CN104157725A - Method for manufacturing GaInP/GaAs/InGaAsP/InGaAs four-junction cascading solar cell - Google Patents
Method for manufacturing GaInP/GaAs/InGaAsP/InGaAs four-junction cascading solar cell Download PDFInfo
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- CN104157725A CN104157725A CN201310176398.XA CN201310176398A CN104157725A CN 104157725 A CN104157725 A CN 104157725A CN 201310176398 A CN201310176398 A CN 201310176398A CN 104157725 A CN104157725 A CN 104157725A
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- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 65
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001039 wet etching Methods 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 3
- 230000010354 integration Effects 0.000 abstract 1
- 230000012010 growth Effects 0.000 description 8
- 241000208340 Araliaceae Species 0.000 description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 description 5
- 235000008434 ginseng Nutrition 0.000 description 5
- 206010040844 Skin exfoliation Diseases 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000013082 photovoltaic technology Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000035618 desquamation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/078—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers including different types of potential barriers provided for in two or more of groups H01L31/062 - H01L31/075
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- 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
- H01L31/1844—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 comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
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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
- 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
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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
- 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
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Abstract
The invention discloses a method for manufacturing a GaInP/GaAs/InGaAsP/InGaAs four-junction cascading solar cell. Based on wafer bonding technology, integration of a GaAs substrate-based GaInP/GaAs double-junction solar cell and an InP substrate-based InGaAsP/InGaAs double-junction solar cell is realized. An InP substrate is stripped, GaAs is adopted as a supporting substrate, a four-junction solar cell with respective band gap energy of 1.89/1.42/1.05/0.72eV is realized, absorption and energy conversion of a full spectrum of sunlight are realized to a greater extent, and the stripped InP substrate can recycled after being polished, thereby reducing consumption of InP substrates. According to the four-junction solar cell provided by the invention, high cost caused by using a plurality of substrates in a mechanical laminate multi-junction solar cell system and optical loss caused by a complicated optical system in an optical integrated cell can be reduced, and the problem of lattice mismatch of material for growing a multi-junction cascading semiconductor solar cell is effectively solved. High voltage and low current output is realized, and resistance consumption in a high-power concentrator cell is reduced.
Description
Technical field
The invention belongs to photovoltaic field, relate in particular to a kind of GaInP/GaAs/InGaAsP/InGaAs tetra-and tie the manufacture method of cascade solar cell.
Background technology
Under the energy crisis of the eighties of last century initiation seventies stimulates, also, under the demand pull of spacecraft energy resource system, photovoltaic technology field constantly makes a breakthrough.Crystal silicon solar energy battery, non-crystal silicon solar cell, amorphous silicon thin-film solar cell, Ⅲ-Ⅴ compound semiconductor solar cell, group Ⅱ-Ⅵ compound semiconductor polycrystal film solar cell etc., increasing solar battery technology reaches its maturity.Improving constantly and the lasting reduction of manufacturing cost of photoelectric conversion efficiency, makes photovoltaic technology all be widely used in space and ground.
Look back photovoltaic technology the development of nearest 10 years, aspect efficiency raising, the solar battery structure of tying tandem type is the most noticeable more.InGaP/(In in 2007) GaAs/Ge tri-average efficiency of tying tandem solar cell large-scale production approached 30%.Under 240 times of optically focused, the lab A M1.5D efficiency of this multijunction solar cell has exceeded 40%.In theory, footing is more, and efficiency is higher.But in practice, be difficult to find so desirable collocation on band gap width, the bi-material that lattice constant is mated again is very much realized entire cascaded battery.Therefore, current multijunction cell structure mainly contains two kinds of thinkings: the one, and pay the utmost attention to Lattice Matching and photoelectric current coupling is placed on to less important position.Adopt the design of Lattice Matching, the efficiency of two knot GaInP/GaAs batteries has reached more than 30%.But the battery structure of Lattice Matching, due to its definite band-gap energy, has limited the coupling of the photoelectric current of sunlight, make it can not realize the full spectral absorption utilization to solar cell.For example, for the GaInP/GaAs/Ge three-junction solar battery of Lattice Matching, the density of photocurrent on end battery Ge is the twice of upper two-layer cell photoelectric current density, thereby has limited the lifting of efficiency.The 2nd, the photoelectric current of paying the utmost attention to multijunction structure mates and the growth pattern of employing lattice mismatch, since 2005, several famous seminar in the world, such as NREL, Toyota, the Sharp etc. of Emcore and Japan pay close attention to the research of the solar battery structure of lattice mismatch more and more.By the adjustment of band-gap energy, utilize the InGaAs/(In of inversion method growth) efficiency of GaAs/InGaP battery is from the 38.9%(81 times of optically focused of 2007, AM1.5D) bring up to 40.8% (326 times of optically focused, the AM1.5G) of 2008.The Eicke professor Weber leader's of nearest German fraunhofer research institute research group has brought up to 41.1% by three knot GaInP/GaInAs/Ge efficiency of solar cell.
However, the structural design of lattice mismatch depends on high-quality Material growth, and large lattice mismatch must bring misfit dislocation, thereby greatly increases non-radiative compound, reduction battery efficiency.This caused direct growth four knot tandem cells efficiency lower than the efficiency of three knots on the contrary.And according to Shockley-Quisser model, four knot band-gap energies are that the solar cell of 1.89/1.42/1.05/0.67 eV can obtain the conversion efficiency that exceedes 45%, compare with the binode GaAs/InGaAs battery proposing than Emcore company under a same bonding technology advantage having in very high efficiency.Simultaneously, because four junction structures more can be realized high voltage, low current output, can effectively reduce the resistance heat loss in super high concentrating solar battery, and superelevation times concentrator cell can reduce solar cell cost widely, thereby for having played greatly, the progress of III-V compound semiconductor solar cell aspect industrialization promote.
The restriction of solar cell based on lattice mismatch on Material growth and the needs of the above battery development of four knots, integrated being proved to be of direct monolithic multijunction cell of realizing large mismatched lattices material by the method for extension Direct Bonding has very large potentiality.Utilize extension bonding not only can solve the Material growth difficult problem that lattice mismatch brings, but also can use Si substrate to replace expensive InP or GaAs, thereby reduce battery cost.In the development of four junction batteries, the scientists of Boeing-spectrum company of the U.S. and Caltech has proposed the InGaAsP/InGaAs(1.0/0.72 eV of the binode GaInP/GaAs battery on Ge substrate and InP Grown) method of bonding, to realize monolithic four, to tie GaInP/GaAs/Ge/InP bonding interface/InGaAsP/InGaAs integrated.Although used the material structure of Lattice Matching, Ge/InP can absorb the sunlight of energy below 1.42 eV, thereby reduces the efficiency of InGaAsP/InGaAs battery.Therefore, must before bonding, obtain Ge thin layer, this can increase the difficulty in process of battery development greatly.
Summary of the invention
In view of above-mentioned taking InGaP/(In) GaAs/Ge tri-ties tandem solar cell and still cannot reach and the optimum Match of solar spectrum as the photovoltaic technology of representative, and the objective difficulty of making lattice mismatch between the semi-conducting material that the above solar cell of monolithic cascade three knots exists, the object of the invention is to propose a kind of manufacture method of four knot GaInP/GaAs/InGaAsP/InGaAs solar cells, inheriting, two knot cascade solar cell photoelectric conversion efficiencys were relatively high in the past, stable, on the basis of life-span length, prepare four statement of account sheet efficient solar batteries, to obtain high voltage, low current output, thereby effectively reduce the ohmic loss in super high concentrating solar battery, realize higher photoelectric conversion efficiency, simultaneously, solar cell of the present invention does not have InP substrate, cost is low.
For achieving the above object, the invention provides following technical scheme:
GaInP/GaAs/InGaAsP/InGaAs tetra-ties a manufacture method for cascade solar cell, comprising:
(1) at the GaInP/GaAs binode battery of GaAs Grown and GaAs Lattice Matching, at the InGaAsP/InGaAs binode battery of InP Grown and InP Lattice Matching;
(2) by GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery bonding;
(3) peel off InP substrate, obtain and only have the GaInP/GaAs/InGaAsP/InGaAs tetra-of GaAs substrate supports to tie cascade solar cell.
As a further improvement on the present invention, described manufacture method specifically comprises:
1) the GaAs resilient coating of first growing on GaAs substrate, the sub-battery of GaAs of then growing, the second tunnel junction, the sub-battery of GaInP and ohmic contact layer,
Grown InP resilient coating first on InP substrate, the InGaAs etching stop layer of 0.1 ~ 1 μ m that then grows, AlInAs sacrifice layer, the ohmic contact layer of 0.2 ~ 1 μ m, the sub-battery of InGaAs of next growing, the first tunnel junction, the sub-battery of InGaAsP and bonded layer;
2), by the bonded layer bonding of the GaAs substrate surface of GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery, form tunnel junction;
3) adopt the method for wet etching to peel off InP substrate;
4) make positive and negative electrode, obtain and only have the GaInP/GaAs/InGaAsP/InGaAs tetra-of GaAs substrate supports to tie cascade solar cell.
As a further improvement on the present invention, in described step 3), the corrosive liquid volume of wet etching is than being HCL: H
3pO
4=1:1.
The invention also discloses a kind of GaInP/GaAs/InGaAsP/InGaAs being made by said method tetra-and tie cascade solar cell.
Compared with prior art, the invention has the advantages that:
The invention provides a kind of manufacture method of four knot GaInP/GaAs/InGaAsP/InGaAs solar cells, two tie on the bases that cascade solar cell photoelectric conversion efficiencys are relatively high, stable, the life-span is long in succession in the past, prepare four statement of account sheet efficient solar batteries, to obtain high voltage, low current output, thereby effectively reduce the ohmic loss in super high concentrating solar battery, realize higher photoelectric conversion efficiency.
On the other hand, the present invention is by after GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery bonding, by InP substrate desquamation, obtain and only had the GaInP/GaAs/InGaAsP/InGaAs tetra-of GaAs substrate supports to tie cascade solar cell, the InP substrate being stripped from can reuse, greatly reduce cost, reduced the consumption of InP substrate, also reduced the cost of manufacture of solar cell.Peel off InP substrate advantage and be to reuse InP substrate, reduce battery cost; Adopt GaAs to be enough to as its mechanical strength of support substrates, without other support substrates.
Brief description of the drawings
In order to be illustrated more clearly in the embodiment of the present application or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, the accompanying drawing the following describes is only some embodiment that record in the application, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Figure 1 shows that the schematic diagram of making GaInP/GaAs binode battery in the specific embodiment of the invention on GaAs substrate;
Figure 2 shows that the schematic diagram of making InGaAsP/InGaAs binode battery in the specific embodiment of the invention on InP substrate;
Figure 3 shows that the schematic diagram of GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery bonding in the specific embodiment of the invention;
Figure 4 shows that the schematic diagram that in the specific embodiment of the invention, InP substrate is stripped from;
Figure 5 shows that in the specific embodiment of the invention, making the GaInP/GaAs/InGaAsP/InGaAs tetra-obtaining ties cascade solar cell.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite of not making creative work, belongs to the scope of protection of the invention.
The manufacture method that GaInP/GaAs/InGaAsP/InGaAs tetra-ties cascade solar cell is as follows:
1) growth of battery before bonding
Shown in ginseng Fig. 1, the GaAs resilient coating of the 0.2-1 μ m that first first grows on GaAs substrate, the sub-battery of GaAs of next growing, the second tunnel junction, the sub-battery of GaInP, 500 nmGaAs contact layers.
Shown in ginseng Fig. 2, first grow on the InP substrate InP resilient coating of 0.2-1 μ m, then the grow InGaAs etching stop layer of 0.1-1 μ m, the AlInAs sacrifice layer of 15nm, the InGaAs contact layer of 0.2-1 μ m, the InGaAs battery of the Lattice Matching of next growing, the first tunnel junction, InGaAsP battery, 20nm N++ InP bonded layer.
All batteries all adopt lattice-matched growth, can not relate to and not mate the difficulty that increases Material growth because of lattice; More can be because of lattice mismatch, epitaxial loayer Stress Release produces dislocation, and affects crystal mass, and then affects device performance.
2) bonding of wafer
Shown in ginseng Fig. 3, in the present embodiment, bonded interface is P++GaAs/N++InP, and P++GaAs needs doping content higher than 1.0 × 10
19/ cm
2; The doping content of N++InP also need be higher than 1.0 × 10
19/ cm
2.P++GaAs/N++InP bonding forms heterogeneous tunnel junction.
3) InP substrate desquamation
Shown in ginseng Fig. 4, after bonding completes, next carry out peeling off of InP substrate, adopt the method for wet etching, InP substrate need to do the back side and sidewall protection, and corrosive liquid is HCL: H
3pO
4=1:1.
Shown in ginseng Fig. 5, after substrate desquamation completes, make respectively positive and negative electrode on two surfaces of four junction battery sheets, complete the making of four-junction solar battery.
It should be noted that, in this article, relational terms such as the first and second grades is only used for an entity or operation to separate with another entity or operating space, and not necessarily requires or imply and between these entities or operation, have the relation of any this reality or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thereby the process, method, article or the equipment that make to comprise a series of key elements not only comprise those key elements, but also comprise other key elements of clearly not listing, or be also included as the intrinsic key element of this process, method, article or equipment.The in the situation that of more restrictions not, the key element being limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment that comprises described key element and also have other identical element.
The above is only the application's embodiment; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the application's protection range.
Claims (4)
1. GaInP/GaAs/InGaAsP/InGaAs tetra-ties a manufacture method for cascade solar cell, it is characterized in that, comprising:
(1) at the GaInP/GaAs binode battery of GaAs Grown and GaAs Lattice Matching, at the InGaAsP/InGaAs binode battery of InP Grown and InP Lattice Matching;
(2) by GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery bonding;
(3) peel off InP substrate, obtain and only have the GaInP/GaAs/InGaAsP/InGaAs tetra-of GaAs substrate supports to tie cascade solar cell.
2. GaInP/GaAs/InGaAsP/InGaAs tetra-according to claim 1 ties the manufacture method of cascade solar cell, it is characterized in that: described manufacture method specifically comprises:
1) the GaAs resilient coating of first growing on GaAs substrate, the sub-battery of GaAs of then growing, the second tunnel junction, the sub-battery of GaInP and ohmic contact layer,
Grown InP resilient coating first on InP substrate, the InGaAs etching stop layer of 0.1 ~ 1 μ m that then grows, AlInAs sacrifice layer, the ohmic contact layer of 0.2 ~ 1 μ m, the sub-battery of InGaAs of next growing, the first tunnel junction, the sub-battery of InGaAsP and bonded layer;
2), by the bonded layer bonding of the GaAs substrate surface of GaInP/GaAs binode battery and InGaAsP/InGaAs binode battery, form tunnel junction;
3) adopt the method for wet etching to peel off InP substrate;
4) make positive and negative electrode, obtain and only have the GaInP/GaAs/InGaAsP/InGaAs tetra-of GaAs substrate supports to tie cascade solar cell.
3. GaInP/GaAs/InGaAsP/InGaAs tetra-according to claim 2 ties the manufacture method of cascade solar cell, it is characterized in that: in described step 3), the corrosive liquid volume of wet etching is than being HCL: H
3pO
4=1:1.
4. the GaInP/GaAs/InGaAsP/InGaAs tetra-of the arbitrary described method making of claims 1 to 3 ties cascade solar cell.
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| CN107546293A (en) * | 2016-06-28 | 2018-01-05 | 江苏宜兴德融科技有限公司 | Double-junction solar battery and preparation method thereof, solar cell epitaxial structure |
| CN111276559A (en) * | 2020-02-17 | 2020-06-12 | 扬州乾照光电有限公司 | Solar cell structure and preparation method thereof |
| CN111463303A (en) * | 2020-04-21 | 2020-07-28 | 扬州乾照光电有限公司 | High-voltage series structure multi-junction solar cell and manufacturing method thereof |
| CN111947777A (en) * | 2020-08-12 | 2020-11-17 | 广州大学 | Gallium arsenide/indium phosphide quantum sensor and use method thereof |
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