CN104332511A - InGaAs quantum dot solar cell and fabrication method thereof - Google Patents
InGaAs quantum dot solar cell and fabrication method thereof Download PDFInfo
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- CN104332511A CN104332511A CN201410636471.1A CN201410636471A CN104332511A CN 104332511 A CN104332511 A CN 104332511A CN 201410636471 A CN201410636471 A CN 201410636471A CN 104332511 A CN104332511 A CN 104332511A
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 134
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 75
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 13
- 239000006117 anti-reflective coating Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001259 photo etching Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000005083 Zinc sulfide Substances 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- MBGCACIOPCILDG-UHFFFAOYSA-N [Ni].[Ge].[Au] Chemical compound [Ni].[Ge].[Au] MBGCACIOPCILDG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 238000012536 packaging technology Methods 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005457 optimization Methods 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 239000002800 charge carrier Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0304—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/544—Solar cells from Group III-V materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an InGaAs quantum dot solar cell and a fabrication method thereof. The InGaAs quantum dot solar cell comprises performing epitaxial growth on a buffer layer, a base, an InGaAs quantum dot superlattice, an emitter, a window layer and a contact layer successively on a GaAs substrate through an epitaxial growth method and manufacturing an InGaAs quantum dot solar cell epitaxial wafer. The InGaAs quantum dot superlattice comprises at least one In*Ga1-*As quantum dot layer and a separation layer arranged between the In*Ga1-*As quantum dot layers. According to the InGaAs quantum dot solar cell and the fabrication method, the density, the size and the band gap of the quantum dot structure are adjusted by adjusting the structure, materials, material components and growth parameters of the InGaAs quantum dot superlattice, carriers on the discrete level in the quantum dot structure have a long service life, and two or more photons can be absorbed in a cascading mode to manufacture the efficient InGaAs quantum dot solar cell.
Description
Technical field
The present invention relates to technical field of solar batteries, specifically, relate to a kind of InGaAs quantum dot solar cell and preparation method thereof.
Background technology
Can produce serious environmental pollution with the traditional energy that coal, oil and natural gas are representative, therefore solar photovoltaic industry is that the renewable clear energy sources of representative is subject to most attention and obtains fast development.18% and about 15% is respectively at present at the monocrystalline silicon of photovoltaic market dominate and the conversion efficiency of polycrystalline solar module.Because silicon materials and GaAs (GaAs) are indirect band gap and direct gap semiconductor material respectively, the theoretical light photoelectric transformation efficiency (23%) of silicon solar cell is far below gallium arsenide solar cell, wherein the theoretical efficiency of the gallium arsenide cells of unijunction is 27%, and the theoretical efficiency of the gallium arsenide cells of many knots is higher than 50%.The sharpest edges of silion cell are the cheap of silicon materials and manufacture craft is ripe, and therefore gallium arsenide cells needs, while the high efficiency advantage of maintenance, by introducing novel device architecture and technique, to reduce costs, winning the market.
According to theoretical prediction, the photoelectric conversion efficiency of the Intermediate Gray solar cell of optimal design can reach 63% (see A.Luque and A.Marti, Phys.Rev.Lett.78,5014 (1997)) respectively in high power concentrator situation.Intermediate Gray (Intermediate-Band, IB) solar cell utilizes energy level to be in semi-conducting material between N-shaped and p-type semiconductor energy gap to absorb the photon of sub-forbidden band (Sub-Bandgap) energy, realizes light induced electron takes conduction band (CB) (i.e. IB-CB) to transition from valence band (VB) to Intermediate Gray (i.e. VB-IB) and centre.Intermediate Gray solar cell absorbs two or more long wavelength photons by relay-type, and realization absorbs energy photons and produces the high-efficiency photovoltaic technology of high output voltage.Such as, optimize the band structure design of Intermediate Gray solar cell, the photon that energy is 0.70 electron-volt (eV) and 1.25eV can be absorbed respectively, excite energy gap to be that the valence-band electrons of the semi-conducting material of 1.95eV realizes VB-IB and IB-CB transition, make the open circuit voltage of battery reach 1.55 volts (V) left and right.
Valence-band electrons realizes from Intermediate Gray to conduction band transitions (IB-CB) from time enough will be had after valence band transits to Intermediate Gray (VB-IB) to absorb another photon, this requires IB-CB transition to occur in before Intermediate Gray relaxation returns valence band (IB-VB), and therefore the band structure of intermediate zone material is the key factor determining solar cell photoelectric conversion efficiency.Current semiconductor-quantum-point is optimal intermediate zone material, is widely used in the research of quantum dot solar cell.In semiconductor-quantum-point, charge carrier is in discrete quantum level because being subject to three-dimensional quantum restriction effect, the energy relaxation process that phonon causes is suppressed, therefore have that carrier lifetime is long, the gain of light is high and the advantage such as temperature dependence is low, be suitable as the opto-electronic devices such as semiconductor laser, light-emitting diode (LED), Infrared Detectors and solar cell.
Change the parameter such as III elemental constituent and growth temperature and can regulate with InGaAs/GaAs the density of the Group III-V semiconductor quantum dot being representative, size and energy gap.The technical problem existed in prior art is the manufacture method how optimizing quantum dot solar cell and the semiconductor-quantum-point active layer how selecting the making material of quantum dot solar cell and component to mate to design absorption spectrum with solar spectral, thus produces high efficiency quantum dot solar cell.
Summary of the invention
For this reason, technical problem to be solved by this invention be existing quantum dot solar cell because of the matching degree of absorption spectrum and solar spectral not high and cause the efficiency of solar cell not high enough, thus propose a kind of each Rotating fields by optimizing solar cell especially the structure of InGaAs quantum dot superlattice, material and component, growth parameter(s) etc. obtain high density, many laminations and the InGaAs quantum dot solar cell epitaxial wafer of few defect, thus produce efficient InGaAs quantum dot solar cell.
For solving the problems of the technologies described above, the invention provides following technical scheme:
A manufacture method for InGaAs quantum dot solar cell, comprises the following steps:
Step S1: utilize epitaxial growth method to produce InGaAs quantum dot solar cell epitaxial wafer after epitaxial growth buffer, base stage, InGaAs quantum-dot superlattice structure, emitter, Window layer and contact layer successively on gaas substrates, InGaAs quantum-dot superlattice structure comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on In
xga
1-xwall between As quantum dot layer, wherein, In
xga
1-xin component 0.0≤x≤1.0 in As quantum dot layer;
Step S2: be divided into battery unit after the GaAs substrate back deposition back electrode of InGaAs quantum dot solar cell epitaxial wafer, and top electrode is set on contact layer surface, produce InGaAs quantum dot solar cell.
As optimization, In
xga
1-xthe growth temperature of As quantum dot layer is 450-540 DEG C, deposition rate is that 0.01-1.0 individual layer is per second, thickness is 1.8-10.0 individual layer, In
xga
1-xin As, In component is 0.4≤x≤1.0.
As optimization, wall and In
xga
1-xas quantum dot layer arranges 1-100 layer respectively.
As optimization, wall is GaAs material, GaAlAs material, GaP material, GaAsP material, GaInP material, GaAlInP material or GaAlAsP material.
As optimization, wall is GaAs material, and its thickness is 10-100nm.
As optimization, wall and/or In
xga
1-xdoped with the donor element of current density being used for strengthening battery in As quantum dot layer, the donor element of doping is element silicon, and the doping content of silicon atom is 1.0 × 10
17-1.0 × 10
18cm
-3.
As optimization, emitter and base stage adopt energy gap to be greater than the semi-conducting material of the wall energy gap adopting GaAs material, comprise GaInP material, GaAlAs material, GaP material, GaAlInP material and GaAlAsP material.
As optimization, also comprise in step S1:
Optimize the lattice constant of base stage and/or emitter semiconductor material, energy gap and/or thickness, reduce the open circuit voltage even eliminated because of caused by the defect of lattice mismatch generation to decline, base stage is N-type GaInP base stage, launch very P type GaInP emitter, the lattice constant of GaInP is 0.56-0.57nm, energy gap is 1.8-1.92eV, the thickness of N-type GaInP base stage is the thickness of 0.5-3.0 μm, P type GaInP emitter is 50-300nm;
1.0 × 10 are adulterated in N-type GaInP base stage
17-1.0 × 10
18cm
-3donor atom, in P type GaInP emitter adulterate 1.0 × 10
17-1.0 × 10
19cm
-3acceptor atom.
As optimization, in step S2:
Comprise and utilize photoetching and etch that the InGaAs quantum dot solar cell epitaxial wafer that deposited back electrode is divided into battery unit, back electrode thickness is 20-200nm, adopts the composite material of gold germanium nickel alloy and gold;
Comprise and utilize photoetching and physical vaporous deposition to arrange top electrode on the contact layer surface of battery unit, power on very titanium alloy or golden kirsite;
Comprise and utilize photoetching and physical gas-phase deposite method being provided with the battery unit surface deposition antireflective coating of top electrode, antireflective coating is the composite membrane of magnesium fluoride and zinc sulphide;
Comprise and utilize pressure welding and packaging technology that the battery unit being provided with top electrode and antireflective coating is made into InGaAs quantum dot solar cell.
A kind of InGaAs quantum dot solar cell, comprise the battery unit of multiple series connection and/or parallel connection, battery unit comprises back electrode, GaAs substrate, resilient coating, base stage, InGaAs quantum-dot superlattice structure, emitter, Window layer, contact layer and top electrode from bottom to up successively, and InGaAs quantum-dot superlattice structure comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on In
xga
1-xwall between As quantum dot layer.
Technique scheme of the present invention has the following advantages compared to existing technology:
1. the manufacture method of InGaAs quantum dot solar cell provided by the invention, the density of InGaAs quantum-dot structure, size and energy gap is regulated by the structure that the adjusts battery unit especially structure of InGaAs quantum-dot superlattice structure, material, material component and its growth parameter(s), the charge carrier in quantum-dot structure in discrete energy levels is made to have longer life, two or more photon can be absorbed in tandem type ground, produce efficient InGaAs quantum dot solar cell.
2. the manufacture method of InGaAs quantum dot solar cell provided by the invention, utilize the stress field that quantum-dot structure is formed in wall, realize the quantum dot laminated construction along epitaxial growth direction ordered arrangement, thus the energy gap of quantum point and absorption spectrum wavelength.By the Intermediate Gray structure that coupled electric field is formed in its conduction band or valence band between quantum dot in this structure, charge carrier wherein can absorb the sunlight of 900-1100nm infrared band, further increases the conversion efficiency of quantum dot solar cell.
3. the manufacture method of InGaAs quantum dot solar cell provided by the invention, utilizes energy gap (E
g) comparatively large (E
g=1.9eV) GaInP retrain electronics in InGaAs/GaAs quantum dot superlattice and hole as base stage and emitter.In this quantum dot superlattice, GaAs wall can absorb the photon of energy higher than 1.42eV, InGaAs quantum dot can absorb the photon of energy higher than 1.0-1.3eV, and in the Intermediate Gray of InGaAs/GaAs quantum dot (micro-band) electronics can absorb energy be the photon transition of 0.6-0.9eV on the conduction band of GaInP emitter and base stage, thus form high efficiency Intermediate Gray quantum dot solar cell.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of InGaAs quantum dot solar cell epitaxial wafer of one embodiment of the invention;
Fig. 2 is a kind of structural representation being provided with the battery unit of top electrode and antireflective coating of one embodiment of the invention;
Fig. 3 is the photoluminescence spectrum of the InGaAs quantum-dot superlattice structure in the embodiment of the present invention;
Fig. 4 is the operation principle schematic diagram of the photoelectric conversion of InGaAs quantum-dot superlattice structure in the embodiment of the present invention.
In figure, Reference numeral is expressed as: 1-contact layer, 2-Window layer, 3-emitter, 4-InGaAs quantum-dot superlattice structure, 5-base stage, 6-resilient coating, 7-GaAs substrate, 8-back electrode, 9-top electrode, 10-antireflective coating.
Embodiment
In order to make content of the present invention more easily be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation.
Embodiment 1
As shown in Figure 1-2, present embodiments provide a kind of manufacture method of InGaAs quantum dot solar cell, comprise the following steps:
Step S1: utilize epitaxial growth method to produce InGaAs quantum dot solar cell epitaxial wafer after epitaxial growth buffer 6, base stage 5, InGaAs quantum-dot superlattice structure 4, emitter 3, Window layer 2 and contact layer 1 successively on GaAs substrate 7, InGaAs quantum-dot superlattice structure 4 comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on In
xga
1-xwall between As quantum dot layer, wherein, In
xga
1-xin component 0.0≤x≤1.0 in As quantum dot layer.Particularly, In
xga
1-xin As quantum dot layer, In component is 0.4≤x≤1.0, preferably, and 0.5≤x≤1.0; In
xga
1-xthe deposition rate of As quantum dot layer is that 0.01-1.0 individual layer is per second, is preferably 0.05-0.5 individual layer per second, specifically can be 0.2 individual layer per second; In
xga
1-xthe growth temperature of As quantum dot layer is 450-540 DEG C, preferably 470-500 DEG C; In
xga
1-xthe thickness of As quantum dot layer is 1.8-10.0 individual layer, preferably 1.8-6.0 individual layer.Particularly, In
xga
1-xas quantum dot layer can arrange 1-100 layer, and correspondingly, wall need arrange 1-100 layer, preferably, and In
xga
1-xas quantum dot layer arranges 5-50 layer, wall arranges 5-50 layer.Wall can be GaAs material, GaAlAs material, GaP material, GaAsP material, GaInP material, GaAlInP material or GaAlAsP material, and be preferably GaAs material, its thickness is 10-100nm, is preferably 10-50nm.The adoptable epitaxial growth method of the present embodiment comprises metal-organic chemical vapor deposition equipment method, molecular beam epitaxy and liquid phase epitaxial method, preferably uses metal-organic chemical vapor deposition equipment method.Particularly, GaAs substrate 7 is N
+gaAs substrate, resilient coating 6 is preferably N
+gaAs resilient coating, Window layer 2 is preferably P
+type AlGaInP Window layer, contact layer 1 is preferably P
+type GaAs contact layer.
Step S2: be divided into battery unit after the GaAs substrate 7 backside deposition back electrode 8 of InGaAs quantum dot solar cell epitaxial wafer, and top electrode 9 is set on contact layer 1 surface, produce InGaAs quantum dot solar cell.
The present embodiment regulates the density of InGaAs quantum-dot structure, size and energy gap by the structure that the adjusts battery unit especially structure of InGaAs quantum-dot superlattice structure part, material, material component and its growth parameter(s), the charge carrier in quantum-dot structure in discrete energy levels is made to have longer life, two or more photon can be absorbed in tandem type ground, produce efficient InGaAs quantum dot solar cell.Meanwhile, the stress field that the present embodiment utilizes quantum-dot structure to be formed in wall, realizes the quantum dot laminated construction along epitaxial growth direction ordered arrangement, thus the energy gap of quantum point and absorption spectrum wavelength.By Intermediate Gray structure that coupled electric field is formed in its conduction band or valence band between quantum dot in this structure, charge carrier wherein can absorb the sunlight of 900-1100nm infrared band, as shown in Figure 3, the conversion efficiency of quantum dot solar cell is further increased, as shown in Figure 4.
Preferably, wall and/or In
xga
1-xdoped with the donor element of current density being used for strengthening battery in As quantum dot layer.Experiment shows, inject 6 electronics by doping donor atom is average in semiconductor-quantum-point, photogenerated current can be made to double, and the photoelectric conversion efficiency of battery increases by 50%.In the present embodiment, wall and/or In
xga
1-xthe preferred silicon atom of As quantum dot layer, its doping content is 1.0 × 10
17-1.0 × 10
18cm
-3, be preferably 1.0 × 10
17-5.0 × 10
17cm
-3.The active silicon atom number of doping during doping content is every cubic centimetre.
Preferably, also comprise in step S1: optimize the lattice constant of the semi-conducting material of base stage 5 and/or emitter 3, energy gap and/or thickness, reduce the open circuit voltage even eliminated because of caused by the defect of lattice mismatch generation and decline.Emitter 3 and base stage 5 can select the energy gaps such as GaInP, GaAlAs, GaP, GaAlInP and GaAlAsP to be greater than the semi-conducting material of wall energy gap.Base stage 5 is N-type GaInP base stage, emitter 3 is P type GaInP emitter, and the lattice constant of GaInP is 0.56-0.57nm, energy gap is 1.80-1.92eV.Specifically can be Ga
0.48in
0.52p material, Ga
0.49in
0.51p material, Ga
0.50in
0.50p material, Ga
0.51in
0.49p material or Ga
0.52in
0.48p material, N-type GaInP base stage and P type GaInP emitter be Ga all preferably
0.51in
0.49p material, Ga
0.51in
0.49the lattice constant of P is 0.565nm, and energy gap is the thickness of 1.90eV, N-type GaInP base stage is 0.5-3.0 μm, and the thickness of preferred 1.0-2.0 μm, P type GaInP emitter is 50-300nm, is preferably 100-150nm.
Preferably, step S1 also comprises: in N-type GaInP base stage, adulterate 1.0 × 10
17-1.0 × 10
18cm
-3donor atom.1.0 × 10 are adulterated in P type GaInP emitter
17-1.0 × 10
19cm
-3acceptor atom.
The present embodiment also utilizes energy gap (E
g) comparatively large (E
g=1.9eV) GaInP retrain electronics in InGaAs/GaAs quantum dot superlattice and hole as base stage and emitter.In this quantum dot superlattice, GaAs wall can absorb the photon of energy higher than 1.42eV, InGaAs quantum dot can absorb the photon of energy higher than 1.0-1.3eV, and in the Intermediate Gray of InGaAs/GaAs quantum dot (micro-band) electronics can absorb energy be the photon transition of 0.6-0.9eV on the conduction band of GaInP emitter and base stage, thus form high efficiency Intermediate Gray quantum dot solar cell.
Particularly, comprise in step s 2:
First, InGaAs quantum dot solar cell epitaxial wafer GaAs substrate 7 backside deposition 20-200nm gold germanium nickel (AuGeNi) alloy and gold (Au) composite material layer as back electrode 8, also can use other metal material make back electrode 8; Then utilize photoetching and caustic solution that the InGaAs quantum dot solar cell epitaxial wafer that deposited back electrode 8 is resolved into battery unit, and utilize photoetching and contact layer 1 surface deposition titanium (TiAu) alloy of physical vapour deposition (PVD) (PVD) method at battery unit or the top electrode 9 of golden zinc (AuZn) alloy; Afterwards, recycling photoetching and physical vapour deposition (PVD) (PVD) method deposited the battery unit surface deposition 100nm magnesium fluoride (MgF of top electrode 9
2) and the composite membrane that forms of 50nm zinc sulphide (ZnS) as antireflective coating 10; Finally, pressure welding and packaging technology is utilized to produce quantum dot solar cell.
Embodiment 2
As shown in Figure 2, present embodiments provide a kind of InGaAs quantum dot solar cell, comprise the battery unit of multiple series connection and/or parallel connection, battery unit comprises back electrode 8, GaAs substrate 7, resilient coating 6, base stage 5, InGaAs quantum-dot superlattice structure 4, emitter 3, Window layer 2, contact layer 1 and top electrode 9, InGaAs quantum-dot superlattice structure 4 from top to bottom successively and comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on In
xga
1-xwall between As quantum dot layer.Wherein, In
xga
1-xthe In of As quantum dot layer
xga
1-xin As, In component is 0.4≤x≤1.0, preferably 0.5≤x≤1.0.In
xga
1-xthe thickness of As quantum dot layer is 1.8-10.0 individual layer, and preferred thickness is 1.8-6.0 individual layer.Wall can be GaAs material, GaAlAs material, GaP material, GaAsP material, GaInP material, GaAlInP material or GaAlAsP material, and be preferably GaAs material, its thickness is 10-100nm, is preferably 10-50nm.Particularly, In
xga
1-xas quantum dot layer can arrange 1-100 layer, and correspondingly, wall need arrange 1-100 layer, preferably, and In
xga
1-xas quantum dot layer arranges 5-50 layer, and wall arranges 5-50 layer.Particularly, GaAs substrate 7 is N
+gaAs substrate, resilient coating 6 is preferably N
+gaAs resilient coating, Window layer 2 is preferably P
+type AlGaInP Window layer, contact layer 1 is preferably P
+type GaAs contact layer.
Optimize the lattice constant of the semi-conducting material of base stage 5, energy gap and/or thickness, reduce the open circuit voltage even eliminated because of caused by the defect of lattice mismatch generation and decline.Base stage 5 can select the energy gaps such as GaInP, GaAlAs, GaP, GaAlInP and GaAlAsP to be greater than the semi-conducting material of wall energy gap.Base stage 5 is N-type GaInP base stage, and the lattice constant of GaInP is 0.56-0.57nm, energy gap is 1.80-1.92eV.Specifically can be Ga
0.48in
0.52p material, Ga
0.49in
0.51p material, Ga
0.50in
0.50p material, Ga
0.51in
0.49p material or Ga
0.52in
0.48p material, the material of N-type GaInP base stage is preferably Ga
0.51in
0.49p, Ga
0.51in
0.49the lattice constant of P is 0.565nm, and energy gap is the thickness of 1.90eV, N-type GaInP base stage is 0.5-3.0 μm, and preferred thickness is 1.0-2.0 μm.
Preferably, wall and/or In
xga
1-xdoped with the donor element of current density being used for strengthening battery in As quantum dot layer.Experiment shows, inject 6 electronics by doping donor atom is average in semiconductor-quantum-point, photogenerated current can be made to double, and the photoelectric conversion efficiency of battery increases by 50%.In the present embodiment, wall and/or In
xga
1-xthe preferred silicon atom of As quantum dot layer, its doping content is 1.0 × 10
17-1.0 × 10
18cm
-3, be preferably 1.0 × 10
17-5.0 × 10
17cm
-3.The active silicon atom number of doping during doping content is every cubic centimetre.
Optimize the lattice constant of the semi-conducting material of emitter 3, energy gap and/or thickness, reduce the open circuit voltage even eliminated because of caused by the defect of lattice mismatch generation to decline, emitter 3 can select the energy gaps such as GaInP, GaAlAs, GaP, GaAlInP and GaAlAsP to be greater than the semi-conducting material of wall energy gap.Emitter 3 is P type GaInP emitter, specifically can be Ga
0.48in
0.52p material, Ga
0.49in
0.51p material, Ga
0.50in
0.50p material, Ga
0.51in
0.49p material or Ga
0.52in
0.48p material, the preferred Ga of P type GaInP emitter
0.51in
0.49p material, the thickness of P type GaInP emitter is 50-300nm, and preferred thickness is 100-150nm.
Preferably, in N-type GaInP base stage doped with 1.0 × 10
17-1.0 × 10
18cm
-3donor atom.Doped with 1.0 × 10 in P type GaInP emitter
17-1.0 × 10
19cm
-3acceptor atom.
Optimally, battery unit also comprises the antireflective coating 10 be arranged on contact layer 1, and antireflective coating 10 specifically can be 100nm magnesium fluoride (MgF
2) and the composite membrane that forms of 50nm zinc sulphide (ZnS).
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to execution mode.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all execution modes.And thus the apparent change of extending out or variation be still among the protection range of the invention.
Claims (10)
1. a manufacture method for InGaAs quantum dot solar cell, is characterized in that comprising the following steps:
Step S1: utilize epitaxial growth method to produce InGaAs quantum dot solar cell epitaxial wafer after epitaxial growth buffer, base stage, InGaAs quantum-dot superlattice structure, emitter, Window layer and contact layer successively on gaas substrates, described InGaAs quantum-dot superlattice structure comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on described In
xga
1-xwall between As quantum dot layer, wherein, described In
xga
1-xin component 0.0≤x≤1.0 in As quantum dot layer;
Step S2: be divided into battery unit after the described GaAs substrate back deposition back electrode of described InGaAs quantum dot solar cell epitaxial wafer, and top electrode is set on described contact layer surface, produce described InGaAs quantum dot solar cell.
2. the manufacture method of InGaAs quantum dot solar cell as claimed in claim 1, is characterized in that, described In
xga
1-xthe growth temperature of As quantum dot layer is 450-540 DEG C, deposition rate is that 0.01-1.0 individual layer is per second, thickness is 1.8-10.0 individual layer, In
xga
1-xin As, In component is 0.4≤x≤1.0.
3. the manufacture method of InGaAs quantum dot solar cell as claimed in claim 1 or 2, is characterized in that, described wall and described In
xga
1-xas quantum dot layer arranges 1-100 layer respectively.
4. the manufacture method of the InGaAs quantum dot solar cell as described in claim 1 or 3, is characterized in that, described wall is GaAs material, GaAlAs material, GaP material, GaAsP material, GaInP material, GaAlInP material or GaAlAsP material.
5. the manufacture method of InGaAs quantum dot solar cell as claimed in claim 4, it is characterized in that, described wall is GaAs material, and its thickness is 10-100nm.
6. the manufacture method of the InGaAs quantum dot solar cell according to any one of claim 1-5, is characterized in that, described wall and/or described In
xga
1-xdoped with the donor element of current density being used for strengthening battery in As quantum dot layer, the described donor element of doping is element silicon, and the doping content of silicon atom is 1.0 × 10
17-1.0 × 10
18cm
-3.
7. the manufacture method of InGaAs quantum dot solar cell as claimed in claim 5, it is characterized in that, described emitter and base stage adopt energy gap to be greater than the semi-conducting material of the described wall energy gap adopting GaAs material, comprise GaInP material, GaAlAs material, GaP material, GaAlInP material and GaAlAsP material.
8. the manufacture method of the InGaAs quantum dot solar cell as described in claim 1 or 7, is characterized in that, also comprise in step S1:
Optimize the lattice constant of described base stage and/or emitter semiconductor material, energy gap and/or thickness, reduce the open circuit voltage even eliminated because of caused by the defect of lattice mismatch generation to decline, described base stage is N-type GaInP base stage, described transmitting is P type GaInP emitter very, the lattice constant of GaInP is 0.56-0.57nm, energy gap is 1.8-1.92eV, the thickness of N-type GaInP base stage is the thickness of 0.5-3.0 μm, P type GaInP emitter is 50-300nm;
1.0 × 10 are adulterated in described N-type GaInP base stage
17-1.0 × 10
18cm
-3donor atom, in described P type GaInP emitter adulterate 1.0 × 10
17-1.0 × 10
19cm
-3acceptor atom.
9. the manufacture method of InGaAs quantum dot solar cell as claimed in claim 1, is characterized in that, in step S2:
Comprise and utilize photoetching and etch that the InGaAs quantum dot solar cell epitaxial wafer that deposited described back electrode is divided into battery unit, described back electrode thickness is 20-200nm, adopts the composite material of gold germanium nickel alloy and gold;
Comprise and utilize photoetching and physical vaporous deposition that top electrode is set on the described contact layer surface of described battery unit, described in power on very titanium alloy or golden kirsite;
Comprise and utilize photoetching and physical gas-phase deposite method being provided with the battery unit surface deposition antireflective coating of described top electrode, described antireflective coating is the composite membrane of magnesium fluoride and zinc sulphide;
Comprise and utilize pressure welding and packaging technology that the described battery unit being provided with top electrode and antireflective coating is made into described InGaAs quantum dot solar cell.
10. an InGaAs quantum dot solar cell, comprise the battery unit of multiple series connection and/or parallel connection, it is characterized in that, described battery unit comprises back electrode, GaAs substrate, resilient coating, base stage, InGaAs quantum-dot superlattice structure, emitter, Window layer, contact layer and top electrode from bottom to up successively, and described InGaAs quantum-dot superlattice structure comprises at least one deck In
xga
1-xas quantum dot layer and be arranged on described In
xga
1-xwall between As quantum dot layer.
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| CN105355683A (en) * | 2015-12-11 | 2016-02-24 | 上海空间电源研究所 | Forward-direction triple junction solar cell based on p-type doped quantum well structure |
| CN111200030A (en) * | 2018-11-19 | 2020-05-26 | 东泰高科装备科技有限公司 | Solar cell and manufacturing method thereof |
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| CN101145590A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院半导体研究所 | Quantum dot material structure and its growth method |
| CN102983203A (en) * | 2012-11-28 | 2013-03-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-junction cascade solar battery and manufacturing method thereof |
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| CN101145590A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院半导体研究所 | Quantum dot material structure and its growth method |
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