CN109560187A - A kind of all solid state photon enhancing thermionic emission device - Google Patents
A kind of all solid state photon enhancing thermionic emission device Download PDFInfo
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- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 4
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910018985 CoSb3 Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The present invention relates to a kind of photo-thermal electricity multiple devices, belong to field of solar energy utilization.Disclose a kind of all solid state photon enhancing thermionic emission device.The device successively includes: including transparent conducting oxide layer from top to bottom, for reducing the back surface field passivation layer of Carrier recombination, for absorbing the cathode absorbed layer of sunlight, highly conductive high insulation semiconductor material layer and the anode for collecting electronics.The device can obtain higher energy conversion efficiency compared to single photovoltaic cell or thermionic emission device by the dual function in conjunction with light induced electron and thermionic emission.All solid state PETE device inserts highly conductive high heat insulation layer between cathode and anode, the relatively conventional photon based on vacuum space gap layer enhances thermionic emission device, its technology difficulty is small, eliminates space charge effect, and efficiency can be realized in the promotion of greater room by level-density parameter.
Description
Technical field
The present invention relates to a kind of photo-thermal electricity multiple devices, belong to field of solar energy utilization.
Background technique
Currently, the energy caused by being mismatched in conventional photovoltaic battery device due to absorbed layer materials band structure and solar spectrum
Loss accounts for about the 50% of overall spectrum energy, this partition losses energy is final mostly to dissipate in the form of heat.Spectral photovoltaic cell,
The technologies such as multijunction solar cell reduce this loss by improving the matching degree of absorbed layer band structure and solar spectrum.But
Spectral photovoltaic cell multiple batteries cost is high and device design and craft is difficult, it is difficult to be widely applied.It proposed in recent years
The hot carrier battery come inhibits lattice thermal losses, theoretically can achieve close to more knot electricity by quickly collecting hot carrier
The high efficiency in pond.Its advantage is that two terminal device structure is simple, without optical electivity, but difficult point is the hot current-carrying to nonequilibrium state
Son is collected.Hot carrier and the thermally equilibrated rate of lattice are high, therefore the requirement to material is very high, realize difficulty too
Greatly.
The 1960s thermionic energy converter (Thermionic energy converters (TECs), i.e., very
Empty thermionic emission device) be suggested and by NASA and the former Soviet Union use deep space aircraft from main power source, efficiency reaches
10%-15%.By the inspiration of this thinking, the researcher of Stanford University [Schwede, J.W., I.Bargatin,
D.C.Riley,B.E.Hardin,S.J.Rosenthal,Y.Sun,F.Schmitt,P.Pianetta,R.T.Howe,Z.-
X.Shen and N.A.Melosh, Nat.Mater., 9,762 (2010)] the thermoelectron hair of photon enhancing was proposed in 2010
Penetrate the concept of (Photon Enhanced Thermionic Emission, PETE).PETE device is based on Vacuum Heat electron emission
On the one hand principle passes through the energy of energy band transition absorption photon, on the other hand passes through heat using semiconductor material as emitter
Electron emission converts heat into electric energy.Compared to traditional Vacuum Heat electron emission device, PETE absorbed layer is because absorb light
Sub- energy, light induced electron fermi level with higher, therefore thermionic emission probability is improved, effectively reduce thermoelectron hair
The temperature penetrated, improves emission current.Energy band absorbs and the combination of thermionic emission takes full advantage of device to the quantum of photon
Absorption and thermal energy, therefore can achieve comprehensive, relatively high incident photon-to-electron conversion efficiency.Simulation calculates discovery, 1000suns's
Its efficiency is up to 60% or more under the conditions of optically focused, considerably beyond the transformation efficiency of current solar battery.From effective absorption and turn
From the perspective of changing photon energy, PETE device and hot carrier battery [A.L.Bris, J.-F.Guillemoles,
Appl.Phys.Lett., 97,113506 (2010)] thinking it is similar.But also there is important difference between the two, hot carrier electricity
Pond is directed to nonequilibrium state carrier, it is desirable that high carrier collection and derived rate are difficult on material and technology
It realizes；And PETE is directed to reach " heat " carrier of thermal equilbrium state with lattice, therefore technical difficulty substantially reduces.
The strategy of energy conversion efficiency is improved in comprehensive solar battery and thermionic emission device, it can be from reduction cathode
Work function inhibits surface carrier recombination rate, raising electric conductivity and thermal stability, inhibition heat loss etc. to further increase light
The energy conversion efficiency of thermoelectricity multiple device.PETE device in order to maintain the biggish temperature difference between anode and cathode and remain one it is micro-
The vacuum space gap layer of meter Hou Du, this brings some important negative effects to the practicability of the device.Firstly, the vacuum gap
Layer also increases biggish difficulty to the preparation process of device, needs to be realized by means of micro electronmechanical (MEMs) technology at present.Its
Secondary, vacuum space gap layer can bring space charge effect under high emission current conditions, and the electronics of emission of cathode is prevented to reach anode,
Reduce thermionic effective transmitting.Have simulation calculate [T.Ito and M.A.Cappelli, Appl.Phys.Letts.101,
213901 (2012)] show that this space charge effect can seriously reduce device under biggish vacuum gap (100 μm)
The working performance of part.In addition, this PETE device is overly dependent upon the work function of cathode, anode, physical essence determines this
Kind device is a kind of low voltage and high current device, can have biggish ohmic loss.To have between cathode and anode biggish net
Emission current, it is necessary to which the work function for reducing cathode, it is to improve having for electron-hit emitting that being coated by cathode surface, which reduces work function,
One of effect means.But have now been found that low work function surface coating (it is common such as alkali metal, based on the chemical combination of alkali metal
Object) temperature stability it is generally not high, such as common Cs2CO3Surface covering just becomes unstable at 120 DEG C or so.Therefore, base
In work function of the PETE device due to depending on cathode and anode unduly of vacuum space gap layer, it is lower to be limited by cathode low work function coating
Temperature stability, it is difficult to really realize high temperature under thermionic emission advantage.
Summary of the invention
It is regarding to the issue above or insufficient, enhance thermionic emission device the invention proposes a kind of all solid state photon, the device from
It successively include: transparent conductive oxide (Transparent and conductive oxides, TCO) layer under, for subtracting
Back surface field (back surface field, BSF) passivation layer of few Carrier recombination, the cathode for absorbing sunlight absorb
Layer, highly conductive high insulation semiconductor material layer and the anode for collecting emission of cathode electronics；
The back surface field passivation layer and cathode absorbed layer include the height junction structure being made of different levels of doping；
The highly conductive high insulation semiconductor material layer is " phonon glasses/electron crystal " (Phonon glass/electron
Crystal, PGEC), there are three types of different crystallographic sites, the atom groups of two of them position for tool in such material crystal structure
At basic crystal structure, and leading band structure, and the third atom is then located at the caged gap position of first two atomic building
Set, and with neighboring atom weak binding, to phonon generate compared with strong scattering, to reduce thermal conductivity.
Between the cathode absorbed layer and highly conductive high heat insulation layer and highly conductive high heat insulation layer and anode conduction band band rank with
Corresponding Valence-band Offsets make electronics transmit to anode and hole is stopped to transport to anode.
The tco layer is p-type or N-type transparent conductive oxide film.
The all solid state photon enhancing thermionic emission device further includes the beam condensing unit being set to above tco layer,
For increasing the intensity for being incident on the incident radiation of absorbed layer.
The present invention between cathode and anode by being inserted into highly conductive high insulation semiconductor material " phonon glasses/electron crystal "
PGEC thermoelectric material carrys out while realizing the transmission of the high temperature difference and charge of cathode and anode, avoids above-mentioned based on vacuum space gap layer
The drawbacks of PETE device, space charge effect is eliminated, reduce device technology difficulty and the dependence to material work functions, increased
Big device efficiency room for promotion.
Detailed description of the invention
Fig. 1 shows photon enhancing thermionic emission technology while utilizing the basic physical thought of photoelectricity and heat to electricity conversion；
Fig. 2 is photon enhancing thermionic emission device principle and band structure schematic diagram based on vacuum space gap layer；
Fig. 3 is the space charge effect schematic diagram in the photon enhancing thermionic emission device based on vacuum space gap layer；
Fig. 4 is the cathode construction schematic diagram with back surface field (BSF) passivation layer and low work function coating；
Fig. 5 is the structural schematic diagram of all solid state photon enhancing thermionic emission device；
Fig. 6 is a kind of level structure figure of all solid state photon enhancing thermionic emission device；
Appended drawing reference: 201- cathode absorbed layer, 202- anode, 203- photon, electronics (205)-hole (204) are right, and 401- is heavily doped
Miscellaneous BSF layer, 501- transparent conductive oxide tco layer, the semiconductor layer of the highly conductive high insulation of 502-, 601- cathode absorbed layer with
Highly conductive high heat insulation layer conduction band band rank, 602- cathode absorbed layer and highly conductive high heat insulation layer Valence-band Offsets, 603- are highly conductive high absolutely
Thermosphere and anode conduction band band rank, the highly conductive high heat insulation layer of 604- and anode Valence-band Offsets.
Specific embodiment
The present invention is to enhance thermionic emission (PETE) principle based on photon, while overcoming the PETE based on vacuum space gap layer again
The shortcomings that technology, belongs to all solid state photon enhancing thermionic emission device, is a kind of novel photo-thermal electricity multiple device.
Fig. 5 shows the structural schematic diagram of all solid state photon enhancing thermionic emission device of the present invention.Photon (203) is from upper
Side is incident, which successively includes: transparent conductive oxide tco layer (501), the BSF layer (401) of heavy doping, yin from top to bottom
Pole absorbed layer (201), the semiconductor layer (502) and anode (202) of highly conductive high insulation.Tco layer therein is p-type or N-type
Transparent conductive oxide.Back surface field passivation layer and the height junction structure of cathode absorbed layer are made of P+-GaAs/P-GaAs.It is high
Conductive high insulation semiconductor material layer had not only been able to achieve charge transmission but also had been able to maintain the biggish temperature difference between cathode and anode.Highly conductive height
Heat insulation layer selects matrix skutterudite (Skutterudite) material of rare earth element filling, skutterudite CoAs3、CoSb3Or
IrSb3, rare earth element is La or Ce, and wherein the atom of host material crystallographic site forms basic crystal structure, and leading
Band structure, and fill rare earth atom La or Ce be then located in the caged clearance position of first two atomic building, and with surrounding
Atom weak binding generates scattering to phonon, to reduce thermal conductivity.The structure does not have vacuum space gap layer, reduces based on vacuum
The manufacturing process difficulty of clearance layer PETE device eliminates negative effect of the space charge effect to device performance.
Fig. 6 is a kind of band structure figure of all solid state photon enhancing thermionic emission device.Photon (203) is inhaled into cathode
It receives layer (201), through photon energy absorption, it is right that electronics (205)-hole (204) is generated in cathode semiconductor material.Highly conductive height
Heat insulation layer (502) is inserted between cathode absorbed layer (201) and anode (202), since this layer of thermal conductivity is very low, can keep yin
The biggish temperature difference between pole, anode.Cathode, highly conductive high heat insulation layer and anode are semiconductor materials, can be adjusted by doping
Respective band structure and level-density parameter between them are saved, as shown in the figure, cathode absorbed layer (201) and highly conductive high heat insulation layer
(502) conduction band is less than corresponding Valence-band Offsets (602) with rank (601) to realize that the selectivity to electronics is transmitted.Made by doping
Conduction band band rank (603) obtained between highly conductive high heat insulation layer and anode passes electronics to anode with corresponding Valence-band Offsets (604)
It is defeated and stop hole to anode transmit.
Fig. 4 shows the cathode construction of back surface field passivation layer (BSF) and low work function coating.Comprehensive solar battery with
The strategy of energy conversion efficiency is improved in thermionic emission device, the combination of cathode BSF and low work function coating can drop simultaneously
The surface recombination loss of low photo-generated carrier and emission of cathode potential barrier layer height.Incident photon (203) passes through heavily doped P+Layer
(401) enter absorbed layer (201), wherein P+Layer plays back surface field passivation, is passivated by field and reduces carrier in back table
The recombination losses in face, the surface covering (402) of cathode absorbed layer is to reduce cathode material work function, to enhance cathode thermoelectricity
Sub- emission probability.
Fig. 1 shows PETE while realizing the basic physical thought of photoelectricity and heat to electricity conversion.Conventional solar battery has
Two big heat loss approach, photon energy h ν are greater than solar battery band gap EgPart h ν-EgSound can be passed to by relaxation process
Son and dissipate；And energy is less than EgPhoton will also be dissipated in the form of heat because of not being absorbed.In crystalline silicon electricity
Chi Zhong, both account for about the 50% of sunlight incidence gross energy.And it is converted and is filled based on the thermionic energy of thermionic emission principle
The heat that this partial loss is fallen in solar battery can be made full use of by setting (thermionic energy converters, TECs)
Energy.Richard-Du Shiman formula [G.N.Hatsopoulos and E.P.Gyftopoulos, Thermionic Energy
Conversion Vol.1 (MIT Press, 1973)] describe heat emission current density, J and temperature TCAnd cathode material work content
Number φCBetween relationship, wherein ACIt is Richard's coefficient of cathode material.PETE device is just being combined with conventional solar battery
In quantums absorption and TECs device thermionic emission process, so energy conversion efficiency with higher.
Fig. 2 gives the principle and band structure schematic diagram of the PETE device based on vacuum space gap layer.Device cathodes absorb
Layer 201 is respectively provided with by vacuum insulation, cathode absorbed layer 201 and anode 202 relative to vacuum level φ with anode 202Very's
Work function φCAnd φA.Cathode material band gap width is Eg, fermi level position is in E before illuminationF, electronics, which occupies, counts such as curve 206
It is shown；Quasi-Fermi level position is in E after illuminationF,n, electronics, which occupies, to be counted as shown in curve 207.Incident photon (203) is incident on yin
When pole, Electron absorption photon energy transits to conduction band from valence band, it is right to generate electronics (205)-hole (204).The electricity being excited
Son reaches new thermal equilibrium state in cathode conduction band rapid thermalization.Electrons spread reaches cathode surface, overcomes surface affinity χ
Heat emission occurs and passes through vacuum area (208) arrival anode, forming thermal electron stream (209) and comparing does not have the case where illumination,
The potential barrier of electron-hit emitting reduces EF,n-EF, the Fermi for reducing just correspondence and illumination quasi-Fermi level and no light of potential barrier
The difference of energy level.That is, illumination effect considerably reduces the threshold temperature of thermionic emission inside semiconductor.Usually heat
Electron emission temperature is in 1100K or more, and the threshold temperature that thermoelectron occurs can be dropped to 500K by photonic absorption by PETE
Left and right.
Fig. 3 is the space charge effect schematic diagram in the photon enhancing thermionic emission based on vacuum space gap layer.Incident light
Sub (203) generation electronics (205) hole (204) in cathode absorbed layer (201) is right, since launching electronics are reached from emission of cathode
Anode (202) needs the regular hour, and electronics is caused to form 301 vacuum gap Potential Distributing in the accumulation of vacuum layer, electricity
Son emits from cathode surface (302), it is necessary to overcome the potential barrier between 302 to 303 to get to anode surface (304), 303 are
Vacuum layer potential highest point.Therefore the electric charge accumulation effect of vacuum layer will be greatly reduced the efficiency of thermionic emission.
Claims (5)
1. a kind of all solid state photon enhances thermionic emission device, from top to bottom successively includes: including transparent conducting oxide layer, be used for
The back surface field passivation layer for reducing Carrier recombination, for absorbing the cathode absorbed layer of sunlight, highly conductive high insulation semiconductor
Material layer and anode for collecting emission of cathode electronics, it is characterised in that:
The back surface field passivation layer and cathode absorbed layer include the height junction structure being made of different levels of doping；
The highly conductive high insulation semiconductor material layer is " phonon glasses/electron crystal ", is had in such material crystal structure
Three kinds of different crystallographic sites, the atom of two of them position forms basic crystal structure, and dominates band structure, and the
Three kinds of atoms are then located at the caged clearance position of first two atomic building, and with neighboring atom weak binding；
Conduction band band rank and corresponding between the cathode absorbed layer and highly conductive high heat insulation layer and highly conductive high heat insulation layer and anode
Valence-band Offsets make electronics to anode transmit and stop hole to transport to anode.
2. all solid state photon enhances thermionic emission device as described in claim 1, it is characterised in that: the transparent conductive oxide
Nitride layer is p-type or N-type transparent conductive oxide film.
3. all solid state photon enhances thermionic emission device as described in claim 1, it is characterised in that: the height junction structure by
P+- GaAs/P-GaAs is constituted.
4. all solid state photon enhances thermionic emission device as described in claim 1-3 is any, it is characterised in that: described highly conductive
High heat insulation layer selects the matrix skutterudite material of rare earth element filling, and rare earth element is at least one of La and Ce, skutterudite
Material is CoAs3、CoSb3Or IrSb3。
5. all solid state photon enhances thermionic emission device as described in claim 1, it is characterised in that: further include one and be set to
Beam condensing unit above including transparent conducting oxide layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970511A (en) * | 2019-12-29 | 2020-04-07 | 中国科学院西安光学精密机械研究所 | All-solid-state photon enhanced thermionic emission photoelectric conversion device with nano spacer layer |
| CN112902491A (en) * | 2021-01-20 | 2021-06-04 | 杭州电子科技大学 | Method and device for refrigeration by photo-induced thermoelectron and photon cooperative emission |
-
2017
- 2017-09-26 CN CN201710883758.8A patent/CN109560187A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110970511A (en) * | 2019-12-29 | 2020-04-07 | 中国科学院西安光学精密机械研究所 | All-solid-state photon enhanced thermionic emission photoelectric conversion device with nano spacer layer |
| CN110970511B (en) * | 2019-12-29 | 2024-05-31 | 中国科学院西安光学精密机械研究所 | All-solid-state photon enhanced thermionic emission photoelectric conversion device with nanometer spacing layer |
| CN112902491A (en) * | 2021-01-20 | 2021-06-04 | 杭州电子科技大学 | Method and device for refrigeration by photo-induced thermoelectron and photon cooperative emission |
| CN112902491B (en) * | 2021-01-20 | 2022-05-03 | 杭州电子科技大学 | Method and device for refrigeration by photo-induced thermoelectron and photon cooperative emission |
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Application publication date: 20190402 |