CN101702415B - Method for manufacturing laminated solar cell - Google Patents

Method for manufacturing laminated solar cell Download PDF

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CN101702415B
CN101702415B CN2009100951400A CN200910095140A CN101702415B CN 101702415 B CN101702415 B CN 101702415B CN 2009100951400 A CN2009100951400 A CN 2009100951400A CN 200910095140 A CN200910095140 A CN 200910095140A CN 101702415 B CN101702415 B CN 101702415B
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growth
layer
gasb
thickness
doping content
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CN101702415A (en
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郝瑞亭
杨培志
申兰先
邓书康
涂洁磊
廖华
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Yunnan Normal University
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Yunnan Normal University
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    • 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
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Abstract

The invention discloses a method for manufacturing a laminated solar cell, comprising the following steps: taking a doped gallium antimonide single chip as a substrate, growing a sub-cell adsorbing layer on the gallium antimonide substrate by using a molecular beam epitaxy MBE growing technique, concretely comprising the steps of growing a GaSb buffer layer on GaSb substrate at first, then orderly growing a GaInAsSb layer, an AlGaAsSb layer, an CdZnSeTe layer, a ZnTe layer and tunnel junctions between layers on the grew GaSb buffer layer, manufacturing a top electrode on the ZnTe layer, and manufacturing a back electrode on the GaSb substrate; and then packaging to manufacture the cell.

Description

A kind of manufacture method of stacked solar cell, cascade solar cell
Technical field
The present invention relates to a kind of manufacture method of stacked solar cell, cascade solar cell, is a kind of semiconductor solar cell, especially relates to many knots efficient solar battery of a kind of currents match and lattice match.
Background technology
Along with the exhaustion of fossil energy and increasingly sharpening of global warming, the utilization of solar energy is just receiving the many attention of People more and more.Solar cell is to be the core devices of electric energy with conversion of solar energy.Efficient solar battery has important purposes at aspects such as Aero-Space, space explorations.The large-scale application of efficient solar battery can alleviating energy crisis cheaply, reduces greenhouse gas emission, and the offspring benefits future generations.Therefore, the efficient solar battery technology is the particularly research fields of developed country's emphasis support of various countries always.
The maximum obstacle of restriction III-V family solar power generation industry development is exactly that the battery component cost is high at present, finally causes the cost of solar power generation higher.The most critical that reduces the solar cell cost of electricity-generating is further to improve the photoelectric conversion efficiency of solar cell.Theoretical Calculation shows, the sub-battery short circuit electric current of each of laminated cell is more near (matching degree is high more), utilizes degree also just high more to spectrum.Regrettably do not find three knots or the above solar cell combination of three knots of satisfying lattice match and currents match simultaneously up to now.
There are the mechanical laminated battery of GaSb/GaAs, GaInP/GaAs/Ge battery etc. in known space with efficient solar battery.The efficient of the GaInP/GaAs/Ge three joint solar cells that the SPECTROLAB of Boeing wholly-owned subsidiary produces reaches 28.3%, by 2006, has sold 2,000,000.GaSb/GaAs machinery laminated battery photoelectric conversion efficiency has reached 37% (AM1.5), is the higher compound semiconductor solar cell of efficient.(application number: 200510084937.2) adopt high-quality GaSb and GaAs single-chip is that raw material are made GaSb/GaAs machinery laminated battery to patent, but because it needs high-quality GaSb, GaAs body material, so cost is high, power-weight ratio is than big.The GaInP/GaAs battery can only absorb the photon of energy greater than 1.4eV, can not cover infrared band, so can't further improve photoelectric conversion efficiency.
Summary of the invention
To the problem that background technology proposes, the object of the present invention is to provide a kind of manufacture method of stacked solar cell, cascade solar cell, the manufacture method of many knots high efficiency semiconductor solar cell of especially a kind of currents match and lattice match.With doping gallium antimonide monocrystalline sheet is substrate, adopts molecular beam epitaxy (MBE) growing technology, the sub-battery obsorbing layer of growth on the gallium antimonide substrate; Detailed process comprises: the GaSb resilient coating of at first on the GaSb substrate, growing; On the GaSb resilient coating of growth, grow successively then tunnel junctions between GaInAsSb layer, AlGaAsSb layer, CdZnSeTe layer, ZnTe layer and each layer is made top electrode on the ZnTe layer, on the GaSb substrate layer, make back electrode; Encapsulate then, obtain finished product.Be used for making the efficient solar battery assembly.
Practical implementation step of the present invention is:
Adopt molecular beam epitaxy (MBE) growing technology; Elder generation's epitaxial growth GaSb layer on the GaSb substrate; On the GaSb layer of growth, grow successively then tunnel junctions between GaInAsSb layer, AlGaAsSb layer, CdZnSeTe layer, ZnTe layer and each layer is made top electrode on the ZnTe layer, on the GaSb substrate, make back electrode; Encapsulate then, obtain finished product.
The present invention compares advantage and the good effect that has with known technology
1, utilizes the present invention, the spectral absorption scope of solar cell is extended to the 0.5-2.3eV wave band, particularly increased absorption, be highly profitable for the conversion efficiency that improves solar cell to infrared part.
2, each battery sublayer is the direct band gap material, and absorption coefficient is big, and capability of resistance to radiation is strong, and the life-span is long.
Description of drawings
Fig. 1 is a solar battery structure sketch map provided by the invention.1 is top electrode among the figure, and 2 is the ZnTe layer, and 3 is n +CdSeTe/p +The ZnSeTe tunnel junctions, 4 is the CdZnSeTe layer, 5 is n +AlAsSb/p +The CdSeTe tunnel junctions, 6 is the AlGaAsSb layer, 7 is n +InAsSb/p +The GaAsSb tunnel junctions, 8 is the GaInAsSb layer, 9 is n +GaSb/p +The InAsSb tunnel junctions, 10 is GaSb substrate layer and resilient coating, 11 is back electrode.
Embodiment
Embodiment
(1): the P that will exempt to clean +-GaSb substrate is placed on the molecular beam epitaxy MBE growth room specimen holder; High temperature deoxidation under 550 ℃ of conditions, and GaSb substrate layer temperature risen to 600 ℃ of high-temperature degassing, then underlayer temperature is reduced to 550 ℃; Carry out the growth of n-GaSb resilient coating, doping content is n 3～5 * 10 18, n-GaSb buffer growth thickness is 0.5 μ m, and said MBE growth room is in high vacuum state before the GaSb buffer growth, and pressure is 5～9 * 10 -9Mbar, growth room pressure in GaSb buffer growth process is 5～5.5 * 10 -8Mbar, the Sb of GaSb resilient coating when growth: Ga line ratio is 5.5: 1;
(2) growth n +GaSb/p +The InAsSb tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that GaSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the InAsSb layer of 0.015 μ m;
(3): close Ga, Sb source stove shutter, underlayer temperature is reduced to 450 ℃, open the shutter of Ga, In, As, Sb source stove, carry out the growth of p-GaInAsSb layer, doping content is p 1～3 * 10 18, growth thickness is 2 μ m, growth room's pressure is 5～6 * 10 -8Mbar, As in the growth course: Sb: Ga: In line ratio is 10: 10: 2: 1;
(4) carry out the growth of n-GaInAsSb layer, doping content is n 1～3 * 10 18, growth thickness is 2 μ m, growth room's pressure is 5～6 * 10 -8Mbar, As in the growth course: Sb: Ga: In line ratio is 10: 10: 2: 1;
(5) growth n +InAsSb/p +The GaAsSb tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that InAsSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the GaAsSb layer of 0.015 μ m;
(6): close Ga, In, As, Sb source stove shutter, underlayer temperature is reduced to 430 ℃, open the shutter of Al, Ga, As, Sb source stove, carry out the growth of p-AlGaAsSb layer, doping content is p 1～3 * 10 18Growth thickness is 1.5 μ m, and growth room's pressure is 7.5～8 * 10 -8Mbar, As in the growth course: Sb: Al: Ga line ratio is 1: 5: 4: 1;
(7) carry out the growth of n-AlGaAsSb layer, doping content is n 1～3 * 10 18, growth thickness is 1.5 μ m, growth room's pressure is in 7.5～8 * 10 -8The mbar scope, As in the growth course: Sb: Al: Ga line ratio is 1: 5: 4: 1;
(8) growth n +AlAsSb/p +The CdSeTe tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that AlAsSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the CdSeTe layer of 0.015 μ m;
(9): close Al, Ga, As, Sb source stove shutter, underlayer temperature is reduced to 330 ℃, open Cd, Zn, Se, Te source stove shutter, carry out the growth of p-CdZnSeTe layer, doping content is p 1～3 * 10 18, growth thickness is 1 μ m, growth room's pressure is 3～5 * 10 -8Mbar, Se in the growth course: Te: Cd: Zn line ratio is 5: 3: 5: 1;
(10) carry out the growth of n-CdZnSeTe layer, doping content is n 1～3 * 10 18Growth thickness is 1 μ m; Growth room's pressure is in 3～5 * 10 -8The mbar scope, Se in the growth course: Te: Cd: Zn line ratio is 5: 3: 5: 1;
(11) growth n +CdSeTe/p +The ZnSeTe tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that CdSeTe layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the ZnSeTe layer of 0.015 μ m;
(12): close Cd, Zn, Se, Te source stove shutter, underlayer temperature is reduced to 300 ℃, open Zn, Te source stove shutter, carry out the growth of p-ZnTe layer, doping content is p 1～3 * 10 18, growth thickness is 0.5 μ m, growth room's pressure is 6～6.5 * 10 -8Mbar, Te in the growth course: Zn line ratio is 3: 1;
(13) carry out n +The growth of-ZnTe layer, doping content are n +7～9 * 10 18, growth thickness is 0.5 μ m, growth room's pressure is in 6～6.5 * 10 -8The mbar scope, Te in the growth course: Zn line ratio is 3: 1;
(14): at n +-ZnTe laminar surface is made top electrode;
(15): at P +-GaSb substrate surface is made back electrode;
(16) making of completion battery encapsulates, and obtains the solar cell finished product.

Claims (1)

1. the manufacture method of a stacked solar cell, cascade solar cell adopts the molecular beam epitaxial growth technology, earlier epitaxial growth GaSb resilient coating on the GaSb substrate; On the GaSb resilient coating of growth, grow successively then tunnel junctions between GaInAsSb layer, AlGaAsSb layer, CdZnSeTe layer, ZnTe layer and each layer; On the ZnTe layer, make top electrode, on the GaSb substrate, make back electrode, encapsulate then; Obtain the solar cell finished product, it is characterized in that:
Described epitaxial growth GaSb resilient coating is with the P that exempts to clean +-GaSb substrate is placed on the specimen holder of molecular beam epitaxial growth chamber; High temperature deoxidation under 550 ℃ of conditions, and GaSb substrate layer temperature risen to 600 ℃ of high-temperature degassing, then underlayer temperature is reduced to 550 ℃; Carry out the growth of n-GaSb resilient coating, the doping content of this n type is 3～5 * 10 18, n-GaSb buffer growth thickness is 0.5 μ m, and said growth room is in high vacuum state before the GaSb buffer growth, and pressure is 5～9 * 10 -9Mbar, growth room pressure in GaSb buffer growth process is 5～5.5 * 10 -8Mbar, the Sb of GaSb resilient coating when growth: Ga line ratio is 5.5: 1;
Growth GaInAsSb layer is that temperature buffer layer is reduced to 450 ℃ on the described GaSb resilient coating, opens the shutter of Ga, In, As, Sb source stove, carries out the growth of p-GaInAsSb layer, and the doping content of this p type is 1～3 * 10 18, growth thickness is 2 μ m, growth room's pressure is 5～6 * 10 -8Mbar, As in the growth course: Sb: Ga: In line ratio is 10: 10: 2: 1; Carry out the growth of n-GaInAsSb layer again, the doping content of this n type is 1～3 * 10 18, growth thickness is 2 μ m, growth room's pressure is 5～6 * 10 -8Mbar, As in the growth course: Sb: Ga: In line ratio is 10: 10: 2: 1;
The growth of described AlGaAsSb layer is that underlayer temperature is reduced to 430 ℃, opens the shutter of Al, Ga, As, Sb source stove, carries out the growth of p-AlGaAsSb layer, and the doping content of this p type is 1～3 * 10 18, growth thickness is 1.5 μ m, growth room's pressure is 7.5～8 * 10 -8Mbar, As in the growth course: Sb: Al: Ga line ratio is 1: 5: 4: 1; Carry out the growth of n-AlGaAsSb layer again, the doping content of this n type is 1～3 * 10 18, growth thickness is 1.5 μ m, growth room's pressure is 7.5～8 * 10 -8Mbar, As in the growth course: Sb: Al: Ga line ratio is 1: 5: 4: 1;
The growth of described CdZnSeTe layer is that underlayer temperature is reduced to 330 ℃, opens Cd, Zn, Se, Te source stove shutter, carries out the growth of p-CdZnSeTe layer, and the doping content of this p type is 1～3 * 10 18, growth thickness is 1 μ m, growth room's pressure is 3～5 * 10 -8Mbar, Se in the growth course: Te: Cd: Zn line ratio is 5: 3: 5: 1; Carry out the growth of n-CdZnSeTe layer again, the doping content of this n type is 1～3 * 10 18Growth thickness is 1 μ m; Growth room's pressure is 3～5 * 10 -8Mbar, Se in the growth course: Te: Cd: Zn line ratio is 5: 3: 5: 1;
The growth of described ZnTe layer is that underlayer temperature is reduced to 300 ℃, opens Zn, Te source stove shutter, carries out the growth of p-ZnTe layer, and the doping content of this p type is 1～3 * 10 18, growth thickness is 0.5 μ m, growth room's pressure is 6～6.5 * 10 -8Mbar, Te in the growth course: Zn line ratio is 3: 1; Carry out n again +The growth of-ZnTe layer, the doping content of this n type are 7～9 * 10 18, growth thickness is 0.5 μ m, growth room's pressure is 6～6.5 * 10 -8Mbar, Te in the growth course: Zn line ratio is 3: 1;
Tunnel junctions between described each layer of growth is (1) n that between GaSb resilient coating and GaInAsSb layer, grows +GaSb/p +The InAsSb tunnel junctions, it comprises n type doping content 1～2 * 10 19, thickness is that GaSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the InAsSb layer of 0.015 μ m; (2) n that between GaInAsSb layer and AlGaAsSb layer, grows +InAsSb/p +The GaAsSb tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that InAsSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the GaAsSb layer of 0.015 μ m; (3) n that between AlGaAsSb layer and CdZnSeTe layer, grows +AlAsSb/p +The CdSeTe tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that AlAsSb layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the CdSeTe layer of 0.015 μ m; (4) n that between CdZnSeTe layer and ZnTe layer, grows +CdSeTe/p +The ZnSeTe tunnel junctions, it comprises that n type doping content is 1～2 * 10 19, thickness is that CdSeTe layer and the p type doping content of 0.015 μ m is 3～4 * 10 19, thickness is the ZnSeTe layer of 0.015 μ m.
CN2009100951400A 2009-11-05 2009-11-05 Method for manufacturing laminated solar cell Expired - Fee Related CN101702415B (en)

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CN105990463A (en) * 2016-05-11 2016-10-05 河海大学 Selective emitter GaInAsSb thermophotovoltaic cell and preparation method thereof
CN106409971A (en) * 2016-06-30 2017-02-15 华南理工大学 High-efficiency nanocrystalline solar cell with bulk heterojunction structure processed by all-solution method and preparation method of high-efficiency nanocrystalline solar cell

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