CN103000759A - Preparation method of gallium arsenide thin-film multijunction stacked solar cells - Google Patents

Preparation method of gallium arsenide thin-film multijunction stacked solar cells Download PDF

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CN103000759A
CN103000759A CN2012103781634A CN201210378163A CN103000759A CN 103000759 A CN103000759 A CN 103000759A CN 2012103781634 A CN2012103781634 A CN 2012103781634A CN 201210378163 A CN201210378163 A CN 201210378163A CN 103000759 A CN103000759 A CN 103000759A
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battery
thickness
layer
gaas
doping
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CN103000759B (en
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高鹏
王帅
刘如彬
康培
孙强
穆杰
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Cetc Blue Sky Technology Co ltd
Cetc Energy Co ltd
Tianjin Lantian Solar Tech Co ltd
CETC 18 Research Institute
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Tianjin Lantian Solar Tech Co ltd
CETC 18 Research Institute
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Abstract

The invention relates to a preparation method of gallium arsenide thin-film multijunction stacked solar cells. The preparation method is characterized by including the steps of firstly, allowing for reverse growth of an epitaxial layer to prepare a GaAs three-junction solar cell; secondly, bonding the cell prepared in the step 1 to a Si substrate; thirdly, stripping a Ge substrate; fourthly, adhering a low-cost substrate; and fifthly, stripping the Si substrate. The preparation method allows for epitaxial growth of a top cell and an intermediate cell prior to growth of a bottom cell, and accordingly the lattice subjected to epitaxial growth firstly is guaranteed to match with perfect epitaxial growth of the top cell and the intermediate cell; doping uniformity and film reliability in large-area epitaxial thin films are increased, and photoelectric conversion efficiency is further improved; by the use of the low-cost support substrate lower than Ge in specific weight, the weight of the cells is reduced, the power ratio of the solar cells is increased, the cost of the cells is reduced effectively, and application prospect of the III-V compound solar cells is improved greatly.

Description

Gallium arsenide film is tied the preparation method of stacked solar cell, cascade solar cell more
Technical field
The invention belongs to technical field of solar cells, particularly relate to the preparation method that a kind of gallium arsenide film is tied stacked solar cell, cascade solar cell more.
Background technology
Product type at photovoltaic market upper film solar cell mainly contains Si based thin film solar cell, CIGS thin-film solar cells and CdTe hull cell etc. at present.These thin-film solar cells can be divided into rigidity (being glass substrate) battery and flexibility (stainless steel or polyester film substrate) battery according to backing material.The common crystal Si solar cell that is about 180 microns-200 microns with thickness is compared, the thin-film material thickness of thin-film solar cells is no more than 50 microns, reduced in a large number the battery material, the application scale in photovoltaic market enlarges gradually, accounts for the market share more than 13% in 2010.But various hull cells have some insoluble bottleneck problems, as: 1., the Si based thin film solar cell, no matter unijunction, binode or three junction batteries, manufacturing process all is chemical vapour deposition (CVD) (PECVD) method that using plasma strengthens, the cleaning of vacuum chamber is fluoride (SF6 or NF3) substantially, and effluent is fluoro-gas.Holland scientist Rob van der Meulen etc. are at the Progress in of the 19th phase in 2011 the photovoltaics:Research and Applications title of publishing an article, and this fluoro-gas compares CO to the greenhouse effect that environment causes 2High 17200-22800 doubly.Solar energy power generating is considered to green electricity all the time, also should adopt green technique so in making link.For Si base film battery manufacturer, the scheme that new purge gas substitutes current fluoride of seeking is arranged, reduce greenhouse gas emission.Another kind of scheme is to improve as early as possible the conversion efficiency of battery, when stabilization efficiency reaches 12%-16%, just might compensate the greenhouse gas of discharging to the impact of environment.In addition because Si film assembly efficient low (5%-7%), unit generated output floor space almost is 2 times of crystal Si assembly (efficient is 13%-15%) in photovoltaic system is used, correspondingly, the cost of unit generated output also will increase, and the photoelectric conversion efficiency that as seen improves the Si based thin film solar cell is the essential condition of winning the market; 2., the CIGS thin-film solar cells, the mass production successful story be Japan SolarFrontier company (predecessor is Showa Shell company); The PV-tech.com website has also been reported the Switzerland scientist in May, 2011 and has been prepared the CIGS battery of 18.7% conversion efficiency in flexible plastic substrate, and the major advantage of flexible battery is to adopt volume to volume technique to reduce manufacturing cost.The technology path of CIGS film is to adopt the evaporation technique sputter to add rear selenization, and the selenization process can produce toxic gas, and evaporation technique is difficult to guarantee uniformity and the reliability of large tracts of land CIGS film, comprises uniformity and the reliability of micro-structural, optics, electricity and the thickness etc. of film; 3., the CdTe hull cell is because material cost is high.People have begun to seek new thin-film material and have prepared solar cell.
Based on the bottleneck problem of said film battery, people search out a kind of typical III-V group iii v compound semiconductor material GaAs, and it has direct band gap, band gap width is 1.42eV(300K), just in time being the function of the value of high-absorbility sunlight, therefore, is very desirable solar cell material.Its main feature: 1. photoelectric conversion efficiency is high: GaAs base solar cell satisfies required material and the structure of solar spectrum coupling, and its photoelectric conversion efficiency record represents the highest photoelectric conversion efficiency of the solar battery record of our times; 2. can be made into film and ultrathin solar cell: GaAs is direct transition shaped material, in visible-range, GaAs optical absorption of materials coefficient is far above the Si material, same 95% the sunlight that absorbs, the GaAs solar cell only needs the thickness of 5-10 μ m, and the Si solar cell then needs greater than 150 μ m, therefore, the GaAs solar cell can be made film-type, and quality can significantly reduce; 3. resistance to elevated temperatures is good: the GaAs solar battery efficiency reduces slower with the temperature rising, can be operated in higher temperature range; 4. anti-radiation performance is strong: GaAs is the direct band gap material, and minority carrier lifetime is shorter, is producing damage from knot outside several diffusances, and all without affecting, therefore, the GaAs solar cell has preferably anti-radiation performance on photoelectric current and dark current; 5. tie the material of stacked solar cell, cascade solar cell more.(the semiconductor material growing technology such as GaInP, AlGaInP, GaInAs are increasingly mature, make the design of battery more flexible, tool the improve a lot efficient of solar cell and the space that reduces cost because III-V family three, quaternary compound.Because These characteristics, GaAs thin film solar cell have become the focus of insider's research.
Find that through retrieval application publication number is the patent of invention that CN101764165A, name are called multijunction gallium arsenide solar cell, comprises main employing MOVPE technique, at P type Ge Grown GaInP/InGaAs/Ge three knot stacked solar cell, cascade solar cells; The top battery that formation is made of GaInP, the middle battery and the main end battery that is made of Ge that mainly are made of InGaAs are provided with AlInP(P between top battery and middle battery +)/AlGaAs(P ++)-GaInP(n ++)/AlInP(n +) the tunnel junctions syndeton, the present invention not only can significantly reduce the incident reflection of light owing to adopted above tunnel junctions syndeton, and the current density of battery in the improvement has also improved the conversion efficiency of three junction batteries.But this structure has limited the development progress of three-junction gallium arsenide solar battery owing to there is the contradiction of top battery and middle battery short circuit currents match.
Also find through retrieval, application publication number is the patent of invention that CN102339890A, name are called novel three-junction gallium arsenide solar battery, the present invention mainly adopts MOCVD technique, battery at the bottom of P type Ge Grown/middle battery/top battery, the present invention is owing to introduce quantum-dot structure in the middle battery intrinsic region, form Intermediate Gray, utilize the strain compensation layer, solved top battery and the unmatched problem of middle battery current; And the quantum dot density on the quantum dot layer reaches 10 11Every square centimeter, solve the inhomogeneous problem of overall dimensions, and improved the conversion efficiency of battery, AMO, under the solar irradiation, expection can be near 40%.But since at the bottom of P type Ge Grown battery/middle battery/top battery, still have lattice mismatch issue, affect the further raising of photoelectric conversion efficiency, and increased battery weight, improved the cost of battery.
Summary of the invention
The present invention provides uniformity and the reliability of a kind of further raising photoelectric conversion efficiency and large area film for solving the technical problem that exists in the known technology, and the gallium arsenide film lightweight, that cost is low is tied the preparation method of stacked solar cell, cascade solar cell more.
The preparation method that gallium arsenide film of the present invention is tied stacked solar cell, cascade solar cell more adopts following technical scheme:
Gallium arsenide film is tied stacked solar cell, cascade solar cell more, is characterized in comprising following preparation process:
Step 1, epitaxial loayer back growth prepare the GaAs three-junction solar battery
The Ge substrate is placed in the MOCVD operating room, growth temperature is set to 500 ℃-800 ℃, on the Ge substrate successively epitaxial growth thickness be the GaInP etch stop layer of GaAs resilient coating, the thickness 0.1-0.3 micron of 0.1-0.3 micron, N-shaped Doped GaAs cap layer that thickness is 100-500nm, the first knot GaInP battery as the top battery, the first tunnel junctions, as in the second knot GaAs battery, the second tunnel junctions, the thickness of battery be the N-shaped doping In of 2-5 μ m x(Al yGa 1-y) 1-xThe As graded bedding and as end battery the 3rd the knot In xGa 1-xThe As battery; Described In x(Al yGa 1-y) 1-x0.03≤x in the As graded bedding≤0.3,0.5≤y≤0.7, described GaAs cap layer and In x(Al yGa 1-y) 1-xThe N-shaped doping content of As graded bedding is 1 * 10 17-1 * 10 18Cm -3, the GaAs three-junction solar battery of formation epitaxial loayer back growth;
Battery and the Si substrate bonding of step 2, step 1 preparation
Behind the one side of the Si sheet after cleaning spin coating BCB glue, stick on the 3rd knot In of step 1 xGa 1-xOn the As battery face, insert the bonding chamber of bonder, bonding is full of N in the chamber 2, when the temperature in the bonding chamber is risen to 80-150 ℃, battery and Si sheet are carried out the 60-120 precuring of second; Then the para-linkage chamber applies the bonding pressure of 1-5kN, when the speed that heats up with 15 ℃/min rises to 250-300 ℃ with the bonding cavity temperature, keep constant temperature, battery and Si sheet carried out 1-2 hour bonding, then the speed with 3 ℃/min cooling drops to room temperature with the temperature in the bonding chamber, and battery and Si substrate form low-temperature bonding;
Step 3, peel off the Ge substrate
Use HF:H 2O 2: H 2O=2:1:1 corrosive liquid corrosion Ge substrate and GaAs resilient coating, Ge substrate and GaAs resilient coating are used HCl: H after being stripped from from battery 2O=1:1 corrosive liquid corrosion GaInP etch stop layer, the GaInP etch stop layer is stripped from from battery, finishes peeling off of Ge substrate;
Step 4, bonding inexpensive substrate
Adopt a kind of material of glass, stainless steel or polyester film as inexpensive substrate, the battery that step 3 is finished is inverted, inexpensive substrate is pasted on the first knot GaInP battery, inexpensive substrate bonding;
Step 5, peel off the Si substrate
Use BCB glue to remove liquid, the battery that step 4 is finished is immersed in ultrasonic erosion in the BCB glue removal liquid, corrosion temperature is room temperature, time 5-10min, supersonic frequency is 700-1000KHz, and BCB glue is corroded, and the Si substrate on the battery together is stripped from thereupon, with deionized water ultrasonic cleaning battery 5 minutes, be the concentrated sulfuric acid: H with volume ratio again 2O 2The SC3 liquid ultrasonic cleaning battery that=3:1 configures 5 minutes; After taking out in 5 minutes with deionized water ultrasonic cleaning battery more at last, namely make gallium arsenide film of the present invention and tie stacked solar cell, cascade solar cell more.
The preparation method that gallium arsenide film of the present invention is tied stacked solar cell, cascade solar cell more can also adopt following technical measures:
Described the first knot GaInP battery of ⑵, the first tunnel junctions, the second knot GaAs battery, the second tunnel junctions, the 3rd knot In in the step 1 xGa 1-xThe As battery comprises respectively following growth course:
The first knot GaInP battery: be grown to successively the p-type doped with Al GaInP back surface field layer of thickness 100-200nm, the p-type doping GaInP base of thickness 1000-2000nm, the N-shaped doping GaInP emitter region of thickness 50-200nm, the N-shaped doped with Al InP Window layer of thickness 30-100nm; Wherein: the doping content of p-type doped with Al GaInP back surface field layer is 1 * 10 17-1 * 10 19Cm -3, the doping content of p-type doping GaInP base is 1 * 10 16-1 * 10 17Cm -3, the doping content of N-shaped doping GaInP emitter region is 1 * 10 17-1 * 10 19Cm -3, the doping content of N-shaped doped with Al InP Window layer is 1 * 10 17-1 * 10 19Cm -3
The first tunnel junctions: be grown to successively the N-shaped GaAs layer of thickness 10nm-100nm and the p-type Al of thickness 10nm-100nm 0.4Ga 0.6The As layer; Wherein: the doping content of N-shaped GaAs layer is 1 * 10 18-1 * 10 20Cm -3, p-type Al 0.4Ga 0.6The doping content of As layer is 1 * 10 18-1 * 10 20Cm -3
The second knot GaAs battery: the p-type doped with Al that is grown to successively thickness 100-200nm xGa 1-xThe p-type Doped GaAs base of As back surface field layer, thickness 3000-4000nm, the N-shaped Doped GaAs emitter region of thickness 50-200nm, the N-shaped doped with Al of thickness 30-100nm xGa 1-xThe As Window layer; Wherein: the p-type doped with Al xGa 1-xThe doping content of As back surface field layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5; The doping content of p-type Doped GaAs base is 1 * 10 16-1 * 10 18Cm -3, the doping content of N-shaped Doped GaAs emitter region is 1 * 10 17-1 * 10 19Cm -3, the N-shaped doped with Al xGa 1-xThe doping content of As Window layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5;
The second tunnel junctions: be grown to successively the N-shaped GaAs layer of thickness 10nm-100nm and the p-type Al of thickness 10nm-100nm 0.4Ga 0.6The As layer; Wherein: the doping content of N-shaped GaAs layer is 1 * 10 18-1 * 10 20Cm -3, p-type Al 0.4Ga 0.6The doping content of As layer is 1 * 10 18-1 * 10 20Cm -3
The 3rd knot In xGa 1-xAs battery: the N-shaped doping In that is grown to successively thickness 100-300nm x(Al yGa 1-y) 1-xAs Window layer, thickness are the N-shaped doping In of 200-400nm xGa 1-xAs emitter region, thickness are the p-type doping In of 1500-2000nm xGa 1-xAs base, thickness are the p-type doping In of 100-200nm x(Al yGa 1-y) 1-xAs back surface field layer, thickness are the p-type doping In of 500-800nm x(Al yGa 1-y) 1-xAs cap layer; Wherein: N-shaped doping In x(Al yGa 1-y) 1-xThe doping content of As Window layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7, N-shaped doping In xGa 1-xThe doping content of As emitter region is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5(x of the present invention preferred value be 0.4), p-type doping In xGa 1-xThe doping content of As base is 1 * 10 16-1 * 10 18Cm -3, 0.3≤x≤0.5(x of the present invention preferred value be 0.4), p-type doping In x(Al yGa 1-y) 1-xThe doping content of As back surface field layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7, p-type doping In x(Al yGa 1-y) 1-xThe doping content of As cap layer is 1 * 10 18-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7.
Si sheet in the step 2 is the p-type Si sheet of thickness 400-500 micron, cleans the Si sheet and dries up according to the cleaning process shown in the table 1:
The cleaning process of table 1Si sheet
Solution Time (Min) Temperature (℃) Frequency (KHz)
1 Deionized water 5 27 700-1000
2 SC1 5 80 700-1000
3 Deionized water 5 27 700-1000
4 SC2 5 80 700-1000
5 Deionized water 5 27 700-1000
6 SC3 5 80 700-1000
7 Deionized water 5 27 700-1000
8 DHF solution 5 27 700-1000
9 Deionized water 5 27 700-1000
10 N 2Air-blowing is done 2 27 700-1000
Wherein: SC1(15%NH 3.H 20+15%H 2O 2+ 70%H 2O, volume ratio)
SC2(15%HCl+15%H 20 2+ 70%H 20, volume ratio)
The SC3(concentrated sulfuric acid: H 20 2=3:1, volume ratio)
DHF (HF:H 20=1:10, volume ratio).
The advantage that the present invention has and good effect:
1, the present invention is by adopting top battery and the intermediate cell of first epitaxial growth Lattice Matching, the battery at the bottom of the InGaAs of a lattice mismatch of growing at last substitutes the reverse growth technology of battery at the bottom of the Ge, the microcell defective that lattice mismatch is produced extends to the upper strata, has guaranteed at first epitaxially grown Lattice Matching top battery and the perfect epitaxial growth of intermediate cell; Connect by the material Direct Bonding of low-temperature bonding technology with the serious mismatch of lattice again, a large amount of dislocations that lattice mismatch produces and defective also all are limited near the coating region of the several nanometers of bonded interface, namely can be to the performance of other region material, uniform doping and the film reliability of large tracts of land epitaxial film have also effectively been improved, further improved photoelectric conversion efficiency, under AMO, the solar irradiation, photoelectric conversion efficiency can reach more than 40%;
2, the present invention adopts lift-off technology, and multi-junction gallium arsenide film epitaxial layer and epitaxially grown Ge substrate desquamation are opened; Employing proportion is lighter than the cheap support substrates of Ge, has namely alleviated the weight of battery, has promoted the power ratio of solar cell, effectively reduces again the cost of battery, has greatly promoted the application prospect of III-V compounds of group solar cell.
Description of drawings
Fig. 1 is the GaAs three-junction solar battery structural representation that forms the epitaxial loayer back growth in the preparation process of the present invention;
Fig. 2 is the structural representation of Fig. 1 battery and Si bonding;
Fig. 3 is the structural representation of peeling off in Fig. 2 battery;
Fig. 4 is the structural representation of bonding inexpensive substrate on Fig. 3 battery;
Fig. 5 is that the gallium arsenide film that the present invention prepares is tied the stacked solar cell, cascade solar cell structural representation more.
Label among the figure is respectively: 1-the 3rd knot In xGa 1-xThe As battery; 2-In x(Al yGa 1-y) 1-xThe As graded bedding; 3-the second tunnel junctions; 4-the second knot GaAs battery; 5-the first tunnel junctions; 6-the first knot GaInP battery; The 7-GaInP etch stop layer; The 8-GaAs resilient coating; The 9-Ge substrate; 10-BCB glue; The 11-Si substrate; The 12-inexpensive substrate.
Embodiment
For further disclosing summary of the invention of the present invention, Characteristic, also be elaborated by reference to the accompanying drawings as follows especially exemplified by following instance.
Embodiment: consult accompanying drawing 1-Fig. 5:
Step 1, epitaxial loayer back growth prepare the GaAs three-junction solar battery
⑴ select the Ge sheet of N-shaped doping as Ge substrate 9, and the thickness of Ge sheet is 150-200 micron (the preferred thickness of the present invention is 150 microns), and doping content is 1 * 10 17-1 * 10 18Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
⑵ adopt MOCVD equipment, above the Ge substrate in ⑴ successively the GaAs cap layer that mixes of epitaxial growth GaAs resilient coating 8, GaInP etch stop layer 7, N-shaped, the first knot GaInP battery 6 as the top battery, the first tunnel junctions 5, as in the In that mixes of the second knot GaAs battery 4, the second tunnel junctions 3, the N-shaped of battery x(Al yGa 1-y) 1-xAs graded bedding 2 and as end battery the 3rd the knot In xGa 1-xAs battery 1, growth temperature are 500 ℃-800 ℃ (the preferred temperature of the present invention is 600 ℃);
Wherein:
1. the GaAs resilient coating is as the nucleating layer of growth GaAs sill, and thickness is 0.1-0.3 micron (preferred thickness of the present invention is 0.2 micron);
2. the GaInP etch stop layer is as the corrosion control layer of peeling off epitaxial growth substrate, thickness 0.1-0.3 micron (preferred thickness of the present invention is 0.2 meter);
3. the GaAs cap layer that mixes of N-shaped (among the figure mark) is as forming the heavy doping epitaxial loayer of ohmic contact with metal electrode, and thickness is that 100-500nm(preferred thickness of the present invention is 200nm), doping content is 1 * 10 18-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
4. be grown to successively the AlGaInP back surface field layer of p-type doping, the GaInP base that p-type is mixed, the GaInP emitter region that N-shaped mixes, the AlInP Window layer that N-shaped mixes as the first knot GaInP battery of top battery;
Wherein:
The AlGaInP back surface field layer thickness that p-type is mixed is that 100-200nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
The GaInP base thickness that p-type is mixed is that 1000-2000nm(preferred thickness of the present invention is 1500nm), doping content is 1 * 10 16-1 * 10 17Cm -3(the preferred doping content of the present invention is 1 * 10 17Cm -3);
The GaInP emitter region thickness that N-shaped mixes is that 50-200nm(preferred thickness of the present invention is 100nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
The AlInP Window layer thickness that N-shaped mixes is that 30-100nm(preferred thickness of the present invention is 50nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
5. the first tunnel junctions is grown to the GaAs layer of N-shaped and the Al of p-type successively 0.4Ga 0.6The As layer;
Wherein:
The GaAs layer growth temperature of N-shaped is 500 ℃-800 ℃ (the preferred temperature of the present invention is 600 ℃), and doping content is 1 * 10 18-1 * 10 20Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), thickness range is that 10nm-100nm(preferred thickness of the present invention is 50nm);
The Al of p-type 0.4Ga 0.6As layer, doping content are 1 * 10 18-1 * 10 20Cm -3(the preferred doping content of the present invention is 1 * 10 19Cm -3), thickness range is that 10nm-100nm(preferred thickness of the present invention is 50nm);
6. second of battery the knot GaAs battery is grown to the Al that p-type is mixed successively in the conduct xGa 1-xThe Al that the GaAs emitter region that the GaAs base that As back surface field layer, p-type are mixed, N-shaped mix, N-shaped mix xGa 1-xThe As Window layer;
Wherein:
The Al that p-type is mixed xGa 1-xAs back surface field layer thickness is that 100-200nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4);
The GaAs base thickness that p-type is mixed is that 3000-4000nm(preferred thickness of the present invention is 3500nm), doping content is 1 * 10 16-1 * 10 18Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
The GaAs emitter region thickness that N-shaped mixes is that 50-200nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
The Al that N-shaped mixes xGa 1-xAs Window layer thickness is that 30-100nm(preferred thickness of the present invention is 50nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4);
7. the second tunnel junctions is grown to the GaAs layer of N-shaped and the Al of p-type successively 0.4Ga 0.6The As layer;
Wherein:
The GaAs layer thickness of N-shaped is that 10nm-100nm(preferred thickness of the present invention is 50nm), doping content is 1 * 10 18-1 * 10 20Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3);
The Al of p-type 0.4Ga 0.6As layer, doping content are 1 * 10 18-1 * 10 20Cm -3(the preferred doping content of the present invention is 1 * 10 19Cm -3), thickness range is that 10nm-100nm(preferred thickness of the present invention is 50nm);
8. the In that mixes of N-shaped x(Al yGa 1-y) 1-xThe As graded bedding is regulated epitaxial loayer as the lattice gradual change, and thickness is that 2-5 μ m(preferred thickness of the present invention is 3 μ m), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.03≤x≤0.3(x of the present invention is 0.1), the preferred value of 0.5≤y≤0.7(y of the present invention is 0.6);
9. tie In as the 3rd of end battery xGa 1-xThe As battery is grown to the In that N-shaped mixes successively x(Al yGa 1-y) 1-xThe In that As Window layer, N-shaped mix xGa 1-xThe In that As emitter region, p-type are mixed xGa 1-xThe In that As base, p-type are mixed x(Al yGa 1-y) 1-xThe In that As back surface field layer, p-type are mixed x(Al yGa 1-y) 1-xAs cap layer;
Wherein:
The In that N-shaped mixes x(Al yGa 1-y) 1-xAs Window layer thickness is that 100-300nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4), the preferred value of 0.5≤y≤0.7(y of the present invention is 0.6);
The In that N-shaped mixes xGa 1-xAs emitter region thickness is that 200-400nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4);
The In that p-type is mixed xGa 1-xAs base thickness is that 1500-2000nm(preferred thickness of the present invention is 1800nm), doping content is 1 * 10 16-1 * 10 18Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4);
The In that p-type is mixed x(Al yGa 1-y) 1-xAs back surface field layer thickness is that 100-200nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 17-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4), the preferred value of 0.5≤y≤0.7(y of the present invention is 0.6);
The In that p-type is mixed x(Al yGa 1-y) 1-xAs cap layer thickness is that 500-800nm(preferred thickness of the present invention is 150nm), doping content is 1 * 10 18-1 * 10 19Cm -3(the preferred doping content of the present invention is 1 * 10 18Cm -3), wherein the preferred value of 0.3≤x≤0.5(x of the present invention is 0.4), the preferred value of 0.5≤y≤0.7(y of the present invention is 0.6);
Above-mentioned preparation process namely forms the GaAs three-junction solar battery of extension back growth as shown in Figure 1.
Battery and Si substrate 11 bondings of step 2, step 1 preparation, the support substrates that the Si substrate shifts as the gallium arsenide epitaxy film epitaxial layer:
Select thickness be 400-500 micron, diameter be 4 inches p-type Si sheet as the Si substrate, clean the Si sheet and dry up according to the cleaning process shown in the table 1:
The cleaning process of table 1Si sheet
Solution Time (Min) Temperature (℃) Frequency (KHz)
1 Deionized water 5 27 800
2 SC1 5 80 800
3 Deionized water 5 27 800
4 SC2 5 80 800
5 Deionized water 5 27 800
6 SC3 5 80 800
7 Deionized water 5 27 800
8 DHF solution 5 27 800
9 Deionized water 5 27 800
10 N 2Air-blowing is done 2 27 800
Annotate: SC1(15%NH 3.H 20+15%H 2O 2+ 70%H 2O, volume ratio)
SC2(15%HCl+15%H 20 2+ 70%H 20, volume ratio)
The SC3(concentrated sulfuric acid: H 20 2=3:1, volume ratio)
DHF (HF:H 20=1:10, volume ratio)
Natural oxidizing layer, granule foreign, metal ion, the organic impurities on Si sheet surface have not only been removed in above-mentioned cleaning, but also have removed surface hydrophilicity or the hydrophobicity that is unfavorable for subsequent process steps.
⑵ be benzocyclobutene glue at the one side of the Si sheet after cleaning spin coating BCB glue 10() after, this face sticks on the knot of the 3rd in step 1 battery In xGa 1-xOn the As battery face, insert the bonding chamber of bonder, bonding is full of N in the chamber 2, when the temperature in the bonding chamber is risen to 80-150 ℃ (preferred temperature of the present invention is 120 ℃), battery and Si sheet are carried out the precuring of 60-120 second (preferred temperature of the present invention is 80 seconds); Then to apply 1-5kN(preferred pressure of the present invention be 3kN in the para-linkage chamber) bonding pressure, when the speed that heats up take 15 ℃/min rises to 250-300 ℃ (preferred temperature of the present invention is as 280 ℃) with the bonding cavity temperature, keep constant temperature, battery and Si sheet are carried out the bonding of 1-2 hour (preferred temperature of the present invention is 1.5 hours), then the speed with 3 ℃/min cooling drops to room temperature with the temperature in the bonding chamber, take out battery, finish the GaAs three-junction solar battery of extension back growth as shown in Figure 2 and the low-temperature bonding of Si substrate.
Step 3, peel off the Ge substrate
Use HF:H 2O 2: H 2O=2:1:1 corrosive liquid corrosion Ge substrate and GaAs resilient coating, Ge substrate and GaAs resilient coating are stripped from from battery; Then use HCl:H 2O=1:1 corrosive liquid corrosion GaInP etch stop layer, the GaInP etch stop layer is stripped from from battery; Finish as shown in Figure 3 peeling off of battery Ge substrate;
Step 4, in the battery that step 3 is finished bonding inexpensive substrate
Adopting glass, stainless steel or polyester film material is polyester film as inexpensive substrate 12(preferred inexpensive substrate material of the present invention), the battery that step 3 is finished to be inverted, polyester film pastes the 3rd knot In xGa 1-xOn the As battery, polyester film is as the support substrates that the gallium arsenide epitaxy film epitaxial layer shifts, and finishes the structure of bonding inexpensive substrate on the battery as shown in Figure 4;
Peeling off of step 5, Si substrate
Use BCB glue to remove liquid, just the battery epitaxial wafer finished of step 4 is immersed in BCB glue and removes ultrasonic erosion in the liquid, corrosion temperature is room temperature, time 5-10min, supersonic frequency is 700-1000KHz, and BCB glue is corroded, and the Si substrate on the battery together is stripped from thereupon, with deionized water ultrasonic cleaning battery 5 minutes, be the concentrated sulfuric acid: H with volume ratio again 20 2The SC3 liquid ultrasonic cleaning battery that=3:1 configures 5 minutes; After taking out in 5 minutes with deionized water ultrasonic cleaning battery more at last, the gallium arsenide film of the present invention of namely making is as shown in Figure 5 tied stacked solar cell, cascade solar cell more.
Although the above is described the preferred embodiments of the present invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms.These all belong within protection scope of the present invention.

Claims (3)

1. gallium arsenide film is tied the preparation method of stacked solar cell, cascade solar cell more, it is characterized in that comprising following preparation process:
Step 1, epitaxial loayer back growth prepare the GaAs three-junction solar battery
The Ge substrate is placed in the MOCVD operating room, growth temperature is set to 500 ℃-800 ℃, on the Ge substrate successively epitaxial growth thickness be the GaInP etch stop layer of GaAs resilient coating, the thickness 0.1-0.3 micron of 0.1-0.3 micron, N-shaped Doped GaAs cap layer that thickness is 100-500nm, the first knot GaInP battery as the top battery, the first tunnel junctions, as in the second knot GaAs battery, the second tunnel junctions, the thickness of battery be the N-shaped doping In of 2-5 μ m x(Al yGa 1-y) 1-xThe As graded bedding and as end battery the 3rd the knot In xGa 1-xThe As battery; Described In x(Al yGa 1-y) 1-x0.03≤x in the As graded bedding≤0.3,0.5≤y≤0.7, described GaAs cap layer and In x(Al yGa 1-y) 1-xThe N-shaped doping content of As graded bedding is 1 * 10 17-1 * 10 18Cm -3, the GaAs three-junction solar battery of formation epitaxial loayer back growth;
Battery and the Si substrate bonding of step 2, step 1 preparation
Behind the one side of the Si sheet after cleaning spin coating BCB glue, stick on the 3rd knot In of step 1 xGa 1-xOn the As battery face, insert the bonding chamber of bonder, bonding is full of N in the chamber 2, when the temperature in the bonding chamber is risen to 80-150 ℃, battery and Si sheet are carried out the 60-120 precuring of second; Then the para-linkage chamber applies the bonding pressure of 1-5kN, when the speed that heats up with 15 ℃/min rises to 250-300 ℃ with the bonding cavity temperature, keep constant temperature, battery and Si sheet carried out 1-2 hour bonding, then the speed with 3 ℃/min cooling drops to room temperature with the temperature in the bonding chamber, and battery and Si substrate form low-temperature bonding;
Step 3, peel off the Ge substrate
Use HF:H 2O 2: H 2O=2:1:1 corrosive liquid corrosion Ge substrate and GaAs resilient coating, Ge substrate and GaAs resilient coating are used HCl:H after being stripped from from battery 2O=1:1 corrosive liquid corrosion GaInP etch stop layer, the GaInP etch stop layer is stripped from from battery, finishes peeling off of Ge substrate;
Step 4, bonding inexpensive substrate
Adopt a kind of material of glass, stainless steel or polyester film as inexpensive substrate, the battery that step 3 is finished is inverted, inexpensive substrate is pasted on the first knot GaInP battery, inexpensive substrate bonding;
Step 5, peel off the Si substrate
Use BCB glue to remove liquid, the battery that step 4 is finished is immersed in ultrasonic erosion in the BCB glue removal liquid, corrosion temperature is room temperature, time 5-10min, supersonic frequency is 700-1000KHz, and BCB glue is corroded, and the Si substrate on the battery together is stripped from thereupon, with deionized water ultrasonic cleaning battery 5 minutes, be the concentrated sulfuric acid: H with volume ratio again 20 2The SC3 liquid ultrasonic cleaning battery that=3:1 configures 5 minutes; After taking out in 5 minutes with deionized water ultrasonic cleaning battery more at last, namely make gallium arsenide film of the present invention and tie stacked solar cell, cascade solar cell more.
2. gallium arsenide film according to claim 1 is tied the preparation method of stacked solar cell, cascade solar cell more, it is characterized in that: described the first knot GaInP battery of ⑵, the first tunnel junctions, the second knot GaAs battery, the second tunnel junctions, the 3rd knot In in the step 1 xGa 1-xThe As battery comprises respectively following growth course:
The first knot GaInP battery: be grown to successively the p-type doped with Al GaInP back surface field layer of thickness 100-200nm, the p-type doping GaInP base of thickness 1000-2000nm, the N-shaped doping GaInP emitter region of thickness 50-200nm, the N-shaped doped with Al InP Window layer of thickness 30-100nm; Wherein: the doping content of p-type doped with Al GaInP back surface field layer is 1 * 10 17-1 * 10 19Cm -3, the doping content of p-type doping GaInP base is 1 * 10 16-1 * 10 17Cm -3, the doping content of N-shaped doping GaInP emitter region is 1 * 10 17-1 * 10 19Cm -3, the doping content of N-shaped doped with Al InP Window layer is 1 * 10 17-1 * 10 19Cm -3
The first tunnel junctions: be grown to successively the N-shaped GaAs layer of thickness 10nm-100nm and the p-type Al of thickness 10nm-100nm 0.4Ga 0.6The As layer; Wherein: the doping content of N-shaped GaAs layer is 1 * 10 18-1 * 10 20Cm -3, p-type Al 0.4Ga 0.6The doping content of As layer is 1 * 10 18-1 * 10 20Cm -3
The second knot GaAs battery: the p-type doped with Al that is grown to successively thickness 100-200nm xGa 1-xThe p-type Doped GaAs base of As back surface field layer, thickness 3000-4000nm, the N-shaped Doped GaAs emitter region of thickness 50-200nm, the N-shaped doped with Al of thickness 30-100nm xGa 1-xThe As Window layer; Wherein: the p-type doped with Al xGa 1-xThe doping content of As back surface field layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5; The doping content of p-type Doped GaAs base is 1 * 10 16-1 * 10 18Cm -3, the doping content of N-shaped Doped GaAs emitter region is 1 * 10 17-1 * 10 19Cm -3, the N-shaped doped with Al xGa 1-xThe doping content of As Window layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5;
The second tunnel junctions: be grown to successively the N-shaped GaAs layer of thickness 10nm-100nm and the p-type Al of thickness 10nm-100nm 0.4Ga 0.6The As layer; Wherein: the doping content of N-shaped GaAs layer is 1 * 10 18-1 * 10 20Cm -3, p-type Al 0.4Ga 0.6The doping content of As layer is 1 * 10 18-1 * 10 20Cm -3
The 3rd knot In xGa 1-xAs battery: the N-shaped doping In that is grown to successively thickness 100-300nm x(Al yGa 1-y) 1-xAs Window layer, thickness are the N-shaped doping In of 200-400nm xGa 1-xAs emitter region, thickness are the p-type doping In of 1500-2000nm xGa 1-xAs base, thickness are the p-type doping In of 100-200nm x(Al yGa 1-y) 1-xAs back surface field layer, thickness are the p-type doping In of 500-800nm x(Al yGa 1-y) 1-xAs cap layer; Wherein: N-shaped doping In x(Al yGa 1-y) 1-xThe doping content of As Window layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7, N-shaped doping In xGa 1-xThe doping content of As emitter region is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5(x of the present invention preferred value be 0.4), p-type doping In xGa 1-xThe doping content of As base is 1 * 10 16-1 * 10 18Cm -3, 0.3≤x≤0.5(x of the present invention preferred value be 0.4), p-type doping In x(Al yGa 1-y) 1-xThe doping content of As back surface field layer is 1 * 10 17-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7, p-type doping In x(Al yGa 1-y) 1-xThe doping content of As cap layer is 1 * 10 18-1 * 10 19Cm -3, 0.3≤x≤0.5,0.5≤y≤0.7.
3. gallium arsenide film according to claim 1 is tied the preparation method of stacked solar cell, cascade solar cell more, it is characterized in that: the Si sheet in the step 2 is the p-type Si sheet of thickness 400-500 micron, cleans the Si sheet and dries up according to the cleaning process shown in the table 1:
The cleaning process of table 1Si sheet
Solution Time (Min) Temperature (℃) Frequency (KHz) 1 Deionized water 5 27 700-1000 2 SC1 5 80 700-1000 3 Deionized water 5 27 700-1000 4 SC2 5 80 700-1000 5 Deionized water 5 27 700-1000 6 SC3 5 80 700-1000 7 Deionized water 5 27 700-1000 8 DHF solution 5 27 700-1000 9 Deionized water 5 27 700-1000 10 N 2Air-blowing is done 2 27 700-1000
Wherein: SC1(15%NH 3.H 2O+15%H 2O 2+ 70%H 2O, volume ratio)
SC2(15%HCl+15%H 2O 2+ 70%H 2O, volume ratio)
The SC3(concentrated sulfuric acid: H 2O 2=3:1, volume ratio)
DHF (HF: H 2O=1: 10, volume ratio).
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CN103904015A (en) * 2014-03-21 2014-07-02 中国电子科技集团公司第五十五研究所 Method for stripping and transferring gallium arsenide based epitaxial layer
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