KR20130136725A - A paste composition of electrode for solar cell of low temperature hardening type - Google Patents

A paste composition of electrode for solar cell of low temperature hardening type Download PDF

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KR20130136725A
KR20130136725A KR1020120060354A KR20120060354A KR20130136725A KR 20130136725 A KR20130136725 A KR 20130136725A KR 1020120060354 A KR1020120060354 A KR 1020120060354A KR 20120060354 A KR20120060354 A KR 20120060354A KR 20130136725 A KR20130136725 A KR 20130136725A
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acrylate
weight
paste composition
low temperature
parts
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KR1020120060354A
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Korean (ko)
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김유성
황건호
박영일
이상덕
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주식회사 동진쎄미켐
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • H01L31/04—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 adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • 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
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Dispersion Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Photovoltaic Devices (AREA)
  • Conductive Materials (AREA)

Abstract

The present invention relates to an electrode paste composition for a solar cell having a hardening property at low temperature. More specifically, when a screen printed electrode is hardened, a part of ITO substrate is selectively etched by adding an inorganic acid having an etching property and carbon black securing a dispersion property to the said composition so as to widen a contact area between the electrode and the ITO, to improve attachment strength and reduce contact resistance.

Description

A paste composition of electrode for solar cell of low temperature hardening type

The present invention relates to an electrode paste composition for a low temperature curable solar cell having excellent adhesion to a substrate and a ribbon and low contact resistance without inserting an SCF.

The low temperature curing solar cell does not undergo a high temperature firing process, unlike a high temperature firing solar cell, and forms an electrode through a curing process at about 200 ° C. The electrode formed by the low temperature process is difficult to improve the adhesion with the substrate, the contact resistance is also formed high, resulting in a problem that the cell efficiency is lowered.

Therefore, in the case of low temperature curing type solar cell, in order to improve adhesion between the electrode and the solder ribbon after cell manufacturing, a soldering process is performed by inserting a solar cell conductive film (SCF) in the middle of the electrode and the solder ribbon during the modularization process. I'm going.

In the case of high temperature calcined solar cells that are widely used at present, adhesion between the solder ribbon and the electrode is sufficiently maintained by the influence of glass and molten Ag contained in the composition of the electrode paste. However, in the low temperature curing type solar cell, the Ag electrode is cured by a binder, and the electrode composition does not include a medium for improving adhesion to the solder ribbon.

The SCF is a film in which a binder is coated with a spherical conductive powder and plays a role only between the electrode and the solder ribbon. Therefore, the use of the SCF made of the material improves the adhesion between the electrode and the solder ribbon, but there is a problem in that the electrical properties are lowered due to the increase in resistance, and consequently, the characteristics in the module manufacturing. In addition, the process of inserting the SCF has the problem of using expensive equipment, the module manufacturing process is complicated, and the manufacturing cost is increased.

Meanwhile, according to Korean Patent Publication No. 2010-0029652, it includes a silver powder and a polyester binder, and an additive selected from acid additives such as stearic acid, phosphoric acid and hydrochloric acid, silicone leveling agents, alcohol leveling agents, ammonium and inorganic fillers. A low temperature curable electrode paste using is disclosed. However, the method has a complicated problem in the manufacturing process because the secondary printing process has to be carried out, and does not address the problem improvement caused by the use of SCF.

In addition, although the etching solution and the etching paste have been partially applied in the crystalline structure for the high efficiency of the solar cell, the above method is used as a method of simply controlling the concentration of the dopant by printing the etching solution and the etching paste before forming the electrode. It is not.

The present invention is to provide an electrode paste composition for a low-temperature curing solar cell that can solve the problem of rising contact resistance while excellent adhesion to the substrate.

Another object of the present invention is to provide an electrode paste composition for a low temperature hardenable solar cell having low contact resistance and improved electrical characteristics.

Another object of the present invention is to form an electrode using the composition, thereby forming a solder ribbon directly on the electrode, showing excellent substrate adhesion and battery efficiency without including SCF between the electrode and the solder ribbon process It is to provide a solar cell module that can be simplified.

The present invention is based on 100 parts by weight of conductive particles selected from silver powder, gold powder, platinum powder, copper powder, nickel powder, mixtures thereof and alloys thereof.

1 to 30 parts by weight of an inorganic acid,

0.01 to 10 parts by weight of carbon black,

0.1 to 10 parts by weight of the binder,

1 to 20 parts by weight of the thermosetting oligomer,

0.1 to 10 parts by weight of the thermosetting monomer,

0.01 to 10 parts by weight of a thermal curing initiator, and

0.5 to 20 parts by weight of solvent

It provides a low temperature curable electrode paste composition comprising a.

In addition, the present invention is an electrode formed using the electrode paste composition described above; And it provides a solar cell module comprising a solder ribbon formed directly on the electrode.

Hereinafter, the present invention will be described in more detail.

Considering the adhesive force of the solder ribbon, SCF using spherical conductive particles was inserted between the electrode and the solder ribbon to improve the adhesion between the electrode and the solder ribbon. However, since the SCF is a form in which the conductive particles are coated in the binder, the SCF binder remains in the upper layer of the electrode after the SCF process is applied, thereby increasing the resistance, and consequently, the characteristics of the module are degraded. In addition, the conductive particles that are currently applied to the SCF is a spherical type, the filling density is low, the contact area between the electrode and the solder ribbon has a problem of increasing the resistance. As such, the method requires a new method for excluding the SCF since electrical properties are degraded due to an increase in resistance by the SCF.

Therefore, in the present invention, by adding a certain amount of the inorganic acid having the etching characteristics of the substrate to the low-temperature curing solar cell composition to improve the adhesion and contact resistance with the substrate, the screen-printed electrode can selectively etch a portion of the ITO substrate under curing conditions As a result, the contact area between the electrode and the ITO is widened, thereby improving the adhesion to the substrate and lowering the contact resistance.

In addition, since the dispersibility is deteriorated when the inorganic acid is included in a specific content or more, in the present invention, there is a feature that can secure dispersibility by adding carbon black to prevent such a problem.

According to one embodiment of the present invention, 0.5 to 30 parts by weight of inorganic acid, carbon based on 100 parts by weight of conductive particles selected from silver powder, gold powder, platinum powder, copper powder, nickel powder, mixtures thereof and alloys thereof Low temperature curing type comprising 0.01 to 10 parts by weight of black, 0.1 to 10 parts by weight of binder, 1 to 20 parts by weight of thermosetting oligomer, 0.1 to 10 parts by weight of thermosetting monomer, 0.01 to 10 parts by weight of thermosetting initiator, and 0.5 to 20 parts by weight of solvent. An electrode paste composition is provided.

The conductive particles may be spherical, flake type, granule type, or mixtures thereof having an average particle diameter of 0.1 μm to 10 μm. It is preferable that the conductive particles use silver powder.

Accordingly, the conductive particles may include silver powder having a spherical, flake, granule, or mixture thereof having an average particle diameter of 0.1 μm to 10 μm. In addition, the silver powder may be more preferably an average particle diameter of 1㎛ 5㎛.

The content of the conductive particles is included as a main component in the total electrode composition, it is used in 100 parts by weight, it can be used as the basis of the remaining components.

In particular, the inorganic acid according to the present invention can impart etching characteristics to the paste composition to selectively etch a portion of the ITO substrate upon curing of the electrode. That is, in the present invention, the inorganic acid is directly added to the paste composition, followed by printing, drying, and curing processes on the low temperature calcined solar cell substrate. Thus, the present invention can selectively etch the substrate while forming the electrode in a simple manner. Therefore, according to the present invention, the contact area between the electrode and the ITO is relatively widened, thereby improving adhesion to the substrate, thereby lowering the contact resistance. In addition, the present invention does not need to perform the process of inserting the SCF separately between the solder ribbon and the electrode.

The inorganic acid may be used one or more selected from the group consisting of phosphoric acid, hydrofluoric acid and hydrochloric acid. The inorganic acid may be an aqueous solution, the concentration of the inorganic acid may be 10 to 70%, preferably 30 to 60%. In addition, the present invention may be further used by mixing one or more organic acids such as acetic acid and formic acid as necessary.

The inorganic acid may be used in an amount of 1 to 30 parts by weight, and more preferably 1 to 15 parts by weight, based on 100 parts by weight of the conductive particles. If the content of the inorganic acid is less than 1 part by weight, there is a problem that selective etching of the ITO substrate is difficult. In addition, when the content exceeds 30 parts by weight, there is a problem in dispersibility due to poor compatibility between the water-soluble inorganic acid component and the organic composition in the paste.

At this time, when the total paste composition based on 100% by weight, even when the inorganic acid is included in less than 1% by weight when not including the carbon black described below may not reduce the dispersibility. However, since the dispersibility is lowered when the content of the inorganic acid is increased, the amount of the inorganic acid may be restricted. Therefore, by using carbon black, the present invention can prevent a decrease in dispersibility due to the inorganic acid content and finally lead to a decrease in contact resistance.

The carbon black may have an average particle diameter of 0.01 μm to 1 μm, more preferably 0.3 μm to 0.6 μm, and most preferably 0.05 μm to 0.8 μm.

The carbon black has many pores on the surface, and the carbon black absorbs the inorganic acid through the pores and releases the inorganic acid under curing conditions, thereby enabling selective etching of the inorganic acid to ITO. That is, carbon black is used to prevent the dispersibility of the inorganic acid from increasing the content, the content is 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, most preferably 0.01 to 100 parts by weight of the conductive particles To 0.5 parts by weight. If the content of the carbon black is less than 0.01 parts by weight, there is a problem of insufficient absorption of the inorganic acid. If the content is more than 10 parts by weight, the inorganic acid is excellent in dispersing the inorganic acid, but since the carbon black which is nanoparticles is added in a large amount, the paste viscosity increases. There is a problem due to poor printability and increased resistance.

The binder may be selected from the group consisting of cellulose resins, acrylic resins and epoxy resins. In addition, the content of the binder is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the conductive particles. If the content of the binder is less than 0.1 parts by weight, there is a problem in paste printability due to insufficient wrapping of the conductive particles, which is inorganic, and if the content is more than 10 parts by weight, the printability is improved, but the resistance is increased due to the organic material remaining after low temperature curing.

The thermosetting oligomer may be one or more selected from the group consisting of an acrylic oligomer, an epoxy acrylate oligomer, an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate oligomer. The weight average molecular weight of the thermosetting oligomer may be 500-1500.

In addition, the content of the thermosetting oligomer is used in 1 to 20 parts by weight based on 100 parts by weight of the conductive particles. If it is out of the content range there is a fear that the oligomer that did not participate in the reaction remains as impurities to reduce the curing rate. In addition, if the content is less than 1 part by weight, the degree of hardening in the curing reaction is weakened, so that the bonding strength between the conductive powders is weakened. As a result, the increase in resistance and adhesion are lowered. Lack of resistance would rather increase.

It is preferable to use an acryl-type monomer as said thermosetting monomer. For example, methyl methacrylate, ethyl methacrylate, tricyclodecanedimetholol dimethacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobornyl acrylate, acryloyloxyethyl succinate, Phenoxyethylene glycol acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, hardoxypropyl acrylate, diethylene glycol dimethacrylate, aryl methacrylate, ethylene glycol dimethacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, glycerol dimethacrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate Isobonyl acrylate , Hexanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate Latex, trimethylolpropane triacrylate, neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane epoxylate triacrylate, trimethylol 1 selected from the group consisting of propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin propoxylated triacrylate and methoxyethylene glycol acrylate It can be used later.

The thermosetting monomer is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the conductive particles. If it is out of the content range there is a fear that the monomer that did not participate in the reaction remains as impurities to reduce the curing rate. In addition, if the content is less than 0.1 part by weight, the amount of monomers participating in the curing reaction is insufficient, so that the strength and the degree of curing of the electrode are weakened, resulting in low adhesion between the substrate, the electrode, and the solder ribbon. If the portion is exceeded, the hardness of the electrode is severely increased and there is a problem that cracks are generated in the electrode during curing.

The thermal curing initiator is used as a radical initiator, it may be used one or more selected from the group consisting of azobis-based initiators, benzoyl peroxide and triphenyl methyl chloride. In addition, the thermal curing initiator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the conductive particles. If the content of the thermal curing initiator is less than 0.01 parts by weight, there is a problem that the electrode is easily damaged due to insufficient curing at the time of low temperature curing of the electrode, and if it exceeds 10 parts by weight, the curing should proceed at low temperature curing of the electrode, but at room temperature Curing proceeds in the state of storage, there is a problem that the stability is poor.

The solvent is ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, butyl carbitol acetate, dipropylene glycol, methyl ether acetate, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpineol, texanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol monomethyl ether, dimethyl Amino formal And the like, hydroxy, methyl ethyl ketone, gamma butyrolactone, ethyl lactate, and these can be used alone or by mixing two or more kinds. Preferably, the organic solvent may be butyl carbitol, butyl carbitol acetate, terpineol or a mixture thereof.

In addition, the content of the solvent is used to adjust the viscosity of the electrode composition, it may be 0.5 to 20 parts by weight based on 100 parts by weight of the conductive particles.

In addition, the present invention may further include an additive in the electrode composition as necessary. The additives include plasticizers, thickeners, stabilizers, dispersants, defoamers and surfactants. For example, the electrode paste composition of the present invention may further include 0.01 to 10 parts by weight of one or more dispersants selected from the group consisting of acidic and basic based on 100 parts by weight of the conductive particles. As the acidic dispersant, one or more selected from the group consisting of stearic acid, palmitic acid, myristic acid, oleic acid, and lauric acid may be used. Also, for example, alkyldibenzyl ammonium chloride may be used.

In addition, the manufacturing method of the electrode composition for low temperature hardening type solar cells according to the present invention is not particularly limited, and each component described above may be put into a paste mixer at once, stirred at a constant speed, and manufactured through a milling process. The electrode composition prepared by this method may be in a paste state having a viscosity of 10,000 cP to 500,000 cP.

Meanwhile, according to another preferred embodiment of the present invention, an electrode formed using the electrode composition for low temperature curing solar cells; And a solder ribbon formed directly on the electrode.

Preferably, the electrode may be prepared by printing coating, drying and curing the one or both surfaces of the substrate for the low-temperature curing solar cell electrode composition.

In addition, in the present invention, the "solder ribbon formed directly on the electrode" is not inserted into the SCF between the electrode and the solder ribbon as in the prior art, the solder ribbon directly on the electrode, without the insertion of the SCF between the electrode and the solder ribbon It means that just formed.

Printing coating method, drying and baking method in the electrode manufacturing process is not particularly limited, it may be carried out by methods well known in the art. For example, in the present invention, an electrode composition in a paste state is coated on both surfaces (front and back) of a substrate by screen printing, followed by drying and curing to manufacture an electrode. The electrode thus prepared may have a thickness of 1 micron to 50 microns. The substrate may be a dried ITO substrate having a front electrode applied thereto, but the type thereof is not limited. In addition, the drying may proceed for 5 to 30 minutes at a temperature of 60 to 180 ℃. The curing may be performed for 5 to 60 minutes at a temperature of 150 to 400 ℃.

Then, the present invention manufactures a solar cell module through a tabbing process of the electrode and the solder ribbon in a conventional method.

In the present invention, by adding a certain amount of an inorganic acid to the paste composition to improve the adhesion and electrical conductivity of the electrode and the solder ribbon to the low temperature curing solar cell electrode composition can reduce the SCF process necessary in the existing module process. That is, in the present invention, by adding a medium having etching characteristics of the substrate to the electrode composition, the adhesion area and the contact resistance can be improved by increasing the contact area between the electrode and the substrate.

In addition, according to the present invention, by using carbon black together, it is possible to ensure dispersibility in forming the electrode, thereby forming a low-temperature curing electrode in an easy manner.

Hereinafter, the present invention will be described with reference to the following examples and comparative examples. However, these examples are for illustrating the present invention, but the present invention is not limited thereto.

Example  One.

Next, an electrode paste composition was prepared in the following composition and content (unit: parts by weight).

That is, 50% concentration of phosphoric acid, ethyl cellulose, thermosetting oligomer (EBECRYL-1200 (acrylate oligomer) and Miramer ME 2010 (epoxy acrylate oligomer) mixed at 4: 1) having a content of Table 1, thermosetting monomer (acrylic type) Monomer) (TMPTA and HDDA mixed at a weight ratio of 7: 3), thermal curing initiator (radical initiator) (benzoyl peroxide), butyl carbitol acetate, dispersant (stearic acid), carbon black (average particle size: 0.3 μm) paste It was put in a paste mixer. Subsequently, the paste mixer was stirred at 500/400 rpm for 5 minutes and then subjected to a 3-roll mill operation to prepare an electrode paste. The viscosity of the paste thus prepared was 190,000 cps. For reference, when converting the electrode paste composition of Table 1 into 100 wt%, 80 wt% silver powder, 5 wt% phosphoric acid, 3 wt% ethyl cellulose, 3 wt% thermosetting oligomer (EBECRYL-1200 and Miramer ME) 2010 at 4: 1), 1 wt% thermosetting monomer (acrylic monomer) (TMPTA and HDDA mixed at a weight ratio of 7: 3), 0.5 wt% radical initiator (benzoyl peroxide), 7 wt% butyl Carbitol acetate and 0.5% dispersant (stearic acid).

In the process of module processing after the front, back printing process, drying process, and curing process for low temperature plastic type solar cell substrate using the prepared paste, tabbing of solder ribbon is performed without inserting SCF. Proceeded.

The curing process was carried out at about 200 ℃, through this process to prepare a low-temperature curing electrode.

Example  2.

A paste manufacturing method, a printing and drying process using a paste, and a module manufacturing process were performed in the same manner as in Example 1 except that 1.25 parts by weight of phosphoric acid was used.

Example  3.

A paste manufacturing method, a printing and drying process using a paste, and a module manufacturing process were performed in the same manner as in Example 1, except that 12.5 parts by weight of phosphoric acid was used.

Example  4.

A paste manufacturing method, a printing and drying process using a paste, and a module manufacturing process were performed in the same manner as in Example 1, except that 6.25 parts by weight of 50% hydrofluoric acid (HF) was used.

Example  5.

The paste composition was prepared as in Example 1, the electrode paste was prepared by a 3-roll mill operation for a dispersion process after stirring for 5 minutes at 500/400 rpm in a paste mixer (paste mixer). .

Using the prepared paste, after the front and back printing process, drying process, and curing process for the silicon substrate, the soldering process was performed after the insertion of the SCF in the process of the module process.

Comparative Example  One.

In the composition of Example 1, the paste was prepared without using phosphoric acid and carbon black, and after the printing and curing process, the solder ribbon was inserted and then the tabbing of the solder ribbon was performed.

Comparative Example  2.

Except that the soldering process was performed without inserting the SCF, the paste of Comparative Example 1 was used to proceed with the printing process, curing process and module process.

Example Comparative Example One 2 3 4 5 One 2 conductivity
particle Silver Powder, 2.5㎛ 100 100 100 100 100 100 100 Etching solution Phosphoric Acid 6.25 1.25 12.5 6.25 Foshan 6.25 bookbinder Ethyl cellulose 3.75 4.75 2.5 3.75 3.75 5 5 Thermosetting oligomers Acrylic oligomers and epoxy acrylate oligomers 3.75 4.75 2.5 3.75 3.75 5 5 Monomer Acrylic monomer 1.25 1.58 0.83 1.25 1.25 1.67 1.67 Thermosetting
Initiator Benzoyl peroxide 0.63 0.79 0.41 0.63 0.63 0.83 0.83 menstruum Butyl Carbitol Acetate 8.75 11.08 5.83 8.75 8.75 11.67 11.67 additive Stearic acid 0.625 0.79 0.42 0.625 0.625 0.83 0.83 Carbon black (average particle size 0.3㎛) 0.3 0.2 0.5 0.3 0.3

< Experimental Example >

Property evaluation

The physical properties of the electrode pastes prepared in Examples and Comparative Examples were evaluated by the following method, and the results are shown in Table 2.

1) resistivity

The electrode pastes prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were printed on a substrate (alumina substrate), respectively, and then dried at 160 ° C. for 10 minutes, then at 180 ° C. for 30 minutes, at 200 ° C. for 30 minutes, and at 220 ° C. After curing for 30 minutes each, the specific resistance was measured using a 4 point probe.

2) contact resistance

The electrode pastes prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were printed on the front surface of the solar cell by screen printing using a mask for TLM (Transfer length method) pattern (for contact resistance measurement) and 160 ° C. After drying for 6 minutes at and baked for 30 minutes at 220 ℃. Then, the contact resistance was measured after the measurement using a wire resistance meter.

3) Board adhesion

Based on the lattice adhesion evaluation (ASTMD3359), 100 lattice patterns were made on the paste cured and printed on the substrate by using a crosscut knife to attach the metal adhesive tapes (3M, # 610), and the number of the lattices dropped was recorded.

4) Solder Ribbon Adhesion

After tabbing the solder ribbon and the electrode, a 90 ° peeling test was conducted using a tensile tester (UTM) to evaluate adhesion. The resultant adhesion was recorded.

5) Aspect ratio (%)

After firing, the height of the electrode pattern and the pattern line width were respectively measured by SEM, and the height / pattern line width ratio of the pattern was obtained, and the aspect ratio (%) was recorded.

6) Viscosity change rate (%)

After changing the electrode pastes prepared in Examples 1 to 5 and 1 and 2 for 3 months at 25 ° C., the viscosity change was measured using a Brookfield HBT viscometer, # 51 spindle to change the 1 rpm viscosity at 25 ° C. Measured.

Example Comparative Example One 2 3 4 5 One 2 Resistivity
(Lee
Sawlingering before) 180 ℃, 30min (* 10 -5 Ωcm) 1.43 1.40 1.47 1.44 1.42 1.37 1.35 200 ℃, 30min (* 10 -5 Ωcm) 1.06 1.05 1.08 1.07 1.07 1.01 1.03 220 ℃, 30min (* 10 -6 Ωcm) 7.68 7.62 7.74 7.64 7.71 7.42 7.51 Contact resistance TLM test (Ω) 0.55 0.57 0.51 0.53 0.53 0.87 0.85 Substrate adhesion Tape adhesion
(ASTM D3359) 0 0 0 0 0 0 0 Solder
Ribbon adhesion Tensile Tester (UTM test, N) 2.7 2.0 2.5 2.0 2.9 2.5 1.6 Aspect ratio (%) Pattern height / pattern line width ratio after firing 33.4 32.6 35.6 33.5 33.2 29.5 28.7 Viscosity change rate
(%) Viscosity change after 3 months at room temperature 2 2 2 2 2 2 2

In the results of Table 2, Example 1-5 of the present invention, compared to Comparative Example 1-2, the contact resistance is low even without the insertion of SCF, the solder ribbon adhesion was excellent. In addition, the present invention was excellent in aspect ratio.

On the other hand, Comparative Example 1 has excellent solder ribbon adhesion, but because SCF is inserted in the modularization process, the cost is increased and the contact resistance is increased. In addition, in Comparative Example 2, the specific resistance was measured to be low, but the contact resistance was higher than that of the Example because no SCF was inserted.

Claims (13)

100 parts by weight of conductive particles selected from silver powder, gold powder, platinum powder, copper powder, nickel powder, mixtures thereof and alloys thereof,
1 to 30 parts by weight of an inorganic acid,
0.01 to 10 parts by weight of carbon black,
0.1 to 10 parts by weight of the binder,
1 to 20 parts by weight of the thermosetting oligomer,
0.1 to 10 parts by weight of the thermosetting monomer,
0.01 to 10 parts by weight of a thermal curing initiator, and
0.5 to 20 parts by weight of solvent
Low temperature curable electrode paste composition comprising a.
The method of claim 1, wherein the conductive particles,
A low temperature curable electrode paste composition comprising a spherical type, a flake type, a granule type, or a mixture thereof having an average particle diameter of 0.1 μm to 10 μm.
The low temperature curable electrode paste composition according to claim 1, comprising carbon black having an average particle diameter of 0.01 µm to 1 µm.
The low temperature curable electrode paste composition according to claim 3, comprising carbon black having an average particle diameter of 0.3 µm to 0.6 µm.
The low temperature curable electrode paste composition of claim 1, wherein the inorganic acid is at least one selected from the group consisting of phosphoric acid, hydrofluoric acid, and hydrochloric acid.
The low temperature curable electrode paste composition of claim 1, wherein the binder is at least one selected from the group consisting of cellulose resins, acrylic resins, and epoxy resins.
The low temperature curable electrode paste composition of claim 1, wherein the thermosetting oligomer is at least one selected from the group consisting of an acrylic oligomer, an epoxy acrylate oligomer, an epoxy acrylate oligomer, a urethane acrylate oligomer, and a polyester acrylate oligomer.
The method of claim 1, wherein the thermosetting monomer is
Methyl methacrylate, ethyl methacrylate, tricyclodecanedimetholol methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobornyl acrylate, acryloyloxy ethyl succinate, phenoxy ethylene glycol Acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, hardoxypropyl acrylate, diethylene glycol dimethacrylate, arylmethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate , Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, glycerol dimethacrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, hydroxy ethyl acrylate, hydroxy propyl acrylate, isobornyl acryl Latex, hexanedi Diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol Propane triacrylate, neopentyl glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane epoxylate triacrylate, trimethylolpropane trimethacrylic At least one aryl selected from the group consisting of latex, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin propoxylated triacrylate and methoxyethylene glycol acrylate Krill-based monomer
A low temperature curable electrode paste composition comprising a.
The low temperature curing electrode paste composition according to claim 1, wherein the thermosetting initiator is at least one selected from the group consisting of an azobis-based initiator, benzoyl peroxide and triphenyl methyl chloride.
The method of claim 1, wherein the solvent is ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate, butyl carbitol acetate, dipropylene glycol, methyl ether acetate, butyl carbitol, propylene glycol monomethyl ether , Dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether propionate, terpineol, texanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene Glycol Monomethyl Ether, Dime Amino-formaldehyde, methyl ethyl ketone, gamma-butyrolactone and ethyl locking one member selected from the group consisting of lactate or more low-temperature curing type electrode paste composition.
The low temperature curable electrode paste composition of claim 1, further comprising 0.01 to 10 parts by weight of at least one dispersant selected from the group consisting of acidic and basic groups with respect to 100 parts by weight of the conductive particles.
12. The method of claim 11,
The acidic dispersant is at least one selected from the group consisting of stearic acid, palmitic acid, myristic acid, oleic acid, and lauric acid,
The basic dispersant is alkyl dibenzyl ammonium chloride,
Low temperature curable electrode paste composition.
An electrode formed using the electrode paste composition according to any one of claims 1 to 12; And
A solder ribbon formed directly on the electrode
Solar cell module comprising a.
KR1020120060354A 2012-06-05 2012-06-05 A paste composition of electrode for solar cell of low temperature hardening type KR20130136725A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105810293A (en) * 2016-05-13 2016-07-27 浙江光达电子科技有限公司 Silver paste for back electrode of crystalline silicon solar cell and preparation method of silver paste
US9966480B2 (en) 2015-04-28 2018-05-08 Samsung Sdi Co., Ltd. Electrode composition, electrode manufactured using the same, and solar cell
CN116206799A (en) * 2023-01-12 2023-06-02 四川东树新材料有限公司 Silane coupling agent modified silver coated copper powder heterojunction battery silver paste and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9966480B2 (en) 2015-04-28 2018-05-08 Samsung Sdi Co., Ltd. Electrode composition, electrode manufactured using the same, and solar cell
CN105810293A (en) * 2016-05-13 2016-07-27 浙江光达电子科技有限公司 Silver paste for back electrode of crystalline silicon solar cell and preparation method of silver paste
CN105810293B (en) * 2016-05-13 2017-07-25 浙江光达电子科技有限公司 A kind of rear electrode for crystal silicon solar battery silver paste and preparation method thereof
CN116206799A (en) * 2023-01-12 2023-06-02 四川东树新材料有限公司 Silane coupling agent modified silver coated copper powder heterojunction battery silver paste and preparation method thereof

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