KR20140082220A - 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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- KR20140082220A KR20140082220A KR1020120151839A KR20120151839A KR20140082220A KR 20140082220 A KR20140082220 A KR 20140082220A KR 1020120151839 A KR1020120151839 A KR 1020120151839A KR 20120151839 A KR20120151839 A KR 20120151839A KR 20140082220 A KR20140082220 A KR 20140082220A
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- South Korea
- Prior art keywords
- sulfate
- composition
- etching
- silicon wafer
- compound
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- 238000005530 etching Methods 0.000 title claims abstract description 88
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 70
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 60
- 235000012431 wafers Nutrition 0.000 title abstract description 101
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 15
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- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 9
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 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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- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
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- General Physics & Mathematics (AREA)
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- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Weting (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a texture etchant composition for crystalline silicon wafers and a method of etching textures thereof. More particularly, the present invention relates to a method of etching a crystalline silicon wafer by forming a fine pyramid structure on the surface of a crystalline silicon wafer by including a sulfate anionic surfactant, 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
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.
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.
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.
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.
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.
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.
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.
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.
Another object of the present invention is to provide a texture etching method using the texture etching solution composition of the crystalline silicon wafer.
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. A texture etching liquid composition for a crystalline silicon wafer comprising a sulfate anionic surfactant.
2. The sulfated anionic surfactant of claim 1, wherein the sulfate anionic surfactant is ammonium dodecyl sulfate, ammonium laureth sulfate, sodium dodecyl sulfate, sodium laureth sulfate, potassium dodecyl sulfate and potassium laureth sulfate, ammonium octyl sulfate, sodium The etching solution composition of a crystalline silicon wafer is at least one selected from the group consisting of octyl sulfate, potassium octyl sulfate, ammonium hexyl sulfate, sodium hexyl sulfate, potassium hexyl sulfate, ammonium stearyl sulfate, sodium stearyl sulfate and potassium stearyl sulfate. .
3. The composition of claim 1, wherein the sulfate anionic surfactant is contained in an amount of 0.000001 to 1% by weight based on 100% by weight of the total etching solution composition.
4. The texture etching liquid composition for a crystalline silicon wafer according to 1 above, further comprising an alkaline compound.
5. The texture etching liquid composition of crystalline silicon wafer according to 1 above, further comprising a polysaccharide.
6. 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.
7. The composition for etching a crystalline silicon wafer according to 5 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.
8. The composition of claim 5 wherein the 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.
9. The texture etching liquid composition for a crystalline silicon wafer according to 1 above, further comprising a monomer polymerized with a monomer substituted with a cyclic compound having 4 to 10 carbon atoms and containing at least one nitrogen atom.
10. The composition of claim 9, wherein the monomer further comprises at least one of oxygen and sulfur atoms in the ring structure.
11. The composition of claim 9 wherein said monomer is selected from the group consisting of N-vinyl pyrrolidone, N-acryloyl morpholine, N-vinylsuccinimide, N-acryloxy succinimide, N-vinyl caprolactam, N- And at least one selected from the group consisting of N, N-dimethylaniline, N, N-dimethylaniline, N, N-acryloylpyrrolidine.
12. The composition of claim 9, wherein the polymer has a weight average molecular weight of 1,000 to 1,000,000.
13. The composition of claim 9, wherein the polymer has a boiling point of at least 100 캜.
14. The composition of claim 9, wherein the polymer is contained in an amount of 10 -12 to 1% by weight based on the total weight of the etchant composition.
15. The texture etch composition of crystalline silicon wafers of claim 1 further comprising a cyclic compound.
16. The composition of claim 15, wherein the cyclic compound has a boiling point of at least 100 < 0 > C.
17. The composition of claim 15, wherein the cyclic compound has a Hansen solubility parameter of 6 to 16.
18. A method of etching a crystalline silicon wafer with an etchant composition according to any one of claims 1 to 17.
19. The etching method according to 18 above, wherein the etching solution composition is sprayed at a temperature of 50 to 100 DEG C for 30 seconds to 60 minutes.
20. The etching method according to 18 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.
21. A method of manufacturing a solar cell comprising the steps of: forming irregularities on one surface of a substrate by the method of 18 above.
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.
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.
1 schematically shows an embodiment of a method for manufacturing a solar cell of the present invention.
The present invention relates to a process for producing a fine pyramid structure on a crystalline silicon wafer by including a sulfate anionic surfactant in order to minimize the quality deviation of the texture by position and 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.
Hereinafter, the present invention will be described in detail.
The texture etchant composition of the crystalline silicon wafer of the present invention comprises a sulfate anionic surfactant.
The sulfate anionic surfactant according to the present invention prevents over etching and accelerated etching by an alkaline compound to form a uniform fine pyramid and at the same time, the hydrogen bubble generated by the etching is quickly dropped from the surface of the silicon wafer, . And has cleaning power to remove impurities on the surface of the silicon wafer to improve the appearance of the wafer surface after the texturing process.
Examples of the sulfate anion surfactant include, but are not limited to, ammonium dodecyl sulfate, ammonium laureth sulfate, sodium dodecyl sulfate, sodium laureth sulfate, potassium dodecyl sulfate, potassium laureth sulfate, ammonium octyl sulfate, Sodium octyl sulfate, ammonium octyl sulfate, sodium hexyl sulfate, potassium hexyl sulfate, ammonium stearyl sulfate, sodium stearyl sulfate, potassium stearyl sulfate, and the like. These may be used alone or in combination of two or more.
The sulfate anionic surfactant may be contained in an amount of 0.000001 to 1% by weight, preferably 0.00001 to 0.1% by weight, more preferably 0.0001 to 0.1% by weight based on 100% by weight of the total amount of the texture etching liquid composition of the crystalline silicon wafer good. When the content falls within the above range, uniform pyramid formation and cleaning performance can be effectively exhibited.
The etching solution composition according to the present invention may further comprise an alkali compound, polysaccharide.
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 of the alkali compound that can be used include potassium hydroxide, sodium hydroxide, ammonium hydroxide, tetrahydroxymethylammonium, and tetrahydroxyethylammonium. Of these, potassium hydroxide and sodium hydroxide are preferable. These may be used alone or in combination of two or more.
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.
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.
Examples of the polysaccharide include a glucan compound, a fructan compound, a mannan compound, a galactan compound, or a metal salt thereof. Among them, a glucan compound and its metal salt (for example, , Alkali metal salts) are preferable. These may be used alone or in combination of two or more.
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.
The polysaccharide may have an average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 200,000.
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.
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.
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.
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.
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.
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.
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.
The polymer according to the present invention may be mixed with a water-soluble polar solvent.
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.
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.
Alternatively, the texture etchant composition of the crystalline silicon wafer of the present invention may further comprise a cyclic compound.
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.
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.
The type of the cyclic compound is not particularly limited so long as it satisfies the solubility parameter of the boiling point and Hansen. Examples of the cyclic compound include piperazine, morpholine, pyridine, piperidine, piperidone, pyrrolidine, Imidazolidinone, furan, aniline, toluidine, amine, lactone, carbonate, and carbazole compounds. 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.
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.
The cyclic compound may be mixed with a water-soluble polar solvent.
As the water-soluble polar solvent, the same solvent as that of the above-mentioned polymer 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 total amount of the cyclic compound.
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.
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 >
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.
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.
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.
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.
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.
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.
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.
The texture etchant composition of the crystalline silicon wafer of the present invention comprising the above components minimizes the quality variation of the texture of the surface of the crystalline silicon wafer by including the sulfate anionic surfactant in particular, 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.
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.
The present invention provides a method of etching a crystalline silicon wafer using the texture etchant composition of the crystalline silicon wafer.
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.
The number of times of deposition and spraying is not particularly limited, and the order of deposition and spraying is not limited.
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.
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.
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.
FIG. 1 schematically shows one embodiment of the method for manufacturing a solar cell of the present invention. Hereinafter, one embodiment of a method for manufacturing a solar cell of the present invention will be described with reference to FIG.
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
The
When the
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.
The size (width) of the
The height of the concavity and
The shape of the concavity and
After the formation of the
Thereafter, the
The
The
Thereafter, an
The
The
The
Thereafter, the
The
The
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.
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.
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
Next, the
The
The
The paste composition for forming the rear electrode may include components conventionally used in a paste for forming a solar cell back electrode.
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.
After the application, a conventional heat treatment process may be performed. The aluminum contained in the paste
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 present invention and are not intended to limit the scope of the appended claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.
Example 1-17 and Comparative Example 1-11
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.
Anionic surfactant
PNAM: poly (N-acryloylmorpholine), CMCNa: carboxylmethylcellulose sodium salt,
SDS: Sodium Dodecyl Sulfate, ADS: Ammonium Dodecyl sulfate,
SDS-1: Sodium laureth sulfate, ADS-1: Ammonium laureth sulfate,
PNVP: poly (N-vinyl pyrrolidone), PNAM: poly (N-acryloylmorpholine)
PNVS: poly (N-vinylsuccinimide), NMM: N-methylmorpholine,
NMP: N-methylpyrrolidone, IPA: isopropanol,
EG: ethylene glycol, MDG: methyl diglycol,
MEA: Monoethanolamine
Experimental Example
Single crystal silicon wafers were immersed and etched in the etching solution compositions for texturing of the crystalline silicon wafers of Examples 1 to 17 and Comparative Examples 1 to 11, respectively. At this time, the texture condition was a temperature of 80 ° C and a time of 20 minutes.
One. texture Appearance evaluation of wafer after wafer
The appearance of the wafer after the texturing was evaluated with the naked eye (digital camera), and the results are shown in Table 2.
◎: Good appearance of wafer front surface condition
○: Wafer bubble stick occurred
DELTA: Badness of etchability (or unetchability) with part of wafer
Х: Etching (or unetchability) defect on the front side of wafer
2. Texture Uniformity evaluation
The uniformity of the texture was evaluated by optical microscope and SEM, and the size of the pyramid was evaluated by SEM. The results are shown in Table 2.
◎: Formation of wafer front pyramid
?: Some of the wafers were not pyramid-formed (less than 5% of the pyramid structure was not formed)
DELTA: Some of the wafers were not pyramid-formed (degree of pyramidal structure unformed to 5 to 50%)
Х: Wafer pyramid not formed (pyramid not formed 90% or more)
Referring to Table 2, the etching solution composition for a texture of the silicon wafers of Examples 1 to 17 showed that the appearance of the wafers after the texturing was satisfactory without occurrence of bubble stick phenomenon or etching defect, there was.
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.
However, it was confirmed that the etchant compositions for texturing the wafers of Comparative Examples 1 to 9 had poor appearance conditions of the wafers after the texturing and poor degree of pyramid formation, unlike the composition of the examples. In the case of Comparative Examples 10 and 11, there was no significance of the texturing due to the occurrence of chemical denaturation.
100: solar cell 110: substrate
115: unevenness 120: emitter layer
130: antireflection film 140: front electrode
150: rear electrode 160: rear front layer
Claims (21)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180110483A (en) * | 2017-03-29 | 2018-10-10 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for display device |
| KR20210119639A (en) * | 2020-03-25 | 2021-10-06 | 주식회사 이엔에프테크놀로지 | Silicon nitride layer etching composition |
| CN113502163A (en) * | 2021-09-10 | 2021-10-15 | 杭州晶宝新能源科技有限公司 | Chemical auxiliary agent for forming solar cell back structure, and preparation method and application thereof |
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2012
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180110483A (en) * | 2017-03-29 | 2018-10-10 | 동우 화인켐 주식회사 | Etchant composition and manufacturing method of an array substrate for display device |
| KR20210119639A (en) * | 2020-03-25 | 2021-10-06 | 주식회사 이엔에프테크놀로지 | Silicon nitride layer etching composition |
| CN113502163A (en) * | 2021-09-10 | 2021-10-15 | 杭州晶宝新能源科技有限公司 | Chemical auxiliary agent for forming solar cell back structure, and preparation method and application thereof |
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