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WO2015160078A1 - Composition de pâte conductrice, et dispositif semi-conducteur comprenant ladite composition - Google Patents

Composition de pâte conductrice, et dispositif semi-conducteur comprenant ladite composition Download PDF

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Publication number
WO2015160078A1
WO2015160078A1 PCT/KR2015/001359 KR2015001359W WO2015160078A1 WO 2015160078 A1 WO2015160078 A1 WO 2015160078A1 KR 2015001359 W KR2015001359 W KR 2015001359W WO 2015160078 A1 WO2015160078 A1 WO 2015160078A1
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Prior art keywords
weight
powder
metal
metal oxide
conductive paste
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English (en)
Korean (ko)
Inventor
손원일
오상진
송재형
조승기
김철희
박정근
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Duksan Hi Metal Co Ltd
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Duksan Hi Metal Co Ltd
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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
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • 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
    • 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

Definitions

  • the present invention relates to a conductive paste composition, and more particularly, to a conductive paste composition in which a thin film pattern such as an electrode or a wiring connecting an electrical signal of a semiconductor device is formed.
  • the present invention also relates to a semiconductor device, in particular a solar cell, in which electrodes or wirings are formed with a conductive paste composition.
  • Conductive paste also called ink
  • Conductive pastes typically include conductive powder, glass frit, and organic medium.
  • the conductive paste is printed onto the substrate as a linear or other pattern and then fired to form a pattern that transmits electrical signals on the substrate.
  • the problems to be solved in the conductive paste are largely classified into printable, adhesive and electrically conductive. That is, the pattern can be printed in a desired line width through a desired printing method, and the electrode formed by the conductive paste is attached to the substrate with durability and high adhesion, and it is necessary to lower the resistance.
  • Printability is required to study the composition having a physical property suitable for the line width and the corresponding printing technology to be fine, mainly the size of the conductive powder or the nature of the organic medium is important.
  • Adhesiveness requires research to stably adhere the conductive paste composition to the substrate for a long time, and the composition of the glass frit is mainly important.
  • the electrical conductivity requires a study for the line resistance and ohmic contact due to the reduction of the line width, the composition of the conductive powder and frit is mainly important.
  • Conductive paste compositions are required to be individually developed in connection with the above-described printability, adhesion, and electrical conductivity according to their use.
  • an anti-reflection film such as silicon nitride, titanium oxide, or silicon oxide is deposited on the semiconductor substrate to promote solar absorption, thus acting as an insulator to form a substrate ( Or damage the flow of electrons from the substrate). Therefore, the conductive paste for heat generation must penetrate the antireflection film during firing to have a smooth electrical contact with the substrate, and also requires specialized development to form strong bonds with the substrate.
  • the conductive paste used for the flexible substrate needs to develop a composition that can maintain adhesion despite the flexibility of the substrate.
  • conductive powder, glass frit, and organic media which are technical elements for achieving the printability, adhesion, and electrical conductivity, which are technical challenges of the conductive paste composition, have antagonistic effects on each other. Balanced technology development is required.
  • the conversion efficiency of the solar cell is obtained by multiplying the open voltage, the short-circuit current density and the FF, so that the conversion efficiency is lowered when the FF becomes small.
  • the characteristic of an electrode is important.
  • the power generation efficiency is increased by lowering the resistance value of the electrode.
  • Prior Document 1 Patent No. 2005-243500 discloses an organic binder, a solvent, a glass frit, a conductive powder, and Ti, Bi, Zn, Y, In, and Mo.
  • the electrically conductive paste containing at least 1 sort (s) of selected metal or its metal compound the electrically conductive paste whose average particle diameter of a metal or its metal compound is 0.001 micrometer or more and less than 0.1 micrometer is disclosed.
  • Prior art 1 describes that by firing a conductive paste containing a metal or a metal compound of ultrafine particles, it is possible to form a front electrode having a stable, high conductivity and excellent adhesion between the semiconductor and the conductive paste present through the antireflection layer. It is.
  • the composition of the conductive paste in particular, the conductive paste containing the ultrafine metal or the metal compound thereof is printed on the semiconductor substrate surface and dried, and then fired, the coating film (paste film) shrinks and the contact resistance is increased.
  • microcracks may occur on the surface of the semiconductor substrate due to a difference in heat shrinkage behavior (linear expansion rate) between the paste film and the semiconductor substrate.
  • linear expansion rate linear expansion rate
  • the present invention has been made in an effort to provide a conductive paste composition having improved printability and electrical conductivity by improving metal oxide powder.
  • Another technical problem to be achieved by the present invention is to provide an improved environmentally friendly conductive paste composition that does not reduce the adhesion even if the content of Pb in the metal oxide powder composition is reduced.
  • Another object of the present invention is to provide a semiconductor device having a reduced line width and excellent durability and improved efficiency.
  • the conductive paste composition according to the present invention comprises a conductive powder, a metal oxide powder, an organic medium and an additive, wherein the metal oxide powder is selected from X1-X2-.
  • Xn is selected from the group consisting of Pb, Te, Bi, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, Mn Essentially Pb, Te and Bi as the metal, n may be an integer of 3 or more.
  • the content of Pb in the metal oxide powder is a weight%
  • the content of Te is b% by weight
  • the content of Bi is c% by weight
  • the metal oxide powder may further include Zn, and when the content of Zn is d% by weight, it is preferable to satisfy the following [Formula 3].
  • the metal oxide powder according to the present invention may be Pb-Te-Bi-Si-B-Zn-Al-O, and the content of each metal of the metal oxide powder is 0.5 to 15 wt% of PbO in terms of oxide relative to the total weight of the metal oxide. %, TeO 2 50-75 wt%, Bi 2 O 3 10-20 wt%, SiO 2 0.1-10 wt%, B 2 O 3 0.1-10 wt%, ZnO 1-8 wt% and Al 2 O 3 0.1 It may be 3% by weight.
  • the metal oxide powder according to the present invention may be Pb-Te-W-Mo-Zn-Bi-Al-O, the content of each metal of the metal oxide powder is PbO 0.5 ⁇ in terms of oxide relative to the total weight of the metal oxide 15 wt%, TeO 2 60-75 wt%, ZnO 0.5-15 wt%, Bi 2 O 3 10-20 wt% and Al 2 O 3 0.1-12 wt% and the sum of WO 3 and MoO 3 is 5-30 Weight percent.
  • the conductive powder includes agglomerates of metal nanopowders having a mean diameter of 1 to 3 ⁇ m and a metal nanopowder of 0.5 to 10 ⁇ m formed by aggregation of metal nanopowders having an average diameter of 100 to 200 nm. can do.
  • the additive in the conductive paste composition of the present invention is included in 1 to 5 parts by weight based on 100 parts by weight of the conductive powder, it may be Te-X-O, Te-Y or Te-Y-Z.
  • X is at least one metal selected from alkali metals or alkaline earth metals
  • Y and Z is at least one metal selected from the group consisting of Zn, Ag, Na, Mg, Al, Y and Z is not the same Not preferred.
  • the conductive paste composition according to the present invention may include 70 to 90 wt% of the conductive powder, 0.7 to 9 wt% of the metal oxide powder, 3.5 to 18 wt% of the organic medium, and 0.7 to 4.5 wt% of the inorganic additive, based on the total weight of the conductive paste composition. Can be.
  • a solar cell comprising: a silicon semiconductor substrate; An emitter layer formed on the substrate; An anti-reflection film formed on the emitter layer; A front electrode penetrating the antireflection film and connected to the emitter layer; And a back electrode connected to a rear surface of the substrate, wherein the front electrode may be formed by applying the conductive paste composition on the antireflection film in a predetermined pattern and firing the same.
  • Conductive paste composition according to the present invention includes a metal oxide powder containing Pb, Te, Bi, has the effect of improving the electrical conductivity and printability.
  • the conductive paste composition according to the present invention contains 1 to 15% by weight of Pb (oxide equivalent, PbO) to the entire metal oxide powder and 60 to 75% by weight of Te, thereby ensuring pn junction stability. There is an effect of reducing the resistance, even if reducing the content of Pb in the metal oxide powder composition does not reduce or rather improve the adhesion.
  • Pb oxide equivalent
  • the electronic device according to the present invention has an effect of improving the efficiency of the semiconductor device by improving the printability and durability of the wiring, the electrode and the like formed of the conductive paste composition.
  • 1 is an electron micrograph of a conductive powder having a size of 0.4-0.6 ⁇ m according to an embodiment of the present invention.
  • FIG. 2 is an electron micrograph of a conductive powder having a protrusion size of 0.1 to 0.2 ⁇ m according to an embodiment of the present invention.
  • 3A is an electron micrograph (MAG 2.50kx) of a metal nanopowder agglomerate according to an embodiment of the present invention.
  • Figure 3b is an electron micrograph (MAG 40.0kx) of the metal nanopowder agglomerates according to an embodiment of the present invention.
  • the conductive paste composition according to one aspect of the present invention includes a conductive powder, a metal oxide powder, an organic medium, and an additive.
  • both conductive organic and inorganic materials may be used. Specifically, silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminum (Al), tin (Sn), lead ( Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni) or ITO (indium tin oxide) Can be used 1 type or in mixture of 2 or more types.
  • the conductive powder may include silver (Ag) as a metal powder.
  • the metal powder (first metal powder) used as the conductive powder may have an average diameter (D50) of 0.1 to 10 ⁇ m, preferably an average particle diameter (D50) of 0.5 to 5 ⁇ m, more preferably 1 It is a metal powder of 3 micrometers.
  • the average diameter (D50) means the powder diameter at the point where the distribution ratio occupies 50%.
  • the shape of the metal powder of this invention is not restrict
  • protrusion shape in the outer surface is preferable.
  • the average diameter is the size including the projections, the projections are not limited to the shape or size to form a bend on the outer surface, the peak of the projections is generally referred to as 0.1 to 0.6 ⁇ m higher than the projections.
  • the conductive powder according to the embodiment of the present invention may further include metal nanopowder aggregates.
  • the aggregate of the metal nanopowder is a powder obtained by agglomeration of nanometal powders having an average diameter (D50) of 100 to 200 nm, and the average diameter (D50) of the aggregate of the metal nanopowder is preferably 0.5 to 10 ⁇ m.
  • Metal nanopowder of 100nm to 200nm increases the adhesion between the substrate and the electrode, but it can increase the line resistance due to sintering shrinkage of the electrode, and physical defects such as cracks occur after firing, resulting in low sintering density. May cause problems that are vulnerable to long-term reliability.
  • the aggregate of the metal nano powder is preferably included in 0.1 to 10 parts by weight with respect to 100 parts by weight of the first metal powder.
  • the conductive powder according to the embodiment of the present invention may further include a second metal powder having an average diameter (D50) of 0.5 to 1 ⁇ m.
  • the average diameter of the second metal powder is smaller than the average diameter of the first metal powder.
  • it is expected to improve the function of reducing the line resistance according to the principle of increasing the packing density.
  • the second metal powder is included, it is preferably included in 10 to 40 parts by weight based on 100 parts by weight of the first metal powder.
  • the specific surface area of a conductive powder is 0.05-5 m ⁇ 2> / g. If it is less than 0.05 m 2 / g, a large particle diameter (fine line, 70 ⁇ m or less) cannot be drawn. If it exceeds 5 m 2 / g, there is a problem that workability deteriorates, such as a large amount of solvent is required for viscosity adjustment.
  • the content of the conductive powder is included in 70 to 90% by weight relative to the total weight of the conductive paste composition. If the conductive powder is included in more than 90% by weight, it may be difficult to form the composition in the paste state because the viscosity is increased, if less than 70% by weight the amount of conductive powder is reduced, the electrical conductivity and the post-printing pattern of the manufactured front electrode The aspect ratio of may be low.
  • the metal oxide powder is formed by X1-X2-.
  • Xn is Pb, Si, Sn, Li, Ti, Ag, Na, K, Rb, Cs, Ge, Ga, Te, In, Ni, Zn, Ca, Mg, Sr, Ba, Se, Mo, W, Y, As, La, Nd, Co, Pr, Gd, Sm, Dy, Eu, Ho, Yb, Lu, Bi, Ta, V, Fe, Hf, Cr, Cd, Sb, Bi, Metals selected from the group consisting of F, Zr, Mn, P, Cu, Ce, Fe and Nb, n is an integer of 2 or more, and the metal oxide powder is selected from X 1 to X 2.
  • -Xn-O may be at least partially crystalline.
  • the metal oxide powder is X1, X2,... Oxides of Xn are mixed, melted, cooled and ground, and the ground material is screened to produce the desired powder size.
  • the average particle diameter (D50) of the metal oxide powder is preferably 0.1 to 3.0 ⁇ m. At this time, it is preferable to use a metal oxide powder having a melting point of 250 to 900 ° C.
  • the metal oxide powder has a softening point of 200 to 550 ° C. so that the conductive paste can be sintered at 600 to 950 ° C., properly moistened, and properly adhered to the substrate. If the softening point is lower than 200 ° C., sintering may proceed and the effect of the present invention may not be sufficiently obtained. If the softening point is higher than 550 ° C., sufficient melt flow is not caused during firing, so that sufficient adhesive strength does not develop and in some cases it is not possible to promote the liquid phase sintering of silver.
  • a "softening point” is a softening point obtained by the fiber elongation method of ASTM C338-57 here.
  • the chemical composition of the metal oxide powder is not limited in the present invention, and this material can be generally used, but the metal oxide powder may be one metal oxide powder or two or more different powders having a glass transition temperature.
  • Xn is composed of Pb, Te, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, Mn It may be at least two or more metals selected from the group.
  • the metal oxide powder preferably contains Pb, Te, and Bi, and when the content of Pb (oxide conversion, PbO) is a wt% based on the total weight of the metal oxide powder, 0.1 ⁇ a ⁇ 20 may be preferable, and more preferably 1 ⁇ a ⁇ 15. In the above range, it is because the pn junction stability can be secured under various sheet resistances and solar cell efficiency can be improved.
  • TeO 2 oxide equivalent, TeO 2
  • the content of Te (oxide equivalent, TeO 2 ) to the total weight of the metal oxide powder is b% by weight, it may be preferable that 50 ⁇ b ⁇ 80, and more preferably 60 ⁇ b ⁇ 75. have.
  • TeO 2 is less than 50% by weight, Ag solidity due to TeO 2 may be reduced, thereby increasing contact resistance. If TeO 2 is more than 80% by weight, the reactivity with the silicon interface may be weakened by excessive addition of TeO 2 , thereby increasing the contact resistance.
  • the metal oxide powder comprising essentially Pb, Te and Bi of the present invention
  • the content of Pb is a weight%
  • the content of Te is b% by weight
  • the content of Bi is c% by weight
  • the a, b and The relationship of c preferably satisfies both the following [formula 1] and [formula 2].
  • the metal oxide powder may further include Zn, and when the content of Zn in the metal oxide powder is d% by weight, it may be desirable to satisfy the following [Equation 3].
  • the metal oxide powder may be Pb-Te-Bi-Si-B-Zn-Al-O.
  • the content of each metal is 0.5 to 15% by weight of PbO, 50 to 75% by weight of TeO 2 , 10 to 20% by weight of Bi 2 O 3 , 0.1 to 10% by weight of SiO 2, and 0.1 to 10% by weight of B 2 O 3 . 10 wt%, ZnO 1-8 wt% and Al 2 O 3 0.1-3 wt%.
  • the metal oxide powder may be Pb-Te-W-Mo-Zn-Bi-Al-O.
  • the content of each metal is 0.5 to 15% by weight of PbO, 60 to 75% by weight of TeO 2 , 0.5 to 15% by weight of ZnO, 10 to 20% by weight of Bi 2 O 3 and 0.1 to 12 of Al 2 O 3.
  • WO 3 and MoO 3 are 5-30% by weight in total.
  • the metal oxide powder is the same as the first metal oxide powder having the first glass transition temperature a ° C. and the second metal oxide powder having the second glass transition temperature b ° C. at the same time. It may include.
  • the first metal oxide powder has a first glass transition temperature of 170 ⁇ a ⁇ 310
  • the second metal oxide powder has a second glass transition temperature of 230 ⁇ b ⁇ 320
  • a second metal oxide powder More preferably, the difference between the second glass transition temperature b and the first glass transition temperature a of the first metal oxide powder satisfies 10 ⁇ ba ⁇ 60.
  • any one of the first and second metal oxide powders acts as a metal oxide powder in the firing process. Because it will not be able to perform.
  • the first metal oxide powder preferably includes Te, and may further include at least one metal selected from the group consisting of Bi, Zn, B, Al, Ba, Si, W, and Fe.
  • the second metal oxide powder preferably includes Pb, and may further include at least one metal selected from the group consisting of Li, Na, Ti, Cu, Ni, V, P, K, and Sn. have.
  • the first metal oxide powder is 80 to 90% by weight, and the second metal oxide powder is 0.5 to 20% by weight relative to the total weight of the metal oxide powder.
  • the metal oxide powder is not particularly limited as long as it is an amount capable of achieving the object of the present invention, but is preferably contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the conductive powder. If the amount of the metal oxide powder is less than 1 part by weight, the adhesive strength may be insufficient. If the amount of the metal oxide powder is greater than 10 parts by weight, it may cause a problem in the solder, which is a subsequent step, by glass floating or the like.
  • the term "organic medium” includes a binder and a solvent, and a solvent may be included in the binder.
  • a viscosity modifier to be described later may be separately added as an additive if necessary.
  • the binder is methyl cellulose, ethyl cellulose, cellulose derivatives such as ethyl hydroxyethyl cellulose, wood rosin, mixture of ethyl cellulose and phenol resin, and lower alcohol.
  • alcohol polymethacrylate and ethylene glycol monoacetate monobutyl ether, acrylic resin, alkyd resin, polypropylene resin, polyvinyl chloride resin, polyurethane resin, Rosin resin, terpene resin, phenolic resin, aliphatic petroleum resin, acrylic ester resin, xylene resin, coumarone-indene resin, styrene resin, dicyclopentadiene resin, poly part
  • Ten resins, polyether resins, urea resins, melamine resins, vinyl acetate resins, and polyisobutyl resins are mentioned. Information that is not.
  • Exemplary solvents include terpenes such as hexane, toluene, ester alcohols and ⁇ - or ⁇ -terpineol, kerosene, dibutyl phthalate, butyl Carbitol, butyl carbitol acetate (acetate), hexylene glycol (glycol), benzyl alcohol, alcohol ester, diethylene glycol diethyl ether, diacetone alcohol tapineol methyl ethyl ketone, ethyl cello Solvents, cyclohexanone, butyl cellosolve, butyl cellosolve acetate, etc. are mentioned, but it is not limited to these.
  • the dibasic ester is dimethyl ester of adipic acid, dimethyl ester of glutaric acid, and dimethyl ester of succinic acid.
  • One or a plurality of compounds selected from the group consisting of can be used.
  • the content of the organic medium may preferably be 5 to 20 parts by weight based on 100 parts by weight of the conductive powder.
  • the organic medium When the organic medium is included in an amount exceeding 20 parts by weight, the electrical conductivity of the manufactured front electrode may be lowered.
  • the organic medium When the organic medium is included in an amount of less than 5 parts by weight, the bonding property with the substrate may be reduced.
  • the conductive paste according to one aspect of the present invention may include inorganic and organic additives.
  • Inorganic additives include Li, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Pb, Cu, Zn, Ag, Te, Zn, Na, Mg, Al, W, Fe Selected metals, metal oxides and alloys or alloy oxides thereof.
  • Examples include PbO, CuO, ZnO, MgO, WO 3 and the like.
  • a metal alloy or a metal alloy oxide containing tellurium (Te) as the inorganic additive, more preferably Te-XO, Te-Y or Te-YZ, wherein X Is at least one metal selected from alkali metals or alkaline earth metals, and Y and Z are at least one metal selected from the group consisting of Zn, Ag, Na, Mg, Al. Y and Z do not use the same metal.
  • Te-XO is Li 2 TeO 3 , Na 2 TeO 3 , SrTeO 3 , BeTeO 3 or MgTeO 3 , Te-Y or Te-YZ is Ag-Te, Li-Te-Zn, Te-Zn -K or Te-Zn-Na.
  • the inorganic additive of the present invention includes a metal that can react with the metal contained in the conductive powder to promote a solid phase reaction, it can promote grain growth of the metal powder, which is a conductive powder even at a low temperature, thereby firing temperature of the paste composition. The range can be widened to improve the electrical conductivity.
  • the average particle size of the additives of the invention is not subject to any particular limitation.
  • the average particle size may have an average particle size of less than 10 ⁇ m.
  • the average particle size may be 0.01 to 5 ⁇ m. More preferably, it may be 50-200 nm.
  • the content of the inorganic additive may be 1 to 10 parts by weight with respect to 100 parts by weight of the conductive powder, preferably 1 to 5 parts by weight.
  • the content of the inorganic additive may be included in an amount of more than 5 parts by weight based on 100 parts by weight of the conductive powder, the amount of the conductive powder may be reduced, thereby increasing the resistance of the front electrode manufactured using the paste composition, thereby decreasing the efficiency of the solar cell. Can be.
  • the content of the inorganic additive is included less than 1 with respect to 100 parts by weight of the conductive powder it may be difficult to fully expect the effect by the additive.
  • Organic additives include, but are not limited to, dispersants, antioxidants, ultraviolet absorbers, antifoams, thickeners, stabilizers, dispersants, viscosity modifiers, and the like. These can be used individually or in mixture of 2 or more types, and can be mix
  • the dispersant may be formulated with a dispersant such as stearic acid, palmitic acid, myristic acid, oleic acid, lauric acid and the like in the conductive paste.
  • a dispersing agent is not limited to an organic acid as long as it is a general thing.
  • the conductive paste of the present invention is prepared by mixing a conductive powder, a metal oxide powder, an organic medium, and an additive with a three-roll kneader.
  • the conductive paste of the present invention is preferably applied to a desired portion of the electronic device by screen printing, but when applied by such printing, it is preferable to have a viscosity in a predetermined range.
  • the viscosity of the conductive paste of the present invention is preferably 50 to 300 PaS when measured using a # 14 spindle with a Brookfield HBT viscometer and using a utility cup at 10 rpm and 25 ° C.
  • the conductive paste of the present invention is applied to the substrate of the semiconductor device to be manufactured by screen printing or the like and dried.
  • the substrate to which the conductive paste is applied is baked at a temperature of about 700 to about 950 ° C. to form a conductive paste pattern.
  • a first silver powder having an average diameter of 2 ⁇ m and a nano silver powder having an average diameter of 200 nm were mixed and used.
  • the metal oxide powder has an average diameter of 2 ⁇ m, and MO3 (4.1 wt% PbO, 72.6 wt% TeO 2 , 15.9 wt% Bi 2 O 3 , 0.7 wt% B 2 O 3 , 4.8 6.5 g of ZnO, 0.5 wt.% Cr 2 O 3 , 0.4 wt.% MnO 2 , 0.7 wt.% CuO 2 , 0.3 wt.% Li 2 O) was used.
  • MO3 4.1 wt% PbO, 72.6 wt% TeO 2 , 15.9 wt% Bi 2 O 3 , 0.7 wt% B 2 O 3 , 4.8 6.5 g of ZnO, 0.5 wt.% Cr 2 O 3 , 0.4 wt.% MnO 2 , 0.7 wt.% CuO 2 , 0.3 wt.% Li 2 O
  • a conductive paste composition was prepared in the same manner as in Example 1, except that the kind of metal oxide powder used was changed according to Table 1.
  • a conductive paste composition was prepared in the same manner as in Example 1 except that the conductive powder used was changed as shown in Table 1, and the kind of metal oxide powder was changed to those according to Table 1.
  • a conductive paste composition was prepared in the same manner as in Examples 4 to 6 except that the kind of inorganic additive used was changed to the component shown in Table 1.
  • a conductive paste composition was prepared in the same manner as in Example 10 except that the type of the inorganic additive and the metal oxide powder used were changed to those shown in Table 1.
  • a conductive paste composition was prepared in the same manner as in Example 1 except that the kind of metal oxide powder used was changed as shown in Table 1.
  • a conductive paste composition was prepared in the same manner as in Example 4 except that the kind of metal oxide powder used was changed as shown in Table 1.
  • Example 1 Ingredient Conductive powder Metal oxide Organic medium Inorganic additives 1st powder Nano silver powder 2nd silver powder First metal oxide Second metal oxide Example 1 70 Turning X 11 Aggregate X - 6.5 MO3 - 10.2 2.3 ZnO Example 2 70 Turning X 11 Aggregate X - 6.5 MO4 - 10.2 2.3 ZnO Example 3 70 Turning X 11 Aggregate X - 6.5 MO5 - 10.2 2.3 ZnO Example 4 63.5 Turning O 5 Aggregate 12.5 6.5 MO3 - 10.2 2.3 ZnO Example 5 63.5 Turning O 5 Aggregate 12.5 6.5 MO4 - 10.2 2.3 ZnO Example 6 63.5 Turning O 5 Aggregate 12.5 6.5 MO5 - 10.2 2.3 ZnO Example 7 63.5 Turning O 5 Aggregate 12.5 6.5 MO6 - 10.2 2.3 ZnO Example 8 63.5 Turning O 5 Aggregate 12.5 6.5 MO3 - 10.2 2.3 Te-Zn-Na Example 9 63.5
  • Solar cells were prepared using the conductive pastes of Examples 1-14 and Comparative Examples 1-5.
  • a silicon substrate was prepared, and a conductive paste (silver paste) for solder connection was applied to the back side by screen printing and dried.
  • a conductive paste for solder connection was applied to the back side by screen printing and dried.
  • an aluminum paste for rear electrode PV333 (manufactured by E.I. du Pont de Nemours and Company) was applied by screen printing and dried so as to partially overlap with the dried silver paste.
  • the drying temperature of each paste was 120 degreeC.
  • the film thickness of each electrode of the back surface was apply
  • the paste of this invention was apply
  • a 1.5 inch evaluation pattern consisting of a finger line 100 ⁇ m wide and a bus bar 2 mm wide was used and the film thickness was 13 ⁇ m after firing.
  • the applied paste was simultaneously fired in the infrared firing furnace under conditions of a peak temperature of about 730 ° C. and an IN-OUT of about 5 minutes to obtain a target solar cell.
  • the solar cell obtained by using the conductive paste of the present invention has an Ag electrode on the light-receiving surface (front side) side, and an Al electrode (first electrode) having Al as a main component on the back side side and a silver electrode having Ag as a main component (manufactured by 2 electrodes).
  • the electrical characteristics (I-V characteristics) of the obtained solar cell substrate were evaluated by a battery tester.
  • the battery tester measured the Eff: conversion efficiency (%) and FF: curve factor using equipment manufactured by NPC (NCT-M-150AA), and the results are shown in Table 4.
  • the adhesive force of the obtained solar cell was heated to a temperature of 200 ° C. using a SnPbAg-based solder ribbon (solder ribbon, 2mm line width, indium corporation, SUNTABTM) on the surface of the front electrode formed by the electrode formation step, and was attached at a length of 10 cm. Grasp one end of the attached part and pull it out with the universal testing tensile strength tester (COMETECH's QC-508E) in the direction of 180 ° and measure the force (N, newton) until the electrode and the solder ribbon are peeled off. , The results of evaluation based on the following criteria are shown as the adhesion force (N) of Table 4 below.

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Abstract

La présente invention concerne une composition de pâte conductrice et, plus particulièrement, une composition de pâte conductrice comprenant : une poudre conductrice ; une poudre d'oxyde métallique comprenant au moins trois types de métaux choisis dans un groupe constitué par Pb, Te, Bi, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, et Mn ; et un milieu organique.
PCT/KR2015/001359 2014-04-15 2015-02-12 Composition de pâte conductrice, et dispositif semi-conducteur comprenant ladite composition Ceased WO2015160078A1 (fr)

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KR10-2014-0044781 2014-04-15

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KR102284981B1 (ko) * 2018-10-17 2021-08-03 창저우 퓨전 뉴 머티리얼 씨오. 엘티디. 나노텍스쳐링 기판 함유 태양 전지의 전극 형성용 조성물, 이로부터 제조된 전극 및 이로부터 제조된 전극을 포함하는 태양 전지

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JP2011119340A (ja) * 2009-12-01 2011-06-16 Harima Chemicals Inc 導電性アルミニウムペースト
KR20130117345A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉을 위한 전도성 후막 페이스트용 텔루륨 무기 반응 시스템
KR20130117344A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉용 전도성 후막 페이스트

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011119340A (ja) * 2009-12-01 2011-06-16 Harima Chemicals Inc 導電性アルミニウムペースト
KR20130117345A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉을 위한 전도성 후막 페이스트용 텔루륨 무기 반응 시스템
KR20130117344A (ko) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 태양 전지 접촉용 전도성 후막 페이스트

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