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WO2013165223A1 - Ink composition capable of being used in manufacturing solar cells and pattern formation method using same - Google Patents

Ink composition capable of being used in manufacturing solar cells and pattern formation method using same Download PDF

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Publication number
WO2013165223A1
WO2013165223A1 PCT/KR2013/003882 KR2013003882W WO2013165223A1 WO 2013165223 A1 WO2013165223 A1 WO 2013165223A1 KR 2013003882 W KR2013003882 W KR 2013003882W WO 2013165223 A1 WO2013165223 A1 WO 2013165223A1
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WO
WIPO (PCT)
Prior art keywords
ink composition
weight
parts
solar cell
fluorine
Prior art date
Application number
PCT/KR2013/003882
Other languages
French (fr)
Korean (ko)
Inventor
유민아
구용성
김준형
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201380002253.6A priority Critical patent/CN103687915B/en
Priority to US14/126,189 priority patent/US9302466B2/en
Priority claimed from KR1020130050314A external-priority patent/KR101431485B1/en
Publication of WO2013165223A1 publication Critical patent/WO2013165223A1/en

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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/14—Production or use of a mask
    • 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells

Definitions

  • the present invention relates to an ink composition and a pattern forming method using the same, which can be used in manufacturing a solar cell that can be patterned on a silicon substrate having surface irregularities by controlling the fluidity of the ink composition.
  • Solar cells are the core elements of photovoltaic power generation that directly converts solar energy into electricity, and are currently applied to various fields such as electricity, electronic products, or electricity supply to houses or buildings.
  • the manufacturing process of the solar cell includes an electroplating or etching process, and during this process, a material for selectively masking a specific portion of the silicon substrate or applying a material to be used as an insulating film in a solar cell is required.
  • a material for selectively masking a specific portion of the silicon substrate or applying a material to be used as an insulating film in a solar cell is required.
  • the screen printing method it is very difficult to form a fine line width required for manufacturing a solar cell.
  • the present invention is to provide an ink composition and a pattern forming method using the same, which can be used in manufacturing a solar cell that can be patterned on a silicon substrate having surface irregularities such as a solar cell by controlling the fluidity of the ink composition.
  • 1st aspect of this invention is a) polymeric compound which has ethylenically unsaturated bond, b) fluorine-type surfactant; And c) a solvent, wherein the solid content is 45 parts by weight to 99.99 parts by weight based on the total ink composition.
  • a second aspect of the present invention provides a pattern forming method comprising applying the ink composition using a head of an inkjet printer and heat treating the applied ink composition.
  • the third aspect of the present invention provides an etching mask formed by using the ink composition on a silicon substrate for solar cells having irregularities.
  • a fourth aspect of the present invention provides an insulating film formed by using the ink composition on a silicon substrate for solar cells having irregularities.
  • the ink composition usable in the solar cell manufacturing according to the present invention can control the fluidity according to the solid content, so that the pattern can be formed on the silicon substrate having the surface irregularities.
  • the pattern forming method using the ink composition is very useful when forming a solar cell because it is possible to form a fine line width in a non-contact manner by using an inkjet printer.
  • the solar cell may be used as an insulating film or as an etch mask in manufacturing the solar cell, and thus has excellent utility.
  • FIG. 1 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 1.
  • FIG. 1 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 1.
  • FIG. 2 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 2.
  • FIG. 2 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 2.
  • FIG. 3 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 3.
  • FIG. 3 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 3.
  • FIG. 4 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 1.
  • FIG. 4 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 1.
  • FIG. 5 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 2.
  • FIG. 5 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 2.
  • FIG. 6 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 3.
  • FIG. 7 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 4.
  • Ink compositions usable in the solar cell production of the present invention include a) a polymerizable compound having an ethylenically unsaturated bond b) a fluorine-based surfactant; And c) a solvent, wherein the solid content is 45 parts by weight to 99.99 parts by weight based on the total ink composition.
  • the a) polymerizable compound having an ethylenically unsaturated bond is formed of a material which can be polymerized by the generated radicals, and is intended to increase durability of the pattern.
  • the polymerizable compound is viscous and can control the fluidity of the ink on the silicon substrate having surface irregularities.
  • the polymerizable compound having a) ethylenically unsaturated bonds is preferably an acrylic monomer. It is preferable that it is a polyfunctional acrylate which can specifically crosslink, For example, neopentyl glycol diacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, butanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol triacrylate, trimethylolpropane triacrylate, tripropylene glycol di It may be two or more selected from the group consisting of acrylate, pentaerythritol triacrylate, propylene glycol diacrylate and hexanediol diacrylate, but is
  • the a) polymerizable compound having an ethylenically unsaturated bond may be dipentaerythritol hexaacrylate, trimethylolpropane triacrylate and / or dipropylene glycol diacrylate.
  • the dipentaerythritol hexaacrylate and trimethylolpropane triacrylate can be cross-linked with a multifunctional acrylate, thereby improving chemical resistance, and dipropylene glycol diacrylate has a low viscosity.
  • the polymerizable compound having an ethylenically unsaturated bond may be 40 parts by weight to 98 parts by weight, 60 parts by weight to 96 parts by weight or 70 parts by weight to 94 parts by weight based on the total ink composition.
  • the content of the polymerizable compound having an ethylenically unsaturated bond satisfies the above numerical range, it is possible to form a good line pattern even on a silicon substrate having surface irregularities, and to improve adhesion by adding a substance other than the polymerizable compound.
  • the addition of a surfactant has the advantage of controlling the spreadability of the ink.
  • the b) fluorine-based surfactant is to control the spreadability of the ink, it is preferable that the excellent defoaming characteristics because the poor discharge occurs when bubbles generated during the ink injection into the inkjet equipment is not easily removed.
  • the b) fluorine-based surfactants more preferably include polyethylene glycol and perfluorocarbon.
  • a fluorine-based surfactant including the polyethylene glycol and perfluorocarbon it is easy to control the spreadability of the ink, and the ink does not flow easily, and thus the pattern is easily formed on the silicon substrate having the surface irregularities. There is an advantage.
  • the fluorine-based surfactant has a surface tension of 20 to 30 mN / m or 23 to 27 mN /, for example, when it is made of a toluene solution containing 0.1 wt% of the fluorine-based surfactant. may be m.
  • the surface tension is preferably 20 to 30 mN / m or 24 to 28 mN / m when made of a propyleneglycolmethylether solution containing 0.1% by weight of the fluorine-based surfactant.
  • the fluorine-based surfactant simultaneously satisfies the surface tension values of the toluene solution and the propylene glycol methyl ether solution each containing 0.1 wt% of the surfactant.
  • the surface tension of the toluene solution and / or the propylene glycol methyl ether solution containing 0.1% by weight of a fluorine-based surfactant satisfies the above numerical range, the ink does not spread too much while appropriately covering the surface of the silicon substrate having surface irregularities. This is because there is an advantage that can be kept stable.
  • the surface tension means a tension between air and the solution.
  • the measurement of the surface tension was performed at room temperature using the Du Nouy ring equipment.
  • the b) fluorine-based surfactant may be included in 0.01 parts by weight to 1.0 parts by weight, 0.01 parts by weight to 0.5 parts by weight or 0.03 parts by weight to 0.1 parts by weight based on the total ink composition.
  • the content of the surfactant satisfies the numerical range, the pattern may be formed reproducibly, and the storage stability of the ink is excellent.
  • the c) solvent is to control the viscosity of the ink and the thickness of the formed film is preferably an organic solvent. More specifically, for example, diethylene glycol butyl methyl ether, dielene glycol monobutyl ether acetate, diethylene glycol monomail ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate , Butyl lactate, ethoxy ethyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethyl ethoxy propionate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether and propylene glycol butyl ether It may be one or more selected from, but is not limited thereto.
  • the c) solvent may include 0.001 parts by weight to 55 parts by weight based on the total ink composition.
  • the content of the solvent satisfies the above numerical range, line patterning can be formed, the spreadability of the ink decreases, and the pattern uniformity increases.
  • the solid content except for c) the solvent is preferably 45 parts by weight to 99.99 parts by weight, 63 to 99.99 parts by weight or 70 to 99.99 parts by weight based on the total ink composition. That is, as the solid content is increased, the spreadability of the ink decreases, and the uniformity of the pattern is increased, so that stable pattern formation is possible.
  • the c) solvent may be one or a mixture of two or more of those having a boiling point of 140 °C to 250 °C.
  • the boiling point of the solvent satisfies the above numerical range, drying does not occur at the nozzle surface of the inkjet printer, so that the ejection is good, and the solvent can be completely dried after the pattern is formed, thereby providing excellent processability.
  • the ink composition according to the present invention may further include an adhesion promoter in order to improve the adhesion property with the silicon substrate.
  • an acid solution treatment is required for selective etching of the emitter layer in manufacturing a solar cell, in order to prevent a problem of dropping of the pattern.
  • the adhesion promoter may be one having a substituent which generates a silanol group by hydrolysis, or one having a methoxy silyl group or an ethoxy silyl group in a molecule.
  • vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane It may be one or more selected from the group consisting of, but is not limited thereto.
  • the adhesion promoter may include 0.1 parts by weight to 5.0 parts by weight based on the total ink composition.
  • the content of the adhesion promoter satisfies the numerical range, there is an advantage in that the storage stability of the ink is excellent.
  • acid solution treatment is required. In this case, separation or dropping of the pattern may be prevented.
  • the ink composition of the present invention may further include at least one additive selected from the group consisting of a polymerization initiator, a binder, and the like.
  • the polymerization initiator is for curing the polymerizable compound having an ethylenically unsaturated bond and may be a thermal initiator, a photoinitiator or a combination thereof.
  • a thermal initiator capable of simplifying the process by completing the curing by only one step of heat treatment without an additional process for removing the solvent is preferable.
  • the polymerization initiator preferably contains 0.1 parts by weight to 5.0 parts by weight based on the total ink composition.
  • the content of the polymerization initiator satisfies the numerical range, radicals are not sufficiently generated to prevent thermal polymerization from progressing, and when the polymerization initiator is well dissolved, the ink composition is used as an insulating film. The incidence of defects can be reduced, and when used as an etching mask, the stripper can be easily removed.
  • the content of the polymerization initiator is also the same when using a thermal initiator, a photoinitiator or a combination thereof.
  • the thermal initiator may be, for example, one or more selected from the group consisting of azo compounds, organic peroxides, and hydrogen peroxide, but is not limited thereto.
  • the photoinitiator may be a photopolymerization initiator or a photosensitizer well known in the art, but is not limited thereto.
  • it may be at least one selected from the group consisting of a triazine compound, a biimidazole compound, an acetophenone compound benzophenone compound, and a thioxanthone compound.
  • the binder is not particularly limited as long as it improves the adhesive properties of the formed ink film, facilitates the formation of the ink film, and controls the strength of the formed ink film without impairing the original properties of the composition.
  • binders include styrene, chloro styrene, ⁇ -methyl styrene, vinyltoluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylic.
  • benzyl (meth) acrylate glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylic Latex, dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Roxybutyl (meth) acrylate, di Methylaminomethyl (meth) acrylate,
  • the binder preferably comprises 0.01 to 8 parts by weight based on the total ink composition.
  • the content of the binder satisfies the numerical range, the viscosity of the ink does not increase, and thus pattern formation is easy.
  • the ink composition usable in the solar cell production according to the invention preferably has a contact angle of 30 ° to 60 °.
  • the contact angle means an angle formed by the tangent leading to the surface of the droplet and the surface of the substrate at the point where the droplet of the dropped ink is in contact with the substrate, and as an apparatus for measuring the contact angle, for example, a contact angle measuring instrument (KRUSS DSA100) There is this.
  • the contact angle is a value measured by dropping ink on a glass substrate.
  • the contact angle of the ink composition satisfies the above numerical range, the spreadability of the ink is small on the silicon substrate having the surface irregularities, so that a pattern having a desired line width can be formed, and the pattern can be formed without breaking the ink without partially clumping the ink. It also has excellent adhesion to the substrate.
  • the pattern forming method includes applying the ink composition according to the present invention using a head of an inkjet printer, and heat treating the applied ink composition.
  • the substrate to which the ink composition is applied may be a glass substrate, a silicon substrate, or a substrate on which metal, SiO 2, or ITO is deposited, and may preferably be a silicon substrate for solar cells having surface irregularities.
  • applying the ink composition may be performed by a method of ejecting ink on a substrate through a inkjet head in a non-contact manner.
  • the inkjet head may be further heated in order to lower the viscosity to allow ink ejection from the inkjet head.
  • the inkjet head is preferably heated to 40 ° C. to 80 ° C. such that the viscosity of the ink composition satisfies 10 cP to 20 cP.
  • the heating temperature of the inkjet head satisfies the numerical range, the viscosity of the ink is low, so that the ejection of the ink from the inkjet head is stable, the problem does not occur in the driving portion of the inkjet equipment, and the storage stability of the ink is increased.
  • the heat treatment step is to dry the film of the applied ink composition, it may be performed using a reduced pressure dryer, a convection oven, a hot plate or an IR oven.
  • the heat treatment temperature may be carried out at 130 °C to 250 °C.
  • thermal curing is insufficient, and thus, the film cannot be used as an etching mask or an insulating film, or when used as an etching mask, it is difficult to remove the pattern and part of the reactant to be reacted is lost by heat. This can prevent problems.
  • the heat treatment step may be performed at a temperature of 160 °C to 200 °C.
  • the heat treatment temperature satisfies the numerical range, the formed etching mask pattern may have a good ability to withstand etching in the selective etching process of the emitter layer for forming the selective emitter, thereby preventing the pattern from falling off or decomposition.
  • removing the etching mask pattern can be easily removed from the alkaline solution.
  • the heat treatment step may be performed at 220 °C to 250 °C.
  • the heat treatment temperature satisfies the above numerical range, a sufficient curing may be achieved since the treatment is performed at a high temperature.
  • the etching mask of the present invention is formed on the silicon substrate for solar cells having irregularities by using the ink composition.
  • the etching mask may be formed by a method well known in the art, for example, may be used as an etching mask after forming a pattern using the pattern forming method according to the present invention.
  • the insulating film of this invention was formed using the said ink composition on the silicon substrate for solar cells with an unevenness
  • the insulating film may be formed by a method well known in the art, but may be used as an insulating film, for example, after forming a pattern using the pattern forming method according to the present invention.
  • V65 1.6 parts by weight was dissolved in a solvent as a thermal initiator in a reaction vessel, and then benzyl methacrylate / methacrylic acid was added at a molar ratio of 68/32. The reaction was carried out for 7.5 hours while maintaining the temperature at 65 ° C. in a nitrogen atmosphere.
  • the copolymer solution obtained above was added to a flask with a stirrer, glycidyl methacrylate was added, and then reacted at 110 ° C. for 6 hours to prepare an acrylic copolymer.
  • V65 1.6 parts by weight was dissolved in a solvent as a thermal initiator in a reaction vessel, and then benzyl methacrylate / styrene / methacrylic acid / lauryl methacrylate was added at a molar ratio of 52/19/12/17.
  • the reaction was carried out for 7.5 hours while maintaining the temperature at 65 ° C. in a nitrogen atmosphere, which was used as a binder resin.
  • the ink composition of the present invention was prepared by mixing 2.00 parts by weight of methoxysilane, 0.04 part by weight of a fluorine-based surfactant, 0.25 parts by weight of V40 manufactured by Wako as an initiator, and 3.47 parts by weight of diethylene glycol methylbutyl ether as a solvent for 2 hours. .
  • the solid content is a value calculated based on the weight part of the total ink composition, excluding the solvent, and the viscosity is a value measured at room temperature (25 ° C.) using a viscometer.
  • Example 1 To the ink composition was prepared in the same manner as in Example 1 in the composition and content shown in Table 1.
  • TMPTA 2 trimethylolpropanetriacrylate
  • ** is when a silicone surfactant is used.
  • Example 1 and Comparative Example 3 were heated to 45.5 ° C, Comparative Example 1 to 37.6 ° C, and Comparative Example 2 to 42.7 ° C.
  • Example 2 Example 3 and Comparative Example 4 discharged the ink at room temperature. After the pattern was formed, the solvent was removed and heat treated at a temperature of 130 ° C. or higher to cure the polymerizable compound having an ethylenically unsaturated bond.
  • FIGS. 4 to 7 are Comparative Examples 1 to 3 It is a photograph showing the pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared according to the fourth.
  • the uniformity of the pattern is reduced when the content of the solid content is 40 parts by weight or less. That is, as the solid content decreases, the spreadability of the ink increases, and when the solid content is 40 parts by weight or less, line patterning is difficult, and the pattern formed by drying the solvent of the ink ensures that the tip of the surface irregularities of the solar cell silicon substrate is properly formed. There was also a problem that could not be covered. In addition, when the fluorine-based surfactant is not used, it can be seen that even if the solid content is high, it is difficult to form a line pattern on a substrate having surface irregularities.

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  • Life Sciences & Earth Sciences (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to an ink composition that can be used in manufacturing solar cells. More particularly, the present invention relates to an ink composition that can be used in manufacturing solar cells, wherein the ink composition comprises a) a polymerizable compound having an ethylenically unsaturated bond, b) a fluorinated surfactant, and c) a solvent, the ink composition having 45 parts by weight to 99.99 parts by weight of a solid content. The present invention also relates to a pattern formation method using the ink composition, and to an insulation film and an etch mask formed from the ink composition.

Description

태양전지 제조에서 이용 가능한 잉크 조성물 및 이를 이용한 패턴형성방법Ink composition usable in solar cell manufacturing and pattern formation method using same
본 발명은 잉크 조성물의 유동성을 조절하여 표면 요철이 있는 실리콘 기판 위에서도 패턴 형성이 가능한 태양전지 제조에서 이용 가능한 잉크 조성물 및 이를 이용한 패턴형성방법에 관한 것이다. The present invention relates to an ink composition and a pattern forming method using the same, which can be used in manufacturing a solar cell that can be patterned on a silicon substrate having surface irregularities by controlling the fluidity of the ink composition.
태양전지는 태양에너지를 직접 전기로 변환시키는 태양광 발전의 핵심소자로, 현재 전기, 전자제품 또는 주택이나 건물의 전기 공급 등에 이르기까지 다양한 분야에 적용되고 있다. Solar cells are the core elements of photovoltaic power generation that directly converts solar energy into electricity, and are currently applied to various fields such as electricity, electronic products, or electricity supply to houses or buildings.
태양전지의 제조 공정 중에는 전기도금 또는 식각 공정 등이 포함되며, 이러한 공정 중에는 실리콘 기판의 특정 부분을 선택적으로 마스킹 하거나, 태양전지 셀에서 절연막으로 사용될 물질을 도포하는 재료가 필요하다. 종래에는 이러한 재료를 스크린 프린팅 방법에 의해 형성하는 것이 일반적이었다. 그러나 스크린 프린팅 방법에 의하는 경우 태양전지 제조시 요구되는 미세한 선폭을 형성하기가 매우 어려운 문제점이 있다. The manufacturing process of the solar cell includes an electroplating or etching process, and during this process, a material for selectively masking a specific portion of the silicon substrate or applying a material to be used as an insulating film in a solar cell is required. In the past, it was common to form such a material by a screen printing method. However, when the screen printing method is used, it is very difficult to form a fine line width required for manufacturing a solar cell.
또한, 태양전지의 제조 비용을 줄이기 위해 실리콘 기판을 박형화 하려는 시도가 있다. 그러나, 스크린 프린팅은 접촉 방식으로 패턴을 형성하므로, 태양전지의 셀이 파손될 수 있는 문제점이 있다. In addition, there is an attempt to thin the silicon substrate to reduce the manufacturing cost of the solar cell. However, since screen printing forms a pattern in a contact manner, there is a problem that a cell of a solar cell may be damaged.
따라서, 접촉 방식인 스크린 프린팅과 달리 비접촉 방식인 잉크젯 패턴 방식으로 패턴을 형성하는 기술에 대한 관심이 증폭되고 있다. 즉, 태양전지의 전극, 부식 막 또는 절연막 등을 형성하는데 있어 미세한 선폭 형성이 가능하며, 비접촉 방식으로 패턴을 형성하는 잉크젯 프린팅 방법을 사용하고자 하는 요구가 있다. Therefore, there is a growing interest in a technology of forming a pattern in a non-contact inkjet pattern method, unlike screen printing, which is a contact method. That is, there is a need to use an inkjet printing method capable of forming a fine line width and forming a pattern in a non-contact manner in forming an electrode, a corrosion film or an insulating film of a solar cell.
그러나, 잉크젯 프린팅 방법에 의하는 경우 종래의 잉크 조성물을 이용하면 잉크의 유동성이 커서 태양전지와 같은 표면 요철이 형성된 실리콘 기판에서는 잉크가 흐르게 되어 패턴 형성이 어려운 문제점이 있다. 따라서, 표면 요철이 형성된 실리콘 기판에서도 패턴 형성이 가능한 잉크젯 프린팅용 잉크 조성물의 개발이 시급하다. However, in the case of the inkjet printing method, when a conventional ink composition is used, ink flows in a silicon substrate on which surface irregularities such as solar cells are formed due to the fluidity of the ink, so that pattern formation is difficult. Therefore, there is an urgent need to develop an ink composition for inkjet printing in which a pattern can be formed even on a silicon substrate having surface irregularities.
이에 본 발명은 잉크 조성물의 유동성을 조절하여 태양전지와 같은 표면 요철이 있는 실리콘 기판 위에서도 패턴 형성이 가능한 태양전지 제조에서 이용 가능한 잉크 조성물 및 이를 이용한 패턴형성방법을 제공하고자 한다. Accordingly, the present invention is to provide an ink composition and a pattern forming method using the same, which can be used in manufacturing a solar cell that can be patterned on a silicon substrate having surface irregularities such as a solar cell by controlling the fluidity of the ink composition.
상기 과제를 해결하기 위해서, 본 발명의 제1태양은 a)에틸렌성 불포화 결합을 갖는 중합성 화합물, b)불소계 계면활성제; 및 c)용매를 포함하며, 고형분의 함량이 전체 잉크 조성물을 기준으로 45 중량부 내지 99.99 중량부인 태양전지 제조에서 이용 가능한 잉크 조성물을 제공한다.In order to solve the said subject, 1st aspect of this invention is a) polymeric compound which has ethylenically unsaturated bond, b) fluorine-type surfactant; And c) a solvent, wherein the solid content is 45 parts by weight to 99.99 parts by weight based on the total ink composition.
본 발명의 제2태양은 상기 잉크 조성물을 잉크젯 프린터의 헤드를 이용하여 도포하는 단계 및 상기 도포된 잉크 조성물을 열처리 하는 단계를 포함하는 패턴형성방법을 제공한다. A second aspect of the present invention provides a pattern forming method comprising applying the ink composition using a head of an inkjet printer and heat treating the applied ink composition.
본 발명의 제3태양은 요철이 있는 태양전지용 실리콘 기판상에 상기 잉크 조성물을 이용하여 형성시킨 식각 마스크를 제공한다. The third aspect of the present invention provides an etching mask formed by using the ink composition on a silicon substrate for solar cells having irregularities.
본 발명의 제4태양은 요철이 있는 태양전지용 실리콘 기판상에 상기 잉크 조성물을 이용하여 형성시킨 절연막을 제공한다. A fourth aspect of the present invention provides an insulating film formed by using the ink composition on a silicon substrate for solar cells having irregularities.
본 발명에 따른 태양전지 제조에서 이용 가능한 잉크 조성물은 고형분 함량에 따라 유동성 조절이 가능하므로 표면 요철이 있는 실리콘 기판 위에서도 패턴 형성이 가능하다. The ink composition usable in the solar cell manufacturing according to the present invention can control the fluidity according to the solid content, so that the pattern can be formed on the silicon substrate having the surface irregularities.
또한, 상기 잉크 조성물을 이용한 패턴형성방법은 잉크젯 프린터를 이용함으로써 비접촉 방식으로 미세한 선폭을 형성하는 것이 가능하므로 태양전지 제조에 이용하는 경우 매우 유용하다. In addition, the pattern forming method using the ink composition is very useful when forming a solar cell because it is possible to form a fine line width in a non-contact manner by using an inkjet printer.
또한, 상기 잉크 조성물에 포함된 접착 증진제의 함량 및 패턴 형성시의 열처리 온도에 따라 태양전지 제조시 절연막으로 사용하거나 식각 마스크로 사용할 수 있어 효용성이 우수한 장점이 있다. In addition, depending on the amount of the adhesion promoter included in the ink composition and the heat treatment temperature at the time of pattern formation, the solar cell may be used as an insulating film or as an etch mask in manufacturing the solar cell, and thus has excellent utility.
도 1은 실시예 1에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.FIG. 1 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 1. FIG.
도 2는 실시예 2에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.FIG. 2 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 2. FIG.
도 3는 실시예 3에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.3 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Example 3. FIG.
도 4는 비교예 1에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.4 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 1. FIG.
도 5는 비교예 2에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.FIG. 5 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 2. FIG.
도 6은 비교예 3에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.6 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 3.
도 7은 비교예 4에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다.7 is a photograph showing a pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared in Comparative Example 4.
이하, 본 발명의 바람직한 실시 형태들을 설명한다. 그러나, 본 발명의 실시형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 또한, 본 발명의 실시형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다. Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
본 발명의 태양전지 제조에서 이용 가능한 잉크 조성물은 a)에틸렌성 불포화 결합을 갖는 중합성 화합물 b)불소계 계면활성제; 및 c)용매를 포함하며, 고형분의 함량이 전체 잉크 조성물을 기준으로 45 중량부 내지 99.99 중량부인 것을 특징으로 한다. Ink compositions usable in the solar cell production of the present invention include a) a polymerizable compound having an ethylenically unsaturated bond b) a fluorine-based surfactant; And c) a solvent, wherein the solid content is 45 parts by weight to 99.99 parts by weight based on the total ink composition.
상기 a)에틸렌성 불포화 결합을 갖는 중합성 화합물은 발생된 라디칼에 의해 중합이 가능한 물질로 형성된 것으로, 패턴의 내구성을 증가시키기 위한 것이다. 또한 상기 중합성 화합물은 점성을 지니고 있는 것으로, 표면 요철이 있는 실리콘 기판에서 잉크의 유동성을 조절할 수 있다. The a) polymerizable compound having an ethylenically unsaturated bond is formed of a material which can be polymerized by the generated radicals, and is intended to increase durability of the pattern. In addition, the polymerizable compound is viscous and can control the fluidity of the ink on the silicon substrate having surface irregularities.
특히, 본 발명의 잉크 조성물에 있어서, 상기 a)에틸렌성 불포화 결합을 갖는 중합성 화합물은 아크릴 모노머인 것이 바람직하다. 구체적으로는 가교 결합이 가능한 다관능성 아크릴레이트인 것이 바람직하며, 예를 들면 네오펜틸글리콜디아크릴레이트, 디트리메틸롤프로판테트라아크릴레이트, 디펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨펜타아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 디프로필렌글리콜디아크릴레이트, 부탄디올디아크릴레이트, 에틸렌글리콜디아크릴레이트, 트리에틸렌글리콜디아크릴레이트, 트리메틸올트리아크릴레이트, 트리메틸롤프로판트리아크릴레이트, 트리프로필렌글리콜디아크릴레이트, 펜타에리트리톨트리아크릴레이트, 프로필렌글리콜디아크릴레이트 및 헥산디올디아크릴레이트 등으로 이루어진 군으로부터 선택된 2종이상일 수 있으나, 이에 제한되는 것은 아니다. In particular, in the ink composition of the present invention, the polymerizable compound having a) ethylenically unsaturated bonds is preferably an acrylic monomer. It is preferable that it is a polyfunctional acrylate which can specifically crosslink, For example, neopentyl glycol diacrylate, ditrimethylol propane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, butanediol diacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol triacrylate, trimethylolpropane triacrylate, tripropylene glycol di It may be two or more selected from the group consisting of acrylate, pentaerythritol triacrylate, propylene glycol diacrylate and hexanediol diacrylate, but is not limited thereto.
특히, 본 발명의 잉크 조성물에 있어서, 상기 a)에틸렌성 불포화 결합을 갖는 중합성 화합물은 디펜타에리트리톨헥사아크릴레이트, 트리메틸롤프로판트리아크릴레이트 및/또는 디프로필렌글리콜디아크릴레이트일 수 있다. 이때, 상기 디펜타에리트리톨헥사아크릴레이트와 트리메틸롤프로판트리아크릴레이트는 다관능성 아크릴레이트로 가교 결합이 가능하여 내화학성을 높일 수 있으며, 디프로필렌글리콜디아크릴레이트는 낮은 점도를 가지므로, 본 발명에 따른 잉크 조성물의 토출이 용이하도록 하는 장점이 있다. In particular, in the ink composition of the present invention, the a) polymerizable compound having an ethylenically unsaturated bond may be dipentaerythritol hexaacrylate, trimethylolpropane triacrylate and / or dipropylene glycol diacrylate. In this case, the dipentaerythritol hexaacrylate and trimethylolpropane triacrylate can be cross-linked with a multifunctional acrylate, thereby improving chemical resistance, and dipropylene glycol diacrylate has a low viscosity. There is an advantage to facilitate the ejection of the ink composition according to.
한편, 상기 a)에틸렌성 불포화 결합을 갖는 중합성 화합물은 전체 잉크 조성물을 기준으로 40 중량부 내지 98 중량부, 60 중량부 내지 96 중량부 또는 70 중량부 내지 94 중량부일 수 있다. 에틸렌성 불포화 결합을 갖는 중합성 화합물의 함량이 상기 수치 범위를 만족하는 경우 표면 요철이 있는 실리콘 기판에서도 선 패턴을 양호하게 형성할 수 있고, 중합성 화합물 이외의 물질을 첨가하여 접착력을 향상시키거나 계면활성제를 첨가하여 잉크의 퍼짐성을 조절할 수 있는 장점이 있다. On the other hand, a) the polymerizable compound having an ethylenically unsaturated bond may be 40 parts by weight to 98 parts by weight, 60 parts by weight to 96 parts by weight or 70 parts by weight to 94 parts by weight based on the total ink composition. When the content of the polymerizable compound having an ethylenically unsaturated bond satisfies the above numerical range, it is possible to form a good line pattern even on a silicon substrate having surface irregularities, and to improve adhesion by adding a substance other than the polymerizable compound. The addition of a surfactant has the advantage of controlling the spreadability of the ink.
다음으로, 상기 b)불소계 계면활성제는 잉크의 퍼짐성을 조절하기 위한 것으로, 잉크젯 장비에 잉크를 주입하는 동안 발생하는 기포가 쉽게 제거되지 않는 경우 토출 불량이 발생하므로 소포 특성이 우수한 것이 바람직하다. Next, the b) fluorine-based surfactant is to control the spreadability of the ink, it is preferable that the excellent defoaming characteristics because the poor discharge occurs when bubbles generated during the ink injection into the inkjet equipment is not easily removed.
특히, 본 발명의 잉크 조성물에 있어서, 상기 b)불소계 계면활성제는 폴리에틸렌 글리콜(polyethylene glycol) 및 퍼플루오로카본(perfluorocarbon)을 포함하는 것이 보다 바람직하다. 상기 폴리에틸렌 글리콜(polyethylene glycol) 및 퍼플루오로카본(perfluorocarbon)을 포함하는 불소계 계면활성제를 사용하는 경우 잉크의 퍼짐성 조절이 용이하고, 잉크가 쉽게 흐르지 않아 표면 요철이 있는 실리콘 기판 위에서도 패턴 형성이 용이한 장점이 있다. In particular, in the ink composition of the present invention, the b) fluorine-based surfactants more preferably include polyethylene glycol and perfluorocarbon. When using a fluorine-based surfactant including the polyethylene glycol and perfluorocarbon, it is easy to control the spreadability of the ink, and the ink does not flow easily, and thus the pattern is easily formed on the silicon substrate having the surface irregularities. There is an advantage.
특히 본 발명에 있어서, 상기 불소계 계면활성제는 예를 들면, 상기 불소계 계면활성제 0.1 중량%를 포함하는 톨루엔 용액 (toluene solution)으로 만들었을 때 표면장력이 20 내지 30 mN/m 또는 23 내지 27 mN/m일 수 있다. 또한, 상기 불소계 계면활성제를 0.1 중량% 포함하는 프로필렌글리콜메틸에테르 용액(propyleneglycolmethylether solution)으로 만들었을 때 표면장력이 20 내지 30 mN/m 또는 24 내지 28 mN/m 인 것이 바람직하다. 본 발명에 따른 잉크 조성물에 있어서, 상기 불소계 계면활성제는 상기 계면활성제를 각각 0.1 중량% 포함하는 상기 톨루엔 용액 및 프로필렌글리콜메틸에테르 용액의 표면장력 값을 동시에 만족하는 것이 보다 바람직하다. 불소계 계면활성제를 0.1 중량% 포함하는 톨루엔 용액 및/또는 프로필렌글리콜메틸에테르 용액의 표면장력이 상기 수치범위를 만족하는 경우, 잉크가 표면 요철이 있는 실리콘 기판의 표면을 적절하게 덮으면서도 너무 번지지 않아서 패턴을 안정적으로 유지할 수 있는 장점이 있기 때문이다. 본 명세서에서 상기 표면장력은 공기와 상기 용액 사이의 장력을 의미한다. 또한, 상기 표면장력의 측정은 Du Nouy ring 장비를 사용하여 상온에서 수행하였다. In particular, in the present invention, the fluorine-based surfactant has a surface tension of 20 to 30 mN / m or 23 to 27 mN /, for example, when it is made of a toluene solution containing 0.1 wt% of the fluorine-based surfactant. may be m. In addition, the surface tension is preferably 20 to 30 mN / m or 24 to 28 mN / m when made of a propyleneglycolmethylether solution containing 0.1% by weight of the fluorine-based surfactant. In the ink composition according to the present invention, it is more preferable that the fluorine-based surfactant simultaneously satisfies the surface tension values of the toluene solution and the propylene glycol methyl ether solution each containing 0.1 wt% of the surfactant. When the surface tension of the toluene solution and / or the propylene glycol methyl ether solution containing 0.1% by weight of a fluorine-based surfactant satisfies the above numerical range, the ink does not spread too much while appropriately covering the surface of the silicon substrate having surface irregularities. This is because there is an advantage that can be kept stable. In the present specification, the surface tension means a tension between air and the solution. In addition, the measurement of the surface tension was performed at room temperature using the Du Nouy ring equipment.
또한, 상기 b)불소계 계면활성제는 전체 잉크 조성물을 기준으로 0.01 중량부 내지 1.0 중량부, 0.01 중량부 내지 0.5 중량부 또는 0.03 중량부 내지 0.1 중량부로 포함될 수 있다. 계면활성제의 함량이 상기 수치 범위를 만족하는 경우 재현성 있게 패턴을 형성할 수 있고, 잉크의 저장 안정성이 우수한 장점이 있다. In addition, the b) fluorine-based surfactant may be included in 0.01 parts by weight to 1.0 parts by weight, 0.01 parts by weight to 0.5 parts by weight or 0.03 parts by weight to 0.1 parts by weight based on the total ink composition. When the content of the surfactant satisfies the numerical range, the pattern may be formed reproducibly, and the storage stability of the ink is excellent.
다음으로, 상기 c)용매는 잉크의 점도 조절 및 형성된 막의 두께를 조절하기 위한 것으로 유기용매가 바람직하다. 보다 구체적으로 예를 들면 디에틸렌글리콜부틸메틸에테르, 디엘렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜모노메일에테르아세테이트, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디프로필렌글리콜메틸에테르아세테이트, 부틸락테이트, 에톡시에틸아세테이트, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노부틸에테르아세테이트, 에틸에톡시프로피오네이트, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르 및 프로필렌그리콜부틸에테르로 이루어진 군으로부터 선택된 1종 이상일 수 있으나, 이에 제한되는 것은 아니다. Next, the c) solvent is to control the viscosity of the ink and the thickness of the formed film is preferably an organic solvent. More specifically, for example, diethylene glycol butyl methyl ether, dielene glycol monobutyl ether acetate, diethylene glycol monomail ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate , Butyl lactate, ethoxy ethyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethyl ethoxy propionate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether and propylene glycol butyl ether It may be one or more selected from, but is not limited thereto.
또한, 상기 c)용매는 전체 잉크 조성물을 기준으로 0.001 중량부 내지 55 중량부를 포함할 수 있다. 용매의 함량이 상기 수치 범위를 만족하는 경우 선 패터닝 형성이 가능하며, 잉크의 퍼짐성이 감소하고, 패턴의 균일성이 증가한다. In addition, the c) solvent may include 0.001 parts by weight to 55 parts by weight based on the total ink composition. When the content of the solvent satisfies the above numerical range, line patterning can be formed, the spreadability of the ink decreases, and the pattern uniformity increases.
다시 말하면, 상기 c)용매를 제외한 고형분 함량은 전체 잉크 조성물을 기준으로 45 중량부 내지 99.99 중량부, 63 내지 99.99 중량부 또는 70 내지 99.99 중량부인 것이 바람직하다. 즉, 고형분 함량이 증가할수록 잉크의 퍼짐성이 감소하고, 패턴의 균일성이 증가되어, 안정적인 패턴 형성이 가능하다. In other words, the solid content except for c) the solvent is preferably 45 parts by weight to 99.99 parts by weight, 63 to 99.99 parts by weight or 70 to 99.99 parts by weight based on the total ink composition. That is, as the solid content is increased, the spreadability of the ink decreases, and the uniformity of the pattern is increased, so that stable pattern formation is possible.
한편, 상기 c)용매는 비점이 140℃ 내지 250℃인 것을 1종 또는 2종을 이상을 혼합한 것일 수 있다. 용매의 비점이 상기 수치 범위를 만족하는 경우 잉크젯 프린터의 노즐면에서 건조가 일어나지 않아 토출이 양호하고, 패턴을 형성한 후에 용매를 완전히 건조시킬 수 있으므로 공정성이 우수하다. On the other hand, the c) solvent may be one or a mixture of two or more of those having a boiling point of 140 ℃ to 250 ℃. When the boiling point of the solvent satisfies the above numerical range, drying does not occur at the nozzle surface of the inkjet printer, so that the ejection is good, and the solvent can be completely dried after the pattern is formed, thereby providing excellent processability.
선택적으로, 본 발명에 따른 잉크 조성물은, 실리콘 기판과의 접착 특성을 향상시키기 위하여 접착 증진제를 추가로 포함할 수 있다. 본 발명의 잉크 조성물이 식각 마스크로 사용되는 경우에는, 태양전지 제조시 에미터층의 선택적 식각을 위해 산 용액 처리가 요구되는바, 이 경우 패턴의 탈락이 발생하는 문제점을 방지하기 위함이다. Optionally, the ink composition according to the present invention may further include an adhesion promoter in order to improve the adhesion property with the silicon substrate. When the ink composition of the present invention is used as an etching mask, an acid solution treatment is required for selective etching of the emitter layer in manufacturing a solar cell, in order to prevent a problem of dropping of the pattern.
상기 접착 증진제는 가수분해에 의해 실란올기를 생성하는 치환기를 가지는 것, 또는 분자내에 메톡시 실릴기나 에톡시 실릴기를 가지는 것 등이 사용될 수 있다. 예를 들면 비닐트리메톡시실란, 비닐트리에톡시실란, 글리시독시프로필트리메톡시실란, 글리시독시프로필트리에톡시실란, 메타크릴록시프로필트리메톡시실란 및 메타크릴록시프로필트리에톡시실란 등으로 이루어진 군으로부터 선택된 1종 이상일 수 있으나, 이에 제한되는 것은 아니다. The adhesion promoter may be one having a substituent which generates a silanol group by hydrolysis, or one having a methoxy silyl group or an ethoxy silyl group in a molecule. For example, vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane It may be one or more selected from the group consisting of, but is not limited thereto.
또한, 상기 접착 증진제는 전체 잉크 조성물을 기준으로 0.1 중량부 내지 5.0 중량부를 포함할 수 있다. 접착 증진제의 함량이 상기 수치 범위를 만족하는 경우 잉크의 저장 안정성이 우수한 장점이 있다. 또한 상기 잉크 조성물을 식각 마스크로 사용하는 경우 산 용액 처리가 요구되는바 이 경우 패턴의 분리 또는 탈락을 방지할 수 있다. In addition, the adhesion promoter may include 0.1 parts by weight to 5.0 parts by weight based on the total ink composition. When the content of the adhesion promoter satisfies the numerical range, there is an advantage in that the storage stability of the ink is excellent. In addition, when the ink composition is used as an etching mask, acid solution treatment is required. In this case, separation or dropping of the pattern may be prevented.
선택적으로, 본 발명의 잉크 조성물은, 중합 개시제 및 바인더 등으로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 추가로 포함할 수 있다. Optionally, the ink composition of the present invention may further include at least one additive selected from the group consisting of a polymerization initiator, a binder, and the like.
여기서, 상기 중합 개시제는 에틸렌성 불포화 결합을 가지는 중합성 화합물을 경화하기 위한 것으로 열개시제, 광개시제 또는 이들의 조합일 수 있다. 특히, 본 발명의 잉크 조성물에 있어서, 용매를 제거하기 위한 추가적인 공정 없이 1 스텝의 열처리만으로도 경화가 완료되어 공정을 간단히 할 수 있는 열개시제가 바람직하다. Here, the polymerization initiator is for curing the polymerizable compound having an ethylenically unsaturated bond and may be a thermal initiator, a photoinitiator or a combination thereof. In particular, in the ink composition of the present invention, a thermal initiator capable of simplifying the process by completing the curing by only one step of heat treatment without an additional process for removing the solvent is preferable.
또한, 상기 중합 개시제는 전체 잉크 조성물을 기준으로 0.1 중량부 내지 5.0 중량부를 포함하는 것이 바람직하다. 중합 개시제의 함량이 상기 수치 범위를 만족하는 경우 라디칼이 충분하게 발생되지 않아 열중합이 진행되지 않는 문제를 방지할 수 있고, 중합 개시제가 잘 용해되어 상기 잉크 조성물을 절연막으로 사용하는 경우에는 그 표면의 불량 발생률을 감소시킬 수 있으며, 식각 마스크로 사용하는 경우에는 스트리퍼에 의해 제거가 용이하다. 또한, 상기 중합 개시제의 함량은 열개시제, 광개시제 또는 이들을 조합하여 사용하는 경우에도 동일하다.In addition, the polymerization initiator preferably contains 0.1 parts by weight to 5.0 parts by weight based on the total ink composition. When the content of the polymerization initiator satisfies the numerical range, radicals are not sufficiently generated to prevent thermal polymerization from progressing, and when the polymerization initiator is well dissolved, the ink composition is used as an insulating film. The incidence of defects can be reduced, and when used as an etching mask, the stripper can be easily removed. In addition, the content of the polymerization initiator is also the same when using a thermal initiator, a photoinitiator or a combination thereof.
한편, 상기 열개시제로는 예를 들면 아조계 화합물, 유기 과산화물, 및 과산화수소로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있으나, 이에 제한되는 것은 아니다.Meanwhile, the thermal initiator may be, for example, one or more selected from the group consisting of azo compounds, organic peroxides, and hydrogen peroxide, but is not limited thereto.
또한, 상기 광개시제는 당해 기술분야에 잘 알려진 광중합 개시제 또는 광증감제를 사용할 수 있으나 이에 제한되는 것은 아니다. 예를 들면, 트리아진 화합물, 비이미다졸 화합물, 아세토페논계 화합물 벤조페논계 화합물 및 티옥산톤계 화합물로 이루어진 군으로부터 선택된 1종 이상일 수 있다.In addition, the photoinitiator may be a photopolymerization initiator or a photosensitizer well known in the art, but is not limited thereto. For example, it may be at least one selected from the group consisting of a triazine compound, a biimidazole compound, an acetophenone compound benzophenone compound, and a thioxanthone compound.
한편, 상기 바인더는, 형성된 잉크막의 접착 특성을 높이고, 잉크막을 용이하게 형성하게 하며, 형성된 잉크막의 강도를 조절하는 물질로서 조성물의 본래 성질을 해치지 않는다면 특별히 제한되지 않는다. 이러한 바인더로는 예를 들면, 스티렌, 클로로 스티렌, α-메틸 스티렌, 비닐톨루엔, 2-에틸헥실(메타)아크릴레이트, 메틸(메타)아크릴레이트, 에틸 (메타)아크릴레이트, 부틸(메타)아크릴레이트, 벤질(메타)아크릴레이트, 글리시딜(메타)아크릴레이트, 디메틸아미노에틸(메타)아크릴레이트, 이소부틸 (메타)아크릴레이트, t-부틸(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 디시클로펜타닐(메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 2-페녹시에틸(메타)아크릴레이트, 테트라히드로퍼프릴(메타)아크릴레이트, 히드록시에틸(메타)아크릴레이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시-3-클로로프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 디메틸아미노메틸(메타)아크릴레이트, 디에틸아미노(메타)아크릴레이트, 아실옥틸옥시-2-히드록시프로필(메타)아크릴레이트, 에틸헥실아크릴레이트, 2-메톡시에틸(메타)아크릴레이트, 3-메톡시부틸(메타)아크릴레이트, 부톡시에틸(메타)아크릴레이트, 에톡시디에틸렌글리콜(메타)아크릴레이트, 메톡시트리에틸렌글리콜(메타)아크릴레이트, 메톡시트리프로필렌글리콜 (메타)아크릴레이트, 메톡시폴리에틸렌글리콜(메타)아크릴레이트, 페녹시디에틸렌글리콜(메타)아크릴레이트, p-노닐페녹시폴리에틸렌글리콜 (메타)아크릴레이트, p-노닐페녹시폴리프로필렌글리콜(메타)아크릴레이트, 테트라플루오로프로필(메타)아크릴레이트, 1,1,1,3,3,3-헥사플루오로이소프로필 (메타)아크릴레이트, 옥타플루오로펜틸(메타)아크릴레이트, 헵타데카플루오로데실 (메타)아크릴레이트, 트리브로모페닐(메타)아크릴레이트, 메틸 α-히드록시메틸 아크릴레이트, 에틸 α-히드록시메틸 아크릴레이트, 프로필 α-히드록시메틸 아크릴레이트, 부틸 α-히드록시메틸 아크릴레이트, 라우릴메타아크릴레이트, N-페닐말레이미드, N-(4-클로로페닐)말레이미드, 메타 아크릴산, 말레인산, 및 이타콘산로 이루어진 군으로부터 선택된 1종 이상을 공중합하여 제조된 것일 수 있으나, 이에 제한되는 것은 아니다. 또한, 상기 바인더는 평균 분자량이 4,000 내지 50,000인 것이 바람직하다.On the other hand, the binder is not particularly limited as long as it improves the adhesive properties of the formed ink film, facilitates the formation of the ink film, and controls the strength of the formed ink film without impairing the original properties of the composition. Examples of such binders include styrene, chloro styrene, α-methyl styrene, vinyltoluene, 2-ethylhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylic. Rate, benzyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylic Latex, dicyclopentanyl (meth) acrylate, isobonyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Roxybutyl (meth) acrylate, di Methylaminomethyl (meth) acrylate, diethylamino (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3 -Methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate , Methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoro Ropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) a Relate, tribromophenyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, It may be prepared by copolymerizing one or more selected from the group consisting of uryl methacrylate, N-phenylmaleimide, N- (4-chlorophenyl) maleimide, methacrylic acid, maleic acid, and itaconic acid, but is not limited thereto. It is not. In addition, the binder preferably has an average molecular weight of 4,000 to 50,000.
또한, 상기 바인더는 전체 잉크 조성물을 기준으로 0.01 중량부 내지 8 중량부를 포함하는 것이 바람직하다. 바인더의 함량이 상기 수치범위를 만족하는 경우 잉크의 점도가 증가하지 않아 패턴 형성이 용이하다. In addition, the binder preferably comprises 0.01 to 8 parts by weight based on the total ink composition. When the content of the binder satisfies the numerical range, the viscosity of the ink does not increase, and thus pattern formation is easy.
본 발명에 따른 태양전지 제조에서 이용 가능한 잉크 조성물은 30°내지 60°의 접촉각을 갖는 것이 바람직하다. 본 명세서에서 접촉각은 드랍된 잉크의 액적과 기재가 접하는 점에서 액적 표면으로 이끄는 접선과 기재 표면과 이루는 각을 의미하며, 접촉각을 측정하는 장치로는 예를 들면, 접촉각 측정기(KRUSS사 DSA100) 등이 있다. 본 명세서에 있어서, 상기 접촉각은 유리기판에 잉크를 드랍시켜 측정한 값이다. 잉크 조성물의 접촉각이 상기 수치 범위를 만족하는 경우 표면 요철이 있는 실리콘 기판에서 잉크의 퍼짐성이 작아 원하는 선폭의 패턴을 형성할 수 있고, 부분적으로 잉크가 뭉치는 현상 없이 패턴이 끊어지지 않게 형성할 수 있으며 기판과의 접착력도 우수하다. The ink composition usable in the solar cell production according to the invention preferably has a contact angle of 30 ° to 60 °. In the present specification, the contact angle means an angle formed by the tangent leading to the surface of the droplet and the surface of the substrate at the point where the droplet of the dropped ink is in contact with the substrate, and as an apparatus for measuring the contact angle, for example, a contact angle measuring instrument (KRUSS DSA100) There is this. In the present specification, the contact angle is a value measured by dropping ink on a glass substrate. When the contact angle of the ink composition satisfies the above numerical range, the spreadability of the ink is small on the silicon substrate having the surface irregularities, so that a pattern having a desired line width can be formed, and the pattern can be formed without breaking the ink without partially clumping the ink. It also has excellent adhesion to the substrate.
다음으로, 본 발명에 따른 패턴형성방법을 설명한다. Next, a pattern forming method according to the present invention will be described.
상기 패턴형성방법은 본 발명에 따른 상기 잉크 조성물을 잉크젯 프린터의 헤드를 이용하여 도포하는 단계 및 상기 도포된 잉크 조성물을 열처리 하는 단계를 포함한다.The pattern forming method includes applying the ink composition according to the present invention using a head of an inkjet printer, and heat treating the applied ink composition.
이때, 상기 잉크 조성물을 도포하는 기판은 유리 기판, 실리콘 기판이거나 메탈, SiO2 또는 ITO가 증착된 기판일 수 있으며, 바람직하게는 표면 요철이 있는 태양전지용 실리콘 기판일 수 있다.In this case, the substrate to which the ink composition is applied may be a glass substrate, a silicon substrate, or a substrate on which metal, SiO 2, or ITO is deposited, and may preferably be a silicon substrate for solar cells having surface irregularities.
또한, 상기 잉크 조성물을 도포하는 단계는 잉크젯 헤드를 통해 기판 위에 잉크를 비접촉 방식으로 토출하는 방법에 의해 수행될 수 있다. 여기서, 상기 잉크젯 헤드로부터 잉크 토출이 가능하도록 점도를 낮추기 위하여 잉크젯 헤드를 추가로 가열할 수 있다. In addition, applying the ink composition may be performed by a method of ejecting ink on a substrate through a inkjet head in a non-contact manner. Here, the inkjet head may be further heated in order to lower the viscosity to allow ink ejection from the inkjet head.
즉, 상기 잉크 조성물을 도포하는 단계는 잉크 조성물의 점도가 10cP 내지 20cP를 만족하도록 잉크젯 헤드를 40℃ 내지 80℃로 가열하는 것이 바람직하다. 잉크젯 헤드의 가열 온도가 상기 수치 범위를 만족하는 경우 잉크의 점도가 낮아 잉크젯 헤드로부터 잉크의 토출이 안정한 효과가 있고, 잉크젯 장비의 구동부에 문제가 발생하지 않으며, 잉크의 저장 안정성이 증가한다. That is, in the step of applying the ink composition, the inkjet head is preferably heated to 40 ° C. to 80 ° C. such that the viscosity of the ink composition satisfies 10 cP to 20 cP. When the heating temperature of the inkjet head satisfies the numerical range, the viscosity of the ink is low, so that the ejection of the ink from the inkjet head is stable, the problem does not occur in the driving portion of the inkjet equipment, and the storage stability of the ink is increased.
다음으로, 상기 열처리 단계는 도포된 잉크 조성물의 막을 건조하기 위한 것으로, 감압건조기, 컨벡션 오븐, 핫 플레이트 또는 IR 오븐 등을 사용하여 수행될 수 있다. 이때, 열처리 온도는 130℃ 내지 250℃에서 수행될 수 있다. 열처리 온도가 상기 수치 범위를 만족하는 경우 열경화가 불충분하여 식각 마스크나 절연막으로서 역할을 할 수 없는 문제점이나 식각 마스크로 사용하는 경우 패턴의 제거가 어렵고, 반응해야 할 반응물의 일부가 열에 의해 소실될 수 있는 문제점을 예방할 수 있다.Next, the heat treatment step is to dry the film of the applied ink composition, it may be performed using a reduced pressure dryer, a convection oven, a hot plate or an IR oven. At this time, the heat treatment temperature may be carried out at 130 ℃ to 250 ℃. When the heat treatment temperature is within the above numerical range, thermal curing is insufficient, and thus, the film cannot be used as an etching mask or an insulating film, or when used as an etching mask, it is difficult to remove the pattern and part of the reactant to be reacted is lost by heat. This can prevent problems.
본 발명에 따른 잉크 조성물을 이용하여 패턴을 형성하는 방법에 있어서, 상기 잉크 조성물을 식각 마스크로 사용하는 경우에는, 상기 열처리 단계는 160℃ 내지 200℃의 온도에서 수행될 수 있다. 열처리 온도가 상기 수치 범위를 만족하는 경우에는 형성된 식각 마스크 패턴이 선택적 에미터 형성을 위한 에미터층의 선택적 식각 공정에서 식각에 견디는 성능이 양호하여 패턴의 탈락이나 분해가 일어나는 문제를 방지할 수 있고, 식각 마스크 패턴 제거시 알칼리 용액에서 용이하게 제거할 수 있다. In the method of forming a pattern using the ink composition according to the present invention, when the ink composition is used as an etching mask, the heat treatment step may be performed at a temperature of 160 ℃ to 200 ℃. When the heat treatment temperature satisfies the numerical range, the formed etching mask pattern may have a good ability to withstand etching in the selective etching process of the emitter layer for forming the selective emitter, thereby preventing the pattern from falling off or decomposition. When removing the etching mask pattern can be easily removed from the alkaline solution.
본 발명에 따른 잉크 조성물을 이용하여 패턴을 형성하는 방법에 있어서, 상기 잉크 조성물을 절연막으로 사용하는 경우에는, 상기 열처리 단계는 220℃ 내지 250℃에서 수행될 수 있다. 열처리 온도가 상기 수치 범위를 만족하는 경우에는 높은 온도에서 처리하므로 충분한 경화가 이루어질 수 있다.In the method of forming a pattern using the ink composition according to the present invention, when the ink composition is used as an insulating film, the heat treatment step may be performed at 220 ℃ to 250 ℃. When the heat treatment temperature satisfies the above numerical range, a sufficient curing may be achieved since the treatment is performed at a high temperature.
본 발명의 식각 마스크는 요철이 있는 태양전지용 실리콘 기판상에 상기 잉크 조성물을 이용하여 형성시킨 것을 특징으로 한다. The etching mask of the present invention is formed on the silicon substrate for solar cells having irregularities by using the ink composition.
상기 식각 마스크는 당해 기술 분야에 잘 알려진 방법으로 형성될 수 있으나, 예를 들면 본 발명에 따른 패턴형성방법을 이용하여 패턴을 형성한 후 식각 마스크로 이용할 수 있다. The etching mask may be formed by a method well known in the art, for example, may be used as an etching mask after forming a pattern using the pattern forming method according to the present invention.
본 발명에 따른 식각 마스크를 이용하여 태양전지를 제조하는 경우 선택적 에미터 형성을 위한 공정에서 식각에 견디는 성능이 우수하고, 알칼리 용액에서 제거가 용이하여 태양전지 제조시 공정 재연성과 안정성을 제공할 수 있는 장점이 있다. When manufacturing a solar cell using an etching mask according to the present invention is excellent in the ability to withstand the etching in the process for forming a selective emitter, can be easily removed from the alkaline solution can provide process reproducibility and stability in the solar cell manufacturing There is an advantage.
본 발명의 절연막은 요철이 있는 태양전지용 실리콘 기판상에 상기 잉크 조성물을 이용하여 형성시킨 것을 특징으로 한다. The insulating film of this invention was formed using the said ink composition on the silicon substrate for solar cells with an unevenness | corrugation. It is characterized by the above-mentioned.
상기 절연막은 당해 기술 분야에 잘 알려진 방법으로 형성될 수 있으나, 예를 들면 본 발명에 따른 패턴형성방법을 이용하여 패턴을 형성한 후 절연막으로 이용할 수 있다.The insulating film may be formed by a method well known in the art, but may be used as an insulating film, for example, after forming a pattern using the pattern forming method according to the present invention.
실시예EXAMPLE
합성예 1 - 바인더 A의 합성Synthesis Example 1 Synthesis of Binder A
반응 용기에 열개시제로서 V65 1.6 중량부를 용매에 녹인 후 벤질메타아크릴레이트/메타아크릴산을 68/32의 몰비로 투입한 후 질소 분위기에서 65℃를 유지하며 7.5시간 반응시켰다. 상기에서 얻은 공중합체 용액을 교반기가 부착된 플라스크에 투입하고, 글리시딜메타아크릴레이트를 가한 다음, 추가로 110℃에서 6시간 동안 반응시켜 아크릴 공중합체를 제조하였다.1.6 parts by weight of V65 was dissolved in a solvent as a thermal initiator in a reaction vessel, and then benzyl methacrylate / methacrylic acid was added at a molar ratio of 68/32. The reaction was carried out for 7.5 hours while maintaining the temperature at 65 ° C. in a nitrogen atmosphere. The copolymer solution obtained above was added to a flask with a stirrer, glycidyl methacrylate was added, and then reacted at 110 ° C. for 6 hours to prepare an acrylic copolymer.
합성예 2 - 바인더 B의 합성Synthesis Example 2 Synthesis of Binder B
반응 용기에 열개시제로서 V65 1.6 중량부를 용매에 녹인 후 벤질메타아크릴레이트/스티렌/메타아크릴산/라우릴메타아크릴레이트를 52/19/12/17의 몰비로 투입하였다. 질소 분위기에서 65℃를 유지하며 7.5시간 반응시켰으며, 이를 바인더 수지로 사용하였다.1.6 parts by weight of V65 was dissolved in a solvent as a thermal initiator in a reaction vessel, and then benzyl methacrylate / styrene / methacrylic acid / lauryl methacrylate was added at a molar ratio of 52/19/12/17. The reaction was carried out for 7.5 hours while maintaining the temperature at 65 ° C. in a nitrogen atmosphere, which was used as a binder resin.
실시예 1Example 1
잉크 조성물 100 중량부에 대해 바인더 A를 1.00 중량부, 중합성 화합물로 디펜타에리트리톨헥사아크릴레이트, 트리메틸롤프로판트리아크릴레이트, 디프로필렌글리콜디아크릴레이트 혼합물을 93.24 중량부, 메타크릴록시프로필트리메톡시실란을 2.00 중량부, 불소계 계면활성제를 0.04 중량부, 개시제로 Wako 사의 V40를 0.25 중량부 및 용매로 디에틸렌글리콜메틸부틸에테르 3.47 중량부를 2시간 동안 혼합하여 본 발명의 잉크 조성물을 제조하였다. 1.00 parts by weight of binder A with respect to 100 parts by weight of the ink composition, 93.24 parts by weight of dipentaerythritol hexaacrylate, trimethylolpropane triacrylate and dipropylene glycol diacrylate as a polymerizable compound, methacryloxypropyltri The ink composition of the present invention was prepared by mixing 2.00 parts by weight of methoxysilane, 0.04 part by weight of a fluorine-based surfactant, 0.25 parts by weight of V40 manufactured by Wako as an initiator, and 3.47 parts by weight of diethylene glycol methylbutyl ether as a solvent for 2 hours. .
이때, 고형분 함량은 용매 제외한 나머지 성분의 합을 전체 잉크 조성물의 중량부를 기준으로 계산한 값이고, 점도는 점도계를 사용하여 상온(25℃)에서 측정한 값이다. In this case, the solid content is a value calculated based on the weight part of the total ink composition, excluding the solvent, and the viscosity is a value measured at room temperature (25 ° C.) using a viscometer.
실시예 2 내지 3 및 비교예 1 내지 4Examples 2 to 3 and Comparative Examples 1 to 4
하기 표 1에 기재된 구성과 함량으로 실시예 1과 동일한 방법을 이용하여 잉크 조성물을 제조하였다.To the ink composition was prepared in the same manner as in Example 1 in the composition and content shown in Table 1.
표 1
구분 실시예1 실시예2 실시예3 비교예1 비교예2 비교예3 비교예4
바인더 A 1.00 1.00 - - 13.14 1.00 1.00
바인더 B - - - 7.88 - - -
중합성 화합물 DPHA1/TMPTA2/DPGDA3 혼합물 93.24 77.09 73.22 31.53 26.27 93.24 77.09
접착 증진제 2.00 1.66 1.55 0.30 0.30 2.00 1.66
계면활성제 0.04 0.04 0.04 0.04 0.04 0.04** 0.04**
개시제 Wako 사의 V40 0.25 0.21 0.19 0.25 0.25 0.25 0.21
용매 디에틸렌글리콜부틸메틸에테르 3.47 20.00 25.00 60.00 60.00 3.47 20.00
고형분(%) 96.53 80.00 75.00 40.00 40.00 96.53 80.00
점도(cP) 30.40 13.10 10.7 25.00 29.60 30.40 13.10
Table 1
division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4
Binder A 1.00 1.00 - - 13.14 1.00 1.00
Binder B - - - 7.88 - - -
Polymerizable compound DPHA 1 / TMPTA 2 / DPGDA 3 mixture 93.24 77.09 73.22 31.53 26.27 93.24 77.09
Adhesion promoter 2.00 1.66 1.55 0.30 0.30 2.00 1.66
Surfactants 0.04 0.04 0.04 0.04 0.04 0.04 ** 0.04 **
Initiator Wako V40 0.25 0.21 0.19 0.25 0.25 0.25 0.21
menstruum Diethylene glycol butylmethyl ether 3.47 20.00 25.00 60.00 60.00 3.47 20.00
Solid content (%) 96.53 80.00 75.00 40.00 40.00 96.53 80.00
Viscosity (cP) 30.40 13.10 10.7 25.00 29.60 30.40 13.10
DPHA1 : 디펜타에리트리톨헥사아크릴레이트 DPHA 1 : dipentaerythritol hexaacrylate
TMPTA2 : 트리메틸올프로판트리아크릴레이트TMPTA 2 : trimethylolpropanetriacrylate
DPGDA3 : 디프로필렌클리콜디아크릴레이트DPGDA 3 : Dipropylene Glycol Diacrylate
**는 실리콘계 계면활성제를 사용한 경우임. ** is when a silicone surfactant is used.
실험예Experimental Example
선 패턴형성여부Line pattern formation
상기 실시예 1 내지 3 및 비교예 1 내지 4에서 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성하였다. 잉크젯 헤드로 잉크를 토출하기 위해 실시예 1 및 비교예 3은 45.5℃, 비교예 1은 37.6℃, 비교예 2는 42.7℃로 열을 가해주었다. 반면에 실시예 2, 실시예 3 및 비교예 4는 상온에서 잉크를 출하였다. 패턴을 형성한 후에, 용매를 제거하고 에틸렌성 불포화 결합을 갖는 중합성 화합물을 경화하기 위해 130℃ 이상의 온도에서 열처리 하였다. By using the ink compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were discharged on the silicon substrate having the surface irregularities to form a pattern. In order to discharge ink to the inkjet head, Example 1 and Comparative Example 3 were heated to 45.5 ° C, Comparative Example 1 to 37.6 ° C, and Comparative Example 2 to 42.7 ° C. On the other hand, Example 2, Example 3 and Comparative Example 4 discharged the ink at room temperature. After the pattern was formed, the solvent was removed and heat treated at a temperature of 130 ° C. or higher to cure the polymerizable compound having an ethylenically unsaturated bond.
실시예 1 내지 3 및 비교예 1 내지 4에 따른 잉크 조성물을 이용하여 선 패턴 형성 여부를 측정한 결과는 표 2와 같다. 선 패턴 형성여부는 광학 현미경을 이용하여 육안으로 측정하였으며, "O"는 선 패턴이 양호하게 형성된 것을 의미하고, "X"는 선 패턴이 형성되지 않은 것을 의미한다. The results of measuring the formation of line patterns using the ink compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 2. Line pattern formation was visually measured using an optical microscope, "O" means that the line pattern is formed well, "X" means that the line pattern is not formed.
표 2
구 분 선 패턴 형성여부
실시예 1 O
실시예 2 O
실시예 3 O
비교예 1 X
비교예 2 X
비교예 3 X
비교예 4 X
TABLE 2
division Line pattern formation
Example 1 O
Example 2 O
Example 3 O
Comparative Example 1 X
Comparative Example 2 X
Comparative Example 3 X
Comparative Example 4 X
도 1 내지 3은 실시예 1 내지 3에 따라 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이고, 도 4 내지 7은 비교예 1 내지 4에 따라 제조한 잉크 조성물을 이용하여 표면 요철이 있는 실리콘 기판 위에 토출하여 패턴을 형성한 후 패턴형성결과를 나타낸 사진이다. 1 to 3 are photographs showing a pattern formation result after ejecting a pattern by discharging onto a silicon substrate having surface irregularities using the ink compositions prepared according to Examples 1 to 3, and FIGS. 4 to 7 are Comparative Examples 1 to 3 It is a photograph showing the pattern formation result after forming a pattern by discharging onto a silicon substrate having surface irregularities using the ink composition prepared according to the fourth.
패턴형성결과, 상기 표 2 및 도 1 내지 도 3에 나타낸 바와 같이 실시예 1 내지 3에 따라 제조한 잉크 조성물을 이용하는 경우 각각 균일한 선 패턴 형성이 가능하였다. 또한, 고형분 함량이 증가할수록 보다 직선형태로 균일한 선 패턴 형성이 가능한 것을 알 수 있다. 그러나, 표 2 및 도 4 내지 7에 나타낸 바와 같이 비교예 1 내지 4에 따라 제조한 잉크 조성물을 이용하는 경우 잉크가 퍼져 선 패턴을 형성할 수 없었다.As a result of pattern formation, when using the ink compositions prepared according to Examples 1 to 3 as shown in Table 2 and FIGS. 1 to 3, uniform line patterns were formed, respectively. In addition, it can be seen that as the solid content increases, a uniform line pattern can be formed in a more linear form. However, when using the ink compositions prepared according to Comparative Examples 1 to 4 as shown in Table 2 and Figs. 4 to 7, the ink could not be spread to form a line pattern.
상기와 같은 결과를 바탕으로, 본 발명에서는 고형분의 함량이 40 중량부 이하인 경우에 패턴의 균일성이 감소됨을 확인하였다. 즉, 고형분 함량이 감소할수록 잉크의 퍼짐성이 증가하며, 고형분 함량이 40 중량부 이하일 경우는 선 패터닝이 어려울 뿐만 아니라 잉크의 용매가 건조되어 생성된 패턴이 태양전지용 실리콘 기판의 표면 요철부의 첨단부를 제대로 덮지 못하는 문제도 발생하였다. 또한, 불소계 계면활성제를 사용하지 않는 경우에는 비록 고형분 함량이 높은 경우에도 표면 요철이 있는 기판에서의 선 패턴 형성이 어려운 것을 알 수 있다. Based on the results as described above, in the present invention it was confirmed that the uniformity of the pattern is reduced when the content of the solid content is 40 parts by weight or less. That is, as the solid content decreases, the spreadability of the ink increases, and when the solid content is 40 parts by weight or less, line patterning is difficult, and the pattern formed by drying the solvent of the ink ensures that the tip of the surface irregularities of the solar cell silicon substrate is properly formed. There was also a problem that could not be covered. In addition, when the fluorine-based surfactant is not used, it can be seen that even if the solid content is high, it is difficult to form a line pattern on a substrate having surface irregularities.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다. Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims (19)

  1. a)에틸렌성 불포화 결합을 갖는 중합성 화합물;a) a polymerizable compound having an ethylenically unsaturated bond;
    b)불소계 계면활성제; 및 b) fluorine-based surfactants; And
    c)용매를 포함하며, c) contains a solvent,
    고형분의 함량이 전체 잉크 조성물을 기준으로 45 중량부 내지 99.99 중량부인 태양전지 제조에서 이용 가능한 잉크 조성물. An ink composition usable in solar cell manufacturing wherein the content of solids is 45 parts by weight to 99.99 parts by weight based on the total ink composition.
  2. 제1항에 있어서,The method of claim 1,
    전체 잉크 조성물 100 중량부에 대하여,Per 100 parts by weight of the total ink composition,
    a)에틸렌성 불포화 결합을 갖는 중합성 화합물 40 중량부 내지 98 중량부;a) 40 parts by weight to 98 parts by weight of a polymerizable compound having an ethylenically unsaturated bond;
    b)불소계 계면활성제 0.01 중량부 내지 1.0 중량부; 및 b) 0.01 to 1.0 parts by weight of fluorine-based surfactant; And
    c)용매 0.001 중량부 내지 55 중량부를 포함하는 태양전지 제조에서 이용 가능한 잉크 조성물.c) Ink composition which can be used in solar cell manufacture containing 0.001 to 55 parts by weight of solvent.
  3. 제1항에 있어서, The method of claim 1,
    상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은 디펜타에리트리톨헥사아크릴레이트, 디프로필렌글리콜디아크릴레이트, 트리메틸로프로판트리아크릴레이트 및 트리프로필렌글리콜디아크릴레이트로 이루어진 군으로부터 선택된 2종이상을 혼합한 것인 태양전지 제조에서 이용 가능한 잉크 조성물.The polymerizable compound having an ethylenically unsaturated bond is a mixture of two or more selected from the group consisting of dipentaerythritol hexaacrylate, dipropylene glycol diacrylate, trimethyl propane triacrylate and tripropylene glycol diacrylate. Ink composition usable in solar cell manufacturing.
  4. 제1항에 있어서,The method of claim 1,
    상기 불소계 계면활성제는 폴리에틸렌 글리콜 및 퍼플루오로카본을 포함하는 것인 태양전지 제조에서 이용 가능한 잉크 조성물.The fluorine-based surfactant is an ink composition that can be used in the manufacture of solar cells containing polyethylene glycol and perfluorocarbon.
  5. 제1항에 있어서,The method of claim 1,
    상기 불소계 계면활성제는 상기 계면활성제를 0.1 중량% 포함하는 톨루엔 용액으로 만들었을 때의 표면장력이 20 mN/m 내지 30 mN/m 범위인 태양전지 제조에서 이용 가능한 잉크 조성물.The fluorine-based surfactant is an ink composition that can be used in the solar cell manufacturing when the surface tension of the toluene solution containing 0.1% by weight of the surfactant ranges from 20 mN / m to 30 mN / m.
  6. 제1항에 있어서,The method of claim 1,
    상기 불소계 계면활성제는 상기 계면활성제를 0.1 중량% 포함하는 톨루엔 용액으로 만들었을 때의 표면장력이 23 mN/m 내지 27 mN/m 범위인 태양전지 제조에서 이용 가능한 잉크 조성물.The fluorine-based surfactant is an ink composition that can be used in the manufacture of solar cells having a surface tension of 23 mN / m to 27 mN / m when made of a toluene solution containing 0.1% by weight of the surfactant.
  7. 제1항에 있어서,The method of claim 1,
    상기 불소계 계면활성제는 상기 계면활성제를 0.1 중량% 포함하는 프로필렌글리콜메틸에테르 용액으로 만들었을 때의 표면장력이 20 mN/m 내지 30 mN/m 범위인 태양전지 제조에서 이용 가능한 잉크 조성물.The fluorine-based surfactant is an ink composition that can be used in the solar cell manufacturing when the surface tension of the propylene glycol methyl ether solution containing 0.1% by weight of the surfactant ranges from 20 mN / m to 30 mN / m.
  8. 제1항에 있어서,The method of claim 1,
    상기 불소계 계면활성제는 상기 계면활성제를 0.1 중량% 포함하는 프로필렌글리콜메틸에테르 용액으로 만들었을 때의 표면장력이 24 mN/m 내지 28 mN/m 범위인 태양전지 제조에서 이용 가능한 잉크 조성물.The fluorine-based surfactant is an ink composition that can be used in the solar cell manufacturing when the surface tension of the propylene glycol methyl ether solution containing 0.1% by weight of the surfactant ranges from 24 mN / m to 28 mN / m.
  9. 제1항에 있어서, The method of claim 1,
    상기 용매는 디에틸렌글리콜메틸부틸에테르, 디엘렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜모노메일에테르아세테이트, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디프로필렌글리콜메틸에테르아세테이트, 부틸락테이트, 에톡시에틸아세테이트, 에틸렌글리콜모노부틸에테르, 에틸렌글리콜모노부틸에테르아세테이트, 에틸에톡시프로피오네이트, 프로필렌글리콜메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르 및 프로필렌글리콜부틸에테르로 이루어진 군으로부터 선택된 1종 이상인 태양전지 제조에서 이용 가능한 잉크 조성물.The solvent is diethylene glycol methyl butyl ether, dielene glycol monobutyl ether acetate, diethylene glycol monomail ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, butyl lac Tate, ethoxy ethyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethyl ethoxy propionate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether and propylene glycol butyl ether Ink composition which can be used for the above-mentioned solar cell manufacture.
  10. 제1항에 있어서, The method of claim 1,
    상기 잉크 조성물은 접착 증진제를 추가로 포함하는 것인 태양전지 제조에서 이용 가능한 잉크 조성물.The ink composition is an ink composition usable in solar cell manufacturing further comprising an adhesion promoter.
  11. 제10항에 있어서, The method of claim 10,
    상기 접착 증진제는 가수분해에 의해 실란올기를 생성하는 치환기를 가지는 것 또는 분자내에 메톡시 실릴기나 에톡시 실릴기를 실릴기를 가지는 것일 수 있으며, 그 함량은 전체 잉크 조성물을 기준으로 0.1 중량부 내지 5.0 중량부인 태양전지 제조에서 이용 가능한 잉크 조성물.The adhesion promoter may have a substituent that generates a silanol group by hydrolysis or may have a methoxy silyl group or an ethoxy silyl group silyl group in the molecule, the content of which is 0.1 parts by weight to 5.0 parts by weight based on the total ink composition Ink composition which can be used in denier solar cell manufacture.
  12. 제1항에 있어서, The method of claim 1,
    상기 잉크 조성물은 중합 개시제 및 바인더로 이루어진 군으로부터 선택된 1종 이상의 첨가제를 추가로 포함하는 것인 태양전지 제조에서 이용 가능한 잉크 조성물.The ink composition is an ink composition usable in solar cell manufacturing further comprising at least one additive selected from the group consisting of a polymerization initiator and a binder.
  13. 제1항 내지 제12항 중 어느 한 항에 있어서, The method according to any one of claims 1 to 12,
    상기 잉크 조성물의 유리기판에서 접촉각은 30°내지 60°인 태양전지 제조에서 이용 가능한 잉크 조성물.The contact angle in the glass substrate of the ink composition is an ink composition that can be used in solar cell manufacturing is 30 ° to 60 °.
  14. 제1항의 잉크 조성물을 잉크젯 프린터를 이용하여 도포하는 단계; 및 Applying the ink composition of claim 1 using an inkjet printer; And
    상기 도포된 잉크 조성물을 130℃ 내지 250℃ 온도로 열처리 하는 단계를 포함하는 패턴형성방법.The pattern forming method comprising the step of heat-treating the applied ink composition to 130 ℃ to 250 ℃ temperature.
  15. 제14항에 있어서,The method of claim 14,
    상기 도포하는 단계는 상기 잉크 조성물의 점도가 10cP 내지 20cP의 범위가 되도록, 잉크젯 프린터의 헤드를 40℃ 내지 80℃로 가열하여 수행되는 것인 패턴형성방법.The applying step is a pattern forming method is performed by heating the head of the inkjet printer to 40 ℃ to 80 ℃, such that the viscosity of the ink composition is in the range of 10 cP to 20 cP.
  16. 제14항에 있어서,The method of claim 14,
    상기 열처리 단계는 160℃ 내지 200℃에서 수행되는 것인 패턴형성방법.The heat treatment step is a pattern forming method that is performed at 160 ℃ to 200 ℃.
  17. 제14항에 있어서,The method of claim 14,
    상기 열처리 단계는 220℃ 내지 250℃에서 수행되는 것인 패턴형성방법.The heat treatment step is a pattern forming method that is performed at 220 ℃ to 250 ℃.
  18. 제1항의 잉크 조성물을 이용하여 형성된 식각 마스크.An etching mask formed using the ink composition of claim 1.
  19. 제1항의 잉크 조성물을 이용하여 형성된 절연막.An insulating film formed using the ink composition of claim 1.
PCT/KR2013/003882 2012-05-03 2013-05-03 Ink composition capable of being used in manufacturing solar cells and pattern formation method using same WO2013165223A1 (en)

Priority Applications (2)

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CN201380002253.6A CN103687915B (en) 2012-05-03 2013-05-03 Ink composition capable of being used in manufacturing solar cells and pattern formation method using same
US14/126,189 US9302466B2 (en) 2012-05-03 2013-05-03 Ink composition usable in solar battery manufacturing process, and method of forming pattern using the same

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KR20120046866 2012-05-03
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KR1020130050314A KR101431485B1 (en) 2012-05-03 2013-05-03 Ink composition for use in manufacturing of solar cell and pattern forming process using the composition
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090005990A (en) * 2007-07-09 2009-01-14 제이에스알 가부시끼가이샤 Photosensitive paste composition and pattern forming method
US20090163615A1 (en) * 2005-08-31 2009-06-25 Izhar Halahmi Uv curable hybridcuring ink jet ink composition and solder mask using the same
KR100955977B1 (en) * 2005-06-03 2010-05-04 다이킨 고교 가부시키가이샤 Surface Treating Agent for Pattern Formation
KR100983010B1 (en) * 2007-12-27 2010-09-17 한국생산기술연구원 manufacturing method of Organic thin film solar cell of using inkket
KR20110120211A (en) * 2010-04-28 2011-11-03 칫소가부시키가이샤 Ink for ink-jet, and uses therefof
KR20120038360A (en) * 2010-10-13 2012-04-23 제이엔씨 주식회사 Photocurable composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100955977B1 (en) * 2005-06-03 2010-05-04 다이킨 고교 가부시키가이샤 Surface Treating Agent for Pattern Formation
US20090163615A1 (en) * 2005-08-31 2009-06-25 Izhar Halahmi Uv curable hybridcuring ink jet ink composition and solder mask using the same
KR20090005990A (en) * 2007-07-09 2009-01-14 제이에스알 가부시끼가이샤 Photosensitive paste composition and pattern forming method
KR100983010B1 (en) * 2007-12-27 2010-09-17 한국생산기술연구원 manufacturing method of Organic thin film solar cell of using inkket
KR20110120211A (en) * 2010-04-28 2011-11-03 칫소가부시키가이샤 Ink for ink-jet, and uses therefof
KR20120038360A (en) * 2010-10-13 2012-04-23 제이엔씨 주식회사 Photocurable composition

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