CN1618131A - Gas specie electron-jump chemical energy converter - Google Patents

Gas specie electron-jump chemical energy converter Download PDF

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CN1618131A
CN1618131A CN02802348.XA CN02802348A CN1618131A CN 1618131 A CN1618131 A CN 1618131A CN 02802348 A CN02802348 A CN 02802348A CN 1618131 A CN1618131 A CN 1618131A
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energy
semiconductor
reaction
substrate
reaction zone
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CN100416862C (en
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安东尼·C·祖佩罗
贾瓦哈·M·吉德瓦尼
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Neokismet LLC
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M27/00—Apparatus for treating combustion-air, fuel, or fuel-air mixture, by catalysts, electric means, magnetism, rays, sound waves, or the like

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Abstract

An apparatus and method for extracting energy is provided. In one aspect the method includes using chemical reactions to generate vibrationally excited molecules (101), such as high-quantum-number-vibrationally-excited gas molecules in a region. The vibration energy in the vibrationally excited molecules is converted into hot electrons when the excited molecules contact a conductor (103). A geometry is provided so that the excited molecules may travel, diffuse or wander into a conductor (103) before loosing a useful fraction of the vibrational energy. Optionally, the generating and the converting process may be thermally separated, at least in part. The short lived hot electrons are converted into longer lived entities such as carriers and potentials in a semiconductor, where the energy is converted into a useful form.

Description

Gaseous matter electronics-transition chemical energy conversion equipment
Invention field
The present invention relates to chemical reaction can be directly changed into the method and apparatus of electric energy, more particularly, the present invention relates to produce the high provocative reaction product of vibration and directly the power conversion of this product is become its useful form such as, hot electron on the metal surface, long-life charge carrier in semiconductor, the method and apparatus of radiation or coherent radiation.
Technical background
Fuel cell is a kind of cleaning and effective electrochemical energy conversion method, normally can directly and effectively convert to by the chemical reaction with reacting gas.Yet, be lower than mechanical energy usually at least by the shown unit mass that goes out of fuel cell system or the energy of unit volume.And then, adopt the liquid fuel of can preserving with remarkable usually the volume of the required volume of the fuel cell that produces institute's accumulators energy greater than battery.This means that no matter the efficient of fuel cell how, owing to there is not the required space of fuel, the present form of fuel cell also can not replace storage battery.
In addition, have the type of the fuel cell of the highest known unit mass-energy, promptly Solid Oxide Fuel Cell need be 600-800 ℃ of operation down.Operation can produce the raw material problem under this temperature.In principle, fuel cell will demonstrate the energy density that need move under the storage battery volume.But the realization of this target is arranged and hindered to heat problem.
The another kind of form of high performance fuel cell is the rotating machinery device.But the mechanical engine of electrogenesis usually must use coil and magnetic device and conversioning mechanical energy is electric energy, thus the unusual heaviness of engine, and energy density can be lower than 2 watts of every grams.
Thereby, still need a kind ofly directly and effectively to convert chemical energy the method and apparatus of electricity to, and need not high temperature and material and need not the method for relative heavy mechanical device.
Chemical reaction can produce the material that excites of highly vibration usually, can promote the carrying out of this reaction by catalyst, injection autocatalyst or other means.When excited species and Metal Contact, the overwhelming majority of excitation energy can be converted into the electronics of energizing in metal, referring to Huang, and Yuhui; Charles T.Rettner, Daniel J.Auerbach, Alec M.Wodtke, Science, Vol.290,6 October 2000, pp 111-113, " facilitated of electron transfer (Vibrational Promotion of Electron Transfer) ".
According to experimental result, the anion of vibrational excitation can absorb electronics, and emitting electrons enters in the lattice once more, and carries most excitation energy.Similarly, but cation excitation electron and absorbing again launch the hole in lattice, and the hole has energy.Electronics or hole are hot carriers.
Experimental observation in Surface Science and theoretical research in recent years confirms, with simple brief contacting (the about 0.1 picosecond) process of metal surface in, can deposit most vibrational energy in the electronics of metal surface even have the weak relatively electronegative gas molecule of the energy of the chemical bond (vibration quantum quantity exceedance amount about 15) that almost can puncture them effectively.With the research of this observation associated with observe and also support to be excited chemical substance and will to be excited by vibration, the sub-power conversion of volume becomes the theory of single electron.
Usually, the oscillatory type energy that surpasses half will be directly changed into the electronics of metal surface, and energy is greater than about 5 vibration quantums.As a result, a large amount of useful vibration excited molecule energy of the electronics portability of metal surface also are referred to as hot carrier as hot electron.
In metal, hot carrier can move in semiconductor.Hot electron converts exciting or potential energy difference in semiconductor to, thereby it is convertible into other useful form as driving the potential energy of electric current in the external circuit, and the reverse sum that semiconductor excites perhaps is sent to the hot carrier of other spendable position.
Hot electron is convertible into the potential energy in the semiconductor.For example, the U.S. the 6th, 222, No. 116 patent is directly collected this hot electron without mechanical device, and is excited the chemical product material on the reaction surface of device or when forming in the several molecule size when vibration, directly they is converted to.Reaction speed is enough high to make its forward bias that maintains usefulness with the vitalizing semiconductor transducer by making, and device produces useful electric energy described in this patent.
Can strengthen this high reaction speed by removing with the product of crossing from the surperficial upward desorb of hot electron collection.The molecule desorb of deenergizing can stay the room and more react.Make these molecules that deenergize walk the reaction of further initiated oxidation agent and fuel from the contact surface migration.
Therefore, need a kind of method to excite material, and the electric energy conversion of the material that excites is taken place in the position of different hotness, and separate by the generation of excited species directly to produce the vibration height by chemical reaction.And then, also need reaction to betide in the volume but not only from the teeth outwards, increase reaction speed when carrying out from the teeth outwards.
Summary of the invention
On the one hand, the invention provides a kind of method, this method adopts chemical reactant to produce vibration in reaction volume or zone to be excited gas molecule, to obtain lot of energy, for example as hot electron on conducting surface, and energy such as hot electron are converted to the useful form of energy.
This method comprises and adopts chemical reaction to produce the vibration excited molecule, and gas molecule is excited in vibration as high quantum number.When excited molecule contact conductor, the vibrational energy in the vibration excited molecule is converted into hot electron.Geometry as the gas reaction area that has several molecule collision mean free path size and partly rebound by conducting surface is provided, thus make excited molecule can be before emission vibrational energy useful part by, spread or drift about in conductor.Optionally, generation and transfer process can be carried out thermal release at least in part.Short-life hot electron is converted into the individuality of longer life in semiconductor, as charge carrier and potential energy, thereby power conversion can be become useful form.
On the other hand, the invention provides a kind of energy-producing device, this device comprises a reaction zone, and in reaction zone, reactant such as fuel and oxidant carry out chemical reaction, and this reaction can produce high vibration excited molecule.Make the refuse that in reaction, produces discharge system.Reaction zone can be enough closely near collecting the surface can not launch its lot of energy before collecting the surface so that be excited product arriving.Collect the surface and can comprise a surface such as conductor,, be excited product power conversion is become hot electron or charge carrier (electronics or hole) or thereon near the conductor place.Transition zone can contact with collecting the surface, and at this, hot electron or charge carrier are converted into useful form, as propping up the potential energy that is held in the semiconductor by the charge carrier that separates.This transition zone can be isolated with the form and the reaction zone of heat at least in part at least.
On the other hand, described method can comprise that shift reaction product excites, as the sub-energy changing of volume of the dipole activated state of vibrational state, this be one type be excited the exciting of chemical product.
Below, describe the structure and the operation of other characteristics of the present invention and advantage and each embodiment of the present invention in conjunction with the accompanying drawings in detail.In the accompanying drawings, same reference number is indicated identical or functionally similar element.
Description of drawings
With reference to the accompanying drawings, embodiment of the present invention are only described by way of example, wherein:
Fig. 1 has shown the schematic cross-section of device, and wherein, the reaction zone of separation produces the molecule of energizing, and collecting region is collected from the energy of the molecule of energizing;
Fig. 2 has shown the schematic cross-section of the energy converter part of device, adopts p-n junction to select to produce useful electromotive force by the energy of the molecule of energizing;
Fig. 3 has shown the schematic cross-section of the energy converter part of device, adopts schottky junction to select to produce useful electromotive force by the energy of the molecule of energizing;
Fig. 4 has shown schematic cross-section, and wherein, reaction zone produces the molecule of energizing, and collecting region is collected from the energy of the molecule of energizing, and adopts schottky junction to produce;
Fig. 5 has shown the schematic cross-section of storing the device that excites that is produced by excited molecule;
Fig. 6 has shown the schematic cross-section that excites the device that is converted to population inversion that excited molecule is produced;
Fig. 7 has the fuel of separation and oxidant channel, the schematic cross-section of the device that reaction that separates and collecting region and heat are isolated; With
Fig. 8 has shown the schematic cross-section of the explanation thermal boundary and the device of reaction that separates and collecting region.
Embodiment
On the one hand, method and apparatus of the present invention can strengthen peak power and energy conversion rate, and further can strengthen the desorb from the refuse and the pollution products of conducting surface.Described method comprises that selection has the catalyst of low relatively affinity to refuse.This catalyst comprises platinum, palladium, and relevant catalyst demonstrates for this kind character of hydrogen with the alcohol burning.
On the other hand, described method comprises makes fuel and oxidant enter reaction zone, makes waste product leave reaction zone.Waste product is extensible and spread out.The method that waste product is weighed up and spread out comprises makes gas reactant flow through reaction surface, and allows waste product leave the surface to enter in the air-flow.On the other hand, device of the present invention can be designed to produce simple disposable pulse power, and in this case, waste product need not to leave reaction zone.
Method of the present invention can comprise that employing moves to the excited molecule of conducting surface by the gas reaction volume.When excited molecule and conducting surface interact, with most chemical vibrational energy with energize, the form of ballistic electron delivers to conducting surface.The conducting surface that forms is extremely thin, and the permission ballistic electron directly moves and diffuses in the Semiconductor substrate.Semiconductor is compared the useful form that electronic switch becomes can store with the life-span (for example 0.01 picosecond) of ballistic electron, have the longer life-span (for example picosecond or longer).Usually, semiconductor forms diode, and the useful form of energy to be the forward bias of conduct in the diode produce.
Conducting surface can comprise catalyst and/or catalyst metals, thereby makes reaction on the catalyst remove adsorbate continuously and the metal of cleaning is provided, vibration be excited gaseous matter can with its interaction.But the additive make-up catalyst of supplying with fuel and/or oxidant.The known unreacted matters that can remove absorption effectively of oxidation reaction.Nearly all fuel-air reaction trends towards supporting or allow to support this oxidation reaction that is used for clean surfaces for the oxygen enrichment reaction.
When even the reactive adsorbate of individual layer occupy on the conducting surface, conducting surface still can be thought and can conduct.This adsorbate comprises oxygen and fuel molecule.Usually, the part single layer oxide can form on the catalyst conducting surface.
On the one hand, device of the present invention can adopt fuel and oxidant with near generation excited molecule conducting surface.In addition, by the reaction of fuel and oxidant such as air, also can produce high vibration excited species near conducting surface, described fuel for example is methyl alcohol, hydrogen or partial oxidation and compound hydrocarbon.Can select fuel from any reducing material or electron donor, include but not limited to: hydrogen, hydrocarbon, compound hydrocarbon, alcohol is as methyl alcohol, ethanol and propyl alcohol, carbohydrate, the hydrocarbon of partial oxidation, diesel fuel, kerosene, the vaporized product of organic substance, product such as the hydrogen and the carbon monoxide of fuel conversion stove, and the inflammable gas that comprises ammonia.Oxidant can comprise any electron acceptor, oxygen, air, hydrogen peroxide and halogen.On the other hand, though also can adopt those its whether be considered to the reactant of fuel and oxidant.Therefore, any generation reaction of being movable to the vibration excited species of collecting region all can be used as energy source.
Other exemplary reactant comprises the combination of alkali metal and water, and waste product will comprise alkali oxide and hydrogen.Other example of reactant comprises chemical reactant, and wherein fuel is identical unsettled molecule with oxidant.The example of this chemical reactant comprises monopropellant such as MMH, the monomethyl hydrazine.
On the one hand, the vibration excited species can produce by any known method.The material that vibration is excited can comprise the chemical substance of partial reaction, as comprises and comprise oh group OH, the reaction intermediate of CO and HCO.These intermediates can comprise other non-reactive material, as refuse and air molecule such as nitrogen or oxygen.These intermediates can obtain vibrational energy from reactant and its accessory substance.Resonance transfer only is to make one of mode that intermediate is excited.
For forming the vibration excited species by the Eley-Rideal method, can allow chemical reactivity free radical such as atomic hydrogen and oxygen to impinge upon oxygen or the fuel that adsorbs on catalyst or the conductive surface.Reactant also can be formed on the metal surface, and for example reacts through Langmuir Hinshelwood method.
On the one hand, can react by means of catalyst and stimulant by making fuel and air, and form vibration in any position and be excited the reaction geometry of gas molecule and produce excited molecule by adopting, in described position, they can be easy to move and diffused to conducting surface before emission excites in a large number.
In operating process, can adopt known stimulating apparatus such as catalyst, response stimulus device method and additive are to produce the vibration excited species after entering reaction zone at reactant.The stimulator method comprises one or more catalyst of employing, the catalyst on reaction surface, discharge, sliding electrical discharge, optics and photolytic process, Optical devices and injecting catalyst, catalysis or autocatalysis agent material.Stimulating apparatus can produce the free radical as stimulant, for example, adopts electricity or luminous energy.
Because the most stable chemical reaction is activated (having the disclosed potential energy barrier of the reactant of maintenance), stimulating apparatus can provide the activation evergy that adopts electric installation.The device that is provided can recover a part of described energy.
Fuel and oxidant mixture produce gaseous product in the aerochemistry reaction, its initial condition is that energy is concentrated with vibration mode substantially.The vibration mode of gas has 10 ' s to 10 usually, the life-span of 000 ' s gas kinetic collision (for the off-resonance effect), and for typical hydrocarbon-air reaction product, the pre-equilibration mean free path is the 50-200 nanometer scale in gas.This means, utilize the reaction channel of this mean free path will have big size: the mean free path of at least 10 ' s to 100 ' s (square root by (time between 3 * vibration life/collision) provides) to the following order of magnitude, thereby will have at the most 20, the size of 000 nanometer scale (.02mm, 1 inch 0.8/1000th).Have 1 or this passage of bigger mean free path size in fact can make.
Even will be low to moderate 1/10th mean free path when the vibration mode life-span, their metal wall surfaces feature or passage are of a size of 1/2 micron number magnitude.Being characterized as of these sizes is easy to structure.Thereby these passages or surface characteristics can be constructed so that gas molecule acted on before balance has been degenerated energy.Therefore, the vibration molecule reach with other pattern as rotation and the balance that shifts before and in the distance of removing from collection of energy and conversion surface, the vibration molecule can be manufactured into metallic walls and collide.
The method that is provided comprises volume or the zone that is used to carry out chemical reaction.Analog value when adopting described volume or zone can allow reaction speed and corresponding power output to be higher than the employing surface.In volume or zone, can take place than more reaction from the teeth outwards.The volumetric reaction speed that forms is usually above the speed relevant with the catalyst turnover number.Because reaction can be at the volumetric region moderate stimulation, collection of energy can realize in surf zone that compare with the mode of surface reaction, this method has kept high power output simultaneously.Usually, compare with the situation of macroreaction volume, S/V is that 1/2 micron situation is very high.Therefore, compare, adopt volume can cause the increase of energy values with only adopting the surface reaction that depends on surface catalysis.
From the power conversion district, separate high reaction speed, during the higher temperature volume area, the surface is a feature, can allow complete electric energy system, the power of the power of unit mass and unit volume performance is near the restriction of the aerodynamics of 10-500 watt/cc, as in rocket engine and ramjet those.Particularly, adopting method and apparatus of the present invention to convert electric energy to by chemical energy does not need mechanical type generator (generator), and this mechanical type generator needs ramjet and turbine system, makes system increase suitable weight like this.
On the other hand, the method that is provided comprises reaction zone that adopts hot mode separation or isolation at least in part that produces heat and the power conversion district that more effectively moves at low temperatures.Used heat also can from reaction zone directly conduct and convective heat transfer to exhaust apparatus.
This isolation allows energy converter to remain below under the temperature of reaction zone.On index, become more effective with thermionic conversion in the semiconductor that conducting surface links to each other as the function that reduces temperature.
This heat isolation also allows reaction volume to remain under the temperature that is higher than the power conversion district.Chemical reaction velocity quickens on index as the function of temperature usually.This higher reaction speed allow with can enter the corresponding to speed supply of reaction zone reactant by the pumping reactant.
On the other hand, the different piece of reaction zone can be moved at elevated temperatures, for example under 600 ℃, to stimulate catalytic reaction and to quicken or keep reaction speed.
The method and apparatus that is provided can adopt near the geometry that produces high vibration excited species conducting surface.Here " near " be meant that vibration is excited to be lower than the distance of gaseous diffusion apart from several times the gaseous matter for height.
Term " closely near conducting surface " is meant the situation of wherein passing the space electric charge ballistic, can refer to that also wherein relevant with chemical substance electricity and magnetic field fades away and can not propagate the situation of waveform, and the size under two kinds of situations all is lower than 1000 nanometers usually.
Diffusion length is relevant with characteristic distance, and before the big energy of emission, vibration is excited to move by characteristic distance, and described diffusion length is referred to as to vibrate diffusion length in this article.The vibration diffusion length is approximately the 1-σ distance of the three-dimensional bell curve Probability Distribution that will move by its material.This dispersal pattern regulation, the vibration diffusion length is collision mean free path and the subduplicate product of following value: 3 multiply by the ratio of time between vibration life and collision.S.T.P. the diffusion length of air surpasses the hundreds of nanometer usually usually far below 20 microns.
On the other hand, method of the present invention can convert long-life charge carrier in semiconductor to short-life trajectory charge carrier (is the hot electron of 0.010 picosecond as the common life-span), and its life-span surpasses several picoseconds usually.
On the other hand, energy converter such as semiconductor or quantum well directly contact with substrate, convert short-life substrate hot carrier to long-life charge carrier or excite in semiconductor or quantum well.
On the other hand, method of the present invention can be injected or change by the surperficial charge carrier that forms with the excited molecule interaction and enter semiconductor diode to produce the charge carrier of being excited of excessive diode.This excessive charge carrier of being excited also can produce the electromotive force that passes diode.
On the other hand, device provided by the invention can comprise the p-n junction diode.The hot electron that produces in conducting surface can pass surface and intermediate materials and entering in the p-N-type semiconductor N substrate.The valence band of horizontal ohmic properties contact of the Fermi of conductor or nearly ohmic properties contact semiconductor (band down).Therefore, its energy of hot electron that energy is higher than band gap also can be higher than conduction band (going up band), and becomes the minority carrier in the conduction band.Then, the conduction band electron transfer is to the p-n junction place, and because of inner electromotive force is attracted at this place, thereby imposes forward bias and produce to diode.Can select semi-conductive polarity and band gap intentionally, so that when hot carrier was in semiconductor, hot carrier became minority carrier.
For example, in p-n junction, can use long-life minority carrier and convert other useful form to.For example, charge carrier is convertible into.Can allow charge carrier to be re-combined into the coherent beam of radiant energy or radiant energy.And then charge carrier can diffuse to other position of device, and is excited charge carrier for further surface reaction provides.Charge carrier is used in the millimicro meter level mechanical system and causes mechanism, and/or the charge carrier that is provided by power supply is provided in semiconductor.Thereby chemical energy can be converted into any other useful form.
Therefore, on the one hand, method of the present invention comprises formation p-n junction diode.This diode can be has that one or two are a large amount of to mix or the diode of the polarity of retrograde dopant.Method of the present invention can comprise the formation doping gradient, and it can be wider or narrower than the interface.Those skilled in the art knows, imposes high-peak power in adopting the semi-conductive p-n junction of low band-gap can increase efficient by adopting the pulse chemical reaction, allows to adopt the spatia zonularis value that is approximately 0.05-0.1eV.
The description that is appreciated that prior art structure p-n junction diode comprises multiple diverse ways.These methods comprise outer field various zones of metal, semiconductor, oxide and diode insulator and combination.The effect in some zone is to form with the ohmic properties of diode to contact or nearly ohmic properties contact.Other function comprises lattice match.Diode can form with the multiple scheme of the combination of mixing.All these variation schemes may all be identical a kind of p-n junction diodes on function.
Method and apparatus of the present invention can comprise that its band gap of employing can be by the semiconducting compound of selecting alloy composition to manufacture.Described manufacturing can be executed near close conducting surface and semiconductor converter or the conducting surface place, for example, produces electromotive force so that charge carrier is swept the semiconductor from conducting surface.These semiconductors comprise InGaAsSb family semiconductor, and wherein, the scope of band gap is approximately 0.1eV to being higher than 1.5eV, and this depends on the ratio of In and Ga and the ratio of As and Sb.
Method and apparatus of the present invention also can comprise employing indirect bandgap semiconductor, as silicon and germanium and their alloy.This material demonstrates usually than the longer carrier lifetime of direct band gap semiconductor.This can increase the efficient of p-n junction, the efficient of the efficient of the concrete scheme of generator and the concrete scheme of storage charge carrier.
Method and apparatus of the present invention can comprise that also operation has the diode of bias voltage to strengthen resonant tunneling effect.A kind of mode is move diode with bias voltage when electron transfer is preponderated, thereby the adsorbate energy level on semi-conductive conduction band and the conducting surface to mate.When the hole transfer was preponderated, the coupling of valence band adapted to.Also can adopt direct band gap semiconductor as semiconductor from InGaAsSb family.Directly the band gap semiconductor allows configuration like this, and it can obtain energy by radiation and the stimulated emission by radiation.
On the one hand, conducting surface can be formed on the metallic contact of Schottky diode.Then, hot electron will move by metal.Hot electron with enough energy can surmount Schottky barrier, and enters in the n N-type semiconductor N of diode.In semiconductor hot electron by with dot matrix collide release energy after, hot electron is caught to combine in semiconductor side, becomes majority carrier, imposes forward bias to diode, produces.When charge carrier enters the ratio of diode when enough, useful generating has just occurred.This energy fluence is corresponding to greater than about 1 watt/cm 2Surface power density.
Thereby method and apparatus provided by the invention can comprise formation Schottky junction diode.On the one hand, these contacts may be up to the potential barrier electromotive force of the forward bias that is enough to allow usefulness, and potential barrier is usually above 0.05 volt.The band gap of Schottky contact can be any useful numerical value, comprises surpassing 5 volts, and it is usually greater than thermionic energy.Change the thickness that semi-conductive band gap (passing through composition gradient) and doped level allow to reduce potential barrier, and, also allow to change relative Fermi's level with the metal side distance of diode.
Described Schottky diode can comprise metal, peg level (pinned-level), low-doped semiconductor, high doping semiconductor, and can manufacture to be presented at potential barrier electromotive force that the low-doped contact of metal place needs and in the required potential barrier at low-doped highly doped contact place.Thin potential barrier allows electron tunneling effect, and it when mixing near retrograde dopant, allows to form nearly ohmic properties contact conversely.
Adopt transformable band gap and transformable doping and form Schottky diode and provide a kind of and form the potential barrier electromotive force and can not disturb obstruction or other character of Metal Contact side in semiconductor side.Transformable band gap can be realized as the function of distance metal surface distance by the composition that changes semiconducting alloy.This method allows diode configuration to become required and the potential barrier of being manufactured and Fermi's horizontality.Adopt the low barrier means of high-peak power operation can increase its efficient, this is well known to a person skilled in the art, allows this low Schottky barrier to be approximately 0.05 to 0.1eV.
On the one hand, can select thickness is that the oxide skin(coating) of 0.1 to 20 nano thickness is to form Schottky barrier and to allow to control better potential barrier.Change the potential barrier tunnel effect of the controllable thickness system of oxide, thereby change the required character of contact by oxide.Oxide can be placed in any position of being excited between product and semiconductor.
Similarly, the charge carrier of energizing is transferable or inject semiconductor or enter the quantum well system.This system can successively or change charge carrier and become electricity, and perhaps emitted radiation maybe can be transferred to charge carrier other position of conversion and become useful form or be used for chemical process.
On the other hand, the inverted population that excites in semiconductor or the quantum well can be collected and convert to the electric energy of formation effectively, and it excites and is convertible into other useful form of energy.
On the other hand, method and apparatus of the present invention has produced the condition on conducting surface, and at this, excited molecule interacts, and the surface is of value to consumingly and produces hot carrier or excite, rather than is excited the substrate vibration, also is referred to as phonon.This advantageous conditions is to produce by the quantum state of manufacturing Fermi surface, uses quantum well with coupling excited molecule state, for example, by use one to the atom metal individual layer of tens of metals to form conducting surface.
Thereby can select can not obtain surfacing such as the metal that adsorbate is useful on the electron transfer of energizing, for example Precious Metals-Gold and silver.From reaction surface geometry, can select to adopt the geometry structure of the intensified response position concentration that helps exciting, as molecule or atomic surface step (step) and edge.And then the material that can select conducting surface is to have phonon band, and its energy is far below the sub-vibration of volume relaxation.The conducting surface that is made of heavy atom such as palladium or platinum can demonstrate this and can be with.Nearly all crystalline material has required phonon can be with frequency.
Reaction surface geometry structure for example can comprise step and/or marginal position, but but its intensified response maybe can comprise the individual layer surface of inhibitory reaction.On the one hand, can select to have Debye frequency extremely can be from the material of required stimulating frequency.
Near the release of energizing of the product that produces conducting surface can comprise that also its energy enters the resonant tunneling effect of substrate energy level.These energy comprise the excited electronic state in metal or semiconductor conduction band of available no particle of the band of non-constant width.When being the hole owing to the product excitation transfer of energizing, these energy levels can comprise the similar band of hole state.
The electronics that is undertaken by the interaction of excited molecule and conducting surface or the emission of hot carrier can be adopted known inverse approach, as by the desorb (DIET) of electron transition or the desorb (DIMET) of polyelectron transition.
On the one hand, conducting surface forms enough thinly, thereby will shift its energy to the energy converter substrate by the charge carrier of being excited that this mode produces, and has only very little energy loss.The thickness of conducting surface can be 1 to thousands of monolayer materials, and its thickness is the engineering parameter that depends on electron energy, dot matrix temperature and material, can construct according to the description of prior art.
On the one hand, conducting surface can form to such an extent that be as thin as and make hot carrier (electronics or hole) before discharging very many energy, passes energy converter, i.e. semiconductor.The size relevant with this ballistic transport is approximately the very little multiple of hot carrier energy dissipation length in conductor or substrate.So-called " very little multiple " is meant the enough thin hot carrier or do not excite and can discharge so many energy of making of thickness, is unpractical low value down to dump energy.Typically, energy square reducing with characteristic size " energy dissipation length " with index.The distance of " 3 " energy dissipation length is meant that being lower than 5% charge carrier has energy identical when approximately beginning with them.
At room temperature, the energy dissipation length dimension be generally the noble metal group as gold and silver in 10 to about 1000 conducting surface metal single layers, it is equivalent to about 3 to 300 nanometers.At room temperature, be lower than the electronics of 1eV for energy, energy dissipation length can excessive 115 nanometers in gold, and it calculates excessive about 150 nanometers concerning the electronics of leV in silver.
Can select to be lower than the skin depth relevant in the size of material between reactant and Semiconductor substrate with the radiative transfer of energy by conductive surface.This concrete scheme has adopted " evanescent wave ", and at this, electromagnetic field has shifted energy.In this concrete scheme, replace electronics emission and absorption again, the internal energy of the product of energizing by intermediate materials such as conducting surface and base substrate resonance be transferred to the charge carrier of semiconductor or quantum well.Such transfer can be resonance transfer.
Energy converter captures by the charge carrier of the product emission of energizing or electromagnetic energy near conducting surface or its, and converts them to useful form.On the one hand, semiconductor diode contact such as p-n contact or Schottky contact are as energy converter.Perhaps, can adopt other known energy converter.This known energy converter can comprise any known design be used to capture by energize product reaction surface or near the charge carrier that sends or the device of electromagnetic energy, as be used for the device of photovoltaic power converter, the metal-insulator-metal type device, metal-oxide-metal device, quantum well and semiconductor device.For example referring to Tiusan, C. etc., Applied Physics Letters, 79 volumes, 25 phases, December 17 calendar year 2001, " quantum is consistent in no semi-conductive metal-insulator body structure shifts class diode effect (Quantum coherent transport versus diode-like effect insemiconductor-free metal-insulator structure) ", for example referring to, Elena A.Guliants etc., Applied Physics Letters, on February 25th, 2002,80 volumes, Issue8, the 1474-1476 page or leaf, " the rectification rate is the polysilicon Schottky diode of 0.5 micron thickness of 1E6 " (" A 0.5-μ m-thick polycrystalline silicon Schottky diodewith rectification ratio of 1E6. ").
As previously mentioned, the chemical reaction that carries out in volume has produced the internal energy that is transferred to surface or energy converter.The useful part of chemical energy is converted into certain other useful form.On the one hand, chemical reactant is used for useful ratio produce power molecule effectively.The example of useful form comprises hot electron, hot hole, electromagnetic radiation, the phonon modes of energizing, the energize chemical species and the piezoelectrics of energizing.
Fig. 1 has shown the cross-sectional view of device, and wherein, reaction zone generates the molecule of energizing, and the collecting region that separates is collected from the energy of the molecule of energizing.Reaction zone 116 makes fuel 112 and oxidant 113 reactions, thereby produces the molecule 1 01 of energizing.The molecule 1 01 of energizing diffuses through reaction zone 115, and moves to collecting region 114, and this district comprises conversion element, and at this, the molecule of energizing contacts with the conducting surface 103 of catalyst 102 and collecting region 114 optionally, carries out power conversion in collecting region.Converters can comprise non-essential catalyst 102, conductor 103, interface conductor 110, interface semiconductor 111, p-N-type semiconductor N 104, semiconductor junction 105 and n-N-type semiconductor N 106, negative electrode 107 and positive electrode 108.
Reaction zone 115 and 116 comprises the element that it is relevant, and for example stimulator 117,118 and 119, and reaction zone is used for generating the molecule 1 01 of energizing, and comprises that the collecting region 114 of the converters that it is relevant is collected from the energy of the molecule 1 01 of energizing.Reaction zone 115,116 and stimulator 117,118,119 make fuel 112 and oxidant 113 reactions, thereby produce the molecule 1 01 of energizing, its diffuse to rapidly and with conducting surface 102,103 contacts near collecting region 114.Betide non-essential catalyst 102 by chemical substance to thermionic power conversion, on the conducting surface 103 and/or in the semiconductor structure 104,105,106.Thermionic another power conversion also betides from conducting surface 103 to interface conductor 110 and interface semiconductor 111 and enter semiconductor diode, and for example the p-N-type semiconductor N 104, and knot 105 and n N-type semiconductor N 106 contact with them.The for example radiation of the power conversion of another type, the near field, the evanescent wave radiation can come across between excited state chemical product 101 and the semiconductor diode.Stimulator 117,118,119 in the reaction zone 116 can consume in the response stimulus process.
On the one hand, any in can the be multiple different configuration of catalyst 102,118 forms, and every kind of configuration has concrete characteristic.Catalyst can form by any way, includes but not limited to: piece, individual layer, bunch, ridge, nosing, quantum dot, quantum well and quantum field.Adopt the configuration of edge and ridge to promote absorption and the activation site of reacting.Adopt the configuration of individual layer can show following advantage: to manufacture and cause, strengthen conversion at these energy place energy at resonance and peak value near the density of Fermi surface electronic state.Bunch can strengthen the ballistic electron life-span and make uncoupling of surphon attitude, increase efficient.
As shown in Figure 1, collecting region can be diode 104,105 and 106.The molecule 1 01 of energizing diffuses to collecting region 114 rapidly by the gas in the diffusion region 115, and at this, they are converted into useful form, as.The molecule 1 09 of deenergizing spreads out from collecting region, also can be called waste gas.
On the other hand, reaction zone 116,115 can be positioned at the zone that is separated by collecting region 114, but on identical structure, for example, comprises conducting surface 102,103 at the above collecting region 114 of identical substrate.The conventional substrate that is used for this embodiment can be represented in the plane that shows.In this configuration, the reaction zone 115,116 that comprises catalyst and/or response stimulus device 117,118,119 can be positioned at the part place of substrate, and the collecting region 114 that comprises converters is on another part.Separate areas also will be described referring to Fig. 7.
Reaction zone 115,116 can be designed so that the desired part diffusion of the molecule of energizing that produces in this district, moves or be transferred into collecting region 114.Even those skilled in the art will appreciate that most of desired portion near consistent, desired part will be the result of engineering design.For example, this design can be selected less relatively reaction zone, is surrounded in the relatively large collecting region in relatively large collecting region or partly.
On the other hand, reaction zone 115,116 can comprise different types of reaction zone, and each handles fuel 112 and oxidant 113 in a different manner, finally is created in the molecule of energizing in the collecting region 114, and leaves this regional waste gas.On the other hand, can use volatility or gaseous fuel and oxidant reactant, make reaction zone 115,116 produce the molecule of energizing.
Be designed to enough short with the energize vibrational excitation of molecule of basic maintenance in the distance of 114 of reaction zone 116 and collecting regions.Energize molecule by gaseous diffusion two interregional walking.And excitation energy is grabbed in the interaction between other gas molecule the most at last, produces heat.Described distance is typically designed to 4 times that are lower than the vibrational energy diffusion length.This diffusion length is known be longer than usually collision balance free travel multiply by 3 to 100 again (vibration diffusion length=collision balance free travel * (with the time between colliding be the square root of 3 times of vibration lifes of unit), vibration life is generally 10 to 10,000).For example, for air molecule, the collision mean free path is approximately 100 nanometers.This means that the distance between reaction zone and collecting region can be longer than 3～100 times of 100 nanometers.Therefore, form reaction zone so that be lower than about 4 times of diffusion length of molecular vibration energy pattern by the distance of molecule of energizing to collecting region.
On the other hand, method of the present invention comprises the conducting surface that formation contacts with semiconductor region.Term " contact " comprises various configurations, at this, and another conducting surface, catalyst, material, oxidant or metal place energizes between molecule and conducting surface or base semiconductor, and is used as the passage of power conversion.This comprises places conducting surface near reaction zone.In one embodiment, " approaching " is meant in following distance: electron excitation can be passed through, to such an extent as to surpass 5% excite and keep surpassing 15% energy, but perhaps wherein enough fast feasible 85% the energy loss of being no more than of resonant tunneling effect transmission of power fall.Method of the present invention also comprises conducting surface is arranged on the reaction surface, and is contiguous or in its lower section.This comprises such as dark V passage and mesa structure.
On the other hand, the path of material can form to be used for carrying He transmission at the conducting surface trajectory.This path is limited to length and is lower than 4 times of about charge carrier energy dissipation length.On the other hand, the part path can be by comprising that any material forms in metal, semiconductor or the insulator, and the energy dissipation length of material surpasses 1 atomic layer.
Method of the present invention provides a kind of surface of reactant of facing certainly to semi-conductive short path.The length in this path preferably is lower than by the hot electron of product production or 4 times of hot hole energy dissipation length of energizing.As a kind of selection, this path also can be made by catalyst metals.When this path is made by good conductor metal such as copper, aluminium, silver and gold, suitable energy dissipation length thickness can be basically greater than in catalyst, as platinum, palladium, iridium, rhodium, ruthenium, vanadium oxide, titanium dioxide, aluminium oxide, ruthenium-oxide, oxide and other compound.The thickness that forms the material of electrode can be 0.3～300 nanometer usually, is equivalent to about 1～1000 individual layer.The thickness that forms the material of catalyst can be 0.3～50 nanometer usually.
On the one hand, device of the present invention can comprise substrate 102,103,110, it comprises oxide, insulator and mixed catalyst, include but not limited to: platinum, palladium, iridium, rhodium, ruthenium, vanadium oxide, ruthenium-oxide, oxide and other compound, no matter and whether these compounds are catalyst, insulator or conductor.For example, substrate can comprise ruthenium-oxide, and it is oxide and conductor simultaneously.
On the one hand, when hot carrier was electronics, selecting semiconductor was the p-type.P-N-type semiconductor N 104 and conducting surface (110 and/or 111) physical connection, thus any potential barrier between them is very little or do not exist.For example, conducting surface 110 can place on the thin electrodes metal 111, and electrode material 111 is bonded on the p-N-type semiconductor N 104.Electricity in metal-metal contact contact 110,111 is built almost always negligible.On the other hand, be interrupted at 110 and 111 materials and can put a required potential barrier with respect to the phonon transmission, therefore with respect to heat transfer.
High doped semiconductor 104 comprises the highly doped restriction that is called retrograde dopant, and by known and form and electrically contact to compatible electric material 110 of semiconductor or 111 Schottky barriers that reduce between electrode and semiconductor.Electrode material 111 also can be another semiconductor, and this is the daily method that adopts in the semiconductor device production technology that is used in.The result is that Fermi's level (top edge of low strap) of conducting surface Fermi level and p-N-type semiconductor N valence band equates.The measurement of hot carrier energy is with respect to the energy of conducting surface Fermi level.The result is that some has the energy that is higher than conducting surface Fermi level near semi-conductive hot carrier, thereby has the identical energy that is approximately higher than p-N-type semiconductor N Fermi level greatly.
Then, hot carrier attempts to enter the semiconductor 104 with excess energy, and its energy value is higher than conductive surface 102,103 and/or 110 and semiconductor 104 valence band.By this design, in fact there is not energy level in semiconductor energy band gap inside for electron excitation.It is only that to can be used in semiconductor 104 thermionic energy level be to be in the conduction band at last band.
On the one hand, select on this position of band to be slightly smaller than the main energy of electronics, thereby electronics can be easy to enter semiconductor 104.Band gap by structure semiconductor 104 perhaps by selecting semiconductor to have desired band gap, can reach described requirement less than the selected energy of this hot electron spectrum.This means that thermionic required part enters the p-N-type semiconductor N in its conduction band.This makes the conduction band of p-N-type semiconductor N 104 have energy.Therefore, electronic switch becomes minority carrier but not the trajectory charge carrier.The life-span that common its life-span of minority carrier is longer than the trajectory charge carrier.
On the other hand, when hot carrier was the hole, selecting semiconductor was the n-type.Referring to the described method of p-N-type semiconductor N, produce identical result, promptly the short life charge carrier is converted into long-life charge carrier.Advantageously, the semi-conducting material with indirect and direct band gap can utilize have energy from the about 0.05eV of minimum to the band energy that is higher than most of reactants, surpass 3eV.
The life-span of minority carrier is generally grown 100 times than the life-span of trajectory charge carrier at least in the semiconductor.This long life-span offers an opportunity for the minority carrier of heat and is attracted to the semiconductor of opposite types, i.e. n-N-type semiconductor N inner region with migration, diffusion or by the semiconductor internal field.P-n junction forms the highfield penetrate it and attracts minority carrier near it.
In semiconductor connected, the minority carrier in the semiconductor ran into its identical situation of being met in photodiode.In photodiode, the electric field of p-n junction is removed the hot carrier of passing this connection, makes this diode generation forward bias and produces useful electromotive force.
On the one hand, select the energy dissipation length of p-N-type semiconductor N 104 diode layer thickness less than energy-delivering minority carrier.This mean free path often refers to diffusion length.Described charge carrier is finally warm in conjunction with also producing again in being longer than the distance of diffusion length.The general order of magnitude of this diffusion length is 200nm or bigger.
On the one hand, diode 104,105,106 can be similar to photodiode, but has crucial, non-marked difference.Known photodiode must be by near forming to the zone of light tie point that is enough to collect by it greatly.It is usually greater than hundreds of nanometers.Collect distance in order to increase light, this semiconductor connects must comprise at least a less doping zone.This restriction forces the n of photodiode or the doping in p district to be significantly smaller than a large amount of doping or the retrograde dopant of being considered.This lower doped level has reduced the resistance area product of diode and has therefore reduced its efficient.
Different with known photodiode is that diode 104,105,106 does not need to collect this photon and do not need big photon collecting zone.Therefore the diode 104,105,106 in the device does not need one or other a plurality of semiconductor regions by low dosed.Therefore diode 104,105,106 can use the free parameter of the semiconductor of high doped or retrograde dopant as engineering design.This doping makes the maximization of resistance area product, thereby makes diode efficient maximum.Therefore, diode 104,105,106 can have the n106 and the p104 district of height or retrograde dopant simultaneously.Different with photodiode is that high doped increases the efficiency of energy collection of diode.High doped also increases electric field, thereby takes advantage of the minority carrier that passes the injection of knot 105 in removing.
Therefore, semiconductor 104 can be by retrograde dopant to the shallow degree of depth, as 0.1-0.5 micron (100-500 nanometer).The semiconductor of high doped and retrograde dopant can be used to that conductor 110,111 is arrived diode 104 surfaces that produce hot carrier and the distance minimization that arrives the p-n junction 105 that produces forward bias.Therefore, high doped and little p-n junction size become a kind of useful method.High doped also allows to use thin semiconductor, as the semiconductor of thickness less than 1 micron.It also allows the example that mixes easily.
The method and apparatus that is provided produces in fact useful efficient (greater than 20%), and can obtain to be low to moderate the molecular energy density of energizing of 10 watts every square centimeter of the order of magnitude.Diode efficient increases rapidly with energy, thereby uses greater than the 10 watts every square centimeter more high efficiency that can cause greater than 10 watts, as non-linear advantage.
Fig. 2 shows an energy converter cross section partly of the device of one embodiment of the invention.In this embodiment, energize molecule 1 01 of gas phase produces the thermal forming electronics that moves to p-n junction semiconductor diode 104,105 and 106, makes its forward biasization and produces electric current.As directed, the molecule 1 01 of energizing flow to conducting surface 102 and 103.The molecule 1 09 that deenergizes also refers to discharge product, leaves conducting surface 102 and 103 zones.The gas surface interaction causes producing hot electron, and it makes the semiconductor diode forward biasization that is formed by p N-type semiconductor N 104, p-n junction 105 and n N-type semiconductor N 106.
Conducting surface comprises non-essential catalyst 102, conductive material 103, non-essential interface conducting electrode 110 and non-essential interface 111, as the p N-type semiconductor N.Conductive material 103 forms substrate, molecule 1 01 interaction that is used for and energizes.Optionally, can on this conductive material 103, form non-essential catalyst structure 102.
Non-essential interface conducting electrode 110 and non-essential interface p N-type semiconductor N 111 show that the restriction of material may cause being forced to the dissimilar material of needs.For example, may need a kind of types of conductive material 103 to be used for optimization and energize the interaction of molecule 1 01.The ohmic properties or the nearly ohmic properties that may need another kind of types of conductive material 110 to be used to form semiconductor 111 connect.The ohmic properties that may need this resistive connection to be used for diode semiconductor 104 connects.When material was compatible, material 102,103 and 110 can be formed by the material such as the conductor of identical materials.Diode material 111 also can be identical with 104.
For example, when semiconductor 111 greatly mixed (also being called retrograde dopant), catalyst 102 or metal 103 or 110 can be connected with semiconductor 111 formation ohmic properties or nearly ohmic properties connects.In this case, catalyst 102 or conductor 103 can be used as substrate 110, so that conducting surface is connected to semiconductor diode.
The hot electron that produces in conducting surface 102 and 103 is the trajectory majority carrier in the conductor.These electronics with the energy that is enough to enter the semiconductor conduction band move to p-N-type semiconductor N 104, and wherein electronics is converted into minority carrier.Electric equilibrium takes place by the p-N-type semiconductor N 104 of the low energy metering-orifice being moved to conducting surface 102 and 103.Minority carrier is by diffusion and tie the p-n junction 105 that 105 internal electric field moves to diode.This internal electric field causes charge carrier to become the majority carrier of the n-N-type semiconductor N 106 of diode, causes diode by forward biasization.The forward bias that produces by diode produces electric current.Get this electric current as the forward current between positive electrode 108 and the negative electrode 107.
On the other hand, with reference to Fig. 2, near 101,109 with can comprise the surface of collecting region 102,103 near 102,103 reaction zone.Catalyst that comprises in 102 and/or the 102 response stimulus mechanisms that comprised that are positioned at simultaneously on the conducting surface 102,103 are used to produce fuel and oxidation 101, and for 109, be included on the surface 102,103 and, or on the conducting surface 102,103 at 102,103 direct neighbor place, surface, form the molecule 1 09 of energizing near in 109 the volume area.Term " approaching " means in some diffusion sizes of the energy excitation product in product stream 109, as described in this manual.
The cross section of the energy converter of Fig. 3 display unit part, in this case, the molecule of energizing produces and moves to the Schottky junction semi-conductor diode, makes its forward biasization and produces the electronics of energizing of the heat of electric current.The gas phase molecule 1 01 of energizing flow on conducting surface 102 and/or 103.The molecule 1 09 that deenergizes also refers to discharge product, leaves the conducting surface zone.This results of interaction produces hot electron.Hot electron with the energy that is higher than Schottky barrier moves to semiconductor diode 110,111 and 104, and with its forward biasization.Form diode 110,111 and 104 by connecting conducting surface 110 and n N-type semiconductor N 111 and 104.
On the other hand, conducting surface can comprise non-essential catalyst 102, conductive material 103, non-essential interface conducting electrode 110 and non-essential interface n N-type semiconductor N 111.Non-essential interface conducting electrode 110 and non-essential interface n N-type semiconductor N 111 show that the restriction of material may be forced to demand side to a kind of types of conductive material 103 of the molecule 1 01 of energizing with in the face of the conductive material 110 of the another kind of type of semiconductor 111 and 104.Conductive material 103 is formed for and preferred interactional substrate takes place the molecule of energizing.Can also on conductive material 103, form non-essential catalyst structure.It can be the schottky junction that the conductive material 110 of another kind of type is used to form semiconductor 111.Semiconductor 111 can be identical with semiconductor 104 in some design.When material was compatible, the material of catalyst 102, substrate 103 and electrode 110 can be formed by identical materials such as conductor.For example, catalyst or metal can form semi-conductive schottky junction.In this embodiment, catalyst 102 or conductor 103 or 110 can be as electrode 110 to be connected to semiconductor diode with conducting surface.
The hot electron that produces on conducting surface 102,103 and 110 is the trajectory majority carrier in the conductor and moves to n-N-type semiconductor N 111 and 104 that wherein these electronics also are majority carriers.In this process, electronics releases energy and is the heat of the difference between Fermi's level of initial energy that is higher than Schottky barrier that approximates them greatly and n N-type semiconductor N.
The lattice in the semiconductor and the collision of electronics are reduced to basically value less than barrier with excessive energy.The result of this energy loss reduces the quantity of the electronics that moves in the opposite direction.This allows to produce forward bias on diode.
By migration generation charge balance from the hole on the conducting surface 110.These electronics cause diode 110,111 and 104 by forward biasization.Produce electric current by the forward biases of passing diode 110,111 and 104 generations, and utilize it as the forward bias between positive electrode 108 and negative electrode 107.
Substrate 110 can be the conductor of selecting to be used to form at the Schottky barrier of metal-semiconductor junction.Therefore substrate 110 can also form the electrical connection of diode, and this is electrically connected and also is called diode electrode.
Fig. 4 is presented at the cross section that is similar on the function with reference to the device of the described device of Fig. 1.Difference is that the semiconductor diode shown in Fig. 4 is the p-n junction of schottky junction rather than Fig. 1.
In the device of Fig. 1 and Fig. 4, can easily infer with the physical location of observing reaction zone 116 and can be following any position: be 1) identical with collecting region 114; 2) adjacent with the collecting region 114 on the same substrate 102,103 and 110; 3) near nanostructure or the collecting region on the micrometer structure 114 near collecting region 114; 4) be totally independent of collecting region; Or 5) be included in the response stimulus thing of the multiple not isotype of diverse location.
On the other hand, Fig. 1 and device shown in Figure 4 have shown how the physical separation of reaction zone and collecting region can help the consideration of hot aspect.That is to say that reaction zone can keep being much higher than the temperature of collecting region owing to physical separation.
Reaction zone 116 shown in Fig. 1 and Fig. 4 can be thin cylinder, and its shape metalloid silk for example is shaped as the collecting region coaxial surrounding of larger sized cylinder or box.Reaction zone 116 can be the plane surface with the collecting region same size, for example as the reverse side of box structure or the reverse side or the wall of channel design.Reaction zone 116 can be one group and be independent of and be positioned at sheet collecting region 114 lip-deep wire-shaped zones.Collecting region 114 can form by wire-shaped reaction zone device, the point-like reaction zone around Ping Qu or post.These structures only are expressed as the method embodiment of separating reaction and collecting region.The structure of Fig. 1 and Fig. 4 is represented the universal of Disengagement zone.
In another embodiment, with reference to Fig. 1 and Fig. 4, reaction zone 115,116 can be designed to work under the temperature more higher than collecting region 114.Reaction zone 115,116 can comprise response stimulus thing 117,118,119, and as electricity, light or chemical injection stimulus, it may require thermal release, electric separation, fiber waveguide and chemical injectors.Reaction zone 115,116 can comprise the heat sink that does not have demonstration in the drawings, and this equipment separates with the heat sink of collecting region 114.Can also remove by the convection action of the air-flow 109 by reaction zone 115,116 and reduce phlegm and internal heat.
Reaction zone 116 comprises stimulus or catalyst.These materials can comprise structure 119, electric stimulus, photic stimuli, be shown generically 117 catalyst, be shown generically 118 the hot wire or chemical irritant such as autocatalyst and the free-radical generator or the response stimulus thing of structure and injection.The additional autocatalyst and the example of free-radical generator comprise use additive such as hydrogen peroxide and methyl alcohol.
Fig. 5 shows the cross section of storage by the device of the stimulation of the molecule generation that excites.This device can be similar with the device of reference Fig. 2 explanation.In device shown in Figure 5, can be different from the another kind of mode that produces electric current and use thermode.The hot electron that is derived from the molecule of energizing forms electronics in the p N-type semiconductor N 104 and the hole in the n N-type semiconductor N 106, and they are diffused into semi-conductive other zone 131, comprise along knot 130.Hot carrier can be used for other purpose there.In Fig. 5, the element of collecting region, reactant 101, effluent 109, non-essential catalyst 102, conducting surface 103, interface conductor 110, interface semiconductor 111, p-N-type semiconductor N 104, knot 105 and n-N-type semiconductor N 106 can with the element functional similarity of Fig. 2.
In fact the semiconductor region 106 that is expressed as the n-type can be to have the doped p type that is lower than p-type district 104, and perhaps zone 106 can be body (not mixing).Between zone 106 and p-type district 104, apply motion and the storage that the signal of telecommunication can be used to control charge carrier.
On the one hand, semiconductor structure can be designed for the electric charge carrier that storage is produced by hot electron.These semiconductors can be collected an electronics in the zone, and allow gained live forever carrier diffuse to other zone.The present invention can be distributed to this long-time charge carrier that exists other position of reaction surface.The charge carrier of these transmission can leave semiconductor then, and at conducting surface or reaction surface conversion resilience road charge carrier, and carry out useful work.These work comprise IR and energy nanochemistry device or molecular energy.The example of these nanochemistry devices comprises nanometer screw, C60 transistor and biomaterial kinesin (kinesin).
Can cause the electronics in the semiconductor and the population inversion in hole at other regional charge carrier, perhaps can cause charge carrier is sent to another surface to be injected to this surface, perhaps can cause charge carrier is sent to the zone of finishing some other useful purpose.
The example of other purpose comprise with carrier injection to semiconductor with Control current, as the electric current in the transistor; Charge carrier is expelled to connected absorbate surface again to cause chemical reaction or to give the absorbate energy so that it becomes and has more reactivity or by energy excitation from the surface of semiconductor 131; Cause chemical reaction; The control chemical reaction; IR; Giving surface adsorption thing energy makes it enter excited state; Give surperficial plasmon energy; With carrier injection to pressure-electricity or electrostriction element to cause conversion to mechanical movement; Cause the population reaction to cause the light emission; Be injected to quantum potential well structure to cause electromagnetic emission; Give the semiconductor circuit energy; And/or be converted to other form, comprise phonon.
Be equal to cross section on Fig. 6 Presentation Function with reference to the device of the described device of Fig. 5.In device shown in Figure 6, the use of the charge carrier in the semiconductor p-n junction 105 is a kind of population of counter-rotating.In this pattern, from diode, obtain energy 111 in the mode that is similar to laser diode or light emitting diode, wherein element 112 is represented optical element.The operation of this laser diode and light emitting diode is normally known to those skilled in the art, thereby this paper no longer makes an explanation.
Fig. 7 shows the device with separating reaction and collecting region.Reaction zone 713, comprise catalyst 703 and/or response stimulus thing 701,702, can be positioned at the part of substrate 710, and comprise that the collecting region 714 of conducting surface 704 and relevant semiconductor converter element (comprising conducting surface 704, interface conductor 705, electrode 706, p-N-type semiconductor N 707, knot 708, n-N-type semiconductor N 709, substrate 710) thereof is positioned at another part of this substrate.
As shown in FIG. 7, reaction zone 713 can be designed as more less than collecting region 714.Reaction zone 713 can also be arranged in the bigger collecting region 714 or by bigger collecting region 714 and partly center on.The catalyst 703 of reaction zone 713 can also separate from collecting region 714, and this collecting region is partly around reaction zone 713.
With reference to Fig. 7, the fuel channel 715 that can formation separates with air or oxidant stream 716.This separation can be adopted various ways.For example, can form the collecting region with hole 712 714 that penetrates into liquid fuel 715 basic sources.Therefore fuel molecule 113 is preponderated the kind of absorption on catalyst 703 or collecting region 714.Catalyst-fuel assembly can be to collect the part on surface 704 or the part of reaction surface 703, or the part of these two.
Fuel and/or fuel vaporization heat can be used to cool off the semiconductor energy energy converter, and this transducer can comprise conducting surface 704, interface conductor 705, electrode 706, p-N-type semiconductor N 707, knot 708, n-N-type semiconductor N 709, substrate 710.This is a kind of new time cooling semiconductor and improves hot carrier utilance and be not converted to the method for electric current again.For example, with reference to Fig. 7, comprise that the fuel 113 of catalyst or conducting surface 704 can absorb the hot electron that does not enter energy converter semiconductor 708.When absorbing, fuel can be separated into active group subsequently and become the part of chemical reaction.Fuel or its separated product can by or not by thermionic situation under desorb, and mix with group in the reaction zone 713.Fuel can also be simply from the zone 712 of semiconductor 708,709 physical connections evaporation, and feed reaction zone 713, cooling semiconductor 708,709.Therefore the vaporized fuel 113 of high concentration can help best the mixing with fuel/oxidant mixture bias voltageization.
With reference to Fig. 8, can and collect in reaction 811 and form thermodynamic barrier 810 between 812 zones, thereby reaction zone 811 can be worked under the temperature that is higher than collecting region 812.These thermodynamic barriers can comprise post 810, have the vacuum or the passage of the physical material of reduction.Thermal source can be connected to reaction zone 811 and heat sink is connected to collecting region 812 so that these zones remain in their desirable working ranges.Reaction zone 811 can be formed by the structure such as bar, Gao Tai and the post 810 that raise.Can be thermal insulation with structural design.
With reference to Fig. 8, insulation barrier 810 can form between two zones 811,812, thereby makes electrical stimulation signal be sent to reaction zone and do not disturb collecting region.Other barrier and structure can for example be used for separating or filter radiation between these zones, or filter chemical by-product, or separation has multiple performance such as translation, rotation or composite behaviour molecule.
The use schottky junction can simplification device as energy converter.Can use the semiconductor of band gap scope, as silicon as 1 volt of the order of magnitude.On the one hand, can use the higher band gap semiconductor, thereby allow these devices being higher than room temperature, as be higher than under 100 degrees centigrade the temperature and work.But the high temperature semiconductors of industrial utilization such as GaN and SiC are the examples of this higher band clearance material.This has expanded operable metal and semi-conductive scope, and causes increasing available power in the every zone.
The applied voltage that the molecule of energizing on the one hand, can be used to produce charge carrier rather than be used for energizing to external device (ED).Therefore the molecule of energizing can be used for power device, otherwise this device must provide energy by current source.For example, chemical reaction can also be used for to the chipset energy supply.Use chemical reaction to allow volume structure, three-dimensional computations system for the chipset energy supply, wherein provide the energy of energy to be fuel-oxidant mixture stream rather than to be electrically connected to them.It is interconnected interconnected with no any structure that this permission system does not have physics, for example in the cobble bed reactor system.The microstack of electric energy can be energized by fuel-oxidant mixture, and wherein this microstack is the part of physical separation " cobble ".This so allow the volume system of self-assembly, and reduce their cost greatly and increase their performance.
On the other hand, use quantum well and it is energized be energy converter.The energy converter of this device charge carrier of will dying young converts the long life charge carrier to, thereby the charge carrier of gained can be used further.The quantum well substrate that comprises tunnelling barrier, metal or semiconductor and another kind of tunnelling barrier can be used to form energy converter.This energy converter can also form with substrate semiconductor and directly contact.The another kind of method that can obtain energy is can be by producing electromotive force.But another kind of method can be the susceptance rice device directly related with the present invention.According to the situation of present technique, foreign current is used for to quantum well and forms near the round dot of 4 desirable level lasers giving energy.In the device that is provided, the trap of same type and round dot can directly be energized by the energy of the charge carrier of injecting.
Quantum well also provides the possibility that produces the resonance of catching the molecular excitation of energizing.The resonance level that forms by quantum well can be designed as with the chemi-excitation product in volume conversion coupling.This coupling provides a kind of energy has been excited to the long life of quantum well from exciting transferred product.For example, the method that is provided can obtain the energy that the stimulating radiation emission produces that passes through from quantum well.
Allow size to be less than or equal to the layer of the order of magnitude of the energy dissipation length of related trajectory charge carrier with the situation of the prior art of semiconductor or metal quantum potential well structurally associated, help making and making creating possibility.
On the one hand, described conducting surface can comprise many materials.Can form fully thin surface on semiconductor structure, for example thickness is littler 10 times than the energy dissipation length of hot electron, thereby makes hot electron discharge essential part, enters semiconductor before for example being not more than 90% energy.
Conducting surface and its semiconductor down can comprise catalyst and other response stimulus system, with the chemical reaction of the molecule that causes energizing or cause energy to walk or transfer to the molecule of energizing from the molecular transfer of energizing.That is to say that conducting surface can also be by applying energy, the part on the reaction of energizing as electric current-stimulation surface.
Conducting surface and the semiconductor under it can comprise catalyst and other response stimulus system.These can be used to prevent absorbate, and as fuel, oxidant, effluent, byproduct of reaction or other clogged with material, gather or disturb conducting surface work, described situation is known to be taken place when forming non-conductor and assemble on conducting surface.The all right accelerated reaction of these catalyst and other response stimulus system, and can cause preferred reaction to take place.
Though specifically show according to embodiment of the present invention and described the present invention, it will be understood by those skilled in the art that the change that to finish in the case of without departing from the spirit and scope of protection of the present invention on above-mentioned embodiment and other form and the details.

Claims (31)

1. method that obtains energy comprises:
In gas volume, cause one or more chemical reactions; With
In gas phase, produce one or more product,
Wherein, one or more product are collided on the surface of substrate and the product relevant with one or more product can be transferred on the surface.
2. according to the process of claim 1 wherein, one or more product comprise one or more intermediate reaction product.
3. according to the method for claim 1, further comprise: from described surface collection energy.
4. according to the process of claim 1 wherein, cause one or more chemical reactions and comprise by injecting one or more stimulants and stimulate one or more reactions at volume.
5. according to the method for claim 4, wherein, one or more stimulants comprise catalyst, autocatalyst, hot carrier, Vladimirovich Terekhin, Anatoli Leontievich, any or multiple in light stimulus agent and the additive.
6. according to the method for claim 3, wherein, comprise that by the surface collection energy energy that makes from the surface is transferred to transducer, power conversion is become the useful energy of one or more forms by transducer.
7. according to the method for claim 6, wherein, transducer comprises diode.
8. according to the method for claim 6, wherein, useful energy comprises one or more in electricity, radiation and the mechanical energy.
9. according to the process of claim 1 wherein, produce one or more product comprise the reactant that makes in gas phase by diffusion move with volume in stimulant react near substrate surface.
10. according to the process of claim 1 wherein, produce one or more product comprise the reactant that makes in gas phase by diffusion move with volume in stimulant react near substrate surface.
11. a device of obtaining energy, it comprises:
The response stimulus device that is used for initiating chamical reaction;
Form the substrate of collecting the surface;
The reaction zone that between response stimulus agent and collection surface, forms; With
The energy converter that contacts with substrate,
Wherein, the chemical reactant in gas phase can in reaction zone, react and with substrate collision, will the reaction energy of product be transferred to substrate in the reaction zone from betiding, the energy of transfer can be converted into the useful form of energy by energy converter.
12. according to the device of obtaining energy of claim 11, wherein, energy converter comprises diode.
13. according to the device of obtaining energy of claim 11, wherein, energy converter comprises the p-n junction diode.
14. according to the device of obtaining energy of claim 11, wherein, energy converter comprises Schottky diode.
15. according to the device of obtaining energy of claim 11, wherein, by reaction zone farthest part be predetermined many times of vibrational energy diffusion length of reactant perpendicular to the distance on surface.
16. according to the device of obtaining energy of claim 11, wherein, reaction zone further comprises the second response stimulus device.
17. according to the device of obtaining energy of claim 16, wherein, the second response stimulus device comprises egersimeter, photic stimulator, catalyst, any or multiple in heated filament and the chemical stimulus.
18. according to the device of obtaining energy of claim 17, wherein, chemical stimulus comprises one or more in autocatalyst and the free radical generating agent.
19. according to the device of obtaining energy of claim 11, wherein, by energy converter to being predetermined length along the distance vertical between surface between conducting surface and reactant with conducting surface.
20. according to the device of obtaining energy of claim 11, wherein, substrate comprises one or more atom metal individual layers of the material of one or more selections.
21. according to the device of obtaining energy of claim 20, wherein, the material of one or more selections comprises any or multiple in metal and the semiconductor.
22. according to the device of obtaining energy of claim 11, wherein, the surface has the geometry that helps excited molecule in course of reaction.
23. according to the device of obtaining energy of claim 22, wherein, the geometry that helps excited molecule comprises the atomic surface step.
24. according to the device of obtaining energy of claim 22, wherein, the geometry that helps excited molecule comprises the atom edge.
25. according to the device of obtaining energy of claim 11, wherein, substrate comprises that one or more can not obtain the metal of adsorbate.
26. according to the device of obtaining energy of claim 25, wherein, one or more metals that can not obtain adsorbate comprise any or multiple in platinum, palladium, rhodium, ruthenium, gold and the silver.
27. according to the device of obtaining energy of claim 11, wherein, substrate comprises the conducting surface with phonon band, its energy is lower than the vibration of volume and discharges.
28. according to the device of obtaining energy of claim 27, wherein, conducting surface comprises crystalline material.
29. according to the device of obtaining energy of claim 27, wherein, conducting surface comprises any or multiple in palladium and the platinum.
30. the device of obtaining energy according to claim 11, further comprise the passage that also forms to reaction zone by below energy converter and substrate by them, wherein, adopt this passage with any or multiple the adding in the reaction zone in reactant and the stimulant.
31. according to the device of obtaining energy of claim 30, wherein, any or multiple cooling energy transducer in reactant in the passage and the stimulant.
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EP1415350A4 (en) 2005-12-28
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RU2004101291A (en) 2005-05-27
CN100416862C (en) 2008-09-03

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