CN104282795B - The preparation method of GaInP/GaAs/InGaAs/Ge solar cells - Google Patents
The preparation method of GaInP/GaAs/InGaAs/Ge solar cells Download PDFInfo
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- CN104282795B CN104282795B CN201310275857.XA CN201310275857A CN104282795B CN 104282795 B CN104282795 B CN 104282795B CN 201310275857 A CN201310275857 A CN 201310275857A CN 104282795 B CN104282795 B CN 104282795B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims abstract description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
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Classifications
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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
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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
Abstract
The present invention relates to a kind of preparation method of GaInP/GaAs/InGaAs/Ge solar cells, including Ge junction batteries and GaInP/GaAs/InGaAs battery packs are made, be characterized in：Also include the n+GalnP of Ge junction batteries2Face and the p+AlGaAs faces of GaInP/GaAs/InGaAs battery packs be surface-treated, be bonded, anneal after, GaAs substrates, cushion and the GaInP etch stop layers in GaInP/GaAs/InGaAs battery packs are peeled off successively, and GaInP/GaAs/InGaAs/Ge solar cells are made after encapsulation.The present invention is by two battery low-temperature bondings, and technique is simple, not warpage, do not crush, the GaInP/GaAs/InGaAs/Ge solar cell energy gaps being made reach 1.9/1.4/1.0/0.67eV.
Description
Technical field
The invention belongs to solar cell manufacture technology field, more particularly to a kind of GaInP/GaAs/InGaAs/Ge is too
The preparation method of positive energy battery.
Background technology
In the case where the energy crisis of the eighties of last century initiation seventies is irritated, field of photovoltaic technology constantly makes a breakthrough.Crystalline silicon
Solar cell, non-crystal silicon solar cell, amorphous silicon thin-film solar cell, Group III-V compound semiconductor solar-electricity
Pond, II-VI group compound semiconductor polycrystal film solar cell etc., increasing solar battery technology reaches its maturity.
The continuous improvement of photoelectric transformation efficiency and the lasting reduction of manufacturing cost so that photovoltaic technology is obtained for extensively in space and ground
General application.Meanwhile, with the energy crisis of global range and going from bad to worse for ecological environment problem, people are this to solar energy
Inexhaustible green energy resource is increasingly paid attention to, and studies the solar energy of high conversion efficiency diligently for a long time
Battery.Wherein, multijunction solar cell expands battery using the sub- battery combination Cheng Xin of different energy gaps structure mostly
To the absorption region of solar spectrum, to realize the high efficiency of battery, its photoelectric transformation efficiency increases with increasing for number of knot.Cause
This, as three-joint solar cell structure is gradually improved, based on the knot of GaAs systems four and more multijunction cell also receives this area
The very big concern of technical staff.
Since 2005, several famous seminar in the world, such as NREL, Toyota, the summer of Emcore and Japan
The research of the solar battery structure for increasingly focusing on lattice mismatch such as general.By the adjustment of band-gap energy, inversion is utilized
The efficiency of InGaAs/ (In) GaAs/lnGaP batteries of method growth was carried from 38.9% (81 times of optically focused, AM1.5D) of 2007
40.8% (326 times of optically focused, AM1.5G) of high to 2008.Professor EickeWeber of fraunhofer research institute of Germany leads recently
The research group led three knot GalnP/GalnAs/Ge solar battery efficiencies have been brought up to 41.1% (454 times of optically focused,
AM1.5G)。
Nevertheless, the structure design of lattice mismatch depends on high-quality Material growth, and big lattice mismatch is inevitable
Misfit dislocation is brought, so as to greatly increase non-radiative recombination, reduction battery efficiency.Which results in four knot tandems of direct growth
Efficiency of the efficiency of battery on the contrary than three knots is low.And according to Shockley-Quisser models, four knot band-gap energies are 1.9/
1.4/1.0/0.67eV solar cell can obtain the conversion efficiency more than 45%.
The most preferable energy gap of four-junction solar cell is 1.9/1.4/1.0/0.7eV.Main preparation method now
It is, by extension back growth, first to grow the battery layers that Lattice Matching band-gap energy is 1.9/1.4eV, regrowth lattice mismatch band
Gap energy is 1.0eV battery layers, and last regrowth lattice mismatch band-gap energy is 0.7eV battery layers.Above-mentioned preparation method
Due to the battery layers of the 0.7eV of regrowth lattice mismatch in the 1.0eV of lattice mismatch battery layers, cause the presence of following ask
Topic：1st, the regrowth mismatched structures in the structure of lattice mismatch, component and lattice constant are controlled very by graded buffer layer
Greatly；2nd, be difficult to grow relaxivity very high epitaxial layer again in lattice mismatched structures, easily cause extension cell piece warpage or
It is broken；3, substantial amounts of defect dislocation is easily caused in battery epitaxial process, causes battery performance to be greatly reduced.
The content of the invention
The present invention provides a kind of making simply to solve technical problem present in known technology, and extension cell piece does not stick up
It is bent, do not crush, the preparation method of the high GaInP/GaAs/InGaAs/Ge solar cells of battery conversion efficiency.
The present invention adopts the following technical scheme that to solve technical problem present in known technology：
The preparation method of GaInP/GaAs/InGaAs/Ge solar cells, including make Ge junction batteries and GaInP/
GaAs/InGaAs battery packs, are characterized in：Also include following preparation process：
(1) by the n+GalnP of Ge junction batteries2Face and the p+AlGaAs faces of GaInP/GaAs/InGaAs battery packs carry out surface
Processing；The surface treatment is that surface particles number is less than 1000, roughness rms to be chemically mechanically polished to polished surface
RMS is less than after 10 angstroms, and it is that 40-50 millitorrs, radio-frequency power are that 50-100W, the gas flow rate of argon gas are 50- to carry out pressure
100sccm, etch period are the plasma-activated processing of argon plasma bombarded surface of 30-60 seconds；
(2) by the n+GalnP after (1) middle surface treatment2Face and p+AlGaAs faces are bonded integral after annealing；The bonding is
250-350 DEG C of temperature, time 3-5 hour, pressure is 1Mpa low-temperature bonding；The annealing temperature is 400-450 DEG C；
(3) GaAs substrates, cushion and the GaInP etching-stops in GaInP/GaAs/InGaAs battery packs are peeled off successively
Layer, completes the manufacturing process of GaInP/GaAs/InGaAs/Ge solar cells after encapsulation.
The present invention can also use following technical measures：
The Ge junction batteries are to be tied by MOCVD on the Ge substrates that N-type is mixed by spreading generation Ge, then epitaxial growth
3rd tunnel junctions, the 3rd tunnel junctions include n+GalnP2The Al of layer and p-type0.3Ga0.7As layers；The GaInP/GaAs/
InGaAs battery packs are by MOCVD grown buffer layer, GaInP etch stop layers, the first knot GaInP successively on gaas substrates
Battery, the first tunnel junctions, the second knot GaAs batteries, the second tunnel junctions, Inx(AlyGa1-y)1-xAs graded beddings and the 3rd knot InGaAs
Battery, the p+AlGaAs is the back surface field of the 3rd knot InGaAs batteries.
The step (3) in stripping means be chemical attack method；The corrosive liquid for peeling off GaAs substrates and cushion is
Volume ratio sulfuric acid：Hydrogen peroxide：Water=1：2：2；The corrosive liquid for peeling off GaInP etch stop layers is concentrated hydrochloric acid.
The present invention has the advantage that and good effect：
1st, the present invention is by bonding method, by the ripe Ge junction batteries of technical matters and GaInP/GaAs/InGaAs batteries
Group is directly connected to, and not only manufacture craft is simple, and connection mechanical strength is very high；And due to the low-temperature bonding and chip
Crystal orientation, lattice constant, crystal habit (monocrystalline, polycrystalline, amorphous or amorphous), doping type, doping concentration and unrelated, the institute of distribution
Do not limited with bonding technology by the lattice and crystal orientation of two kinds of wafer materials, can be very good to realize the combination of the big mismatch of lattice, together
When keep good optics, electrical interface and lattice quality, the taboo for the GaInP/GaAs/InGaAs/Ge solar cells being made
Bandwidth has reached 1.9/1.4/1.0/0.67eV.
2nd, the present invention is due to using low-temperature bonding, it is to avoid four knot GaInP/GaAs/InGaAs/Ge solar cells are in system
Occur piece warpage, Fragmentation Phenomena during work, improve the qualification rate of battery, reduce the cost of manufacture of battery.
Brief description of the drawings
Fig. 1 is Ge junction battery structural representations；
Fig. 2 is three knot GaInP/GaAs/InGaAs battery pack structure schematic diagrames；
Fig. 3 is that Fig. 1 and Fig. 2 batteries are bonded integral structural representation by the present invention；
Fig. 4 is the GaInP/GaAs/InGaAs/Ge solar cell schematic diagrames that the present invention is made.
Label in figure is respectively：1-Ge substrates；2-Ge is tied；The tunnel junctions of 3- the 3rd；The knot InGaAs batteries of 4- the 3rd；5-
Inx(AlyGa1-y)1-xAs graded beddings；The tunnel junctions of 6- second；7- the second knot GaAs batteries；The tunnel junctions of 8- first；The knots of 9- first
GaInP batteries；10-GaInP etch stop layers；11- cushions；12-GaAs substrates.
Embodiment
Further to disclose the invention, features and effects of the present invention, especially exemplified by following instance and with reference to accompanying drawing 1-4
It is described in detail as follows.
The preparation method of GaInP/GaAs/InGaAs/Ge solar cells, including make Ge junction batteries and GaInP/
GaAs/InGaAs battery packs.
The present invention includes following innovative point：
(1) by the n+GalnP of Ge junction batteries2Face and the p+AlGaAs faces of GaInP/GaAs/InGaAs battery packs carry out surface
Processing；
(2) by the n+GalnP after (1) middle surface treatment2Face and p+AlGaAs faces are bonded integral after annealing；
(3) GaAs substrates, cushion and the GaInP etching-stops in GaInP/GaAs/InGaAs battery packs are peeled off successively
Layer, completes the manufacturing process of GaInP/GaAs/InGaAs/Ge solar cells of the present invention after encapsulation.
It is described (2) in bonding be low-temperature bonding that 250-350 DEG C of temperature, time 3-5 hour, pressure are 1Mpa；It is described to move back
Fiery temperature is 400-450 DEG C.
It is described (1) in Ge junction batteries be by MOCVD on the Ge substrates that N-type is mixed by spreading generation Ge knots, it is then outer
The tunnel junctions of epitaxial growth the 3rd, the 3rd tunnel junctions include n+GalnP2The Al of layer and p-type0.3Ga0.7As layers；It is described (1) in
GaInP/GaAs/InGaAs battery packs be by MOCVD on gaas substrates successively grown buffer layer, GaInP etch stop layers,
First knot GaInP batteries, the first tunnel junctions, the second knot GaAs batteries, the second tunnel junctions, Inx(AlyGa1-y)1-xAs graded beddings and
3rd knot InGaAs batteries, the p+AlGaAs is the back surface field of the 3rd knot InGaAs batteries.
It is described (1) in surface treatment for be chemically mechanically polished to polished surface be surface particles number be less than 1000, roughness
Root-mean-square value RMS is less than after 10 angstroms, and progress pressure is 40-50 millitorrs, and radio-frequency power is 50-100W, and the gas flow rate of argon gas is
50-100sccm, etch period is the plasma-activated processing of argon plasma bombarded surface of 30-60 seconds.
It is described (3) in stripping means be chemical attack method；The corrosive liquid for peeling off GaAs substrates and cushion is volume
Compare sulfuric acid：Hydrogen peroxide：Water=1：2：2；The corrosive liquid for peeling off GaInP etch stop layers is concentrated hydrochloric acid.
Embodiment：
1. make Ge junction batteries as shown in Figure 1：It is metal organic chemical vapor deposition technology in Ge substrates using MOCVD
1 diffusion generation Ge knots 2, then the tunnel junctions 3 of epitaxial growth the 3rd above；3rd tunnel knot includes the outermost n+ of Ge junction batteries
GalnP2Face and the Al of p-type0.3Ga0.7As layers, the growth temperature for making Ge junction batteries is 500 DEG C -800 DEG C, and doping concentration 1 ×
1018-1×1020cm-3, the thickness 10nm-50nm of Ge junction batteries；
2. make GaInP/GaAs/InGaAs battery packs as shown in Figure 2：It is Metallo-Organic Chemical Vapor using MOCVD
Deposition technique grown buffer layer 11, GaInP etch stop layers 10, the first knot GaInP batteries 9, successively on GaAs substrates 12
One tunnel junctions 8, the second knot GaAs batteries 7, the second tunnel junctions 6, Inx(AlyGa1-y)1-xThe knot InGaAs of As graded beddings 5 and the 3rd electricity
Pond 4, wherein the back surface field of the 3rd knot InGaAs batteries is p+AlGaAs faces；The In of epitaxial growthx(AlyGa1-y)1-xIn As graded beddings,
0.03≤x≤0.3,0.5≤y≤0.7；The growth temperature for making GaInP/GaAs/InGaAs battery packs is 500 DEG C -800
DEG C, doping concentration 1 × 1017-1×1019cm-3, battery pack 2-5 μm of thickness；
3. the n+GalnP of pair Ge junction batteries2Face and the p+AlGaAs faces of GaInP/GaAs/InGaAs battery packs are used as two
Two bonded interfaces are chemically-mechanicapolish polished the rough polishing in (CMP), essence and thrown and water throwing, then carried out by bonded interface respectively
Surface plasma is activated；Wherein rough polishing is using 60-70nm silica sol granules as mechanical abrasive material, and essence, which is thrown, uses 10-20nm silicon
Sol particle is as mechanical abrasive material, and the slurry oxidant in chemically mechanical polishing is H2O2, polyhydroxy polyamines organic base adjusts as pH value
Agent is saved, pH value 10-11 is adjusted to, the granule number of two after water throwing bonded interface is respectively less than 1000, roughness rms
After RMS is respectively less than 10, two bonded interfaces are carried out pressure be 40-50 millitorrs, the gas that radio-frequency power is 50-100W, argon gas
The argon plasma bombarded surface activation process that flow velocity is 50-100sccm, etch period is 30-60 seconds；
4. by the n+GalnP after surface treatment2It is 250-350 DEG C that trip temperature is entered in face and p+AlGaAs faces, and the time is that 3-5 is small
When, pressure be 1Mpa low-temperature bonding, 400-450 DEG C of low-temperature bonding laggard trip temperature, annealing, naturally cool to room
Temperature, Ge junction batteries and the bonding of GaInP/GaAs/InGaAs battery packs are integral, as shown in Figure 3；
5. it is volume ratio sulfuric acid by corrosive liquid：Hydrogen peroxide system：Water=1：2：2, GaInP/GaAs/ is peeled off successively
GaAs substrates, cushion in InGaAs battery packs, GaInP etch stop layers are peeled off by concentrated hydrochloric acid, are completed after encapsulation
The manufacturing process of GaInP/GaAs/InGaAs/Ge solar cells of the present invention as shown in Figure 4.
Although the preferred embodiments of the present invention are described above in conjunction with accompanying drawing, the invention is not limited in upper
The embodiment stated, above-mentioned embodiment is only schematical, be not it is restricted, this area it is common
Technical staff in the case of present inventive concept and scope of the claimed protection is not departed from, may be used also under the enlightenment of the present invention
To make many forms.These are belonged within protection scope of the present invention.
Claims (3)
- The preparation method of 1.GaInP/GaAs/InGaAs/Ge solar cells, including make Ge junction batteries and GaInP/GaAs/ InGaAs battery packs, it is characterised in that：Also include following preparation process：(1) by the n+GalnP of Ge junction batteries2Face and the p+AlGaAs faces of GaInP/GaAs/InGaAs battery packs are surface-treated； The surface treatment is that surface particles number is less than 1000 to be chemically mechanically polished to polished surface, and roughness rms RMS is small In after 10 angstroms, it is that 40-50 millitorrs, radio-frequency power are that 50-100W, the gas flow rate of argon gas are 50-100sccm, quarter to carry out pressure The erosion time is the plasma-activated processing of argon plasma bombarded surface of 30-60 seconds；(2) by the n+GalnP after (1) middle surface treatment2Face and p+AlGaAs faces are bonded integral after annealing；The bonding is temperature 250-350 DEG C, time 3-5 hour, pressure is 1Mpa low-temperature bonding；The annealing temperature is 400-450 DEG C；(3) GaAs substrates, cushion and the GaInP etch stop layers in GaInP/GaAs/InGaAs battery packs are peeled off successively, The manufacturing process of GaInP/GaAs/InGaAs/Ge solar cells is completed after encapsulation.
- 2. the preparation method of GaInP/GaAs/InGaAs/Ge solar cells according to claim 1, it is characterised in that： The Ge junction batteries are to be tied by MOCVD on the Ge substrates that N-type is mixed by spreading generation Ge, then the tunnelling of epitaxial growth the 3rd Knot, the 3rd tunnel junctions include n+GalnP2The Al of layer and p-type0.3Ga0.7As layers；The GaInP/GaAs/InGaAs batteries Group is by MOCVD grown buffer layer, GaInP etch stop layers, the first knot GaInP batteries, first successively on gaas substrates Tunnel junctions, the second knot GaAs batteries, the second tunnel junctions, Inx(AlyGa1-y)1-xAs graded beddings and the 3rd knot InGaAs batteries, it is described P+AlGaAs is the back surface field of the 3rd knot InGaAs batteries.
- 3. the preparation method of GaInP/GaAs/InGaAs/Ge solar cells according to claim 1, it is characterised in that： The step (3) in stripping means be chemical attack method；The corrosive liquid for peeling off GaAs substrates and cushion is volume ratio sulphur Acid：Hydrogen peroxide：Water=1：2：2；The corrosive liquid for peeling off GaInP etch stop layers is concentrated hydrochloric acid.
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| CN105576068B (en) * | 2015-12-17 | 2017-03-22 | 中国电子科技集团公司第十八研究所 | Double-face-growing InP five-junction solar battery |
| CN106252451B (en) * | 2016-09-27 | 2018-08-28 | 中国电子科技集团公司第十八研究所 | Five knot stacked solar cell, cascade solar cells of one kind and preparation method thereof |
| CN110534607A (en) * | 2018-05-25 | 2019-12-03 | 中国电子科技集团公司第十八研究所 | A GaInP/GaAs/μ c-Si: h three-junction laminated solar cell |
| CN111463303B (en) * | 2020-04-21 | 2022-06-10 | 扬州乾照光电有限公司 | High-voltage series structure multi-junction solar cell and manufacturing method thereof |
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| CN102790117A (en) * | 2012-07-19 | 2012-11-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | GaInP/GaAs/InGaNAs/Ge four-junction solar cell and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807626A (en) * | 2010-03-17 | 2010-08-18 | 中国科学院半导体研究所 | GaAs/InP chip low-temperature direct bonding method for multi-junction solar cell |
| CN101859813A (en) * | 2010-05-07 | 2010-10-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for manufacturing quadri-junction GaInP/GaAs/InGaAs/Ge solar cells |
| CN102790117A (en) * | 2012-07-19 | 2012-11-21 | 中国科学院苏州纳米技术与纳米仿生研究所 | GaInP/GaAs/InGaNAs/Ge four-junction solar cell and preparation method thereof |
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