Organosilanes have a well established chemistry as decomposition precursors to silicon.
- the gas-phase, ultraviolet (UV) photolysis the of organosilanes, tetraethyl- and tetravinyl-silane shows a stepwise elimination of 2- carbon aliphatics, resulting in the production of SiH 4 , using the ArF laser line at
- the UV absorption cross section of silanes and disilanes of the form R 4 Si and R ⁇ Sij, respectively, generally increases at longer wavelengths with increased molecular weight and increased bond delocalization.
- Silanes also show a shift to longer wavelengths in the absorption cross section upon dissolution in a solvent. The shift to longer wavelengths is more pronounced in a polar solvent, such as ethanol as compared to nonpolar solvent such as isooctane.
- the "red" shift in absorption is associated with an increased stability.
- Organosilanes also form polysilanes under certain reaction conditions. Common reactions leading to polysilanes include condensation with alkali metals, dehydrogenative coupling in the presence of a suitable catalyst, and strained cyclosilane ring opening polymerization. A general discussion of polysilane chemistry is included in Inorganic Polymers by J. E Mark, H. R. Allcock and R. West, Prentice Hall, Englewood Cliffs, New Jersey, 1992, Chapter 5; which is incorporated herein by reference. Polysilanes generally undergo chain scission upon exposure to ultraviolet light. Under exhaustive UV exposure disilane is a major scission product of polysilane reaction.
- aryl, and carbon-carbon double bond containing groups bound to the silicon atoms of a polysilane are known to undergo free radical cross-linking, as well as chain scission under UV exposure, thereby creating silicon atoms which are indirectly linked by means of the aliphatic units.
- organosilanes analogous chemistries exist for organogermanium and organotin compounds.
- the photochemical decomposition of such organometallics are shown in the instant invention to be amenable to the production of particles of silicon, germanium and tin with properties heretofore unattainable.
- the photolysis of the organometallics has often been carried out with UV photon sources
- infrared multiphoton decomposition of tetra-ethylsilane, -germanium and -tin has been reported to initiate with the cleavage of the (Group IV element)- carbon bond, as reported by T.Majima, K. Nagahama, T. Ishii, Reza Kagaku Kenkyu, 9, 17 (1987).
- the Group IV elements silicon, germanium and tin form nanocrystalline particles of the separate elements, by the photolysis of organometallic precursors of the aforementioned elements in a solvent that further contains a passivating agent to stabilize the particles upon formation.
- Ultraviolet light is the preferred photolysis light source.
- the factors involved in selecting an organometallic precursor which is operative in the instant invention include: absorption cross section at the incident light source wavelength(s), solubility in the solvent, and chemical driving force for the removal of precursor organic fragments. Photolysis of the Group IV precursor of the instant invention in a suitable reaction vessel creates nanocrystalline domains of the Group IN element.
- An organometallic precursor of second element which is not restricted to Group IV is optionally added to the reaction to create doped nanocrystals. These particles are also amenable to incorporation of dopant ions known to the art of bulk Group IV technology, in order to modify illustratively the electronic, luminescent and physical properties of the nanocrystals.
- a passivating agent serves to keep the nanocrystal particles from aggregating and additionally to exert control over particle solubility and surface chemistry.
- the photolysis reactions described herein are generally performed under an inert atmosphere of about one atmosphere pressure or below.
- the instant invention creates particles of silicon and germanium that are themselves novel. Particles are formed which have a size distribution of less than twenty percent of the particle diameter in the size regime wherein quantum size effects are observed. Quantum size effects are defined to include non-bulk: energy band gap, or photoluminescence or melting behavior observed in particles of a given size.
- the particles are optionally stable in solution phase and have a selectively controllable surface chemistry via the surface passivating agents employed. Furthermore, the resulting particles are generally free from reaction byproducts.
- Figure 1 is a schematic diagram of a an operative arrangement of reaction components in the instant invention.
- Figure 2 is a transmission electron micrograph showing a field of silicon nanocrystals produced by the current invention, as described with reference to Example 1.
- the length bar represents 50 nanometers and the arrows point to individual particles contrasted against an amorphous carbon support film.
- Figure 3 is a transmission electron micrograph showing a field of silicon nanocrystals produced by the current invention, as described with reference to Example 4.
- the length bar represents 50 nanometers.
- the basis of the current invention is the identification of reagents and conditions for the photolytic formation of silicon, germanium or tin particles in a liquid solvent. While it is appreciated that the photonic reaction energy may be supplied from various portions of the light spectrum, it is a preferred embodiment that ultraviolet radiation be used, owing to several considerations including the photon energy, intensity and ease of use of commercially available UV lamps and lasers. In another embodiment of the invention, infrared energy is supplied to the reaction mixture.
- FIG. 1 illustrates an operative arrangement of reaction components within the scope of the invention.
- a reaction vessel, 10 is placed in line to the photolysis light source, 20 such as a UV lamp or an excimer laser pulse beam. Due to the danger associated with exposure to high intensity UV light, the reaction vessel is placed within a containment shroud, 30. In the case wherein a UV lamp is present, the lamp is also within the enclosure (not shown).
- the containment shroud interior is coated with a UV reflective coating, 40 to redirect transmitted and scattered UV light back through the reaction vessel, thereby increasing the probability of photon absorption by a reactant molecule within the reaction vessel.
- a reflective coating also serves to partially offset the inverse distance squared drop off of intensity associated with radiative sources.
- the reflective coating is of a conventional type used with UV light such as polished metal structures or films of aluminum, stainless steel and the like.
- the photolysis light source is any number of conventional light sources, the choice of a specific electric arc lamp or laser line is dictated by the absorption cross-section of the organometallic precursor.
- a quartz mercury vapor lamp while only radiating about 10 percent of its spectral output at wavelengths below 250 nm is often a satisfactory photolysis source owing to the high wattage of such lamps.
- Photolysis wavelengths between 180 nm and 250 nm are preferred for UV photolysis within the instant invention.
- Such lamps in providing a variety of radiative wavelengths may induce deleterious side reactions in the reaction mixtures of the present invention.
- filters are introduced between the lamp and reaction vessel to limit the light wavelengths entering the reaction mixture. Filters invariably attenuate the desired wavelengths to some extent, thereby increasing reaction times.
- Excimer laser light sources such as the ArF laser provide monochromatic light in high intensity to a small spatial area, thus precluding the need for filters. Regardless of the nature of the light source, relative transparency of the reaction vessel, solvent, and passivating agent; and a high absorption cross section by the organometallic precursor are determinative of the selection of each.
- the reaction vessel containing the solvent, particle precursor and passivating agent is composed of a conventional material for UV transmittance, such as quartz glass.
- the reaction vessel is composed of far UV quartz glass, which is defined as having greater than 70% transmittance to 200 nm incident light. Suitable reaction vessel materials are commercially available under a variety of brand names including SUPRASILTM.
- the reaction vessel is sealable by means of a stopper.
- the reaction vessel has a stopcock and a ground glass fitting, thereby making the vessel adaptable to linkage to conventional air sensitive glassware, such as a Schlenk line.
- a fitting allows for the evacuation of the reaction vessel and or filling with various gaseous materials under controlled conditions.
- the reaction vessel also has a fitting sealed by a septum, thereby allowing for aliquot removal of headspace gases and or reaction mixture by means of a syringe or similar conventional transfer techniques.
- the reaction vessel is optionally in contact with a thermal source, such that the reaction mixture temperature is selectively increased or decreased relative to ambient temperature.
- the UV photolysis solvent is principally unreactive under exposure to the incident light. This does not mean that the solvent always has a low absorption cross section relative to the incident light, since a solvent which acts as a photocatalyst is also operative.
- hydrocarbon solvents such as hexanes have low absorption cross sections as UV solvents, conjugated multiple bonds systems in general, and aromatics in particular have higher cross sections than the hydrocarbons, but nonetheless serve as solvents under certain reaction conditions within the instant invention. Examples of the latter include benzene and toluene.
- a low absorption cross section is defined herein as being less than about one photon being absorbed per every 1,000,000 photons, on average at the selected wavelength to which the molecule is exposed.
- reaction mixture concentrations are preferred to be greater than about 10 6 molar in the particle precursor molecule, greater than about 10 8 molar for polymeric passivating agents and greater than about 10 ⁇ 7 molar for passivating agents with a molecular weight of less than about 500 and a moiety suitable to absorb onto the particle surface.
- a broad range of reaction mixture concentrations offers some benefits in adding an additional parameter for the kinetic control of particle production.
- the reactions of the instant invention are carried out with the exclusion of air and water. Furthermore, in those reactions of the instant invention which use a UV excitation source, oxygen and water have complex photochemistries that may interfere with the production of particles. Thus, the reactions of the instant invention are conducted with solvents which have been dried and stored under an inert gas. Conventional means of drying solvents that are known in the art are operative herein.
- the solvent boiling point is not a principal consideration in comparison to the aforementioned factors when selecting a solvent for UV photolysis as described in the current invention.
- infrared or thermal decomposition reaction of the instant invention often are accompanied by more than transitory elevated temperatures, relative to ambient room temperature.
- the infrared wavelength regime is defined herein to be between 750 nm and 1200 nm. In such instances a high boiling temperature, aprotic solvent is preferred.
- High boiling temperature is defined herein to be greater than about 110 °C.
- solvents illustratively include glymespyridine, nitrobenzene, formamide, N- methylformamide dimethylformamide, N-methylacetamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, ethylene carbonate, propylene carbonate, tributyl phosphates, hexamethylphosphoryltriamide, and the like.
- a neat reaction proceeds according to the instant invention.
- a neat reaction is defined as a reaction in which only substances catalyzing or being consumed by the reaction are present.
- the headspace in the reaction vessel is maintained to promote the decomposition reaction and quell side reactions.
- the headspace is purged of oxygen and water vapor. This is accomplished by loading the reaction cell in a controlled atmosphere, such as a glove box, or alternatively by evacuating the reaction vessel and then transferring the reaction mixture thereto by means of a canula or other standard air sensitive handling techniques.
- a headspace pressure which is lower than that of the surrounding room atmosphere facilitates advancement of the reaction wherein the decomposition reaction liberates gaseous by products.
- the headspace volume is optionally filled with an inert gas illustratively including dinitrogen, argon, helium, and krypton.
- the headspace in addition to an inert gas also contains a gas which either catalyzes the reaction and or serves to passivate the particle surface.
- a gas capable of serving both these functions is dihydrogen wherein silicon particles are being formed.
- gases include deuterium, chlorine and gaseous monomers which polymerize in the course of the reaction to yield a stabilizing polymer such as alkenes, alkene oxides, alkynes and other hydrocarbon gaseous species containing a polymerizable multiple bond.
- a satisfactory passivating agent for use in the UV photolysis embodiment of the present invention exists in many forms.
- the passivating agent is required to be essentially unreactive under the reaction photolysis conditions and to yield the particle at suspendable in the reaction solvent, and preferably soluble.
- Representative passivating agents which are operative in the instant invention when soluble in the reaction solvent include: hydrogen, fluorine, perfluoroalkene-, perfluoroalklene-sulfonic acid-, alkylene-methacrylic acid-, polyesters-polymers, nonionic surfactants; and small orgamc molecules of a molecular weight less than about 500 and containing a nonfacile heteroatom moiety suitable to absorb onto the particle surface, the heteroatom illustratively being: fluorine, oxygen, nitrogen, sulfur, phosphorus, or the like.
- the passivating agent be saturated in the case of surfactants and organic alcohols in order to prevent UV absorptions and reaction.
- the polymeric passivating agents are modified and chain lengths increased by having a degree of saturation within the polymers or polymer precursors. While in situ control of polymer characteristics is desirable, the cost for such control is an increased reaction dynamic complexity. The more moieties within the passivating agent the more likely the occurrence of interacting with particle formation.
- Still a further class of passivating agents for producing particles of silicon, germanium or tin are unsymmetric organometallics. Unsymmetric is defined as wherein the organic adducts are not all identical about the Group IV central atom.
- a Group IV atom which does not readily undergo bond scission with at least one of its adducts, upon addition to a growing particle, truncates the growth phase of the particle at that surface site.
- suitable passivating organometallics include species of the formula R ⁇ M) ⁇ , wherein n is 1, 2 or 3; R is an aliphatic group containing less than 9 carbon atoms, X is hydrogen or fluorine, and M is silicon, germanium or tin.
- Tetraorganometallics wherein the metal is silicon, germanium, and tin are the preferred precursors for the creation of particles of these elements. It is a more preferred embodiment, that the tetraorganometallics are symmetric organometallics.
- a symmetric organometallic is defined as one where all four groups bonded to the metal center are compositionally identical.
- the organic groups bonded to the Group IV metal center are volatiles upon photolysis, meaning that organics are capable of leaving the reaction mixture in some from as gaseous species.
- R, R', R" and R'" are all the same or different, including hydrogen, alkyls containing less than 13 carbon atoms, monounsaturated alkenyls containing less than 9 carbon atoms, alkynyls containing less than 9 carbon atoms and aromatics containing less than 20 carbon atoms, and the like and M is silicon or germanium or tin are operative as Group IV particle precursors.
- organometallic precursor is controlled not only by practical considerations such as cost and ease of synthesis of the precursor, but also the absorption cross section of the precursor at the incident photolysis wavelengths and the solubility in the solvent.
- the passivating agent may be dissolved in the liquid precursor and the reaction run neat.
- the particles created in the instant invention are themselves novel and heretofore unattainable.
- Particles of silicon having a size distribution that varies by less than 20% of the particle diameter in the size regime wherein the quantum size effects are observed that are: stable in solution phase; have a selectively controllable surface chemistry; and generally free from reaction by- products, contaminating the resulting particles result from the organosilane precursor syntheses of the instant invention.
- the preferred particle sizes produced within the instant invention are less than 30 nm in diameter and are generally spherical in shape.
- a still more preferred average particle diameter within the instant invention is less than 6 nm.
- the silicon particles so synthesized are amenable to reduced temperature annealing as compared to bulk silicon, thereby improving the crystallinity of the nanocrystals and or modifying the particle surface properties.
- Figure 2 shows a transmission electron micrograph of a field of particles so produced dispersed on an amorphous carbon film of about 60 nm thickness.
- the preferred particle sizes produced within the instant invention are less than 30 nm in diameter and are generally spherical in shape.
- a still more preferred average particle diameter within the instant invention is less than 8 nm.
- the germanium particles so synthesized are amenable to reduced temperature annealing as compared to bulk germanium, thereby improving the crystallinity of the nanocrystals.
- the Group IV nanocrystals are also synthesized containing controlled quantities of dopants.
- the dopant precursors are preferably introduced to the reaction mixture in the form of organometallics.
- the organometallic dopant precursors are symmetric organometallics with properties similar to those detailed for the Group IV particle precursors.
- the dopant is any one of the conventional ions known to the art that modifies the electronic band gap, electroluminesence, photoluminesce, or fluorescence of bulk Group IV elements silicon, germanium and tin; illustratively, some of these include: lithium, beryllium, boron, nitrogen, sodium, magnesium, aluminum, phosphorus, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, indium and antimony. It is appreciated that the photolysis reaction rate of the dopant is often not identical to that of the Group IV particle precursor. It is therefore optional that the dopant precursor be introduced to the reaction mixture during the growth phase of the silicon, germanium, or tin nanoparticles. Due to the more ionic nature of dopant ion-carbon bonds, many dopant organometallics have a greater decomposition reaction driving force, thereby making them often faster to react.
- 0.025 grams of tetraphenylsilane is placed in a far UV quartz cuvette under an atmosphere of dinitrogen.
- the cuvette is sealed and evacuated using a mechanical vacuum pump.
- About 3.0 milliliters of dry, distilled toluene is introduced to the cuvette.
- the reaction mixture is colorless.
- the cuvette is then placed in direct line with a 450 Watt water cooled mercury vapor arc lamp operating at 60 Hertz, 120 volts.
- the distal portion of the cuvette relative to the lamp is wrapped with reflective aluminum foil to increase light flux through the reaction mixture.
- the lamp and cuvette are placed within a light proof enclosure to prevent the escape of UN light into the surrounding environment. The lamp is then energized.
- the reaction mixture After 90 minutes of UN light exposure, the reaction mixture is a pale yellow color with an absorption maximum at 330 nanometers and an absorption tail extending to beyond 500 nanometers.
- the resulting solution contains nanocrystals of silicon measuring about 4 nanometers in diameter based on electron micrographs.
- Example 2 The experiment as described in Example 1 is repeated for 60 minutes UN exposure in hexane, resulting in a pale yellow solution. 0.05 grams of dibutyl lithium in about one milliliter of dry, distilled hexane is added thereto. The lamp is energized for a further 30 minutes. The resulting solution has silicon nanocrystals and reflux behavior similar to that described in Example 1.
- Example 1 The experiment as described in Example 1 is repeated using hexane as a solvent and in later reactions with benzene as a solvent. Yielding equivalent silicon particles in similar reaction times. Subsequent refluxing of the nanocrystal containing solution resulted in a gradual color change from pale yellow to bright yellow to orange to red. The color change is consistent with increasing domain size of silicon nanocrystals.
- Tetravinylsilane is an air and moisture sensitive liquid compound. 0.3 milliliters of tetravinylsilane is placed in an evacuated far UN quartz cuvette and
- FIG. 1 shows a transmission electron micrograph of a field of particles so produced dispersed on an amorphous carbon film of about 60 nm thickness.
- Example 5 The reaction of Example 3 is conducted with the addition of 0.10 grams of ⁇ -vinylpyrrolidone polymer and the substitution of a 1200 Watt UN lamp for that of the 450 Watt lamp. Upon exposure to UN light about 5 nanometer particles of silicon resulted which are stable in solution for more than one month.
- Tetraethylsilane is a moisture sensitive liquid and as such is stored in a glovebox under a dry, dinitrogen atmosphere.
- a weighed, far UN quartz Schlenk flask is loaded within the glovebox, with 0.0035 mols of tetrethylsilane, and 0.015 grams of poly(butylmethacrylate) of an average molecular weight of about 330 kiloDaltons.
- the flask is then sealed and brought into room air. 50 grams of hexane is then added the flask.
- the hexane is dried over benzophenone and sodium metal prior to introduction to the flask.
- the flask Upon dissolution of the poly(butylmethacrylate) in hexane the flask is placed adjacent to a 450 W water cooled mercury arc lamp operating at 60 Hertz, 120 volts. The distal portion of the flask relative to the lamp is wrapped with reflective aluminum foil to increase light flux through the reaction mixture. The lamp and flask are placed within a light proof enclosure to prevent the escape of UN light into the surrounding environment. The lamp is then energized. Aliquots of the reaction mixture are withdrawn at regular time intervals and placed in a cuvette. The cuvette UN- visible light absorption spectrum is recorded and a droplet of the reaction mixture is placed on a transmission electron microscopy grid for subsequent real space imaging and electron diffraction study.
- the reaction mixture initially is a colorless solution with an absorption maximum at 332 nanometers. After one hour of exposure to the lamp, a tail in the absorption spectrum is observed to extend just beyond 500 nanometers and the absorption maximum is observed at 386 nanometers. A pale yellow color is observed to the reaction mixture.
- Example 7 0.2 grams of tetrethlygermanium is placed in an evacuated far UN quartz cuvette, to which 3 milliliters of dry, distilled hexane is added, along with 0.05 grams of poly(butylmethacrylate) having an average molecular weight of 330 kiloDaltons. Upon reaction as per Example 1, nanocrystals of germanium are produced on the order of 6 nanometers in diameter. The reaction is repeated in toluene as the solvent to give a similar result.
- Example 8 0.3 grams of tetrabutyltin is substituted for tetraethiygermanium of Example 6. The reaction is conducted as per Example 1, resulting in nanocrystals of tin on the order of 6 nanometers in diameter.
Abstract
Description
Claims
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Cited By (3)
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US6819845B2 (en) | 2001-08-02 | 2004-11-16 | Ultradots, Inc. | Optical devices with engineered nonlinear nanocomposite materials |
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US6268041B1 (en) | 2001-07-31 |
US5850064A (en) | 1998-12-15 |
AU6963198A (en) | 1998-11-11 |
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