WO2001028677A1 - Solid state surface catalysis reactor - Google Patents
Solid state surface catalysis reactor Download PDFInfo
- Publication number
- WO2001028677A1 WO2001028677A1 PCT/US2000/028801 US0028801W WO0128677A1 WO 2001028677 A1 WO2001028677 A1 WO 2001028677A1 US 0028801 W US0028801 W US 0028801W WO 0128677 A1 WO0128677 A1 WO 0128677A1
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- Prior art keywords
- emitter
- excitation
- catalyst
- catalytic collector
- excitations
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Classifications
-
- B01J35/33—
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
- H02N11/002—Generators
Definitions
- the present invention relates generally to an energy generator and more specifically to a method and apparatus to couple the excitation structure of a semiconductor substrate to the excitation structure of reactive adsorbates on the surface of a catalyst.
- hot electrons that diffuse to a catalyst metal surface interact strongly with the adsorbed surface chemicals, also called adsorbates, and can do so at a rate faster than the process of electrons thermalizing with the lattice of catalyst metal atoms. It has also been recently discovered that the adsorbates acquire vibrational energy when interacting with hot electrons from the catalyst surface. It has been further discovered that adsorbate vibrational energy strongly enhances the rate of chemical reactions, and in some cases enable reactions that do not occur by thermal means because of the activation energies or chemical thermodynamics involved. Hot electrons stimulate adsorbate chemical reactions on a catalyst surface. The reverse of this process has also been observed, where a surface chemical reaction resulted in the production of hot electrons.
- the presence of hot electrons on the surface of the catalyst can cause a pseudo-thermal regime in which the surface vibrations of adsorbate molecules, either against themselves or against the catalyst, are in equilibrium with the temperature of the substrate hot electrons rather than with the physical temperature of the substrate itself. This means the vibrations can be at several thousand degrees while the catalyst is at ambient temperature. Hot electrons excite the adsorbate from the bottom of its adsorption well in a stepwise manner, and may even do so until it overcomes the adsorption barrier and hops to a neighboring potential well, reacts or desorbs.
- the hot electron energy or frequency need not exactly match that of the adsorbates.
- the adsorbate excitation structure is generally very broad, being spread over many frequencies, and the mechanism is often via an electronic excited state. That is, when the adsorbate acquires an electron it transitions to an excited electronic state. Within a few tens of femtoseconds it begins to move outward away from the surface, and then releases the electron. The adsorbate now transitions back to a non-electronic excited state. However, it retains the extra energy given to it by the hot electron. As a result, the adsorbate is in a higher vibration state.
- the tens of femtosecond lifetime for the process causes a broadband resonance feature and hence permits an energy mismatch between hot electron and the receiving adsorbate energy levels.
- the substrate electron in effect deposits energy into a vibration mode of adsorbate reactant, such as the vibration of the atoms in the adsorbate reactant molecule or in the vibration of the adsorbate against the catalyst surface.
- This process can repeat itself many times, to the point where the adsorbate desorbs. In the literature this is called “Desorption Induced by (Multiple) Electronic Transitions," Abbreviated DIMET or DIET. This is the stimulator process.
- the generator process works in reverse .
- this specie in the excited electron state decays and ejects an electron.
- the effect is that the energetically excited reactant on the surface of the catalyst gave a fraction of its energy to an electron in the catalyst.
- This generator process This generator or reverse process has been observed in laboratories.
- the laboratory detector measured a current in a short circuit diode, which means the detector generated almost exactly zero power. However, the detector confirmed the existence of the generator mode. Both hot electrons and hot holes were observed, and with energies in excess of the Schottky barrier in silicon, which is of order 0.5 eV.
- Hot electrons on a catalyst surface have been shown to accelerate reactions.
- Experiments with vibrationally excited Nitrogen Oxide (NO) molecules interacting with a copper (Cu) surface showed thousand-fold enhancement of surface reactivity. Up to near unit reaction probability was observed. In that work, neither reactant translational energy nor surface temperature had a strong effect on the reaction probability, confirming the efficacy of using hot electrons.
- carbon monoxide (CO) was oxidized on a ruthenium surface. A 1.5 eV, 110 femtosecond laser pulse duration created the hot electrons. It was observed that sub-picosecond reactions of adsorbed O with CO to produce C02 in a reaction that is energetically not possible at all without the hot electrons.
- the excitation structure of the chemically reactive adsorbate-catalyst system is dominated by vibrations of the atoms and molecules with themselves and against the substrate, forming energy level bands, and the energy level bands due to electronic excited states of these specie, where the adsorbates may acquire a transient or permanent charge .
- Coupling of these structures occurs mainly by two paths, either directly through the direct, typically ballistic transport of the hot carriers such as hot electrons or hot holes, between adsorbate and semiconductor, or by resonant tunneling of energy.
- Resonant tunneling couples the two structures through oscillating electric fields produced by the excitation structures in the semiconductor and adsorbate-catalyst system. The coupling is greatly enhanced when the frequencies of the excitations on either side are close to each other.
- Hot electrons are the easiest excitation to work with.
- the current method of choice to produce and inject the hot electrons into a metal catalyst surface relies on a pulsed laser.
- the usual method to produce these hot electrons is to irradiate the surface of the metal with a short laser pulse, typically with pulse duration in the range of 50 to 1000 femtoseconds and with photon energies of 1 eV or greater (0.2 to 1.5 micron wavelength) .
- the photons are adsorbed and produce electrons with energies between 0 eV and up to the photon energy, splitting the energy with a hot hole, and with hot electron energies averaging approximately half the incident photon energy.
- a laser is one of the most expensive energy sources available.
- a Schottky junction diode has been used in experiments for hot electron injection into solutions. One of the co-authors of that work suggests that they did not achieve the success they wanted because the surface states associated with the electrolyte cooled the electrons.
- a catalyst electrode Schottky junction made of n-silicon and platinum metal was used to inject electrons into a reactive electrolyte solution.
- the platinum thickness was varied from less than the mean free path to several times thicker than the mean free path of hot electrons in platinum. They achieved some success, and also suffered severe problems with interactions between hot electrons and electrolyte. Flooding the surface with liquid electrolyte destroys the effectiveness of hot electrons. Metal-oxide junction surface states have been an unsolved problem with this approach, where liquids flood the reactive surface.
- the duration of the pulses generating hot electrons is less than the time associated with electron thermalization with the lattice.
- the sudden burst of chemical reactions causes a flood of hot electrons on the catalyst surface. This in turn causes a flood of electrons in the conduction band of the semiconductor substrate collecting those hot electrons.
- a sufficiently short burst causes the number of generated electrons to exceed the thermally occurring short circuit electrons, thereby increasing the efficiency of the generation of electricity.
- Missing in the public domain are methods to tailor the surface of the catalyst to enhance resonant tunneling, to enhance the activation of selected energy bands, to enhance the probability of desired energy transitions, or to enhance the selected reaction pathways .
- the present invention is directed to a method and apparatus to couple the excitation structure of a semiconductor substrate to the excitation structure of reactive adsorbates on the surface of a catalyst.
- the coupling is reversible.
- the reversible reactor uses excitations originating in a semiconductor substrate to stimulate chemical reactions by the adsorbate species on the surface of a catalyst, and uses the reverse process to generate excitations in the substrate as the result of reactions.
- the method and apparatus when operated in the stimulator mode uses electrical or other forms of energy input to the semiconductor substrate to manipulate the reaction path so as to accelerate reactions, to steer the reactions, to manipulate the forms of energy produced by the reaction, and to reduce the temperature needed to stimulate surface catalytic reactions; when operated in the generator mode the apparatus converts excitation energy of the adsorbate-catalyst system into electricity or other forms of energy in the semiconductor substrate; and when operated in the stimulator-generator mode, may use electricity or other forms of energy to manipulate reactions and at the same time may generate electricity or other forms of energy from the adsorbate-catalyst system chemical reaction energy.
- electricity or other forms of energy are used to create and inject excitation energy, such as hot carriers, into adsorbates on a catalyst surface and to stimulate adsorbate-surface catalytic reactions; and, because of the reversible nature of the process, one and the same type of apparatus may also be directed to collecting excitations that result from surface chemical reactions, such as hot carriers in a semiconductor substrate, and converting them into electricity or other forms of energy.
- the present invention uses electronically energized semiconductor diodes in a novel way to stimulate the reactions.
- the present invention utilizes a p-n junction as the creator of hot carriers and as the injection mechanism to couple them into thin metal overlayer structures of catalyst material and to adsorbates on the catalyst surface .
- the same embodiment may use the same p-n junction to collect hot carriers in the semiconductor diode, forward biasing it and hence generating electricity.
- the present invention includes a hot carrier emitter, also known as an excitation emitter, in intimate contact with a catalyst ensemble energy collector also known as a catalytic collector.
- the excitation emitter includes a semiconductor diode.
- excitation energy originating in a catalyst- adsorbate system is coupled into semiconductor band excitations, which can typically cause a forward bias in the semiconductor and generate electricity or other useful forms of energy.
- the catalytic collector is placed in intimate contact with the emitter and includes a catalyst, an optional underlayer, and optional reaction accelerator- decelerator materials. Elements of the catalytic collector may be one and the same with elements of the emitter. A surface of the catalyst and of the optional reaction accelerator-decelerator materials comes in intimate contact with the reactant chemicals.
- Various regions of a device using this invention may include various and different catalytic collectors, hot carrier emitters and various modes of energy coupling, including ballistic transport and resonant tunneling. Further features and advantages of the present invention as well as the structure and operation of various embodiments of the present invention are described in detail below with reference to the accompanying drawings. In the drawings, like reference numbers indicate identical or functionally similar elements .
- Figure 1 shows a general schematic cross section of a solid state surface catalysis reactor device of the present invention in one embodiment
- Figure 2 illustrates a cross section of a catalytic collector in one embodiment of the present invention
- Figure 3 shows a cross section of a reaction stimulator device with catalyst clusters forming the catalytic collector
- Figure 4 shows a cross section of a solid state surface catalysis reactor device with a thin electrode forming a substrate for catalyst clusters as part of a catalytic collector and also forming the electrical connection for the hot carrier emitter;
- Figure 5 illustrates a cross section of a solid state surface catalysis reactor with reaction accelerator-decelerator materials surrounding or adjacent to catalyst metal
- Figure 6 illustrates a cross section of the solid state surface catalysis reactor having a single metal element that is at the same time an electrical connection to the emitter, the underlayer of the catalytic collector and forming the metal element of a Schottky diode;
- Figure 7 shows the electronic energy level diagram for the a solid state surface catalysis reactor, illustrating the regions from the n+ n type base to the adsorbate .
- An exemplary embodiment of the present invention uses electrons as the hot carriers and a p-n junction diode as the semiconductor diode.
- the base is n type semiconductor and the emitter is an p type semiconductor.
- a forward bias on the p-n junction diode injects minority carrier electrons into the conduction band of the p type emitter where they become minority carriers.
- the minority carriers diffuse and migrate to the catalytic collector and may also be resonantly coupled into the excitation structure of the adsorbate-catalyst system provided that the distance from the junction to the catalytic collector is less than several times the diffusion length of minority carriers in the p type semiconductor. For example, when InSb, InAs, or some alloy of InGaAsSb is the semiconductor, then the diffusion length can range from approximately 100 nanometers to several microns.
- the minority carrier electrons are injected or resonantly coupled into the catalytic collector with an energy in excess of the Fermi level of the catalytic collector.
- This excess energy is nearly mono-energetic and has a value approximately equal to the forward bias on the diode .
- the semiconductor is a p-n junction diode
- the semiconductor diode is a Schottky junction the carrier energy may be within approximately several kT of the energy needed to overcome the Schottky barrier.
- the electrons with forward bias energy may rapidly permeate on to a surface of the catalyst facing and in intimate contact with reactants if, for example, the distance from the p type semiconductor to the surface in contact with the reactants is less than the several times the energy mean free path of electrons in the catalytic collector.
- the catalyst is a metal such as platinum, palladium, rhodium or ruthenium the energy mean free path ranges between 5 and 50 nanometers.
- the underlayer is copper or gold the energy mean free path ranges between 50 and 200 nanometers.
- the flux of hot electrons interacting with the reactant chemicals is approximately that of the diode forward current if the distance from the catalytic collector to the diode junction is within the diffusion length of the emitter semiconductor and energy mean free path lengths of the catalyst and underlayer, as specified herein. Hot electrons interact strongly with adsorbates .
- Another aspect of the present invention uses a Schottky diode designed to have a low barrier height, also referred to as a tunneling junction.
- a Schottky diode designed to have a low barrier height, also referred to as a tunneling junction.
- Such a device is constructed by choosing the doping between the metal and the semiconductor of the Schottky junction to be intermediate between the very high doping used to make an almost ohmic junction, typical for making electrical contacts with the semiconductor, and the medium doping used to make a normal Schottky diode .
- the doping controls the width of the depletion region and hence the strength of the Schottky barrier.
- the value of the doping may be chosen between degenerate or high doping and conventional or moderate doping, depending on the application.
- the doping may be adjusted to an effective value of order 0.1 eV.
- High doping in silicon yields effectively 0.0 eV barrier and normal doping yields barriers typically between 0.5 and 1.5 eV barrier.
- This tunneling junction Schottky diode permits the use of common semiconductor materials such as silicon. The use of such a diode is appropriate for use in the generator mode where reactions are pulsed.
- the hot carrier emitter may generate its electrons by resonant coupling of energy from the excitation structure of the adsorbate-catalyst system.
- the hot electrons go into the diode junction towards the base instead of out of the diode junction from the base. In so doing, the hot electrons maintain a forward bias on the diode, thereby generating electricity.
- This reversible nature of the present invention permits the device to generate electricity as a direct result of chemical reactions. This is a generator mode .
- This same device may operate both in a stimulator and generator mode simultaneously, and thereby generate electricity more efficiently than operation in the generator mode alone.
- the stimulator apparatus triggers and stimulates adsorbate reactions by the application of electricity or other forms of energy to the semiconductor diode. This initiates and causes the reactions to complete in a short time, for example, in the order of picoseconds.
- the burst of reactions result in a high peak power burst of chemical reactions, with concomitant release of electrons.
- the resulting flood of electrons may then be collected, thereby generating electricity.
- the resulting electrons may also stimulate more chemical reactions and may initiate a chain reaction analogous to an explosion or detonation. The result is a form of surface explosion.
- the electrons may then generate electricity much more efficiently in the semiconductor diode.
- the electric generating efficiency of a diode is a strong function of the peak power, and the stimulator may create a condition where the reactions achieve such high power.
- energy may be collected in any manner including by operating the solid state surface catalytic reactor in the generator mode.
- Other modes of collecting energy include but are not limited to collecting radiations emanating from reactions that have been stimulated, or by collecting heat, or by collecting the reaction products themselves, or by capturing the kinetic energy of the products as they desorb, or by collecting the phonons, or by stimulating and collecting coherent acoustic or optical radiation, or by stimulation of piezoelectric devices.
- stimulation may be achieved in any manner, including by operating the solid state surface catalytic reactor in the generator mode.
- Other modes of stimulation include but are not limited to stimulation using pulsed laser light, a simple light flash, or the hot carriers generated on other regions of the device by other reactions whose energy outputs may include hot carriers and other catalytic products that stimulate reactions.
- semiconductors with band gaps starting from approximately 0.05 eV to 5 eV may be used with room temperature heat sink operation, and band gaps less than 0.05 eV may be used when the system is operated at lower than room temperature. This does not preclude using materials with higher bandgaps, such as insulators like CaF2 with 12 eV bandgap, or any other material with higher bandgap.
- the commonly used InSb and InGaAsSb materials have band gaps that may be continuously chosen in the range 0.1 to 1.5 eV by suitable choice of the In / Ga ratio and the As / Sb ratio.
- the resulting range of band gaps lie precisely in the range of energies associated with hydrocarbon chemical bonds.
- the InSb material produces 0.18 eV electrons, which is ideal for favoring reaction stimulation Vs desorption, because higher energy electrons may stimulate an undesirable large fraction of desorptions, as opposed to surface reactions.
- the p-n junction embodiment of this invention provides a substrate whose energy levels match the excited state energy levels of the adsorbates. This greatly enhances resonant transfers, in either direction, that is, to or from the adsorbate.
- the metals of the catalytic collector provide a resonant tunneling coupling, for example, via plasmons, between the adsorbate and the semiconductor substrate .
- the resonant tunneling coupling effectively connects the energy band structure of the substrate to the energy band structure of the adsorbates .
- An ohmic or almost ohmic junction between the catalytic collector and the semiconductor effectively pins the Fermi level of the catalytic collector to the valence band of the semiconductor.
- the conduction band of the semiconductor being higher than the valence band by an amount equal to the band gap of the semiconductor, then appears above the Fermi level of the catalytic collector by the same amount, namely the band gap energy.
- the bandgap may be chosen from a palate between 0.05 to 5 eV, the bandgap energy may be made to match nearly any energy level of the system having the adsorbate and the catalytic collector.
- the semiconductor band gap By choosing the semiconductor band gap to match the energy level of an adsorbate on the catalytic collector, one may effectively couple the two together through the well known and commonly used process of resonant tunneling. Resonant tunneling greatly increases the cross section for the transfer of energy.
- the hot carriers may then generate electricity at a rate faster than they loose energy by generating heat.
- hot carrier emitters are fabricated using degeneratively doped or highly doped p- n junctions.
- the switching speed can approach that of the Schottky junction because of the high carrier densities, and also because the high semiconductor doping densities form abrupt junctions, similar to that of a Schottky diode. High switching speed enhances the ability to pulse the stimulator and cause high peak power reactions.
- the p-n junction may provide lower energy hot carriers, as low as 0.05 eV and certainly below 0.4 eV, and determined by the chosen bandgap.
- the p-n junction may provide very high energy monochromatic hot carriers, with energies equal to the semiconductor band gap, which exceed 5 eV for known devices.
- the p-n junction provides a much longer diffusion dimension than that of the Schottky junction, between 200 nanometers and several microns, over which the hot carrier can migrate and interact with surface catalysts, permitting much larger and manufacturable semiconductor devices. Further, highly doped or degeneratively doped semiconductor junctions may be produced with nearly ohmic contacts, mitigating the surface state problems.
- Another novel aspect of the present invention is the co-location of both an electrically powered reaction stimulator and its inverse, a reaction driven electric generator.
- the stimulation causes a high rate of reaction, resulting in high peak power which in turn makes the energy generator more efficient.
- the present invention allows the device to act as both stimulator and generator.
- the uses of combined reaction stimulation include: 1) controlling catalytic reactions; 2) monitoring those reactions using the generated electrical signal; 3) accelerating reactions on catalysts that have undesirable slow reaction rates but highly desirable selectivity; 4) causing non-thermal steering of reaction paths; 5) stimulating extremely rapid surface chain reactions to achieve high peak power while maintaining low average power; 6) causing chemical reaction temperatures like that of the hot carriers in the catalyst, which may be far in excess of the catalyst physical temperature; 7) in the stimulator-generator mode, using one type of stimulator to pulse the device to make electricity and another type to cause a self cleaning of the device, for example to remove unwanted chemical byproduct that may build up and accumulate with use, 8) initiating reaction avalanches such that the chemical reactions create their own hot carriers, forcing hot carriers to diffuse in the reverse direction, and causing the device to be an electric generator.
- the present invention is directed to various aspects of the methods and devices that stimulate and manipulate chemical reactions using electrical energy input on selected catalyst surfaces, and that produce electrical energy through an inverse process .
- the present invention is directed to a method and apparatus for making a device that will generate hot carriers, especially hot electrons, transport them and couple them to reactant adsorbates on a catalyst surface and cause such adsorbates to acquire an effective vibrational temperature in excess of the temperature of the catalytic surface.
- Vibrational energy and temperature are used interchangeably.
- Energy is the product of the Boltzman constant and absolute temperature.
- Such an effective vibrational temperature in turn accelerates the reaction rates on the catalyst.
- Excited vibrational states of atomic and molecular adsorbates, both against the catalyst surface and internal to the adsorbates, are observed to be orders of magnitude more reactive than adsorbates in ground states.
- one aspect of the present invention is directed to a reaction stimulator method and device to use electricity to create energetic carriers, particularly hot electrons, in a hot carrier emitter and inject those carriers efficiently into a catalytic collector.
- the catalyst or substrate temperature need not be raised during the reaction stimulation.
- the present invention is directed to methods and apparatus for a reaction stimulator - generator that efficiently collects energetic carriers generated by reactions on a catalyst surface, particularly hot electrons, and cause them to charge a forward biased diode through an emitter-base junction, thereby generating electricity.
- the present invention is directed to a reaction stimulator that injects hot carriers or hot electrons with the range of energies needed to selectively favor desired types of surface chemical reactions.
- the reaction stimulator is simple in design, rugged in construction, and economical to manufacture.
- the present invention is directed to a reaction stimulator that is reversible, wherein the diffusion of hot carriers may proceed in either direction, that is, either from a chemical adsorbate reaction to a hot carrier emitter, which generates electricity, or from a hot carrier emitter to a chemical adsorbate, which uses electricity to stimulate reactions.
- the present invention uses the heat of vaporization of a reactant as a coolant for the operation of the semiconductor junction.
- the method to stimulate reactions includes using electrical energy to forward bias a semiconductor diode, wherein an electric potential across the electrical contacts of the semiconductor diode creates hot carriers such as hot electrons that diffuse out of the diode junction and are transported through the catalytic collector to the chemical adsorbate, thereby stimulating the adsorbate to react.
- the method to generate electricity includes creating hot carriers in the catalytic collector using chemical adsorbate reaction energy and transporting or coupling the hot carriers into the junction of the semiconductor diode, causing the diode to become forward biased and thereby generating electricity.
- the method also includes utilizing a carrier diffusion process that transports the energetic carriers such as hot electrons to and from the diode junction to the catalytic collector.
- the method also includes using a catalytic collector either to collect hot carriers provided by the emitter to transport or couple them to a chemical adsorbate on a catalyst surface or to optional reaction accelerator-decelerator materials, or, the reverse process, to collect hot carriers generated by the chemical adsorbate on a catalyst or optional reaction accelerator-decelerator materials and transport or couple them to an emitter.
- a catalytic collector either to collect hot carriers provided by the emitter to transport or couple them to a chemical adsorbate on a catalyst surface or to optional reaction accelerator-decelerator materials, or, the reverse process, to collect hot carriers generated by the chemical adsorbate on a catalyst or optional reaction accelerator-decelerator materials and transport or couple them to an emitter.
- the method also includes forming metal clusters, layers, atomically uniform monolayers, surface structures, crystalline layers or 1, 2 or 3 dimensional quantum confinement structures such as quantum dots, quantum stadia, quantum corrals and quantum wells from materials comprising the catalytic collector.
- the method includes using such layers and quantum confinement structures to tailor the density of electron and hole states of the materials, which in turn cause favorable conditions for the formation of or reaction with hot carriers. Such conditions include depletion of the number of electrons available for the decay of vibrational energies of the adsorbate-substrate system with values of transition energy less than that of the bandgap of the substrate .
- the electron density of states may also be modified by forming electron interferometer structures using catalyst and other substrate materials to form structures to cause multiple path reflections of electrons including but not limited to steps, channels, stadia, corrals, pyramids, polygons, valleys, walls, periodic reflectors, and chaotic reflectors.
- the method also may include using combinations of different catalyst materials and of optional reaction accelerator-decelerator materials as part of the catalytic collector, and of forming such materials in any geometry, including but not limited to pillars, islands, clusters, interdigital and random structures and stripes .
- the method also may include choosing catalyst and optimal accelerator-decelerator materials that delay or retard reactions of adsorbates, so that use of the stimulation mode may better control the reaction rates. Such materials may be part of the catalyst itself, adjacent to the catalyst, and may be expendables carried by the fuel - oxidizer mixture.
- the method also may include choosing catalyst materials with Debye frequency lower than that of the desired hot carrier energy, to enhance the probability that the hot electron will interact with the adsorbate rather than with the phonon vibrations of the catalyst.
- the shape of the device may fit contours specified by the user because the basic shape is determined by elements that are only limited in thickness by the dimensions of the semiconductor and in length and breadth by the ability to cut or form parts, which limitations permit component dimensions with less than 10 microns. This permits device contouring to nearly any macroscopic physical shape.
- the method also includes using pulsed stimulation.
- Pulsed operation stimulates the reactions to occur with high peak power and short duration. This permits the device to remain relatively cool during the longer periods of zero stimulation after the reactions have completed and it permits the reactions to occur at a high temperature and high peak power during the relatively short periods of pulsed stimulation. Pulsing allows reactions to occur before thermal processes cause the reactions to occur. Pulsing permits the complete depletion of reactants in a time shorter than they can be replenished by the reactant gas mixture, that is, through gas kinetic means.
- the method also includes using an optional underlayer material as part of the catalytic collector.
- the underlayer may be a metal such as copper, gold, silver or aluminum, and is chosen to be compatible with obtaining the desired properties with the semiconductor component of the hot carrier emitter. One desired property is an ohmic or almost ohmic junction.
- the underlayer may be used as an electrical connection in the hot carrier emitter and may also be used as an electrical connection to the catalytic collector.
- the underlayer may be used as a substrate upon which to fabricate catalyst structures, more underlayers or specified geometries and crystal orientations of materials deposited as part of the catalytic collector, or to tailor the lattice constants of materials deposited on the underlayer.
- the method also includes limiting the thickness of the underlayer to less than several energy mean free paths of the hot carrier chosen for the device.
- any underlayer may be between one monolayer (approximately 0.3 nanometers) and 50 nanometers when the underlayer metal includes but is not limited to platinum, nickel, palladium, rhodium, rhenium, copper, gold, silver or aluminum.
- the method includes enclosing all or selected components of the device in an optical cavity tuned to an energy associated with the excitation structure of the semiconductor, or of the catalytic collector or of the adsorbates or of some combination of these elements.
- An apparatus to stimulate reactions or to generate electricity according to the present invention includes a hot carrier emitter and a catalytic collector.
- the hot carrier emitter belonging to this apparatus includes a semiconductor diode.
- the semiconductor diode includes a semiconductor base, a diode junction also called an emitter-base junction, and an emitter.
- the emitter includes a semiconductor or a metal as a diode element .
- the apparatus may also include a first electrical connection to the emitter and a second electrical connection to the base.
- An apparatus to stimulate reactions or to generate electricity may include an optional optical cavity tuned to a desired energy level transition of either the excitation structure of the semiconductor or of the system including the catalytic collector and chemical adsorbate.
- Such cavities may include and are not limited to metal and dielectric microcavities, periodic structures that exhibit photonic band gap properties, fabrey-perot cavities, textured mirrors, distributed Bragg reflectors, single and coupled semiconductor microcavities, external cavities with a wavelength filter or a large dispersion, quantum dot vertical cavities, microdisk cavities, quantum dot microdisk cavities, laser waveguides with or without cladding, dielectric slab waveguides, cavities associated electromagnetic surface waves, also called surface plasmons, at a metal-semiconductor interface where no additional confinement layer is needed, chaotic resonators, optical resonators with deformed cross section, resonator designs that incorporate chaotic ray motion, and symmetric resonators with whispering-gallery modes.
- the hot carriers are electrons
- the diode is a p-n junction made of InSb with n type base and p type emitter and the catalytic collector is located or co-located in the proximity of the emitter electrical contact.
- the catalyst ensemble includes a catalyst metal such as any alloy of platinum and palladium and deposited in a surface structure, cluster or quantum confined structure.
- the configuration or geometry of the catalyst for example, is such that the distance to the semiconductor from regions of catalyst exposed to adsorbates is predominantly less than 3 times the energy mean free path in platinum, which mean free path is approximately 20 nm.
- the catalyst metal is in direct contact with the semiconductor of the emitter, which semiconductor is degeneratively doped to form an ohmic or tunneling junction.
- the p- n junction is formed a distance from the catalytic collector that is less than 3 times the diffusion distance for electrons in the conduction band of p type InSb, which diffusion distance may be as little as 200 nanometers .
- the device may be operated in the stimulator mode, the generator mode or the sti ulator- generator mode, and where the hot electrons may be created either by the chemical adsorbate reactions or by electrical energy input to the semiconductor diode.
- the reversible solid state surface catalysis excitation transfer reaction apparatus in the present invention couples the excitation band structures of the adsorbate-catalyst system with the excitation band structure of the semiconductor substrate.
- the apparatus may be designed to operate on gaseous reactants.
- the energies of excitations associated with chemical reactions of adsorbates on and with the surface of a catalytic collector are converted into excitations such as hot carriers and electromagnetic fields .
- the energies of excitations associated with reactions of adsorbates include excited reactant molecular vibrations molecule-surface vibrations, atom- surface vibrations, adsorption reactions, chemical reactions and excited electronic states.
- the converted excitations such as hot carriers and electromagnetic fields are transported to the excitation emitter where semiconductor or emitter excitations are created and may be converted into useful forms of energy.
- the emitter excitations include minority carriers, hot carriers, carrier diffusion, coupling electric fields, excitons, and plasmons in the semiconductor.
- pulses of excitation energies associated with chemical reactions of adsorbates occurring on and with the surface of a catalytic collector may be converted into excitations such as hot carriers and electromagnetic fields.
- excitations such as hot carriers and electromagnetic fields.
- excitations are transported to an emitter or the excitation emitter where excitations such as minority carriers, hot carriers, carrier diffusion, coupling electric fields, excitons, and plasmons in the- semiconductor are created and may be converted into useful forms of energy.
- Figure 1 illustrates a general schematic cross section of a solid state surface catalysis reactor device.
- the device 100 comprises an emitter 102 and a catalytic collector 104, formed on a base 108.
- a semiconductor p-n junction 110 is formed between the emitter 102 and the base 108.
- An emitter electrical connection 114 and catalytic collector 104 are arranged as shown in Figure 1.
- a base electrical connection 112 is also arranged in contact with the base 108 as shown in Figure 1. Reactants and products interact on the catalyst surface 116 of the catalytic collector 104.
- the reactants may include but are not limited to the hydrocarbon chains, ethane, ethylene, propane, propylene, propene, butane, butene, cetane, isomers thereof .
- the device 100 utilizes electrical energy to create energetic carriers, also referred to as hot carriers or hot electrons.
- the hot carriers diffuse into the catalytic collector 104, interact strongly with reactants on the catalyst surface 116 and accelerate the reactions to produce reaction products.
- the stimulated reactions may cause a chain reaction or the equivalent of a surface explosions.
- the stimulated reactions may also cause an autocatalyzed chain reaction.
- the hot electrons generated by chemical reactions occurring on the catalyst surface 116 and diffusing across the junction 110, for example, a p-n junction, cause a forward bias across the junction and generate electrical energy.
- a p-n junction is used with p type emitter and n-type base to create hot electrons.
- the junction 110 may be forward biased.
- the junction may be a p-n junction with p type emitter and n-type base.
- the junction may be a Schottky junction with a metal emitter and n-type semiconductor base.
- the forward biased junction 110 creates hot electrons.
- the base contact 112 is biased negative and the emitter contact 114 is biased positive, hot electrons are created in the junction 110.
- the hot electrons diffuse through the emitter 102 and ballistically transport through the catalytic collector 104 to the catalyst surface 116.
- hot electrons originating on the catalyst surface 116 may also ballistically transport through the catalytic collector 104 and diffuse to the junction 110, causing the emitter-base junction diode 110 to become forward biased.
- the base contact 112 becomes biased negative and the emitter contact 114 becomes biased positive, and the diode in the present invention becomes an electron source instead of a sink.
- These hot electrons migrate or diffuse to or from the emitter 102, and to or from the catalyst surface 116.
- the distance from the diode junction 110 to the adsorbates on the surface of the catalyst 116 is formed to be less than the distance over which the energy of these carriers degrades. This distance is generally less than several times the energy mean free path of such energetic hot electrons when evaluated over the path from the emitter-base junction 110 to the adsorbates on the catalyst surface 116.
- the catalytic collector 104 includes catalyst materials in layers, clusters, atomically uniform monolayers, or surface structures. Preferably, the layers or clusters have thickness dimension less than several times the total energy mean free path of hot electrons in the catalyst . The layers or clusters are formed close enough to the diode junction 110 such that hot electrons may diffuse directly between the junction 110 and the catalyst surface 116.
- the total energy mean free path of hot electrons in catalysts such as platinum or palladium is of order 20 nanometers and is far shorter than in Au, Ag or Cu. Therefore, according to an exemplary embodiment, catalyst clusters or layers are fabricated with cluster, layer thickness or thickness dimension less than this smaller value.
- the electron energy lifetime has been measured in Tantalum, a representative transition metal electronically similar to the platinum group, and is of order 15 fs .
- the calculated lifetime in palladium based on the Fermi inverse square scaling would be 600 fs at 0.3 eV and giving a total energy mean free path of 840 nanometers. Instead of this optimistic large value, it is presumed the lifetime is as poor as that measured in tantalum.
- the catalyst dimension is less than the measured energy mean free path of the hot electrons.
- the methods provided in the present invention generate electrons that have energies in the range that favor reaction over desorption. These energies are in the range 0.05 to 0.4 eV.
- the method to collect electrons generated by chemical reactions on the catalyst surfaces collect electrons whose energies are also in the range of 0.05 to 0.4 eV.
- a semiconductor material with band gap less than approximately 0.4 eV may be used. Examples of such semiconductor material include indium antimonide (InSb) or indium arsenide (InAs) which have band gaps of 0.18 eV and 0.35 eV, respectively.
- the energetic electrons produced with these semiconductors have energy approximately equal to the band gap in the p type semiconductor emitter. Hot electrons diffusing back into the n-type base generate electric potentials whose magnitude approaches the band gap energy.
- the value of the band gap is selected based on the nature of the reactants and the energies associated with their surface activity.
- the catalyst clusters may further include activators, de-activators, decelerator or accelerators placed in their proximity, such as oxides or other materials, as shown in cross section in Figure 2.
- Figure 2 illustrates a cross section 200 of a catalytic collector including reaction accelerator-decelerator materials 206 adjacent to and co-located with the catalyst materials 202.
- the hot electron catalytic collector includes the catalyst materials 202, an optional thin electrode underlayer 204, and reaction accelerator-decelerator materials 206 such as oxides.
- oxides of the catalyst itself, of cerium, titanium or aluminum may be formed between the catalyst islands or layers .
- the total dimension of the catalyst and thin electrode underlayer 204 is preferably less than several times the total energy mean free path of a hot electron.
- the catalyst may include materials such as Au, Ag, Pt, Pd, Cu, In, Fe, Ni, Sn, and Mo.
- the catalyst may be formed into structures including metal clusters, pillars, islands, layers, crystalline layers, atomically uniform monolayers, interdigital and random structures, stripes, or surface structures.
- the catalyst may also be formed into one, two, or three dimensional quantum confinement structures such as quantum dots, quantum stadia, quantum corrals and quantum wells.
- Figure 3 shows a cross section 300 of the solid state surface catalysis reactor device comprising a hot carrier emitter where the carrier is an electron, a catalytic collector.
- the catalytic collector ensemble includes catalyst islands 302, preferably formed such that the distance to the semiconductor 304 less than the three times the total energy mean free path of the hot electron in the catalyst 302.
- the catalyst islands 302 are bonded to the p doped or heavily p doped, p+ region of the semiconductor 304.
- the catalyst materials 302 are spread over the surface of the semiconductor.
- the catalyst is formed with surface structures containing atomically uniform monolayers.
- the hot, for example, electron, carrier emitter includes the semiconductor diode formed by negative electrode 306 in contact with n type semiconductor 308, p type semiconductor 312, p-n junction 310 formed between the n type semiconductor 308 and the p type semiconductor 312, p doped or heavily p doped p+ semiconductor 304, and positive electrode 314.
- FIG. 4 illustrates a cross section 400 of a solid state surface catalysis reactor device with thin electrode 402 forming a substrate for catalyst structures.
- the catalytic collector includes a thin electrode underlayer 402, catalyst structures 404 and a bus bar electrical connection 406 in electrical contact with the thin electrode underlayer 402.
- the hot electron emitter includes a semiconductor diode formed by negative electrical connection 408, n- type semiconductor 410, p-n junction 412, p type semiconductor 414, p doped or heavily p doped p+ semiconductor 416, and thin electrode underlayer 402.
- the thin electrode underlayer 402 may be common to the hot electron emitter and the catalytic collector.
- the thin electrode underlayer 402 may be a thin positive electrode.
- the thin electrode underlayer 402 is preferably selected from those materials that make an ohmic or almost ohmic junction to the semiconductor .
- the thin electrode underlayer 402 provided in the present invention forms ohmic or almost ohmic junctions to the semiconductor 416 while also providing a path for hot electrons to enter or leave the catalyst 404.
- the ohmic properties of the junction between the semiconductor 416 and catalyst 404 may form a Schottky junction instead.
- a layer of metal i.e., the thin electrode underlayer 402 is used as the means to form a practically ohmic junction, which may be almost ohmic or a tunneling Schottky junction.
- the catalyst clusters or layers 404 are then placed on top of the thin electrode underlayer metal 402.
- the thickness of the electrode underlayer 402 is selected to be much less than the energy mean free path of the hot electrons passing through it.
- This thin layer e.g., the thin electrode 402 assures that the Fermi level of the catalyst and the Fermi level of the p type semiconductor emitter are the same or practically the same.
- a thin, 1 to 20 nm layer of metal such as Au, Ag or Cu may be used as the electrode 402 or substrate for the catalyst ensemble. It should further be appreciated that the present invention does not limit the choice of contact metal used to form the electrode to Au, Ag or Cu, and other metals, alloys or semi-metals may be selected to form at least a nearly ohmic junction with the semiconductor.
- the material used for the thin electrode 402 may be selected so that the junction between the electrode 402 and the heavily doped semiconductor 416 forms at least an almost ohmic junction.
- the junction formed is an ohmic junction.
- the semiconductor doping is selected sufficiently high so that the dimension or thickness of any Schottky barrier formed by this junction is sufficiently small that electron tunneling dominates the current flow.
- the p type semiconductor may be heavily or degeneratively doped near the region of contact with the metal.
- Figure 3 shows this heavily doped region 304 near both the emitter electrical connection 314 and catalyst clusters 302.
- Figure 4 shows this heavily doped region 416 in contact with the thin electrode underlayer 402.
- a preferred doping of 2el9 per cc donors in InSb or InAs is considered to be such a heavy doping.
- Degenerative doping of the semiconductor to 2e20 per cc and bonding a suitable metal, such as Au, Ag, or cu, as the thin metal contact can make an almost ohmic electrical connection to the semiconductor.
- any metal may form such an almost ohmic junction because the junction dimension under heavy or degenerative doping is of order 1 nanometer or less, and at this dimension tunneling across the junction is predominating.
- a junction of this type typically has characteristic p-n junction dimension of order 3 nanometers or less and electron diffusion length in the emitter and collector regions in excess of 1 micron. The dimension may be limited by Auger recombination.
- the junction between the emitter and the catalytic collector elements of the present invention can be readily constructed since .1 micron thickness and greater dimension is routinely achieved in practice.
- the thin electrode is bonded to the p type semiconductor surface.
- the catalyst clusters or layers are placed on the thin electrode and preferably near to the p-n junction. "Near” is defined to be "a distance that is within the diffusion dimension of minority carriers in the emitter semiconductor.” This dimension is typically of order 0.1 micron or more.
- the calculated diffusion length of electrons in p type InSb doped to 2e20 per cc is of order 7 microns and 5.5 microns in InAs. However, observed Auger lifetimes of 1 picosecond suggest the diffusion length is of order 1 micron.
- the catalyst metal 302 and 404 or the thin metal contact underlayer 402 may serve as both the catalytic collector and an emitter positive electrical connection. This also reduces the cost and complexity of fabrication.
- Figure 5 shows a cross section 500 of a solid state surface catalysis reactor device similar to that illustrated in Figure 4 and with reaction accelerator- decelerator materials 502 surrounding or adjacent to catalyst structures 404.
- the catalyst clusters may further include chemical surface reaction activators, accelerators or decelerators placed in their proximity, such as oxides or other materials.
- the catalytic collector includes the catalyst structures 404, an optional thin electrode underlayer
- catalyst accelerators or decelerators 502 such as oxides.
- oxides of the catalyst itself, or oxides of cerium, titanium or aluminum may be formed between the catalyst islands or layers.
- the distance a hot electron must travel through the catalyst 404 and thin electrode underlayer 402 is preferably less than several times the total energy mean free path.
- Figure 6 shows a cross section 600 of the solid state surface catalysis reactor device including a single metal element 605 that is at the same time an electrical connection to the emitter, the underlayer of the catalytic collector and forms the metal element of a Schottky diode .
- Shown in Figure 6 is a solid state surface catalysis reactor device using a Schottky diode. Reactants adsorb on the catalytic collector 605, 606 and 607.
- a Schottky diode is formed between the thin metal underlayer 605, the more heavily doped semiconductor 604 shown as n type for illustration appropriate for the hot carrier being hot electrons, the lesser doped semiconductor region 601, and the thicker negative electrical connection 606.
- Bus bar 602 provides the electrical connection for the current-carrying, positive, thin electrode 605.
- the diode is pulsed with a forward bias, that is, electrode 606 is pulsed negative with respect to positive electrode 605, consuming electric power.
- This triggers surface reactions on the catalyst ensemble 607 and causes products to be formed. Excess reaction energy may produce a burst of hot electrons which travel through the thin catalyst structure 607 and element 605, surpass the Schottky barrier potential and enter the diode regions 601 and 604, forward biasing the diode and producing electric power.
- reaction stimulation properties of the same device may be its principle function.
- electrical generation properties may be the principle function.
- Figure 7 illustrates the electronic energy levels diagram 700 of the elements of the solid state surface catalysis reactor device appropriate for the case where the hot carrier is a hot electron.
- These elements include an adsorbate 702, catalyst 704, positive electrode or electrical connection 718, electrode junction, highly doped semiconductor in the collector- emitter region 706, p doped semiconductor region 708, p- n junction region 710, n doped 712 and the heavily n doped 714 region.
- a forward bias 716 drives electrons from the n+ region 714 where they are majority carriers, into the p-n junction 710, into the p type region 708 of the semiconductor where they are minority carriers, into the catalyst 704, and then to the catalyst surface where they interact with the adsorbate 706.
- the hot electron excites states in the adsorbate which stimulate reactions.
- a point of novelty of this invention also include the use of forward biased devices for the purpose of reaction stimulation or electric generation.
- the invention has been particularly shown and described with respect to a preferred embodiment thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made therein without departing from the spirit and scope of the invention.
- those skilled in the art will appreciate that the features of the invention may sometimes be used to advantage without a corresponding use of the other features shown or described herein above.
- some features may be combined, within the scope and equivalents of the present invention, to achieve a desired result.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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AU12131/01A AU1213101A (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
MXPA02004031A MXPA02004031A (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor. |
CA002388424A CA2388424A1 (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
BR0014956-0A BR0014956A (en) | 1999-10-20 | 2000-10-18 | Reversible, solid state surface catalysis excitation transfer reaction apparatus, process for converting adsorption reaction energy into power and process for stimulating reactions |
EP00973637A EP1232005A4 (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
KR1020027005133A KR20020070269A (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
APAP/P/2002/002500A AP2002002500A0 (en) | 1999-10-20 | 2000-10-18 | Solid State surface catalysis reactor. |
JP2001531501A JP2003512153A (en) | 1999-10-20 | 2000-10-18 | Solid surface catalytic reactor |
IL14922000A IL149220A0 (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
NO20021871A NO20021871L (en) | 1999-10-20 | 2002-04-19 | Semiconductor Surface Catalyst Reactor |
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US16053199P | 1999-10-20 | 1999-10-20 | |
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US09/631,463 | 2000-08-03 | ||
US09/631,463 US6916451B1 (en) | 1999-05-04 | 2000-08-03 | Solid state surface catalysis reactor |
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PCT/US2000/028801 WO2001028677A1 (en) | 1999-10-20 | 2000-10-18 | Solid state surface catalysis reactor |
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EP (1) | EP1232005A4 (en) |
JP (1) | JP2003512153A (en) |
CN (1) | CN1409651A (en) |
AP (1) | AP2002002500A0 (en) |
AU (1) | AU1213101A (en) |
BR (1) | BR0014956A (en) |
CA (1) | CA2388424A1 (en) |
IL (1) | IL149220A0 (en) |
MX (1) | MXPA02004031A (en) |
NO (1) | NO20021871L (en) |
OA (1) | OA12068A (en) |
WO (1) | WO2001028677A1 (en) |
Cited By (15)
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EP1232546A1 (en) * | 1999-10-20 | 2002-08-21 | Neokismet L.L.C. | Surface catalyst infra red laser |
WO2002091479A1 (en) | 2001-05-10 | 2002-11-14 | Neokismet L.L.C. | Gas specie electron-jump chemical energy converter |
WO2003019764A1 (en) * | 2001-08-24 | 2003-03-06 | Neokismet, L.L.C. | Pulsed electron jump generator |
EP1358682A2 (en) * | 2001-01-17 | 2003-11-05 | Neokismet L.L.C. | Electron-jump chemical energy converter |
US6678305B1 (en) | 1999-05-04 | 2004-01-13 | Noekismet, L.L.C. | Surface catalyst infra red laser |
US6916451B1 (en) * | 1999-05-04 | 2005-07-12 | Neokismet, L.L.C. | Solid state surface catalysis reactor |
US7119272B2 (en) | 1999-05-04 | 2006-10-10 | Neokismet, L.L.C. | Gas specie electron-jump chemical energy converter |
US7122735B2 (en) | 2001-06-29 | 2006-10-17 | Neokismet, L.L.C. | Quantum well energizing method and apparatus |
US7371962B2 (en) | 1999-05-04 | 2008-05-13 | Neokismet, Llc | Diode energy converter for chemical kinetic electron energy transfer |
US9437892B2 (en) | 2012-07-26 | 2016-09-06 | Quswami, Inc. | System and method for converting chemical energy into electrical energy using nano-engineered porous network materials |
US10833199B2 (en) | 2016-11-18 | 2020-11-10 | Acorn Semi, Llc | Nanowire transistor with source and drain induced by electrical contacts with negative Schottky barrier height |
US10872964B2 (en) | 2016-06-17 | 2020-12-22 | Acorn Semi, Llc | MIS contact structure with metal oxide conductor |
US10879366B2 (en) | 2011-11-23 | 2020-12-29 | Acorn Semi, Llc | Metal contacts to group IV semiconductors by inserting interfacial atomic monolayers |
US10937880B2 (en) | 2002-08-12 | 2021-03-02 | Acorn Semi, Llc | Method for depinning the Fermi level of a semiconductor at an electrical junction and devices incorporating such junctions |
US11043571B2 (en) | 2002-08-12 | 2021-06-22 | Acorn Semi, Llc | Insulated gate field effect transistor having passivated schottky barriers to the channel |
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US7663053B2 (en) * | 2007-01-05 | 2010-02-16 | Neokismet, Llc | System and method for using pre-equilibrium ballistic charge carrier refraction |
US20160211435A9 (en) | 2007-01-05 | 2016-07-21 | Neokismet, Llc | System and Method for Using Pre-Equilibrium Ballistic Charge Carrier Refraction |
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CN105073241B (en) * | 2013-03-14 | 2017-10-03 | 艾迪·陈 | The electrical activation method and apparatus of catalyst |
US20160030622A1 (en) * | 2014-07-29 | 2016-02-04 | Nano And Advanced Materials Institute Limited | Multiple Plasma Driven Catalyst (PDC) Reactors |
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US6114620A (en) * | 1999-05-04 | 2000-09-05 | Neokismet, L.L.C. | Pre-equilibrium chemical reaction energy converter |
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DE3519397A1 (en) * | 1985-05-30 | 1986-12-04 | Siemens AG, 1000 Berlin und 8000 München | Sensor for gas analysis and detection |
DE3743399A1 (en) * | 1987-12-21 | 1989-07-06 | Siemens Ag | Sensor for detecting gases by means of exothermic catalytic reactions |
GB9317256D0 (en) * | 1993-08-19 | 1993-10-06 | Boc Group Plc | Molecular processes and apparatus therefore |
US6084173A (en) * | 1997-07-30 | 2000-07-04 | Dimatteo; Robert Stephen | Method and apparatus for the generation of charged carriers in semiconductor devices |
-
2000
- 2000-10-18 AP APAP/P/2002/002500A patent/AP2002002500A0/en unknown
- 2000-10-18 OA OA1200200115A patent/OA12068A/en unknown
- 2000-10-18 BR BR0014956-0A patent/BR0014956A/en not_active Application Discontinuation
- 2000-10-18 AU AU12131/01A patent/AU1213101A/en not_active Abandoned
- 2000-10-18 CA CA002388424A patent/CA2388424A1/en not_active Abandoned
- 2000-10-18 MX MXPA02004031A patent/MXPA02004031A/en unknown
- 2000-10-18 WO PCT/US2000/028801 patent/WO2001028677A1/en not_active Application Discontinuation
- 2000-10-18 EP EP00973637A patent/EP1232005A4/en not_active Withdrawn
- 2000-10-18 JP JP2001531501A patent/JP2003512153A/en active Pending
- 2000-10-18 CN CN00817067A patent/CN1409651A/en active Pending
- 2000-10-18 IL IL14922000A patent/IL149220A0/en unknown
-
2002
- 2002-04-19 NO NO20021871A patent/NO20021871L/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US6114620A (en) * | 1999-05-04 | 2000-09-05 | Neokismet, L.L.C. | Pre-equilibrium chemical reaction energy converter |
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US7122735B2 (en) | 2001-06-29 | 2006-10-17 | Neokismet, L.L.C. | Quantum well energizing method and apparatus |
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Also Published As
Publication number | Publication date |
---|---|
CN1409651A (en) | 2003-04-09 |
AP2002002500A0 (en) | 2002-06-30 |
NO20021871D0 (en) | 2002-04-19 |
EP1232005A4 (en) | 2004-08-25 |
EP1232005A1 (en) | 2002-08-21 |
BR0014956A (en) | 2002-10-15 |
CA2388424A1 (en) | 2001-04-26 |
AU1213101A (en) | 2001-04-30 |
JP2003512153A (en) | 2003-04-02 |
IL149220A0 (en) | 2002-11-10 |
OA12068A (en) | 2006-05-03 |
MXPA02004031A (en) | 2004-08-23 |
NO20021871L (en) | 2002-06-20 |
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