CN102983210B - Method for manufacturing four solar cells of GaAs system - Google Patents
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- CN102983210B CN102983210B CN201210378165.3A CN201210378165A CN102983210B CN 102983210 B CN102983210 B CN 102983210B CN 201210378165 A CN201210378165 A CN 201210378165A CN 102983210 B CN102983210 B CN 102983210B
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Abstract
The invention relates to a method for manufacturing four solar cells of a GaAs system. The method is characterized in that MOCVD is adopted to sequentially generating a first Ge cell, a nucleating layer, a buffer layer, a first tunnel, a second GaInAs cell, a second tunnel, a third AlxGal-xAs cell, a third tunnel, a four GaInP2 cell and a GaAs cap layer. Due to the fact that GaInP2/AlxGa1-xAs/GaInAs/Ge sub-cell material and a manufacture process which are completely matched with a Ge substrate lattice are adopted, the efficiency of solar cells is improved effectively. Open-circuit voltage is improved to 4V, and a high-voltage low-current characteristic is achieved. A cell device manufacture technology can be completely compatible with GaInP2/GaInAs/Ge solar cells, the manufacture process is simplified, the manufacture cost is reduced, and the method is easily achieved in the feasibility aspect.
Description
Technical field
The invention belongs to technical field of solar cells, particularly relate to a kind of preparation method of GaAs system four-junction solar cell.
Background technology
Along with the energy crisis of global range and going from bad to worse of ecological environment problem, people more and more pay attention to this inexhaustible green energy resource of solar energy, study the solar battery structure of high conversion efficiency for a long time diligently.Wherein, multijunction solar cell structure adopts the sub-battery pack of different energy gap to synthesize new structure, expands the absorption region of battery to solar spectrum, to realize the high efficiency of battery.At present, the three-junction solar battery technology that the GaInP/GaInAs/Ge that, lattice constant desirable with the collocation of material band gap width is mated again is very much representative is gradually improved.Because photoelectric conversion efficiency increases along with increasing of footing, tie based on GaAs system four and very big concern that more multijunction cell structure receives again various countries solar cell researcher.
Although the theoretical efficiency of four knots and above each multijunction solar cell illustrates tempting prospect, but in the actual preparation of solar cell, in the most basic material, there are following three very scabrous problems: (1) due to the band gap of Ge substrate be 0.67eV, lower than the requirement of the end cell band gap that the best band gap of each multijunction solar cell requires, hamper obtaining of maximum theoretical efficiency; (2) arsenide and phosphide make two of solar cell the most ripe material systems, and the material of nearly all practical application in solar cell is all from this two large bodies system.But in these two material systems, it is very difficult for obtaining band gap at the battery knot of more than 2.0eV.Its main cause is, must contain a large amount of Al, and Al element is active especially, is very easy to from environment, absorb oxygen, forms deep energy level defect in high band gap materials, thus the performance of deterioration of device.What MOCVD grew usually because of the compound of charge carrier via Al-O micro-structural, thus can shorten the diffusion length of minority carrier greatly containing Al compound, causes the reduction of efficiency of solar cell; (3) be difficult to excellent, band gap about 1.0eV solar cell knot.In arsenide and phosphide two large bodies system, band gap is not mated with the lattice constant of Ge substrate mostly at the material of about 1.0eV, thus limits their application in solar cell.Outside this bi-material system, also someone proposes, and InGaAsN material is a kind of material being expected to implementation efficiency and breaking through that energy gap meets about 1eV, lattice and also can mate with Ge substrate.But long-term research shows, due to being incorporated to of N, form the deep energy level that N-N, N-As interstitial impurity causes, the minority diffusion length of this material is very short.This is a very serious problem for solar cell application, collects because photo-generated carrier can not be diffused into p-n junction effectively.From the progress of recent years, the solution of this problem does not also reach requirement that can be practical.
At present known be widely studied based in GaAs system four-junction solar battery, solve above-mentioned three insoluble problems in various degree, but still there is the problem that each sub-battery material can not mate completely with the lattice of Ge substrate, battery device manufacture craft can not be completely compatible with GaInP/GaInAs/Ge tri-junction battery, add manufacture difficulty and the cost of battery.
Summary of the invention
The present invention for solve in known technology the technical problem that exists and provide that a kind of each sub-battery material mates completely with Ge substrate lattice, battery device manufacture craft and GaInP/GaInAs/Ge three-junction solar battery completely compatible, efficiency of solar cell is high, high voltage low current characteristic is good, preparation technology is simple, cost of manufacture is low, feasibility aspect the most easily realizes, and is more suitable for the preparation method of the GaAs system four-junction solar cell of concentration applications.
The preparation method of GaAs system four-junction solar cell of the present invention comprises following technical scheme:
The preparation method of GaAs system four-junction solar cell, is characterized in: comprise following preparation process: adopt metal organic chemical vapor deposition technology on Ge substrate, grow the first knot Ge battery, nucleating layer, resilient coating, the first tunnel junction, the second knot GaInAs battery, the second tunnel junction, the 3rd knot Al successively
xga
1-xas battery, the 3rd tunnel junction, the 4th knot GaInP
2battery and GaAs cap layers, described first knot Ge battery, comprises Ge substrate that base is p-type doping, emitter region is spread by phosphorus N-shaped Ge and GaInP obtained
2window layer; Described emitter region phosphorus diffusion temperature is 500 DEG C-800 DEG C, the time is 30-60 second, thickness is 140-200 μm; The doping content of described emitter region is 1 × 10
17-1 × 10
19cm
-3; Described nucleating layer is GaInP
2, growth temperature is 500 DEG C-800 DEG C, growth time is 30-60 second, and thickness is 10-50nm; Described resilient coating is Ga
0.99in
0.01as, growth temperature is 500 DEG C-800 DEG C, growth time is 10-60 minute, thickness is 0.5-3 μm; Described first tunnel junction comprises N-shaped GaInP
2the Al of layer and p-type doping
0.3ga
0.7as layer, thickness is 10nm-50nm, and growth temperature is 500 DEG C-800 DEG C, growth time is 30-60 second, described N-shaped GaInP
2the Al of layer and p-type doping
0.3ga
0.7as layer doping content is 1 × 10
18-1 × 10
20cm
-3; Described second knot GaInAs battery AlGaAs back surface field layer, Ga
0.99in
0.01as base, Ga
0.99in
0.01as emitter region, AlInP
2window layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 20-80 minute, and thickness is 1-5 μm, and doping content is 1 × 10
17-1 × 10
19cm
-3; Described second tunnel junction, comprises the GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 30-60 second, and doping content is 1 × 10
18-1 × 10
20cm
-3, thickness is 10nm-50nm; Described 3rd knot Al
xga
1-xas battery, comprises AlGaInP back surface field layer, Al
xga
1-xas base, Al
xga
1-xas emitter region and AlInP
2window layer, wherein 0.1≤x≤0.3, growth temperature is 500 DEG C-800 DEG C, and growth time is 40-80 minute, and thickness is 1-5 μm, and doping content is 1 × 10
17-1 × 10
19cm
-3; 3rd tunnel junction, comprises the GaInP of N-shaped
2the Al of layer and p-type
0.3ga
0.7as layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 30-60 second, and doping content is 1 × 10
18-1 × 10
20cm
-3, thickness is 10nm-50nm; 4th knot GaInP
2battery AlGaInP back surface field layer, GaInP
2base, GaInP
2emitter region and AlInP
2window layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 10-20 minute, and thickness is 500-1000nm, and doping content is 1 × 10
17-1 × 10
19cm
-3; GaAs cap layers, growth temperature is 500 DEG C-800 DEG C, and growth time is 5-20 minute, and thickness is 100-1000nm, and doping content is 1 × 10
18-1 × 10
19cm
-3, namely complete GaInP/Al of the present invention
xga
1-xthe making of As/GaInAs/Ge four-junction solar cell.
The advantage that the present invention has and good effect:
1, the present invention is owing to have employed the GaInP mated completely with Ge substrate lattice
2/ Al
xga
1-xthe manufacturing process of each sub-battery material of As/GaInAs/Ge, effectively improves the efficiency of solar cell; Open circuit voltage brings up to 4V by current known 3.4V, achieves high voltage low current characteristic; Battery device manufacture craft can be completely compatible with GaInP/GaInAs/Ge three-junction solar battery, simplifies preparation technology, reduce cost of manufacture, is very easy to realize in feasibility;
2, spectrum can segment by the present invention further, and therefore, short-circuit current density roughly becomes 2/3 of GaInP/GaInAs/Ge three-junction solar battery, and resistance power loss is similar to and becomes original 4/9, is more suitable for concentration applications.
Accompanying drawing explanation
Fig. 1 is GaAs system four-junction solar cell schematic diagram prepared by the present invention.
Label in figure is respectively: 1-first ties Ge battery; 2-nucleating layer; 3-resilient coating; 4-first tunnel junction; 5-second ties GaInAs battery; 6-second tunnel junction; 7-the 3rd ties Al
xga
1-xas battery; 8-the 3rd tunnel junction; 9-the 4th ties GaInP
2battery; 10-GaAs cap layers.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, especially exemplified by following instance and by reference to the accompanying drawings 1 be described in detail as follows.
Embodiment:
Adopt MOCVD and metal organic chemical vapor deposition technology on Ge substrate, grow the first knot Ge battery 1, nucleating layer 2, resilient coating 3, first tunnel junction 4, second knot GaInAs battery 5, second tunnel junction 6, the 3rd knot Al successively
xga
1-xas battery 7, the 3rd tunnel junction 8, the 4th knot GaInP
2battery 9, GaAs cap layers 10, wherein:
First knot Ge battery, comprises Ge substrate that base is p-type doping, emitter region is spread by phosphorus N-shaped Ge and GaInP obtained
2window layer; The emitter region phosphorus diffusion temperature of the first knot Ge battery is 500 DEG C-800 DEG C (the present embodiment optimum growth temp is 600 DEG C), the time is 30-60 second (the optimum growh time of the present embodiment is 40 seconds), thickness is 140-200 μm (the present embodiment optimum thickness is 140 μm), and wherein the emitter region doping content of Ge battery is 1 × 10
17-1 × 10
19cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
Nucleating layer is GaInP
2, growth temperature is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 30-60 second (the optimum growh time of the present embodiment is 40 seconds), thickness is 10-50nm (optimum thickness of the present embodiment is 12nm);
Resilient coating is Ga
0.99in
0.01as, growth temperature is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 10-60 minute (the optimum growh time of the present embodiment is 20 minutes), thickness is 0.5-3 μm (optimum thickness of the present embodiment is 0.7 μm);
First tunnel junction, comprises the GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer; The growth temperature of the first tunnel junction is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 30-60 second (the optimum growh time of the present embodiment is 40 seconds), thickness is 10nm-50nm (optimum thickness of the present embodiment is 12nm), the wherein GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer doping content is 1 × 10
18-1 × 10
20cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
Second knot GaInAs battery, comprises AlGaAs back surface field layer, Ga
0.99in
0.01as base, Ga
0.99in
0.01as emitter region, AlInP
2window layer; The growth temperature of the second knot GaInAs battery is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 20-80 minute (the optimum growh time of the present embodiment is 40 minutes), thickness is 1-5 μm (optimum thickness of the present embodiment is 2 μm), wherein AlInP
2the doping content of Window layer is 1 × 10
17-1 × 10
19cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
Second tunnel junction, comprises the GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer; The growth temperature of the second tunnel junction is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 30-60 second (the optimum growh time of the present embodiment is 40 seconds), thickness is 10nm-50nm (optimum thickness of the present embodiment is 12nm), the wherein GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer doping content is 1 × 10
18-1 × 10
20cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
3rd knot Al
xga
1-xas battery, comprises AlGaInP back surface field layer, Al
xga
1-xas base, Al
xga
1-xas emitter region and AlInP
2window layer; 3rd knot Al
xga
1-xthe growth temperature of As battery is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 40-80 minute (the optimum growh time of the present embodiment is 50 minutes), thickness is 1-5 μm (optimum thickness of the present embodiment is 2 μm), wherein AlInP
2the doping content of Window layer is 1 × 10
17-1 × 10
19cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3), 0.1≤x≤0.3 (in the present embodiment, the optimum value of x is 0.2);
3rd tunnel junction, comprises the GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer; The growth temperature of the 3rd tunnel junction is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 30-60 second (the optimum growh time of the present embodiment is 40 seconds), thickness is 10nm-50nm (optimum thickness of the present embodiment is 12nm), the wherein GaInP of N-shaped
2the Al of layer and p-type doping
0.3ga
0.7as layer doping content is 1 × 10
18-1 × 10
20cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
4th knot GaInP
2battery, comprises AlGaInP back surface field layer, GaInP
2base, GaInP
2emitter region and AlInP
2window layer; 4th knot GaInP
2the growth temperature of battery is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 10-20 minute (the optimum growh time of the present embodiment is 15 minutes), thickness is 500-1000nm (optimum thickness of the present embodiment is 600nm), wherein AlInP
2the doping content of Window layer is 1 × 10
17-1 × 10
19cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3);
GaAs cap layers, growth temperature is 500 DEG C-800 DEG C (optimum growth temp of the present embodiment is 600 DEG C), growth time is 5-20 minute (the optimum growh time of the present embodiment is 15 minutes), thickness is 100-1000nm (optimum thickness of the present embodiment is 200nm), and wherein the doping content of GaAs cap layers is 1 × 10
18-1 × 10
19cm
-3(optimum doping concentration of the present embodiment is 1 × 10
18cm
-3); Namely GaAs system GaInP of the present invention is completed
2/ Al
xga
1-xthe making of As/GaInAs/Ge four-junction solar cell.
Although be described the preferred embodiments of the present invention by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (1)
- The preparation method of 1.GaAs system four-junction solar cell, is characterized in that: comprise following preparation process: adopt metal organic chemical vapor deposition technology on Ge substrate, grow the first knot Ge battery, nucleating layer, resilient coating, the first tunnel junction, the second knot GaInAs battery, the second tunnel junction, the 3rd knot Al successively xga 1-xas battery, the 3rd tunnel junction, the 4th knot GaInP 2battery and GaAs cap layers, described first knot Ge battery, comprises Ge substrate that base is p-type doping, emitter region is spread by phosphorus N-shaped Ge and GaInP obtained 2window layer; Described emitter region phosphorus diffusion temperature is 500 DEG C-800 DEG C, the time is 30-60 second, thickness is 140-200 μm; The doping content of described emitter region is 1 × 10 17-1 × 10 19cm -3; Described nucleating layer is GaInP 2, growth temperature is 500 DEG C-800 DEG C, growth time is 30-60 second, and thickness is 10-50nm; Described resilient coating is Ga 0.99in 0.01as, growth temperature is 500 DEG C-800 DEG C, growth time is 10-60 minute, thickness is 0.5-3 μm; Described first tunnel junction comprises N-shaped GaInP 2the Al of layer and p-type doping 0.3ga 0.7as layer, thickness is 10nm-50nm, and growth temperature is 500 DEG C-800 DEG C, growth time is 30-60 second, described N-shaped GaInP 2the Al of layer and p-type doping 0.3ga 0.7as layer doping content is 1 × 10 18-1 × 10 20cm -3; Described second knot GaInAs battery AlGaAs back surface field layer, Ga 0.99in 0.01as base, Ga 0.99in 0.01as emitter region, AlInP 2window layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 20-80 minute, and thickness is 1-5 μm, and doping content is 1 × 10 17-1 × 10 19cm -3; Described second tunnel junction, comprises the GaInP of N-shaped 2the Al of layer and p-type doping 0.3ga 0.7as layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 30-60 second, and doping content is 1 × 10 18-1 × 10 20cm -3, thickness is 10nm-50nm; Described 3rd knot Al xga 1-xas battery, comprises AlGaInP back surface field layer, Al xga 1-xas base, Al xga 1-xas emitter region and AlInP 2window layer, wherein 0.1≤x≤0.3, growth temperature is 500 DEG C-800 DEG C, and growth time is 40-80 minute, and thickness is 1-5 μm, and doping content is 1 × 10 17-1 × 10 19cm -3; 3rd tunnel junction, comprises the GaInP of N-shaped 2the Al of layer and p-type 0.3ga 0.7as layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 30-60 second, and doping content is 1 × 10 18-1 × 10 20cm -3, thickness is 10nm-50nm; 4th knot GaInP 2battery AlGaInP back surface field layer, GaInP 2base, GaInP 2emitter region and AlInP 2window layer, growth temperature is 500 DEG C-800 DEG C, and growth time is 10-20 minute, and thickness is 500-1000nm, and doping content is 1 × 10 17-1 × 10 19cm -3; GaAs cap layers, growth temperature is 500 DEG C-800 DEG C, and growth time is 5-20 minute, and thickness is 100-1000nm, and doping content is 1 × 10 18-1 × 10 19cm -3, namely complete GaInP/Al of the present invention xga 1-xthe making of As/GaInAs/Ge four-junction solar cell.
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| CN104241416B (en) * | 2014-09-18 | 2017-01-25 | 瑞德兴阳新能源技术有限公司 | Three-junction solar cell with quantum well structure |
| CN107871799B (en) * | 2016-09-27 | 2023-11-07 | 中国电子科技集团公司第十八研究所 | Forward mismatched four-junction solar cell |
| CN109103278B (en) * | 2018-08-15 | 2020-03-10 | 中山德华芯片技术有限公司 | Aluminum-free efficient six-junction solar cell and preparation method thereof |
| CN110233187B (en) * | 2019-06-19 | 2022-01-25 | 扬州乾照光电有限公司 | Lattice mismatched multi-junction solar cell structure |
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| CN101388419A (en) * | 2008-10-27 | 2009-03-18 | 厦门乾照光电有限公司 | Three connection solar cell having reflection layer and manufacturing method therefor |
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| CN101388419A (en) * | 2008-10-27 | 2009-03-18 | 厦门乾照光电有限公司 | Three connection solar cell having reflection layer and manufacturing method therefor |
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Effective date of registration: 20190530 Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Co-patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Co-patentee after: China Electric Power Shenzhen Group Co.,Ltd. Address before: 300384 No. 15, Sidao, Haitai Development, Huayuan Industrial Park, Xiqing District, Tianjin Co-patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: CETC Blue Sky Technology Co.,Ltd. Address before: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: CETC Energy Co.,Ltd. Address after: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee after: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee after: The 18th Research Institute of China Electronics Technology Group Corporation Patentee after: CETC Energy Co.,Ltd. Address before: 300384 Tianjin Binhai New Area Huayuan Industrial Zone (Outside Rim) No. 6 Solar Cell and Controller Workshop, Haitai Huake 7th Road, Second Floor Patentee before: TIANJIN LANTIAN SOLAR TECH Co.,Ltd. Patentee before: The 18th Research Institute of China Electronics Technology Group Corporation Patentee before: China Electric Power Shenzhen Group Co.,Ltd. |