CN104178172A - Etching solution for selectively etching gallium arsenide solar cell cap layer and preparation method thereof - Google Patents
Etching solution for selectively etching gallium arsenide solar cell cap layer and preparation method thereof Download PDFInfo
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- CN104178172A CN104178172A CN201410408330.4A CN201410408330A CN104178172A CN 104178172 A CN104178172 A CN 104178172A CN 201410408330 A CN201410408330 A CN 201410408330A CN 104178172 A CN104178172 A CN 104178172A
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- gallium arsenide
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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 an etching solution for selectively etching a gallium arsenide solar cell cap layer, which is composed of the following components in parts by mass: 5-150 parts of component A, 10-100 parts of component B, 1-20 parts of component C, 1-20 parts of component D and 100 parts of component E. The component A is solid citric acid; the component B is oxydol; the component C is amine compounds; the component D is amino acid compounds; and the component E is deionized water. Preferably, the purity of the component A is greater than 99.8%, and the mass concentration of the component B is 30%. The invention also discloses a preparation method of the etching solution. The etching solution can well control the etching rate, has higher etching uniformity, and thoroughly removes the residues, thereby obtaining the cell gate line structure with smooth side bench.
Description
Technical field
The present invention relates to the chemical corrosion liquid that solar cell is used in producing, especially a kind of gallium arsenide solar cell cap layer is carried out to corrosive fluid of selective corrosion and preparation method thereof.
Background technology
It shown in accompanying drawing 1, is a kind of epitaxy junction composition of optically focused three-junction gallium arsenide solar battery, it is that three sub-batteries of battery at the bottom of battery, Ge in GaInP top battery, GaAs are connected in series, GaInP top battery absorbs the sunlight that photon energy is greater than 1.85eV, in GaAs, battery absorbs the sunlight that photon energy is greater than 1.42eV, at the bottom of Ge, battery absorbs the sunlight that photon energy is greater than 0.67eV, wave band 380～the 1850nm absorbing, nearly cover all sunlight wave bands, because of but in current all kinds of solar cell, change most effective battery.
In the middle of the manufacture craft of optically focused three-junction gallium arsenide solar battery chip, after electrode evaporation grid line, removing grid line GaAs cap layer is in addition one of critical process of chip manufacturing.The existing grid line GaAs cap layer in addition that removes has two class techniques.The first kind is to adopt dry etching, and employing dry etching is selected larger frequently, and side step is smooth, but easily damages the Window layer material (AlInP) of top battery, thus damage device.Equations of The Second Kind is wet etching, utilizes chemical corrosion liquid to carry out selective corrosion.The composition of existing published chemical corrosion liquid mainly contains citric acid-hydrogen peroxide system and ammoniacal liquor-hydrogen peroxide system.No matter but which kind of system, all exist corrosion unclean, to adopt optically focused gallium arsenide three-junction solar battery chip grid line after the existing citric acid-hydrogen peroxide system selective corrosion corrosion schematic diagram under metaloscope as shown in Figure 2, it also has more residue on gate electrode line side, these residues can produce extinction phenomenon, affect photoelectric conversion efficiency of the solar battery.On the other hand, the existing corrosive fluid of part, carrying out being longitudinally attended by horizontal sideetching effect in corrosion, gently affects current expansion, causes battery chip internal resistance resistance significantly to rise, and when serious, can cause grid line to come off; And etching process window is little, wayward.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, can better control the erosion rate of corrosive fluid, strengthen the homogeneity of corrosion, thoroughly remove residue, to obtain the smooth battery grid line structure of side step.
For achieving the above object, technical scheme of the present invention is: a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, is comprised of following A, B, C, D, five kinds of components of E:
A component is solid citric acid;
B component is hydrogen peroxide;
C component is aminated compounds;
D component is amino acids;
E component is deionized water;
The add-on of said components is by mass: A component is 5～150 parts, and B component is 10～100 parts, and C component is 1～20 part, and D component is 1～20 part, and E component is 100 parts.
Preferred described C component is selected from one or more in ammonia, methylamine, ethamine, quadrol, 1,2 one propylene diamine, 1,3 one propylene diamine, diethylenetriamine, triethylene tetramine, three amido triethylamines, aniline or phenylenediamine and mixes.
Preferred described D component is selected from one or more in glycine, moon bright propylhomoserin, anthranilic acid, aspartic acid, L-glutamic acid, dithiocarbamic acid, imido disulfonic acid, ammonia oxalic acid, nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA), diethyl three ammonia pentaacetic acids, HEDTA or aromatic nucleus amino acid and mixes.
Preferred described A component purity is that top grade is pure, and purity is greater than 99.8%.
The mass concentration of preferred described B component is 30 %.
Further, described A, B, C, D, five kinds of components of E are mixed after fully dissolving, and adding sodium hydroxide or potassium hydroxide to regulate the pH value of whole mixed solution is 8-10.Obtain the more stable corrosive fluid of performance.
The present invention also provides the preparation method of above-mentioned corrosive fluid, comprises the following steps:
1, solid citric acid is poured in quartzy cylinder;
2, in quartzy cylinder, add deionized water;
3, in quartzy cylinder, add aminated compounds and amino acids, with glass stick, stir simultaneously to quartzy cylinder heating simultaneously;
4, after fully dissolving, add hydrogen peroxide;
5, stir after fully mixing, with sodium hydroxide or potassium hydroxide solution, regulate the pH value of mixed solution to 8-10.
The present invention by adding amine and amino acids on the basis of citric acid-hydrogen peroxide system, complex ability and the sequestering action of enhancing to Ga, As ion, better control the erosion rate of corrosive fluid, strengthen the homogeneity of corrosion, thoroughly remove residue, can obtain more for convenience the smooth battery grid line structure of side step.
Corrosion process technique of the present invention is simple, stable, has fine repeatability.
Preparation method provided by the invention, operation and the equipment needing are simple, can reduce preparation cost.
Accompanying drawing explanation
Fig. 1 is a kind of existing optically focused three-junction solar battery epitaxial structure schematic diagram;
Fig. 2 adopts optically focused gallium arsenide three-junction solar battery chip grid line after the existing citric acid-hydrogen peroxide system selective corrosion corrosion schematic diagram under metaloscope;
Fig. 3 is optically focused gallium arsenide three-junction solar battery chip grid line after the corrosive fluid of the present invention corrosion schematic diagram under metaloscope.
Embodiment
Below in conjunction with concrete embodiment, the present invention is described in further detail.
Embodiment mono-, a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, select purity to be greater than 99.8% solid citric acid 800g, hydrogen peroxide 500 g, methylamine and ethamine mixture 35 g, glycine and moon bright propylhomoserin mixture 25 g, deionized water 1000 g that mass concentration is 30% and carry out mixed dissolution, after fully dissolving, with sodium hydroxide or potassium hydroxide solution, regulate pH to 8-10, just make corrosive fluid.
Concrete operation step is:
1, first purity being greater than to 99.8% solid citric acid 800g pours in quartzy cylinder;
2, in quartzy cylinder, add 1000 g deionized waters;
3, simultaneously toward the methylamine and ethamine mixture and 25 g glycine and the moon bright propylhomoserin mixture that add 35 g in quartzy cylinder, with glass stick, stir simultaneously and heat to quartzy cylinder;
4,, after fully dissolving, adding mass concentration is 30% hydrogen peroxide 500 g;
5, stir after fully mixing, with sodium hydroxide or potassium hydroxide solution, regulate the pH value of mixed solution to 8-10.
Embodiment bis-, a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, select purity to be greater than 99.8% solid citric acid 1500g, hydrogen peroxide 800 g, methylamine and ethamine mixture 180 g, glycine and moon bright propylhomoserin mixture 180g, deionized water 1000 g that mass concentration is 30% and carry out mixed dissolution, after fully dissolving, with sodium hydroxide or potassium hydroxide solution, regulate pH to 8-10, just make corrosive fluid.
Concrete operation step is:
1, first purity being greater than to 99.8% solid citric acid 1500g pours in quartzy cylinder;
2, in quartzy cylinder, add 1000 g deionized waters;
3, simultaneously toward the methylamine and ethamine mixture and 180 g glycine and the moon bright propylhomoserin mixture that add 180 g in quartzy cylinder, with glass stick, stir simultaneously and heat to quartzy cylinder;
4,, after fully dissolving, adding mass concentration is 30% hydrogen peroxide 800 g;
5, stir after fully mixing, with sodium hydroxide or potassium hydroxide solution, regulate the pH value of mixed solution to 8-10.
Embodiment tri-, a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, select purity to be greater than 99.8% solid citric acid 100g, hydrogen peroxide 150 g, methylamine and ethamine mixture 15 g, glycine and moon bright propylhomoserin mixture 15g, deionized water 1000 g that mass concentration is 30% and carry out mixed dissolution, after fully dissolving, with sodium hydroxide or potassium hydroxide solution, regulate pH to 8-10, just make corrosive fluid.
Concrete operation step is:
1, first purity being greater than to 99.8% solid citric acid 100g pours in quartzy cylinder;
2, in quartzy cylinder, add 1000 g deionized waters;
3, simultaneously toward the methylamine and ethamine mixture and 15 g glycine and the moon bright propylhomoserin mixture that add 15 g in quartzy cylinder, with glass stick, stir simultaneously and heat to quartzy cylinder;
4,, after fully dissolving, adding mass concentration is 30% hydrogen peroxide 150 g;
5, stir after fully mixing, with sodium hydroxide or potassium hydroxide solution, regulate the pH value of mixed solution to 8-10.
While adopting above-mentioned any corrosive fluid to carry out selective corrosion to gallium arsenide solar cell cap layer, open heating unit constant temperature, and be 30-50 ℃ by Temperature Setting, solar cell piece interval is inserted in the special-purpose gaily decorated basket of etching along grid line direction, immerse above-mentioned any corrosive fluid and shake gently the gaily decorated basket, the shake gaily decorated basket adopts significantly slow frequency, after manual time-keeping 1-10 minute, the gaily decorated basket is taken out rapidly together with cell piece, put into tank, fast row washes by water, with nitrogen, blow away after the large water drop of gaily decorated basket both sides afterwards, put into high speed spinner, be spin-dried for, processing procedure finishes.Gallium arsenide three-junction solar battery chip grid line structure after corrosion as shown in Figure 3, gallium arsenide three-junction solar battery chip grid line periphery does not have GaAs residual substantially, prove that corrosive fluid of the present invention better controls the erosion rate of corrosive fluid, strengthen the homogeneity of corrosion, thoroughly remove residue, can obtain more for convenience the smooth battery grid line structure of side step.Adopt the corrosive fluid of above-mentioned three kinds of embodiment, its corrosion speed can be different, but that it bears results is basic identical.The present invention has high selective corrosion, and corrosive fluid preparation is convenient, and corrosion process technique is simple, stable, has advantages of good repeatability.
Below being only the several preferred embodiments of the present invention, is not the concrete restriction to protection domain of the present invention, and the change that those skilled in the art does to be equal to by claim all falls into the protection domain of this case.
Claims (7)
1. a corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion, is comprised of following A, B, C, D, five kinds of components of E:
A component is solid citric acid;
B component is hydrogen peroxide;
C component is aminated compounds;
D component is amino acids;
E component is deionized water;
The add-on of said components is by mass: A component is 5～150 parts, and B component is 10～100 parts, and C component is 1～20 part, and D component is 1～20 part, and E component is 100 parts.
2. a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion according to claim 1, it is characterized in that: described C component is selected from ammonia, methylamine, ethamine, quadrol, 1, one or more in 2 one propylene diamine, 1,3 one propylene diamine, diethylenetriamine, triethylene tetramine, three amido triethylamines, aniline or phenylenediamine mix.
3. a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion according to claim 1, is characterized in that: described D component is selected from one or more in glycine, moon bright propylhomoserin, anthranilic acid, aspartic acid, L-glutamic acid, dithiocarbamic acid, imido disulfonic acid, ammonia oxalic acid, nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA), diethyl three ammonia pentaacetic acids, HEDTA or aromatic nucleus amino acid and mixes.
4. a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion according to claim 1, is characterized in that: described A component purity is that top grade is pure, and purity is greater than 99.8%.
5. a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion according to claim 1, is characterized in that: the mass concentration of described B component is 30 %.
6. according to a kind of corrosive fluid that gallium arsenide solar cell cap layer is carried out to selective corrosion described in claim 1 to 5 any one, it is characterized in that: described A, B, C, D, five kinds of components of E are mixed after fully dissolving, adding sodium hydroxide or potassium hydroxide to regulate the pH value of whole mixed solution is 8-10.
7. a preparation method for corrosive fluid described in the claims 1 to 6 any one, comprises the following steps:
1, solid citric acid is poured in quartzy cylinder;
2, in quartzy cylinder, add deionized water;
3, in quartzy cylinder, add aminated compounds and amino acids, with glass stick, stir simultaneously to quartzy cylinder heating simultaneously;
4, after fully dissolving, add hydrogen peroxide;
5, stir after fully mixing, with sodium hydroxide or potassium hydroxide solution, regulate the pH value of mixed solution to 8-10.
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| CN201410408330.4A CN104178172A (en) | 2014-08-19 | 2014-08-19 | Etching solution for selectively etching gallium arsenide solar cell cap layer and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109698123A (en) * | 2017-10-24 | 2019-04-30 | 山东浪潮华光光电子股份有限公司 | A kind of substrate etching method of GaAs base LED wafer |
| WO2023036720A1 (en) * | 2021-09-07 | 2023-03-16 | Merck Patent Gmbh | Selective self-assembled monolayers via spin-coating method for use in dsa |
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| JP2005307187A (en) * | 2004-03-19 | 2005-11-04 | Air Products & Chemicals Inc | Alkaline cleaning composition used after chemical mechanical planarization |
| CN1796604A (en) * | 2004-12-30 | 2006-07-05 | 中国科学院半导体研究所 | Chemical corrosion liquid in high selection ratio of gallium arsenide in aluminum arsenide / gallium arsenide |
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2014
- 2014-08-19 CN CN201410408330.4A patent/CN104178172A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH11168091A (en) * | 1997-12-04 | 1999-06-22 | Fujitsu Quantum Device Kk | Manufacture of semiconductor device |
| US20050161749A1 (en) * | 2002-05-07 | 2005-07-28 | California Institute Of Technology | Apparatus and method for vacuum-based nanomechanical energy force and mass sensors |
| CN1918698A (en) * | 2004-02-09 | 2007-02-21 | 三菱化学株式会社 | Cleaning liquid for substrate for semiconductor device and cleaning method |
| JP2005307187A (en) * | 2004-03-19 | 2005-11-04 | Air Products & Chemicals Inc | Alkaline cleaning composition used after chemical mechanical planarization |
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| CN102627972A (en) * | 2012-03-23 | 2012-08-08 | 中国科学院半导体研究所 | Formula of GaAs semiconductor material etching liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109698123A (en) * | 2017-10-24 | 2019-04-30 | 山东浪潮华光光电子股份有限公司 | A kind of substrate etching method of GaAs base LED wafer |
| CN109698123B (en) * | 2017-10-24 | 2020-09-18 | 山东浪潮华光光电子股份有限公司 | Substrate corrosion method of GaAs-based LED wafer |
| WO2023036720A1 (en) * | 2021-09-07 | 2023-03-16 | Merck Patent Gmbh | Selective self-assembled monolayers via spin-coating method for use in dsa |
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Application publication date: 20141203 |