KR101994084B1 - Texture etching solution composition and texture etching method of crystalline silicon wafers - Google Patents
Texture etching solution composition and texture etching method of crystalline silicon wafers Download PDFInfo
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- KR101994084B1 KR101994084B1 KR1020120151841A KR20120151841A KR101994084B1 KR 101994084 B1 KR101994084 B1 KR 101994084B1 KR 1020120151841 A KR1020120151841 A KR 1020120151841A KR 20120151841 A KR20120151841 A KR 20120151841A KR 101994084 B1 KR101994084 B1 KR 101994084B1
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- silicon wafer
- composition
- texture
- compound
- crystalline silicon
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- 238000011077 uniformity evaluation Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
Abstract
본 발명은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것으로서, 보다 상세하게는 화학식 1로 표시되는 염을 포함함으로써, 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화하여 광 효율을 증가시키고, 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a texture etchant composition of a crystalline silicon wafer and a method of etching the same, and more particularly, to a method of etching a crystalline silicon wafer by incorporating a salt represented by the general formula (I) into a fine pyramid structure on the surface of a crystalline silicon wafer. And to improve the appearance of the surface of the wafer after the texture process by removing impurities on the surface of the silicon wafer by minimizing the quality deviation of the silicon wafer and the texture etching method of the crystalline silicon wafer.
Description
본 발명은 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차를 최소화하여 광효율을 높일 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.
The present invention relates to a texture etching liquid composition for a crystalline silicon wafer and a texture etching method capable of increasing light efficiency by minimizing a texture quality deviation of a surface of a crystalline silicon wafer.
최근 들어 급속하게 보급되고 있는 태양전지는 차세대 에너지원으로서 클린 에너지인 태양 에너지를 직접 전기로 변환하는 전자 소자로서, 실리콘에 붕소를 첨가한 P형 실리콘 반도체를 기본으로 하여 그 표면에 인을 확산시켜 N형 실리콘 반도체층을 형성시킨 PN 접합 반도체 기판으로 구성되어 있다.In recent years, solar cells, which are rapidly spreading, are electronic devices that convert solar energy, which is a clean energy source, into direct electricity as a next-generation energy source. P-type silicon semiconductor doped with boron is used as silicon, And a PN junction semiconductor substrate in which an N-type silicon semiconductor layer is formed.
PN 접합에 의해 전계가 형성된 기판에 태양광과 같은 빛을 조사할 경우 반도체 내의 전자(-)와 정공(+)이 여기되어 반도체 내부를 자유로이 이동하는 상태가 되며, 이러한 PN 접합에 의해 생긴 전계에 들어오게 되면 전자(-)는 N형 반도체에, 정공(+)은 P형 반도체에 이르게 된다. P형 반도체와 N형 반도체 표면에 전극을 형성하여 전자를 외부회로로 흐르게 하면 전류가 발생하게 되는데, 이와 같은 원리로 태양 에너지가 전기 에너지로 변환된다. 따라서 태양 에너지의 변환 효율을 높이기 위해서 PN 접합 반도체 기판의 단위 면적당 전기적 출력을 극대화시켜야 하며, 이를 위해서 반사율은 낮게 하고 광 흡수량은 최대화시켜야 한다. 이러한 점을 고려하여 PN 접합 반도체 기판을 구성하는 태양전지용 실리콘 웨이퍼의 표면을 미세 피라미드 구조로 형성시키고 반사 방지막을 처리하고 있다. 미세 피라미드 구조로 텍스쳐링된 실리콘 웨이퍼의 표면은 넓은 파장대를 갖는 입사광의 반사율을 낮춰 기 흡수된 광의 강도를 증가시킴으로써 태양전지의 성능, 즉 효율을 높일 수 있게 된다.When a light such as sunlight is irradiated to a substrate formed with an electric field by PN junction, electrons (-) and holes (+) in the semiconductor are excited to move freely in the semiconductor, and the electric field generated by the PN junction When it comes in, the electrons (-) lead to the N-type semiconductor and the positive (+) lead to the P-type semiconductor. When an electrode is formed on the surface of a p-type semiconductor and an n-type semiconductor and an electron flows to an external circuit, a current is generated. This principle converts solar energy into electrical energy. Therefore, in order to increase the conversion efficiency of solar energy, the electrical output per unit area of the PN junction semiconductor substrate must be maximized. For this, the reflectance should be lowered and the light absorption amount should be maximized. In consideration of this point, the surface of the silicon wafer for a solar cell constituting the PN junction semiconductor substrate is formed into a fine pyramid structure and the antireflection film is processed. The surface of a silicon wafer textured with a fine pyramid structure lowers the reflectance of incident light having a wide wavelength band to increase the intensity of the absorbed light, thereby enhancing the performance, i.e., efficiency, of the solar cell.
실리콘 웨이퍼 표면을 미세 피라미드 구조로 텍스쳐하는 방법으로, 미국특허 제4,137,123호에는 0-75부피%의 에틸렌글리콜, 0.05-50중량%의 수산화칼륨 및 잔량의 물을 포함하는 이방성 에칭액에 0.5-10중량%의 실리콘이 용해된 실리콘 텍스쳐 에칭액이 개시되어 있다. 그러나, 이 에칭액은 피라미드 형성 불량을 일으켜 광 반사율을 증가시키고 효율의 저하를 초래할 수 있다.US Pat. No. 4,137,123 discloses a method of texturing a surface of a silicon wafer with a fine pyramid structure by adding 0.5 to 10 wt. % Of silicon is dissolved in a solvent. However, this etchant may cause pyramid formation failure to increase the light reflectance and lower the efficiency.
또한, 유럽특허 제0477424호에는 에틸렌글리콜, 수산화칼륨 및 잔량의 물에 실리콘을 용해시킨 텍스쳐 에칭액에 산소를 공급시키는, 즉 에어레이팅 공정을 수행하는 텍스쳐 에칭 방법이 개시되어 있다. 그러나, 이 에칭 방법은 피라미드 형성 불량을 일으켜 광 반사율 증가와 효율의 저하를 초래할 뿐만 아니라 별도의 에어레이팅 장비의 설치를 필요로 한다는 단점이 있다.European Patent No. 0477424 discloses a texture etching method in which oxygen is supplied to a texture etchant in which silicon is dissolved in water of ethylene glycol, potassium hydroxide and a residual amount, that is, an air-bearing process is performed. However, this etching method has a disadvantage in that pyramid formation failure is caused to increase the light reflectance and the efficiency, and also requires installation of a separate air-rating equipment.
또한, 한국등록특허 제0180621호에는 수산화칼륨 용액 0.5-5%, 이소프로필알코올 3-20부피%, 탈이온수 75-96.5부피%의 비율로 혼합된 텍스쳐 에칭 용액이 개시되어 있고, 미국특허 제6,451,218호에는 알칼리 화합물, 이소프로필알코올, 수용성 알카리성 에틸렌글리콜 및 물을 포함하는 텍스쳐 에칭 용액이 개시되어 있다. 그러나, 이들 에칭 용액은 비점이 낮은 이소프로필알코올을 포함하고 있어 텍스쳐 공정 중 이를 추가 투입해야 하므로 생산성 및 비용 면에서 경제적이지 못하며, 추가 투입된 이소프로필알코올로 인해 에칭액의 온도 구배가 발생하여 실리콘 웨이퍼 표면의 위치별 텍스쳐 품질 편차가 커져 균일성이 떨어질 수 있다.
Korean Patent No. 0180621 discloses a texture etching solution mixed at a ratio of 0.5-5% of a potassium hydroxide solution, 3-20% by volume of isopropyl alcohol and 75-96.5% by volume of deionized water, and US Patent No. 6,451,218 Discloses a texturing etch solution comprising an alkaline compound, isopropyl alcohol, water soluble alkaline ethylene glycol and water. However, since these etching solutions contain isopropyl alcohol having a low boiling point, it is not economical from the viewpoint of productivity and cost, because it is required to add the additional isopropyl alcohol in the texture process, and the temperature gradient of the etchant is generated due to the added isopropyl alcohol, And the uniformity of the texture may be deteriorated.
본 발명은 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화하여 광 효율을 증가시키고, 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.The present invention relates to a method and apparatus for forming a fine pyramid structure on a surface of a crystalline silicon wafer by minimizing the quality deviation of the texture by position to increase the light efficiency and to remove impurities on the surface of the silicon wafer to improve the appearance of the wafer surface after the texturing process And to provide a textured etchant composition for a crystalline silicon wafer which can be used as an etching solution.
본 발명은 에칭 공정 중 별도의 에칭액 성분의 투입과 에어레이팅 공정의 적용이 필요 없는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a texture etchant composition for a crystalline silicon wafer which does not require the application of a separate etchant component during the etching process and the application of an air-raining process.
본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 텍스쳐 에칭방법을 제공하는 것을 다른 목적으로 한다. Another object of the present invention is to provide a texture etching method using the texture etching solution composition of the crystalline silicon wafer.
본 발명은 상기 조성물로 웨이퍼 기판에 균일하고 미세한 요철을 형성하는 태양전지의 제조방법을 제공하는 것을 다른 목적으로 한다.
It is another object of the present invention to provide a method of manufacturing a solar cell that forms uniform and fine irregularities on a wafer substrate with the above composition.
1. 하기 화학식 1로 표시되는 염을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물:1. A texture etching liquid composition for a crystalline silicon wafer comprising a salt represented by the following Chemical Formula 1:
[화학식 1][Chemical Formula 1]
M2SiX6 M 2 SiX 6
(식 중, M은 NH4 +, K+, Na+ 및 Li+로 이루어진 군에서 선택된 양이온이고;Wherein M is a cation selected from the group consisting of NH 4 + , K + , Na +, and Li + ;
X는 F-, Cl- 및 Br-로 이루어진 군에서 선택된 음이온임).X is an anion selected from the group consisting of F - , Cl - and Br - ).
2. 위 1에 있어서, 상기 화학식 1의 염은 플루오르화규산나트륨(Na2SiF6), 플루오르화규산칼륨(K2SiF6), 플루오르화규산암모늄((NH4)2SiF6) 및 플루오르화규산리튬(Li2SiF6)로 이루어진 군에서 선택된 적어도 1종인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.2. The method of claim 1 wherein the salt of Formula 1 is selected from the group consisting of sodium fluorosilicate (Na 2 SiF 6 ), potassium fluorosilicate (K 2 SiF 6 ), ammonium fluorosilicate ((NH 4 ) 2 SiF 6 ) And lithium fluorosilicate (Li 2 SiF 6 ).
3. 위 1에 있어서, 상기 화학식 1의 염은 에칭액 조성물 총 100중량%에 대하여 0.01 내지 5중량%로 포함되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.3. The composition of claim 1, wherein the salt of Formula 1 is contained in an amount of 0.01 to 5% by weight based on 100% by weight of the total etching solution composition.
4. 위 1에 있어서, 알칼리 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.4. The texture etching liquid composition for a crystalline silicon wafer according to 1 above, further comprising an alkaline compound.
5. 위 4에 있어서, 상기 알칼리 화합물은 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄 및 테트라히드록시에틸암모늄으로 이루어진 군으로부터 선택되는 적어도 1종인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.5. The composition for etching a crystalline silicon wafer according to 4 above, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium.
6. 위 4에 있어서, 상기 알칼리 화합물은 에칭액 조성물 총 100중량%에 대하여 0.1 내지 20중량%로 포함되는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.6. The composition for etching a crystalline silicon wafer according to 4 above, wherein the alkali compound is contained in an amount of 0.1 to 20% by weight based on 100% by weight of the total etching solution composition.
7. 위 1에 있어서, 다당류를 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.7. The texture etching liquid composition of the crystalline silicon wafer according to 1 above, further comprising a polysaccharide.
8. 위 7에 있어서, 상기 다당류는 글루칸계 화합물, 프룩탄계 화합물, 만난계 화합물, 갈락탄계 화합물 및 이들의 금속염으로 이루어진 군으로부터 선택되는 적어도 1종인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.8. The composition for etching a crystalline silicon wafer according to 7 above, wherein the polysaccharide is at least one selected from the group consisting of a glucan compound, a fructan compound, a mannan compound, a galactan compound, and a metal salt thereof.
9. 위 7에 있어서, 상기 다당류는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 및 이들의 금속염으로 이루어진 군으로부터 선택되는 적어도 1종인 글루칸계 화합물인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.9. The composition of claim 7 wherein said polysaccharide is selected from the group consisting of cellulose, dimethylaminoethylcellulose, diethylaminoethylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, 4-aminobenzylcellulose, triethylaminoethylcellulose, Cellulose derivatives such as cellulose, ethylcellulose, methylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin,? -Cyclodextrin,? -Cyclodextrin,? -Cyclodextrin, hydroxypropyl-beta-cyclodextrin, methyl- beta -cyclodextrin, dextran, dextran sulfate sodium, saponin, glycogen, ximosan, lentinan, syzofinan and metal salts thereof At least one kind of crystalline compound Texture etching liquid composition of the silicon wafer.
10. 위 1에 있어서, 고리형 화합물을 더 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.10. The texture etchant composition of crystalline silicon wafer as in 1 above, further comprising a cyclic compound.
11. 위 10에 있어서, 고리형 화합물은 비점이 100℃ 이상인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.11. The composition for etching a crystalline silicon wafer of claim 10, wherein the cyclic compound has a boiling point of 100 deg.
12. 위 10에 있어서, 고리형 화합물은 한센의 용해도 파라미터가 6 내지 16인 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물.12. The composition of claim 10, wherein the cyclic compound has a Hansen solubility parameter of 6 to 16.
13. 위 1 내지 12 중 어느 한 항의 에칭액 조성물에 의한 결정성 실리콘 웨이퍼의 텍스쳐 에칭 방법.13. A method of etching a crystalline silicon wafer with an etchant composition according to any one of claims 1 to 12.
14. 위 13에 있어서, 상기 에칭액 조성물을 50 내지 100℃의 온도에서 30초 내지 60분 동안 분무시키는 것을 포함하는 에칭 방법.14. The method of claim 13, comprising spraying the etchant composition at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
15. 위 13에 있어서, 상기 에칭액 조성물에 상기 웨이퍼를 50 내지 100℃의 온도에서 30초 내지 60분 동안 침적시키는 에칭 방법. 15. The etching method according to 13 above, wherein the wafer is immersed in the etching solution composition at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
16. 위 13의 방법으로 기판의 일면에 요철을 형성하는 단계를 포함하는 태양전지의 제조 방법.
16. A method of manufacturing a solar cell comprising the steps of: forming irregularities on one surface of a substrate by the above method 13;
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 따르면 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐의 품질 편차를 최소화, 즉 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시킬 뿐만 아니라 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있다.According to the texture etchant composition and texture etching method of the crystalline silicon wafer of the present invention, it is possible to maximize the amount of absorbed sunlight by minimizing the quality deviation of the texture of the crystalline silicon wafer surface, that is, by improving the texture uniformity, The impurities on the surface can be removed to improve the appearance of the wafer surface after the texturing process.
텍스쳐 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 품질과 생산성을 향상시킬 수 있고 공정 비용 면에서도 경제적이다.
There is no need to add a separate etching solution component in the texture process and there is no need to introduce air rating equipment, which can improve quality and productivity, and is economical in terms of process cost.
도 1은 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물로 텍스쳐된 단결정 실리콘 웨이퍼의 표면을 나타낸 SEM 사진이다.
도 2는 실시예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 이용하여 에칭된 단결정 실리콘 웨이퍼의 텍스쳐를 나타낸 광학현미경 사진이다.
도 3은 비교예 1의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물로 텍스쳐된 단결정 실리콘 웨이퍼의 표면을 나타낸 광학현미경 사진이다.
도 4는 본 발명의 태양전지의 제조 방법의 일 구현예를 개략적으로 도시한 것이다.1 is an SEM photograph showing the surface of a single crystal silicon wafer textured with the etching solution composition for a texture of the crystalline silicon wafer of Example 1. Fig.
2 is an optical microscope photograph showing the texture of a single crystal silicon wafer etched using the etching solution composition for a texture of the crystalline silicon wafer of Example 1. Fig.
3 is an optical microscope photograph showing the surface of a single crystal silicon wafer textured with the etching solution composition for a texture of the crystalline silicon wafer of Comparative Example 1. Fig.
4 schematically shows an embodiment of a method for manufacturing a solar cell according to the present invention.
본 발명은, 화학식 1로 표시되는 염을 포함함으로써, 결정성 실리콘 웨이퍼의 표면에 미세 피라미드 구조를 형성함에 있어서 위치별 텍스쳐의 품질 편차를 최소화하여 광 효율을 증가시키고, 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 및 텍스쳐 에칭방법에 관한 것이다.The present invention relates to a method for forming a fine pyramid structure on a surface of a crystalline silicon wafer by minimizing the quality deviation of the texture by position in order to increase the light efficiency and to remove impurities on the surface of the silicon wafer To a texture etchant composition and a texture etching method of a crystalline silicon wafer capable of improving the appearance of a wafer surface after a texturing process.
이하, 본 발명을 구체적으로 설명하도록 한다.Hereinafter, the present invention will be described in detail.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 하기 화학식 1로 표시되는 염을 포함한다.The texture etchant composition of the crystalline silicon wafer of the present invention comprises a salt represented by the following formula (1).
[화학식 1][Chemical Formula 1]
M2SiX6 M 2 SiX 6
(식 중, M은 NH4 +, K+, Na+ 및 Li+로 이루어진 군에서 선택된 양이온이고;Wherein M is a cation selected from the group consisting of NH 4 + , K + , Na +, and Li + ;
X는 F-, Cl- 및 Br-로 이루어진 군에서 선택된 음이온임).X is an anion selected from the group consisting of F - , Cl - and Br - ).
화학식 1로 표시되는 염은 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시킬 뿐만 아니라 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선한다.The salt represented by formula (1) not only improves the uniformity of the texture to maximize the absorption of sunlight but also removes impurities on the surface of the silicon wafer to improve the appearance of the wafer surface after the texturing process.
화학식 1로 표시되는 염의 종류는 특별히 한정되지 않으며, 예를 들면 플루오르화규산나트륨(Na2SiF6), 플루오르화규산칼륨(K2SiF6), 플루오르화 규산암모늄((NH4)2SiF6), 플루오르화규산리튬(Li2SiF6) 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of the salt represented by the formula (1) is not particularly limited, and examples thereof include sodium fluorosilicate (Na 2 SiF 6 ), potassium fluorosilicate (K 2 SiF 6 ), ammonium fluorosilicate ((NH 4 ) 2 SiF 6 ), Lithium fluorosilicate (Li 2 SiF 6 ), and the like. These may be used alone or in combination of two or more.
화학식 1로 표시되는 염은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 0.01 내지 5중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 0.01 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 텍스쳐 균일성 향상 및 웨이퍼 표면의 외관 개선 효과가 극대화된다.The salt represented by the formula (1) is preferably contained in an amount of 0.01 to 5% by weight, more preferably 0.01 to 1% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, the effect of improving the texture uniformity and improving the appearance of the wafer surface is maximized.
본 발명에 따른 에칭액 조성물은 알칼리 화합물을 더 포함할 수 있다.The etching solution composition according to the present invention may further comprise an alkali compound.
알칼리 화합물은 결정성 실리콘 웨이퍼의 표면을 에칭하는 성분으로서 당분야에서 통상적으로 사용하는 알칼리 화합물이라면 제한없이 사용될 수 있다. 예를 들면 수산화칼륨, 수산화나트륨, 수산화암모늄, 테트라히드록시메틸암모늄, 테트라히드록시에틸암모늄 등을 들 수 있으며, 이 중에서 수산화칼륨, 수산화나트륨이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The alkali compound can be used without limitation as long as it is an alkaline compound commonly used in the art as a component for etching the surface of a crystalline silicon wafer. Examples thereof include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium, among which potassium hydroxide and sodium hydroxide are preferable. These may be used alone or in combination of two or more.
알칼리 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 0.1 내지 20중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 5중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면을 에칭할 수 있게 된다.The alkali compound is preferably contained in an amount of 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, the surface of the silicon wafer can be etched.
선택적으로, 본 발명에 따른 에칭액 조성물은 다당류를 더 포함할 수 있다.Alternatively, the etchant composition according to the present invention may further comprise polysaccharides.
다당류(polysaccharide)는 단당류 2개 이상이 글리코시드 결합하여 큰 분자를 만들고 있는 당류로서, 알칼리 화합물에 의한 과에칭과 에칭 가속화를 방지함으로써 균일한 미세 피라미드를 형성하는 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 빨리 떨어뜨려 버블 스틱 현상을 방지하는 성분이다.A polysaccharide is a saccharide in which two or more monosaccharides are linked by a glycosidic bond to form a large molecule. By preventing over etching and accelerated etching by an alkaline compound, a uniform fine pyramid is formed, and a hydrogen bubble generated by etching It is a component that prevents the bubble stick phenomenon by dropping rapidly from the silicon wafer surface.
다당류의 종류는 특별히 한정되지 않으며, 예를 들면 글루칸계(glucan) 화합물, 프룩탄계(fructan) 화합물, 만난계(mannan) 화합물, 갈락탄계(galactan) 화합물 또는 이들의 금속염 등을 들 수 있으며, 이 중에서 글루칸계 화합물과 이의 금속염(예컨대, 알칼리 금속염)이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polysaccharide include, but are not limited to, a glucan compound, a fructan compound, a mannan compound, a galactan compound, or a metal salt thereof. , A glucan compound and a metal salt thereof (for example, an alkali metal salt) are preferable. These may be used alone or in combination of two or more.
글루칸계 화합물로는 셀룰로오스, 디메틸아미노에틸셀룰로오스, 디에틸아미노에틸셀룰로오스, 에틸히드록시에틸셀룰로오스, 메틸히드록시에틸셀룰로오스, 4-아미노벤질셀룰로오스, 트리에틸아미노에틸셀룰로오스, 시아노에틸셀룰로오스, 에틸셀룰로오스, 메틸셀룰로오스, 카르복시메틸셀룰로오스, 카르복시에틸셀룰로오스, 히드록시에틸셀룰로오스, 히드록시프로필셀룰로오스, 알긴산, 아밀로오스, 아밀로펙틴, 펙틴, 스타치, 덱스트린, α-시클로덱스트린, β-시클로덱스트린, γ-시클로덱스트린, 히드록시프로필-β-시클로덱스트린, 메틸-β-시클로덱스트린, 덱스트란, 덱스트란설페이트나트륨, 사포닌, 글리코겐, 자이모산, 렌티난, 시조피난 또는 이들의 금속염 등을 들 수 있다.Examples of the glucan compound include cellulose, dimethylaminoethylcellulose, diethylaminoethylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, 4-aminobenzylcellulose, triethylaminoethylcellulose, cyanoethylcellulose, ethylcellulose, But are not limited to, cellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin,? -Cyclodextrin,? -Cyclodextrin, Cyclodextrin, methyl- beta -cyclodextrin, dextran, sodium dextran sulfate, saponin, glycogen, zymo acid, lentinan, sijofinan or metal salts thereof.
다당류는 평균 분자량이 5,000 내지 1,000,000인 것일 수 있으며, 바람직하게 50,000 내지 200,000인 것이 좋다.The polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
다당류는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 10-9 내지 0.5중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 0.1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭과 에칭 가속화를 효과적으로 방지할 수 있다. 함량이 0.5중량% 초과인 경우 알칼리 화합물에 의한 에칭 속도를 급격하게 저하시켜 원하는 미세 피라미드를 형성하기 어렵다.The polysaccharide may be contained in an amount of 10 -9 to 0.5% by weight, preferably 10 -6 to 0.1% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, etching and etching acceleration can be effectively prevented. When the content is more than 0.5% by weight, the etching rate by the alkali compound is rapidly lowered and it is difficult to form the desired fine pyramid.
선택적으로, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 고리형 화합물을 더 포함할 수 있다.Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a cyclic compound.
고리형 화합물은 탄소수 4-10의 고리형 탄화수소; 및 N, O 또는 S의 헤테로원자를 1개 이상 포함하는, 탄소수 4-10의 헤테로고리형 탄화수소를 포함하는 화합물을 의미하며, 결정성 실리콘 웨이퍼 표면의 젖음성을 개선시켜 알칼리 화합물에 의한 과에칭을 방지함으로써 텍스쳐의 품질 편차를 최소화시키는 동시에 에칭에 의해 생성된 수소 버블의 양을 빠르게 감소시킴으로써 버블 스틱 현상이 발생하는 것도 방지할 수 있는 성분이다. 또한, 비점이 높아 종래 사용되고 있는 이소프로필알코올에 비해 적은 함량으로 사용이 가능할 뿐만 아니라 동일 사용량에 대한 처리 매수도 증가시킬 수 있다.The cyclic compound is a cyclic hydrocarbon having 4-10 carbon atoms; And a heterocyclic hydrocarbon having 4 to 10 carbon atoms and containing at least one hetero atom of N, O or S. The wettability of the surface of the crystalline silicon wafer is improved, Thereby minimizing the quality deviation of the texture, and at the same time, rapidly reducing the amount of hydrogen bubbles generated by etching, thereby preventing occurrence of bubble stick phenomenon. In addition, since it has a high boiling point, it can be used in a small amount as compared with isopropyl alcohol which is conventionally used, and the number of treatments for the same amount can also be increased.
고리형 화합물은 비점이 100℃ 이상으로 높은 것이 바람직하고, 보다 바람직하게는 150 내지 400℃인 것이 좋다. 동시에, 고리형 화합물은 한센의 용해도 파라미터(Hansen solubility parameter(HSP), δp)가 6 내지 16인 것이 에칭액 조성물에 포함되는 다른 성분들과의 상용성 면에서 바람직하다.The cyclic compound preferably has a boiling point of 100 占 폚 or higher, more preferably 150 to 400 占 폚. At the same time, it is preferable that the cyclic compound has a solubility parameter (Hansen solubility parameter (HSP),? P) of 6 to 16 in view of compatibility with other components contained in the etching solution composition.
고리형 화합물은 비점과 한센의 용해도 파라미터를 만족시키는 것이라면 그 종류가 특별히 한정되지 않으며, 예를 들면 피페라진계, 모르폴린계, 피리딘계, 피페리딘계, 피페리돈계, 피롤리딘계, 피롤리돈계, 이미다졸리디논계, 퓨란계, 아닐린계, 톨루이딘계, 아민계, 락톤계, 카보네이트계, 카바졸계 화합물 등을 들 수 있다. 구체적인 예로는, 피페라진, N-메틸피페라진, N-에틸피페라진, N-비닐피페라진, N-비닐메틸피페라진, N-비닐에틸피페라진, N-비닐-N'-메틸피페라진, N-아크릴로일피페라진, N-아크릴로일-N'-메틸피페라진, 히드록시에틸피페라진, N-(2-아미노에틸)피페라진, N,N'-디메틸피페라진; 모르폴린, N-메틸모르폴린, N-에틸모르폴린, N-페닐모르폴린, N-비닐모르폴린, N-비닐메틸모르폴린, N-비닐에틸모르폴린, N-아크릴로일모르폴린, N-코코모르폴린, N-(2-아미노에틸)모르폴린, N-(2-시아노에틸)모르폴린, N-(2-히드록시에틸)모르폴린, N-(2-히드록시프로필)모르폴린, N-아세틸모르폴린, N-포밀모르폴린, N-메틸모르폴린-N-옥사이드; 메틸피리딘; N-메틸피페리딘, 3,5-디메틸피페리딘, N-에틸피페리딘, N-(2-히드록시에틸)피페리딘; N-비닐피페리돈, N-비닐메틸피페리돈, N-비닐에틸피페리돈, N-아크릴로일피페리돈, N-메틸-4-피페리돈, N-비닐-2-피페리돈; N-메틸피롤리딘; N-비닐피롤리돈, N-비닐메틸피롤리돈, N-비닐에틸-2-피롤리돈, N-아크릴로일피롤리돈, N-메틸피롤리돈, N-에틸-2-피롤리돈, N-이소프로필-2-피롤리돈, N-부틸-2-피롤리돈, N-t-부틸-2-피롤리돈, N-헥실-2-피롤리돈, N-옥틸-2-피롤리돈, N-벤질-2-피롤리돈, N-시클로헥실-2-피롤리돈, N-비닐-2-피롤리돈, N-(2-히드록시에틸)-2-피롤리돈, N-(2-메톡시에틸)-2-피롤리돈, N-(2-메톡시프로필)-2-피롤리돈, N-(2-에톡시에틸)-2-피롤리돈; N-메틸 이미다졸리디논, 디메틸이미다졸리디논, N-(2-히드록시에틸)-2-이미다졸리디논; 테트라히드로퓨란, 테트라히드로-2-퓨란메탄올; N-메틸아닐린, N-에틸아닐린, N,N-디메틸아닐린, N-(2-히드록시에틸)아닐린, N,N-비스-(2-히드록시에틸)아닐린, N-에틸-N-(2-히드록시에틸)아닐린; N,N-디에틸-o-톨루이딘, N-에틸-N-(2-히드록시에틸)-m-톨루이딘; 디메틸벤질아민; γ-부티로락톤; 에틸렌카보네이트, 프로필렌카보네이트; N-비닐카바졸, N-아크릴로일카바졸 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The type of the cyclic compound is not particularly limited as long as it satisfies the solubility parameter of the boiling point and Hansen. Examples of the cyclic compound include piperazine, morpholine, pyridine, piperidine, piperidine, pyrrolidine, Pyran, aniline, toluidine, amine, lactone, carbonate, carbazole, and the like. Specific examples include piperazine, N-methylpiperazine, N-ethylpiperazine, N-vinylpiperazine, N-vinylmethylpiperazine, N-vinylethylpiperazine, N-vinyl- N-acryloylpiperazine, N-acryloyl-N'-methylpiperazine, hydroxyethylpiperazine, N- (2-aminoethyl) piperazine, N, N'-dimethylpiperazine; Methylmorpholine, N-ethylmorpholine, N-phenylmorpholine, N-vinylmorpholine, N-vinylmethylmorpholine, N-vinylethylmorpholine, N-acryloylmorpholine, N N- (2-hydroxyethyl) morpholine, N- (2-hydroxyethyl) morpholine, N- Morpholine, N-acetylmorpholine, N-formylmorpholine, N-methylmorpholine-N-oxide; Methyl pyridine; N-methylpiperidine, 3,5-dimethylpiperidine, N-ethylpiperidine, N- (2-hydroxyethyl) piperidine; N-vinylpiperidone, N-vinylmethylpiperidone, N-vinylethylpiperidone, N-acryloylpiperidone, N-methyl-4-piperidone, N-vinyl-2-piperidone; N-methylpyrrolidine; N-vinylpyrrolidone, N-vinylmethylpyrrolidone, N-vinylethyl-2-pyrrolidone, N-acryloylpyrrolidone, N-methylpyrrolidone, Butyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-butyl- Pyrrolidone, N-benzyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N- - (2-methoxyethyl) -2-pyrrolidone, N- (2-methoxypropyl) -2-pyrrolidone, N- (2-ethoxyethyl) -2-pyrrolidone; N-methylimidazolidinone, dimethylimidazolidinone, N- (2-hydroxyethyl) -2-imidazolidinone; Tetrahydrofuran, tetrahydro-2-furan methanol; N, N-dimethylaniline, N, N-bis (2-hydroxyethyl) aniline, N-ethyl- 2-hydroxyethyl) aniline; N, N-diethyl-o-toluidine, N-ethyl-N- (2-hydroxyethyl) -m-toluidine; Dimethylbenzylamine; ? -butyrolactone; Ethylene carbonate, propylene carbonate; N-vinylcarbazole, N-acryloylcarbazole, etc. These may be used alone or in admixture of two or more.
고리형 화합물은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 100중량%에 대하여 0.1 내지 50중량%로 포함되는 것이 바람직하고, 보다 바람직하게는 1 내지 10중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 실리콘 웨이퍼 표면의 젖음성을 효과적으로 개선시켜 텍스쳐 품질 편차를 최소화킴으로써 균일성을 향상시킬 수 있다.The cyclic compound is preferably contained in an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight based on 100% by weight of the total amount of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, the wettability of the surface of the silicon wafer is effectively improved, thereby minimizing the texture quality deviation, thereby improving the uniformity.
고리형 화합물은 수용성 극성 용매와 혼합된 것일 수도 있다.The cyclic compound may be mixed with a water-soluble polar solvent.
수용성 극성 용매는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 포함되는 다른 성분들 및 물과 상용성이 있는 것이라면 그 종류가 특별히 한정되지 않으며, 양자성 또는 비양자성 극성 용매를 모두 사용할 수 있다.The type of the water-soluble polar solvent is not particularly limited as long as it is compatible with other components contained in the texture etching solution composition of the crystalline silicon wafer and with water, and both quantum and aprotic polar solvents can be used.
양자성 극성 용매로는 에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노메틸에테르, 폴리에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르, 트리에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르 등의 에테르계 화합물; 프로판올, 부탄올, 이소프로판올, 테트라하이드로퍼푸릴알코올, 에틸렌글리콜, 프로필렌글리콜 등의 알코올계 화합물 등을 들 수 있으며, 비양자성 극성 용매로는 N-메틸포름아미드, N,N-디메틸포름아미드 등의 아미드계 화합물; 디메틸술폭사이드, 술폴란 등의 술폭사이드계 화합물; 트리에틸포스페이트, 트리부틸포스페이트 등의 포스페이트계 화합물 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the protonic polar solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; And alcoholic compounds such as propanol, butanol, isopropanol, tetrahydroperfuryl alcohol, ethylene glycol and propylene glycol. Examples of the aprotic polar solvent include amides such as N-methylformamide and N, N-dimethylformamide Based compound; Sulfoxide compounds such as dimethyl sulfoxide and sulfolane; And phosphate-based compounds such as triethyl phosphate and tributyl phosphate. These may be used alone or in combination of two or more.
수용성 극성 용매는 고리형 화합물 총 100중량%에 대하여 0.1 내지 30중량%로 포함될 수 있다.The water-soluble polar solvent may be contained in an amount of 0.1 to 30% by weight based on 100% by weight of the total amount of the cyclic compound.
선택적으로, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 질소 원자를 적어도 하나 포함하는 탄소수 4 내지 10인 고리 화합물로 치환된 단량체가 중합된 고분자를 더 포함할 수 있다.Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a polymer in which a monomer substituted with a cyclic compound having 4 to 10 carbon atoms containing at least one nitrogen atom is polymerized.
상기 고분자는 실리콘 결정 방향에 대한 에칭 속도의 차이를 제어함으로써 알칼리 화합물에 의한 과에칭을 방지함으로써 텍스쳐의 품질 편차를 최소화할 수 있으며, 에칭에 의해 생성된 수소 버블의 양을 빠르게 감소시킴으로써 버블 스틱 현상이 발생하는 것도 억제한다.By controlling the difference in the etching rate with respect to the direction of the silicon crystal, the polymer prevents the over etching by the alkaline compound, thereby minimizing the quality deviation of the texture. By rapidly reducing the amount of hydrogen bubbles generated by etching, the bubble stick phenomenon Is suppressed.
본 발명에 따른 고분자는 질소 헤테로 원자를 적어도 하나 포함하는 탄소수 4 내지 10인 고리 화합물이 치환된 단량체가 중합되어 형성되며, 상기 단량체는 질소 외에 산소, 황 원자를 단독으로 또는 모두를 각각 적어도 하나 이상 그 고리 구조에 더 포함할 수 있다. 이러한 단량체로서 구체적인 예를 들면, N-비닐피롤리돈, N-아크릴로일 모르폴린, N-비닐석신이미드, N-아크릴옥시석신이미드, N-비닐카프로락탐, N-비닐카바졸, N-아크릴로일피롤리딘 등으로 이루어진 군에서 선택되는 1종 이상일 수 있다.The polymer according to the present invention is formed by polymerizing monomers substituted with a cyclic compound having 4 to 10 carbon atoms and having at least one nitrogen heteroatom, and the monomer may contain oxygen or sulfur atoms alone or in combination with at least one And may further include the ring structure. Specific examples of such monomers include N-vinylpyrrolidone, N-acryloylmorpholine, N-vinylsuccinimide, N-acryloxysuccinimide, N-vinylcaprolactam, N-vinylcarbazole, N-acryloylpyrrolidine, and the like.
본 발명에 따른 고분자는 중량평균 분자량이 1,000 내지 1,000,000인 것이 피라미드의 밑변각을 높힘으로써 반사율을 낮출 수 있을 뿐만 아니라 단결정 실리콘 웨이퍼 전면에 균일한 피라미드를 형성시킬 수 있다는 점에서 바람직하다.The polymer according to the present invention has a weight average molecular weight of 1,000 to 1,000,000, which is preferable because it can lower the reflectance by increasing the angle of the base of the pyramid, and can form a uniform pyramid on the entire surface of the single crystal silicon wafer.
또한, 본 발명에 따른 고분자는 비점이 100℃ 이상으로 높은 것이 사용량을 줄일 수 있는 측면에서 바람직하고, 보다 바람직하게는 150 내지 400℃인 것이 좋다.The polymer according to the present invention has a boiling point of 100 ° C or higher, which is preferable in view of reducing the amount of use, and more preferably 150 to 400 ° C.
본 발명에 따른 고분자는 그 함량이 에칭액 조성물 총 중량 대비 10-12 내지 1 중량%로 포함될 수 있다. 함량이 상기 범위에 해당되는 경우 실리콘의 결정방향에 대한 에칭 속도 차이를 제어하는 효과가 극대화된다.The content of the polymer according to the present invention may be in the range of 10 -12 to 1% by weight based on the total weight of the etchant composition. When the content is within the above range, the effect of controlling the etching rate difference with respect to the crystal direction of silicon is maximized.
본 발명에 따른 고분자는 수용성 극성 용매와 혼합된 것일 수도 있다.The polymer according to the present invention may be mixed with a water-soluble polar solvent.
수용성 극성 용매는 상기 고리형 화합물의 경우와 동일한 용매를 사용할 수 있다. 수용성 극성 용매는 고분자 총 100중량%에 대하여 0.1 내지 30중량%로 포함될 수 있다.As the water-soluble polar solvent, the same solvent as the above-mentioned cyclic compound can be used. The water-soluble polar solvent may be contained in an amount of 0.1 to 30% by weight based on 100% by weight of the polymer.
선택적으로, 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 지방산 또는 이의 금속염; 및 폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 더 포함할 수 있다.Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may comprise a fatty acid or a metal salt thereof; And at least one additive selected from the group consisting of a polyoxyethylene (POE) compound, a polyoxypropylene (POP) compound, and a copolymer thereof, which are surfactants.
지방산 및 이의 금속염은 다당류와 함께 사용되어 알칼리 화합물에 의한 과에칭을 방지함으로써 균일한 미세 피라미드를 형성하고 동시에 에칭에 의해 생성된 수소 버블을 실리콘 웨이퍼 표면으로부터 빨리 떨어뜨려 버블 스틱 현상이 발생하는 것도 방지하는 성분이다.Fatty acids and their metal salts are used in combination with polysaccharides to prevent over-etching by alkaline compounds to form uniform fine pyramids and at the same time to quickly drop hydrogen bubbles generated by etching from the silicon wafer surface to prevent bubble sticking Lt; / RTI >
지방산은 카르복시기를 함유하는 탄화수소 사슬의 카르복시산으로서, 구체적으로 아세트산, 프로피온산, 부틸산, 발레르산, 에난틱산, 카프릴산, 펠라곤산, 카프릭산, 라우르산, 미리스트산, 팔미트산, 스테아르산, 아라키드산, 베헨산, 리그노세린산, 세로트산, 에이코사펜타엔산, 도코사헥사엔산, 리놀레산, α-리놀렌산, γ-리놀렌산, 디호모-γ-리놀렌산, 아라키돈산, 올레산, 엘라이드산, 에루스산, 네르본산 등을 들 수 있다. 또한, 지방산의 금속염은 위 지방산과 NaOH 또는 KOH와 같은 금속염의 에스테르 반응물을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The fatty acid is a carboxylic acid of a hydrocarbon chain containing a carboxy group and specifically includes acetic acid, propionic acid, butyric acid, valeric acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, But are not limited to, stearic acid, arachidic acid, behenic acid, lignoceric acid, cetric acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid,? -Linolenic acid,? -Linolenic acid, dihomo- Oleic acid, elaidic acid, erucic acid, nerbonic acid, and the like. The metal salt of the fatty acid may be an ester reaction product of a fatty acid and a metal salt such as NaOH or KOH. These may be used alone or in combination of two or more.
지방산 및 이의 금속염은 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 10-9 내지 10중량%로 포함될 수 있으며, 바람직하게는 10-6 내지 1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 과에칭을 효과적으로 방지할 수 있다.The fatty acid and its metal salt may be contained in an amount of 10 -9 to 10% by weight, preferably 10 -6 to 1% by weight, based on the total weight of the texture etching liquid composition of the crystalline silicon wafer. When the content falls within the above range, etching can be effectively prevented.
폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체는 히드록시기를 갖는 계면활성제로서 텍스쳐 에칭액 조성물 중 히드록시 이온[OH-]의 활동도를 조절하여 Si100 방향과 Si111 방향에 대한 에칭 속도의 차이를 감소시킬 뿐만 아니라 결정성 실리콘 웨이퍼 표면의 젖음성을 개선시켜 에칭에 의해 생성된 수소 버블을 빠르게 떨어뜨려 버블 스틱 현상이 발생하는 것도 방지하는 성분이다.Polyoxyethylene-based (POE) with a compound, polyoxypropylene-based (POP) compounds and their copolymers control the activity of the hydroxyl ions [OH-] of the texture etching solution composition as a surface active agent having a hydroxy group to Si direction 100 Not only the difference in the etching rate with respect to the Si 111 direction is reduced but also the wettability of the surface of the crystalline silicon wafer is improved to rapidly drop the hydrogen bubble generated by the etching to prevent the occurrence of the bubble stick phenomenon.
폴리옥시에틸렌계(POE) 계면활성제로는 폴리옥시에틸렌글리콜, 폴리옥시에틸렌글리콜메틸에테르, 폴리옥시에틸렌모노알릴에테르, 폴리옥시에틸렌네오펜틸에테르, 폴리에틸렌글리콜모노(트리스티릴페닐)에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌트리데실에테르, 폴리옥시에틸렌데실에테르, 폴리옥시에틸렌옥틸에테르, 폴리옥시에틸렌비스페놀-A에테르, 폴리옥시에틸렌글리세린에테르, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌벤질에테르, 폴리옥시에틸렌페닐에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌페놀에테르, 알킬기의 탄소수가 6-30인 폴리옥시에틸렌알킬시클로헥실에테르, 폴리옥시에틸렌β-나프톨에테르, 폴리옥시에틸렌 캐스터 에테르(polyoxyethylene castor ether), 폴리옥시에틸렌 수소화 캐스터 에테르(polyoxyethylene hydrogenated castor ether); 폴리옥시에틸렌라우릴에스테르, 폴리옥시에틸렌스테아릴에스테르, 폴리옥시에틸렌올레일에스테르; 폴리옥시에틸렌라우릴아민, 폴리옥시에틸렌스테아릴아민, 폴리옥시에틸렌탈로우아민 등을 들 수 있다. 또한, 폴리옥시프로필렌계(POP) 계면활성제로는 폴리프로필렌글리콜을 들 수 있다. 또한, 폴리옥시에틸렌계(POE) 화합물과 폴리옥시프로필렌계(POP)계 화합물의 공중합체로는 폴리옥시에틸렌-폴리옥시프로필렌 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 운데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 도데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 테트라데카닐에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 2-에틸헥실에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 라우릴에테르 공중합체, 폴리옥시에틸렌-폴리옥시프로필렌 스테아릴에테르 공중합체, 글리세린 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체, 에틸렌디아민 부가형 폴리옥시에틸렌-폴리옥시프로필렌 공중합체 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the polyoxyethylene (POE) surfactant include polyoxyethylene glycol, polyoxyethylene glycol methyl ether, polyoxyethylene monoallyl ether, polyoxyethylene neopentyl ether, polyethylene glycol mono (tristyrylphenyl) ether, polyoxyethylene Polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene tridecyl ether, polyoxyethylene decyl ether, polyoxyethylene octyl ether, polyoxyethylene bisphenol-A, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Ether, polyoxyethylene glycerin ether, polyoxyethylene nonylphenyl ether, polyoxyethylene benzyl ether, polyoxyethylene phenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene phenol ether, polyoxyethylene having 6 to 30 carbon atoms in the alkyl group Ethylene alkyl cyclohexyl ether, polyoxyethylene beta -naphthol ether, polyoxyethylene Ethylene castor ether (polyoxyethylene castor ether), polyoxyethylene hydrogenated castor ether (polyoxyethylene hydrogenated castor ether); Polyoxyethylene lauryl ester, polyoxyethylene stearyl ester, polyoxyethylene oleyl ester; Polyoxyethylene laurylamine, polyoxyethylene stearylamine, polyoxyethylenetraelamine, and the like. As the polyoxypropylene (POP) surfactant, polypropylene glycol can be mentioned. As a copolymer of a polyoxyethylene (POE) compound and a polyoxypropylene (POP) based compound, a polyoxyethylene-polyoxypropylene copolymer, a polyoxyethylene-polyoxypropylene decaneyl ether copolymer, a polyoxyethylene Polyoxyethylene-polyoxypropylene dodecanyl ether copolymer, polyoxyethylene-polyoxypropylene tetradecanyl ether copolymer, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether copolymer Polyoxyethylene-polyoxypropylene lauryl ether copolymer, polyoxyethylene-polyoxypropylene stearyl ether copolymer, glycerin addition type polyoxyethylene-polyoxypropylene copolymer, ethylenediamine addition type polyoxyethylene-polyoxypropylene Copolymers and the like. These may be used alone or in combination of two or more.
폴리옥시에틸렌계(POE) 화합물, 폴리옥시프로필렌계(POP) 화합물 및 이들의 공중합체인 계면활성제는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물 총 중량 대비 10-9 내지 10중량%로 포함될 수 있고, 바람직하게는 10-6 내지 1중량%, 보다 바람직하게는 0.00001 내지 0.1중량%인 것이 좋다. 함량이 상기 범위에 해당되는 경우 결정성 실리콘 웨이퍼 표면의 텍스쳐 시 위치별 텍스쳐 품질의 편차를 감소시킬 수 있다.The polyoxyethylene (POE) compound, the polyoxypropylene (POP) compound and the surfactant which is a copolymer thereof may be contained in an amount of 10 -9 to 10% by weight based on the total weight of the texture etching liquid composition of the crystalline silicon wafer, Is preferably 10 -6 to 1% by weight, more preferably 0.00001 to 0.1% by weight. When the content falls within the above range, it is possible to reduce a variation in the texture quality of the surface of the crystalline silicon wafer at each texture position.
본 발명에 따른 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 상기 성분들을 구체적인 필요에 따라 적절하게 채택한 후, 물을 첨가하여 전체 조성을 조절하게 되어 전체 조성물의 잔량은 물이 차지한다. 바람직하게는 상기 성분들이 전술한 함량 범위를 갖도록 조절한다.The texture etchant composition of the crystalline silicon wafer according to the present invention may appropriately employ the above-mentioned components according to specific needs, and then add water to adjust the overall composition, so that the remaining amount of the entire composition is occupied by water. Preferably, the components are adjusted to have the aforementioned content ranges.
물의 종류는 특별히 한정되지 않으나, 탈이온 증류수인 것이 바람직하고, 보다 바람직하게는 반도체 공정용 탈이온 증류수로서 비저항값이 18㏁/㎝ 이상인 것이 좋다.The kind of water is not particularly limited, but it is preferably deionized distilled water. More preferably, it is deionized distilled water for semiconductor processing and has a resistivity value of 18 M OMEGA. / Cm or more.
상기와 같은 성분을 포함하여 구성되는 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은, 특히 화학식 1로 표시되는 염을 포함함으로써 결정성 실리콘 웨이퍼 표면의 위치별 텍스쳐의 품질 편차를 최소화, 즉 텍스쳐의 균일성을 향상시켜 태양광의 흡수량을 극대화시킬뿐만 아니라 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있다. 또한, 텍스쳐 에칭 공정 중 별도의 에칭액 성분을 투입할 필요가 없고 에어레이팅 장비도 도입할 필요가 없어 생산성과 비용 면에서 이점이 있다.The texture etching solution composition of the crystalline silicon wafer of the present invention comprising the above-mentioned components minimizes the quality deviation of the texture of the crystalline silicon wafer surface by the position of the surface represented by the formula (1) It is possible to maximize the amount of sunlight absorption by improving the uniformity and to remove the impurities on the surface of the silicon wafer to improve the appearance of the wafer surface after the texturing process. In addition, there is no need to add a separate etching solution component in the texture etching process and there is no need to introduce an air-rating equipment, which is advantageous in terms of productivity and cost.
본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물은 통상의 에칭 공정, 예컨대 딥방식, 분무방식 및 매엽방식의 에칭 공정에 모두 적용 가능하다.The texture etchant composition of the crystalline silicon wafer of the present invention can be applied to a general etching process, for example, a dip process, a spray process, and a sheet-process etching process.
본 발명은 상기 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물을 이용한 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법을 제공한다.The present invention provides a method of etching a crystalline silicon wafer using the texture etchant composition of the crystalline silicon wafer.
결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물에 결정성 실리콘 웨이퍼를 침적시키는 단계, 또는 본 발명의 결정성 실리콘웨이퍼의 텍스쳐 에칭액 조성물을 결정성 실리콘 웨이퍼에 분무하는 단계, 또는 상기 두 단계를 모두 포함한다.The method of texturing a crystalline silicon wafer includes the steps of depositing a crystalline silicon wafer on the texture etchant composition of the crystalline silicon wafer of the present invention or by spraying a textured etchant composition of the crystalline silicon wafer of the present invention onto a crystalline silicon wafer Step, or both of the above steps.
침적과 분무의 횟수는 특별히 한정되지 않으며, 침적과 분무를 모두 수행하는 경우 그 순서도 한정되지 않는다.The number of times of deposition and spraying is not particularly limited, and the order of deposition and spraying is not limited.
침적, 분무 또는 침적 및 분무하는 단계는 50 내지 100℃의 온도에서 30초 내지 60분 동안 수행될 수 있다.The step of depositing, spraying or depositing and spraying can be carried out at a temperature of 50 to 100 캜 for 30 seconds to 60 minutes.
상기한 바와 같은 본 발명의 결정성 실리콘 웨이퍼의 텍스쳐 에칭방법은 산소를 공급시키는 별도의 에어레이팅 장비를 도입할 필요가 없어 초기 생산 및 공정 비용 면에서 경제적일 뿐만 아니라 간단한 공정으로도 균일한 미세 피라미드 구조의 형성을 가능하게 하게 하며, 실리콘 웨이퍼 표면의 불순물을 제거하여 텍스쳐 공정 후 웨이퍼 표면의 외관을 개선할 수 있다. The texture etching method of the crystalline silicon wafer of the present invention as described above is not only economical in terms of initial production and processing cost but also requires no separate airrating equipment for supplying oxygen, Structure can be formed, and the appearance of the wafer surface after the texturing process can be improved by removing impurities on the surface of the silicon wafer.
본 발명은 상기 결정성 실리콘 웨이퍼 기판의 텍스쳐 에칭 방법으로 기판의 일면에 요철을 형성하는 단계를 포함하는 태양전지의 제조 방법을 제공한다.The present invention provides a method of manufacturing a solar cell including a step of forming irregularities on one surface of a substrate by a texture etching method of the crystalline silicon wafer substrate.
도 4에 본 발명의 태양전지의 제조 방법의 일 구현예가 개략적으로 도시되어 있는데, 이하 도 4를 참조하여 본 발명의 태양전지의 제조 방법의 일 구현예를 설명한다.Fig. 4 schematically shows one embodiment of the method for manufacturing the solar cell of the present invention. Hereinafter, an embodiment of the method for manufacturing the solar cell of the present invention will be described with reference to Fig.
본 발명의 태양전지의 제조 방법에 의하면, 먼저 상기 결정성 실리콘 웨이퍼 기판의 텍스쳐 에칭 방법으로 기판(110)의 일면에 요철을 형성한다.According to the manufacturing method of the solar cell of the present invention, the concave and convex portions are formed on one surface of the
기판(110)은 단결정 또는 다결정 실리콘 웨이퍼 기판으로, P형 불순물로서 3족 원소인 B, Ga, In 등이 도핑된 것일 수 있다.The
기판(110)을 에칭액 조성물에 침지하거나 에칭액 조성물을 기판에 분무하면 에칭이 진행되어 기판(110)의 표면에 요철이 형성된다.When the
요철 형성에 의해 기판의 표면이 거칠어지면 입사되는 광의 반사율이 감소하여 광 포획량이 증가하므로 광학적 손실이 감소된다.If the surface of the substrate is roughened by the unevenness formation, the reflectance of the incident light decreases, and the optical trapping amount increases, thereby reducing the optical loss.
요철(115)의 크기(가로폭) 특별히 한정되지 않으며, 예를 들면 1 내지 10㎛의 크기로 형성될 수 있다.The size (width) of the
요철(115)의 높이는 특별히 한정되지 않으며, 예를 들면 1 내지 15㎛일 수 있다. 요철(115)의 높이가 상기 범위에 해당하는 경우, 180㎛ 이하의 두께를 가지는 기판(110)에 적용할 수 있으며, 이후에 요철(115) 상에 형성될 수 있는 에미터층이 균일한 도핑 프로필을 가지고 형성되어 기판과 에미터 층의 계면의 P-N접합의 균일도가 향상될 수 있으며, 이후에 전면 전극 형성용 페이스트가 요철(115)의 형상에 따라 형성된 오목한 부분까지 충진되어 도포될 수 있어 반사방지막(130)과의 사이에서 공극이 발생하는 것을 방지할 수 있으며, 이에 따라 전면 전극(140)의 저항이 감소할 수 있다.The height of the concavity and
요철(115)의 형태는 특별히 한정되지 않으며, 예를 들면 피라미드형, 정사각형, 삼각형 등을 들 수 있다.The shape of the concavity and
요철(115) 형성 이후에 통상적인 태양전지의 제조 공정을 거쳐서 태양전지를 제조할 수 있으며, 예를 들면 요철 상에 에미터층(120)을 형성하는 단계; 에미터층 상에 반사방지막(130)을 형성하는 단계; 반사방지막을 관통하여 에미터층과 접속하는 전면 전극(140)을 형성하는 단계; 및 기판 후면에 후면 전극(150)을 형성하는 단계를 포함하여 제조할 수 있다.After the formation of the
이후, 요철이 형성된 기판 상에 에미터층(120)을 형성한다.Thereafter, the
에미터층(120)은 기판(110) 상에 기판(110)과 반대 도전형을 가지고 형성될 수 있다. 일 예로 에미터층(120)은 N형 불순물로서 5족 원소인 P, As, Sb 등으로 도핑될 수 있다. 이와 같이, 기판(110)과 에미터층(120)에 반대 도전형의 불순물이 도핑 되면, 기판(110)과 에미터층(120)의 계면에는 P-N 접합(junction)이 형성되고, P-N 접합에 광이 조사되면 광전효과에 의해 광기전력이 발생할 수 있다.The
에미터층(120)은 확산법, 스프레이법, 주입법, 프린팅 공정법 등에 의한 방법에 의해 형성될 수 있다. 일 예로, 에미터층(120)은 P형 반도체 기판(110)에 N형 불순물을 주입함으로써 형성될 수 있다.The
이후, 에미터층(120) 상에 반사방지막(130)을 형성한다.Thereafter, an
반사방지막(130)은 에미터층(120)의 표면 또는 벌크 내에 존재하는 결함을 부동화하고 기판(110)의 전면으로 입사되는 태양광의 반사율을 감소시킨다. 에미터층(120)에 존재하는 결함이 부동화되면 소수 캐리어의 재결합 사이트가 제거되어 태양전지(100)의 개방전압(Voc)이 증가하고, 태양광의 반사율이 감소되면 P-N 접합까지 도달되는 광량이 증대되어 태양전지(100)의 단락전류(Isc)가 증가하므로 태양전지(100)의 변환효율이 개선된다.The
반사방지막(130)은 예를 들면, 실리콘 질화막, 수소를 포함한 실리콘 질화막, 실리콘 산화막, 실리콘 산화 질화막, MgF2, ZnS, TiO2 및 CeO2로 이루어진 군에서 선택된 어느 하나의 단일막 또는 2개 이상의 막이 조합된 다층막 구조를 가질 수 있다.The
반사방지막(130)은 진공 증착법, 화학 기상 증착법, 스핀 코팅, 스크린 인쇄 또는 스프레이 코팅에 의해 형성될 수 있으나, 이에 한정되는 것은 아니다.The
이후에, 반사방지막(130) 상에 전면 전극(140)을 형성한다.Thereafter, the
전면 전극(140)은 반사방지막(130)을 관통하여 에미터층(120)과 접하며, 광전효과에 의해 발생하는 캐리어의 이동통로로 사용된다.The
전면 전극(140)은 전면 전극 형성용 페이스트 조성물을 반사방지막 상에 바 형태(145)로 도포하여 형성할 수 있다.The
전면 전극 형성용 페이스트 조성물은 태양 전지 전면 전극 형성용 페이스트에 통상적으로 사용되는 성분을 포함할 수 있다.The paste composition for forming the front electrode may include a component conventionally used in the paste for forming the front electrode of the solar cell.
도포 방법은 특별히 한정되지 않으며, 예를 들면 스핀 코팅법, 캐스팅법, 마이크로그라비아 코팅법, 그라비아 코팅법, 바 코팅법, 롤 코팅법, 와이어 바 코팅법, 침지 코팅법, 스프레이 코팅법, 스크린 인쇄법, 플렉소 인쇄법, 오프셋 인쇄법, 잉크젯 인쇄법, 노즐 프린팅법 등을 들 수 있다.The coating method is not particularly limited and includes, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, an immersion coating method, A flexographic printing method, an offset printing method, an inkjet printing method, a nozzle printing method, and the like.
도포 이후에 통상적인 열처리 과정을 거칠 수 있다. 열처리에 의해 은 분말이 고온에서 액상이 되었다가, 다시 고상으로 재결정되면서, 유리 프릿을 매개로 하여 반사방지막(130)을 관통하는 파이어 스루(fire through) 현상에 의해 전면 전극(140)이 에미터층(120)과 접속하게 된다.After the application, a conventional heat treatment process may be performed. The silver powder becomes a liquid phase at a high temperature by the heat treatment and is then recrystallized into a solid phase and is subjected to a fire through phenomenon through the
다음으로, 기판 후면에 후면 전극(150)을 형성한다.Next, the
후면 전극(150)은 광전효과에 의해 발생하는 또다른 캐리어의 이동통로로 작용한다. 한편, 후면 전극(150)과 기판(110)의 경계면에는 후면 전계(Back Surfacefield)층(160)이 형성될 수 있다. 후면 전계층(160)은 캐리어가 기판(110)의 배면으로 이동하여 재결합되는 것을 방지할 수 있으며, 캐리어의 재결합이 방지되면 개방전압이 상승하여 태양전지(100)의 효율이 향상될 수 있다.The
후면 전극(150)은 후면 전극 형성용 페이스트 조성물을 기판 후면에 도포하여 형성할 수 있다.The
후면 전극 형성용 페이스트 조성물은 태양 전지 후면 전극 형성용 페이스트에 통상적으로 사용되는 성분을 포함할 수 있다.The paste composition for forming the rear electrode may include components conventionally used in a paste for forming a solar cell back electrode.
도포 방법은 특별히 한정되지 않으며, 예를 들면 스핀 코팅법, 캐스팅법, 마이크로그라비아 코팅법, 그라비아 코팅법, 바 코팅법, 롤 코팅법, 와이어 바 코팅법, 침지 코팅법, 스프레이 코팅법, 스크린 인쇄법, 플렉소 인쇄법, 오프셋 인쇄법, 잉크젯 인쇄법, 노즐 프린팅법 등을 들 수 있다.The coating method is not particularly limited and includes, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, an immersion coating method, A flexographic printing method, an offset printing method, an inkjet printing method, a nozzle printing method, and the like.
도포 이후에 통상적인 열처리 과정을 거칠 수 있다. 열처리에 의해, 후면 전극 형성용 페이스트 조성물 도포부(155)에 포함된 알루미늄이 기판(110)의 후면을 통해 확산함으로써, 후면 전극(150)과 기판(110)의 경계면에서 후면전계층(160)을 형성한다. 후면전계층(160)은 태양광에 의해 생성된 전자의 후면 재결합을 최소화하여 태양전지의 효율 향상에 기여한다.After the application, a conventional heat treatment process may be performed. The aluminum contained in the paste
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
실시예Example 1-7 및 1-7 and 비교예Comparative Example 1-3 1-3
하기 표 1에 기재된 성분 및 조성비(중량%)에 잔량의 물을 첨가하여 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물을 제조하였다.A residual amount of water was added to the components and composition ratios (% by weight) described in Table 1 below to prepare an etching liquid composition for a texture of a crystalline silicon wafer.
PCNMP
PC
0.51.5
0.5
PCNMP
PC
0.51.5
0.5
NMP: N-메틸피롤리돈, TP : 트리에틸포스페이트
PC : 프로필렌 카보네이트KOH: potassium hydroxide, CMCNa: sodium carboxylmethylcellulose,
NMP: N-methylpyrrolidone, TP: triethyl phosphate
PC: propylene carbonate
실험예Experimental Example
단결정 실리콘 웨이퍼를 실시예 1 내지 실시예 7 및 비교예 1 내지 비교예 3의 결정성 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물에 각각 침지시켜 에칭하였다. 이 때 텍스쳐 조건은 온도 80℃, 시간 20분이었다.Single crystal silicon wafers were immersed and etched in the etching solution compositions for texturing of the crystalline silicon wafers of Examples 1 to 7 and Comparative Examples 1 to 3, respectively. At this time, the texture condition was a temperature of 80 ° C and a time of 20 minutes.
1. One. 텍스쳐의Texture 균일성 평가 Uniformity evaluation
텍스쳐의 균일성은 광학 현미경, SEM을 이용하고 피라미드 크기는 SEM을 이용하여 평가하였으며, 그 결과를 표 2 및 도 1 및 2(실시예 1)와 도 3(비교예 1)에 나타내었다.The uniformity of the texture was evaluated using an optical microscope and SEM, and the pyramid size was evaluated using SEM. The results are shown in Table 2, FIGS. 1 and 2 (Example 1) and FIG. 3 (Comparative Example 1).
◎: 웨이퍼 전면 피라미드 형성◎: Formation of wafer front pyramid
○: 웨이퍼 일부 피라미드 미형성 (피라미드 구조 미형성 정도 5% 미만)?: Some of the wafers were not pyramid-formed (less than 5% of the pyramid structure was not formed)
△: 웨이퍼 일부 피라미드 미형성 (피라미드 구조 미형성 정도 5 내지 50%)DELTA: Some of the wafers were not pyramid-formed (degree of pyramidal structure unformed to 5 to 50%)
Х: 웨이퍼 피라미드 미형성 (피라미드 미형성 정도 90% 이상)
Х: Wafer pyramid not formed (pyramid not formed 90% or more)
2. 2. 텍스쳐의Texture 반사율 평가 Reflectance evaluation
텍스쳐 반사율은 자외선을 이용하여 400 내지 800㎚의 파장대를 갖는 빛을 조사하였을 때의 평균 반사율을 측정하였으며, 그 결과를 표 2에 나타내었다.
The texture reflectance was measured by measuring the average reflectance when light having a wavelength band of 400 to 800 nm was irradiated using ultraviolet rays, and the results are shown in Table 2.
표 2, 도 1 및 도 2를 참고하면, 실시예 1 내지 7의 실리콘 웨이퍼의 텍스쳐용 에칭액 조성물은 텍스쳐 후 웨이퍼의 외관 상태가 버블 스틱 현상의 발생이나 에칭의 불량이 없이 모두 양호한 것을 확인할 수 있었다.Referring to Table 2, Figs. 1 and 2, it was confirmed that the appearance of the wafer after the texturing of the etchant composition for a texture of the silicon wafer of Examples 1 to 7 was satisfactory without occurrence of a bubble stick phenomenon or etching defect .
그리고 3D 광학 현미경 또는 SEM 분석을 통해 고배율로 확대하여 피라미드 형성 정도를 확인한 결과 고밀도의 피라미드가 형성됨을 확인할 수 있었다.It was confirmed that pyramid formation at high magnification was confirmed by 3D optical microscope or SEM analysis. As a result, high density pyramid was formed.
하지만, 도 3을 참고하면, 비교예 1 내지 3의 웨이퍼의 텍스쳐용 에칭액 조성물은 실시예 조성물과 달리 텍스쳐 후 웨이퍼 외관 상태 및 피라미드 형성 정도가 불량함을 확인할 수 있었다.
However, referring to FIG. 3, it was confirmed that the etchant compositions for texturing of wafers of Comparative Examples 1 to 3 were inferior to the composition of the examples in terms of the appearance of the wafer after the texturing and the degree of pyramid formation.
100: 태양전지 110: 기판
115: 요철 120: 에미터층
130: 반사방지막 140: 전면 전극
150: 후면 전극 160: 후면전계층100: solar cell 110: substrate
115: unevenness 120: emitter layer
130: antireflection film 140: front electrode
150: rear electrode 160: rear front layer
Claims (16)
하기 화학식 1로 표시되는 염을 포함하는 결정성 실리콘 웨이퍼의 텍스쳐 에칭액 조성물:
[화학식 1]
M2SiX6
(식 중, M은 NH4+, K+, Na+ 및 Li+로 이루어진 군에서 선택된 양이온이고;
X는 F-, Cl- 및 Br-로 이루어진 군에서 선택된 음이온임).
Alkaline compounds; And
A texture etching liquid composition for a crystalline silicon wafer comprising a salt represented by the following formula (1):
[Chemical Formula 1]
M 2 SiX 6
Wherein M is a cation selected from the group consisting of NH4 + , K + , Na +, and Li + ;
X is an anion selected from the group consisting of F - , Cl - and Br - ).
The method of claim 1, wherein the salt of Formula 1 is selected from the group consisting of sodium fluorosilicate (Na 2 SiF 6 ), potassium fluorosilicate (K 2 SiF 6 ), ammonium fluorosilicate ((NH 4) 2 SiF 6 ), and lithium fluorosilicate (Li 2 SiF 6) texture etching liquid composition of at least one kind crystal selected from the group consisting of a silicon wafer.
[2] The composition of claim 1, wherein the salt of Formula 1 is contained in an amount of 0.01 to 5% by weight based on 100% by weight of the total etching solution composition.
The composition according to claim 1, wherein the alkali compound is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium.
The composition according to claim 1, wherein the alkali compound is contained in an amount of 0.1 to 20% by weight based on 100% by weight of the etching solution composition.
The texture etching liquid composition of claim 1, further comprising a polysaccharide.
[Claim 7] The composition of claim 7, wherein the polysaccharide is at least one selected from the group consisting of a glucan compound, a fructan compound, a mannan compound, a galactan compound, and a metal salt thereof.
[8] The method of claim 7, wherein the polysaccharide is selected from the group consisting of cellulose, dimethylaminoethylcellulose, diethylaminoethylcellulose, ethylhydroxyethylcellulose, methylhydroxyethylcellulose, 4-aminobenzylcellulose, triethylaminoethylcellulose, There may be mentioned cellulose derivatives such as ethylcellulose, methylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, alginic acid, amylose, amylopectin, pectin, starch, dextrin,? -Cyclodextrin,? -Cyclodextrin, At least one selected from the group consisting of dextrin, hydroxypropyl-beta-cyclodextrin, methyl- beta -cyclodextrin, dextran, sodium dextran sulfate, saponin, glycogen, xylose, lentinan, Crystalline, a kind of glucan-based compound A texture etchant composition for a silicon wafer.
The texture etching liquid composition of claim 1, further comprising a cyclic compound.
The composition according to claim 10, wherein the cyclic compound has a boiling point of 100 ° C or higher.
11. The composition of claim 10, wherein the cyclic compound has a Hansen solubility parameter of 6 to 16.
A method of etching a crystalline silicon wafer using the etchant composition according to any one of claims 1 to 3 and 5 to 12.
14. The method of claim 13, comprising spraying the etchant composition at a temperature of 50-100 DEG C for 30 seconds to 60 minutes.
14. The etching method according to claim 13, wherein the wafer is immersed in the etching liquid composition at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
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US4137123A (en) | 1975-12-31 | 1979-01-30 | Motorola, Inc. | Texture etching of silicon: method |
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