WO2015160078A1 - Conductive paste composition, and semiconductor device comprising same - Google Patents

Conductive paste composition, and semiconductor device comprising same 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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weight
powder
metal
metal oxide
conductive paste
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PCT/KR2015/001359
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French (fr)
Korean (ko)
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손원일
오상진
송재형
조승기
김철희
박정근
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덕산하이메탈(주)
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Publication of WO2015160078A1 publication Critical patent/WO2015160078A1/en

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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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  • Conductive Materials (AREA)

Abstract

The present invention relates to a conductive paste composition and, more particularly, to a conductive paste composition comprising: a conductive powder; a metal oxide powder comprising at least three types of metal selected from a group consisting of Pb, Te, Bi, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P and Mn; and an organic medium.

Description

전도성 페이스트 조성물 및 이를 포함하는 반도체 장치Conductive Paste Composition and Semiconductor Device Comprising the Same
본 발명은 전도성 페이스트 조성물에 관한 것으로, 보다 상세하게는 반도체 장치의 전기적 신호를 연결하는 전극 또는 배선 등의 박막 패턴을 형성한 전도성 페이스트 조성물에 관한 것이다.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.
또한 본 발명은 전도성 페이스트 조성물로 전극 또는 배선이 형성되는 반도체 장치, 특히 태양전지에 관한 것이다.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.
전도성 페이스트(또는 잉크(ink)라고도 함)는 기판 상에 형성되어 전기적 신호를 전달하는 패턴을 형성하는 데 사용된다. 전도성 페이스트는 전형적으로 전도성 분말, 유리 프릿(glass frit), 및 유기 매질을 포함한다. 기판 상에서 전기적 신호를 전달하는 패턴으로 형성되기 위해 전도성 페이스트는 선형 또는 다른 패턴으로서 기판 위로 인쇄된 다음 소성(fire)된다.Conductive paste (also called ink) is formed on the substrate and used to form a pattern that transmits an electrical signal. 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.
전도성 페이스트에서 해결해야할 과제는 크게 인쇄성, 접착성, 전기전도성 과제로 구분된다. 즉, 원하는 인쇄방식을 통해 원하는 선폭으로 패턴이 인쇄될 수 있도록 하여야 하며, 전도성 페이스트가 형성하는 전극 등이 기판상에 내구성을 가지면서 부착되어 접착력이 높아야 하며, 저항을 낮추는 것이 필요하다. 인쇄성은 미세화되는 선폭 및 이에 대응하는 인쇄기술에 적합한 물성을 가지는 조성에 대한 연구가 필요하며, 이에는 주로 전도성 분말의 크기나 유기매질의 성질이 중요하다. 접착성은 기판에 전도성 페이스트 조성물이 장시간 안정적으로 부착되기 위한 연구가 필요하며, 이에는 주로 유리프릿의 조성이 중요하다. 또한 전기전도성은 선폭감소에 따른 선저항 및 오믹컨택을 위한 연구가 필요하며, 이에는 주로 전도성 분말 및 프릿의 조성이 중요하다. 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. In addition, 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.
한편 전도성 페이스트 조성물은 그 용도에 따라서 전술한 인쇄성, 접착성, 전기전도성에 관련하여 개별적으로 특성화된 개발이 요구된다. 예를 들면, 결정질 실리콘 태양전지의 전극용으로 사용될 경우 태양광 흡수를 촉진시키기 위해 질화규소, 산화티타늄 또는 산화규소와 같은 반사방지(Anti Reflection)막이 반도체기판 상에 성막되므로 절연체로서 작용하여 기판으로(또는 기판으로부터) 전자의 흐름을 손상시키는 문제점이 있다. 따라서 발열용 전도성 페이스트는 기판과의 원활한 전기적 접촉을 갖기 위해 소성 동안에 반사방지막에 침투해야 하고, 또한 기판과의 사이에서 강한 결합을 형성하는 특성화된 개발이 필요하다. 또한 플렉서블 기판에 사용되는 전도성 페이스트는 기판의 유연성에도 불구하고 밀착성을 유지할 수 있는 조성개발이 필요하다. Conductive paste compositions, on the other hand, are required to be individually developed in connection with the above-described printability, adhesion, and electrical conductivity according to their use. For example, when used as an electrode of a crystalline silicon solar cell, 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. In addition, the conductive paste used for the flexible substrate needs to develop a composition that can maintain adhesion despite the flexibility of the substrate.
이 때 전도성 페이스트 조성물의 기술적 해결과제인 인쇄성, 접착성, 전기전도성을 달성하기 위한 기술요소인 전도성 분말, 유리 프릿(glass frit), 및 유기 매질은 서로 길항적인 영향을 주어 각 기술요소에 대한 균형잡힌 기술개발이 요구되고 있다.At this time, 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.
태양전지의 변환 효율은 개방 전압, 단락 전류 밀도 및 FF를 곱하여 얻어지기 때문에 FF가 작아지면 변환 효율은 저하되어 버린다. 그런데, 태양전지에 있어서 발전 특성을 높이기 위해서는 전극의 특성이 중요하다. 예를 들면, 전극의 저항값을 내리는 것에 의하여 발전 효율이 높아진다. 이 목적을 달성하기 위해, 예를 들면, 선행문헌1(특개 2005-243500호 공보)에는 유기 바인더와, 용제와, 유리 프리트와, 도전성 분말과, Ti, Bi, Zn, Y, In 및 Mo으로부터 선택된 적어도 1종의 금속 또는 그 금속 화합물을 포함하는 도전성 페이스트에 있어서, 금속 또는 그 금속 화합물의 평균 입경이 0.001㎛ 이상 0.1㎛ 미만인 도전성 페이스트가 개시되어 있다. 선행문헌1에는 초미립자의 금속 또는 그 금속 화합물을 포함하는 도전성 페이스트를 소성하여 반사 방지층을 통해 존재하는 반도체와 도전성 페이스트와의 사이에 안정되고 높은 도통성과 뛰어난 접착력을 갖는 전면전극을 형성할 수 있다고 기재되어 있다. 그러나, 도전성 페이스트의 조성, 특히 선행문헌1과 같이, 초미립자의 금속 또는 그 금속 화합물을 포함하는 도전성 페이스트를 반도체 기판 표면에 인쇄, 건조 후, 소성하면, 도막(페이스트 막)이 수축하여 접촉 저항이 증대하거나, 경우에 따라서는, 페이스트 막과 반도체 기판의 열수축 거동(선팽창율)의 차이에 의하여, 반도체 기판 표면에 마이크로 크랙이 발생하기도 한다. 접촉 저항이 증대하면, 상기와 같이 FF가 작아지고, 변환 효율이 저하되어 버리는 문제점이 있다.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. By the way, in order to improve the power generation characteristic in a solar cell, the characteristic of an electrode is important. For example, the power generation efficiency is increased by lowering the resistance value of the electrode. In order to achieve this object, for example, 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. In 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. However, when 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. In some cases, 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. When the contact resistance increases, there is a problem that FF becomes small as described above and the conversion efficiency decreases.
본 발명이 이루고자 하는 기술적 과제는 금속산화물분말을 개선하여 인쇄성 및 전기전도성이 향상된 전도성 페이스트 조성물을 제공하는 데 있다. SUMMARY OF THE INVENTION 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.
본 발명이 이루고자 하는 또 다른 기술적 과제는 금속산화물 분말 조성 중 Pb의 함량을 줄여도 부착력이 감소하지 않거나 오히려 개선된 환경친화적인 전도성 페이스트 조성물을 제공하는 데 있다. 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.
또한 본 발명이 이루고자 하는 기술적 과제는 선폭을 줄이면서도, 내구성이 좋고, 효율이 향상된 반도체 장치를 제공하는 데 있다.Another object of the present invention is to provide a semiconductor device having a reduced line width and excellent durability and improved efficiency.
본 발명에 따른 전도성 페이스트 조성물은 전도성 분말, 금속산화물분말, 유기매질 및 첨가제를 포함하며, 상기 금속산화물분말은 X1-X2-…-Xn-O로 Xn은 Pb, Te, Bi, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, Mn으로 이루어진 군에서 선택되는 금속으로서 Pb, Te 및 Bi를 필수적으로 포함하며, n은 3 이상의 정수일 수 있다. 상기 금속산화물분말 중 Pb의 함량을 a중량%, Te의 함량을 b중량%, Bi의 함량을 c중량%라고 할 때, 하기 [식 1] 및 [식 2]를 모두 만족하는 것이 바람직 할 수 있다.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. When the content of Pb in the metal oxide powder is a weight%, the content of Te is b% by weight, and the content of Bi is c% by weight, it may be preferable to satisfy both the following [Formula 1] and [Formula 2]. have.
[식 1][Equation 1]
70≤a+b+c≤90 (이 때, 1≤a≤15, 60≤b≤75)70≤a + b + c≤90 (where 1≤a≤15, 60≤b≤75)
[식 2][Equation 2]
2.5≤b/c≤7.5 (이 때, 60≤b≤75)2.5≤b / c≤7.5 (at this time 60≤b≤75)
본 발명에 따른 전도성 페이스트 조성물 중 상기 금속산화물분말은 Zn을 더 포함하는 것이 바람직하며, Zn의 함량을 d중량% 라고 할 때 하기 [식 3]을 만족하는 것이 바람직하다.In the conductive paste composition according to the present invention, 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].
[식 3][Equation 3]
0.5≤d/a≤3.5 (이 때, 1≤a≤15)0.5≤d / a≤3.5 (where 1≤a≤15)
본 발명에 따른 금속산화물분말은 Pb-Te-Bi-Si-B-Zn-Al-O일 수 있으며, 상기 금속산화물분말의 각 금속의 함유량은 금속산화물 전체 중량 대비 산화물환산으로 PbO 0.5~15 중량%, TeO2 50~75 중량%, Bi2O3 10~20 중량%, SiO2 0.1~10 중량%, B2O3 0.1~10 중량%, ZnO 1~8 중량% 및 Al2O3 0.1~3 중량%일 수 있다.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.
또한, 본 발명에 따른 금속산화물분말은 Pb-Te-W-Mo-Zn-Bi-Al-O 일 수 있으며, 상기 금속산화물분말의 각 금속의 함유량은 금속산화물 전체 중량 대비 산화물환산으로 PbO 0.5~15 중량%, TeO2 60~75 중량%, ZnO 0.5~15 중량%, Bi2O3 10~20 중량% 및 Al2O3 0.1~12 중량% 및 WO3와 MoO3의 합계가 5~30 중량%일 수 있다.In addition, 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.
본 발명의 전도성 페이스트 조성물 중 상기 전도성 분말은 평균직경이 1 내지 3㎛ 제1금속분말, 및 평균직경이 100 내지 200nm인 금속나노분말이 응집하여 이루어지는 0.5 내지 10㎛인 금속나노분말의 응집체를 포함할 수 있다.In the conductive paste composition of the present invention, the conductive powder includes agglomerates of metal nanopowders having a mean diameter of 1 to 3 μm and a metal nanopowder of 0.5 to 10 μm formed by aggregation of metal nanopowders having an average diameter of 100 to 200 nm. can do.
본 발명의 전도성 페이스트 조성물 중 상기 첨가제는 전도성 분말 100 중량부에 대해서 1 내지 5 중량부로 포함되며, Te-X-O, Te-Y 또는 Te-Y-Z일 수 있다. 이 때, 상기 X는 알칼리금속 또는 알칼리토금속 중 선택된 적어도 하나 이상의 금속이며, Y 및 Z는 Zn, Ag, Na, Mg, Al로 구성되는 군에서 선택되는 적어도 하나 이상의 금속이되 Y와 Z는 같지 않은 것이 바람직하다.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. In this case, 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.
본 발명에 따른 전도성 페이스트 조성물은 전도성 페이스트 조성물 전체 중량대비 전도성 분말 70 내지 90 중량%, 금속산화물 분말 0.7 내지 9 중량%, 유기 매질 3.5 내지 18 중량%, 및 무기첨가제 0.7 내지 4.5 중량%를 포함할 수 있다.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.
본 발명의 또 다른 양태인 태양전지는 실리콘 반도체 기판; 상기 기판 상부에 형성되는 에미터층; 상기 에미터층 상에 형성된 반사방지막; 상기 반사방지막을 관통하여 상기 에미터층에 접속된 전면 전극; 및 상기 기판의 배면에 접속된 후면 전극을 포함하는 실리콘 태양전지로서, 상기 전면 전극은 상기 전도성 페이스트 조성물을 상기 반사방지막 상에 소정의 패턴으로 도포하고 소성시켜 형성될 수 있다Another aspect of the present invention provides 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.
본 발명에 따른 전도성 페이스트 조성물은 Pb와 Te, Bi를 포함하는 금속산화물분말을 포함하여, 전기전도성 및 인쇄성을 향상시키는 효과가 있다. 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.
또한 본 발명에 따른 전도성 페이스트 조성물은 Pb의 함유량(산화물 환산, PbO)을 금속산화물 분말 전체에 대해서 1 내지 15 중량%, Te의 함유량을 60 내지 75 중량% 포함하여, pn 접합 안정성을 확보하며 접촉저항을 감소시키는 효과가 있으며, 금속산화물분말 조성 중 Pb의 함량을 줄여도 부착력이 감소하지 않거나 오히려 개선되는 효과가 있다. In addition, 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.
또한, 본 발명에 따른 전자장치는 전도성 페이스트 조성물로 형성하는 배선, 전극등의 인쇄성 및 내구성이 향상되어 반도체 장치의 효율을 높이는 효과가 있다. In addition, 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.
도1은 본 발명의 일실시예에 따른 돌기의 크기가 0.4~0.6㎛인 전도성 분말의 전자현미경 사진이다.1 is an electron micrograph of a conductive powder having a size of 0.4-0.6 μm according to an embodiment of the present invention.
도2는 본 발명의 일실시예에 따른 돌기의 크기가 0.1~0.2㎛인 전도성 분말의 전자현미경 사진이다.2 is an electron micrograph of a conductive powder having a protrusion size of 0.1 to 0.2 μm according to an embodiment of the present invention.
도3a는 본 발명의 일실시예에 따른 금속나노분말응집체의 전자현미경 사진(MAG 2.50kx)이다.3A is an electron micrograph (MAG 2.50kx) of a metal nanopowder agglomerate according to an embodiment of the present invention.
도3b는 본 발명의 일실시예에 따른 금속나노분말응집체의 전자현미경 사진(MAG 40.0kx)이다.Figure 3b is an electron micrograph (MAG 40.0kx) of the metal nanopowder agglomerates according to an embodiment of the present invention.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 첨부하는 특허청구의 범위에 의해서만 한정되는 본 발명의 범위를 한정하려는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한은 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다.Prior to describing the present invention in detail below, it is understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise indicated.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한, 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다. Throughout this specification and claims, unless stated otherwise, the term “comprise, comprising, comprising” means to include the referenced article, step, or group of articles, and step, and any other It is not intended to exclude any object, step, or group of things or group of steps.
한편, 본 발명의 여러 가지 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히, 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징 및 특징들과 결합될 수 있다.On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. In particular, any feature indicated as being preferred or advantageous may be combined with any other feature and features indicated as being preferred or advantageous.
전도성 페이스트 조성물Conductive paste composition
본 발명의 일측면에 따른 전도성 페이스트 조성물은 전도성 분말, 금속산화물 분말, 유기매질 및 첨가제를 포함한다. 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.
1.전도성 분말1.conductive powder
본 발명에서 사용되는 전도성 분말은 도전성을 가지는 유기물 또는 무기물이 모두 사용될 수 있다. 구체적으로는 은(Ag), 금(Au), 팔라듐(Pd), 백금(Pt), 구리(Cu), 크롬(Cr), 코발트(Co), 알루미늄(Al), 주석(Sn), 납(Pb), 아연(Zn), 철(Fe), 이리듐(Ir), 오스뮴(Os), 로듐(Rh), 텅스텐(W), 몰리브덴(Mo), 니켈(Ni) 또는 ITO(인듐틴옥사이드) 등의 금속분말을 1종 또는 2종 이상 혼합하여 사용할 수 있다. 바람직하게는 상기 전도성 분말은 금속분말로 은(Ag)을 포함할 수 있다. As the conductive powder used in the present invention, 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. Preferably, the conductive powder may include silver (Ag) as a metal powder.
상기 전도성 분말로 사용되는 금속분말(제1금속분말)은 평균직경(D50)이 0.1 내지 10㎛인 것을 사용할 수 있으며, 바람직하게는 평균입경(D50)이 0.5 내지 5㎛, 더욱 바람직하게는 1 내지 3㎛인 금속분말이다. 본 명세서에서 평균직경(D50)이란 분말이 차지하는 분포율이 50%가 되는 지점에서의 분말직경을 의미한다.The metal powder (first metal powder) used as the conductive powder may have an average diameter (D50) of 0.1 to 10㎛, preferably an average particle diameter (D50) of 0.5 to 5㎛, more preferably 1 It is a metal powder of 3 micrometers. In the present specification, the average diameter (D50) means the powder diameter at the point where the distribution ratio occupies 50%.
본 발명의 금속분말의 형상은 제한이 없으나, 외면에 돌기형상을 구비한 구형분말이 바람직하다. 외면에 돌기 형상을 구비하는 경우 비표면적 증가원리에 따라서 소결특성을 향상시키는 기능을 수행하는 것으로 예상된다. 이 때 평균직경은 돌기를 포함한 크기이며, 돌기는 외면에 굴곡을 형성하는 형상이나 크기에 제한없이 돌기의 최고점은 돌기가 없는 부분보다 0.1 내지 0.6㎛ 더 높은 것을 통칭한다. Although the shape of the metal powder of this invention is not restrict | limited, The spherical powder provided with the processus | protrusion shape in the outer surface is preferable. When provided with a projection shape on the outer surface it is expected to perform a function to improve the sintering properties according to the specific surface area increase principle. At this time, 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㎛ higher than the projections.
본 발명의 실시예에 따른 전도성 분말은 금속나노분말 응집체를 더 포함할 수 있다. 금속나노분말의 응집체는 평균직경(D50)이 100 내지 200nm인 나노금속분말이 응집하여 이루어지는 분말로서, 금속나노분말의 응집체의 평균직경(D50)은 0.5 내지 10㎛인 것이 바람직하다. 100nm 내지 200nm의 금속나노분말은 기판과 전극사이의 접착력을 증대시키는 역할을 하지만, 전극의 소결수축으로 인해 선저항을 증가시킬 수 있으며, 소성 후에 크랙과 같은 물리적인 결함이 발생하여 소결 밀도가 낮아져 장기 신뢰성에 취약한 문제를 유발시킬 수 있다. 그러나, 금속나노분말을 응집체로 만들 경우 소결밀도를 향상시키면서, 크랙이 없어 장기신뢰성을 확보할 수 있는 효과가 있다. 금속나노분말의 응집체는 제1금속분말 100 중량부에 대해서 0.1 내지 10중량부로 포함되는 것이 바람직하다. 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 µm. 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. However, when the metal nanopowder is made into agglomerates, there is an effect of ensuring long-term reliability without cracking while improving sintered density. 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.
본 발명의 실시예에 따른 전도성 분말은 평균직경(D50) 0.5 내지 1㎛인 제2금속분말을 더 포함할 수 있다. 제2금속분말의 평균직경은 제1금속분말의 평균직경보다 작다. 제2금속분말을 사용하는 경우 충전밀도(packing density)의 증가 원리에 따라서 선저항을 감소시키는 기능을 향상시키는 것으로 예상된다. 제2금속분말이 포함되는 경우 제1금속분말 100 중량부에 대해서 10 내지 40 중량부로 포함되는 것이 바람직하다. 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㎛. The average diameter of the second metal powder is smaller than the average diameter of the first metal powder. In the case of using the second metal powder, it is expected to improve the function of reducing the line resistance according to the principle of increasing the packing density. When 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.
전도성 분말의 비표면적은 0.05 내지 5m2/g인 것이 바람직하다. 0.05m2/g 미만이면 입경이 커서 가는 라인(fine line, 70㎛이하)을 그릴 수 없다. 5m2/g를 초과하면 점도 조정에 다량의 용제가 필요해지는 등 작업성이 나빠지게 되는 문제점이 있다.It is preferable that 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 μm 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.
본 발명의 목적이 달성될 수 있게 하는 양이라면 전도성 분말의 함량에 대한 특별한 제한은 없지만, 바람직하게는 전도성 분말은 전도성 페이스트 조성물 전체 중량대비 70 내지 90 중량%로 포함된다. 전도성 분말이 90 중량%를 초과하여 포함되면 점도가 상승되어 조성물을 페이스트 상태로 형성하기 어려울 수 있으며, 70 중량% 미만으로 포함되면 전도성 분말의 양이 줄어들어 제조된 전면전극의 전기전도도 및 인쇄 후 패턴의 종횡비가 낮을 수 있다.There is no particular limitation on the content of the conductive powder as long as the object of the present invention can be achieved, but preferably 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.
2. 금속산화물 분말(X1-X2-…-Xn-O 분말)2. Metal oxide powder (X1-X2-… -Xn-O powder)
금속산화물 분말은 X1-X2-…-Xn-O 산화물 분말로서, Xn은 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, F, Zr, Mn, P, Cu, Ce, Fe 및 Nb로 구성되는 군에서 선택되는 금속들이며, n은 2 이상의 정수이고, 금속산화물 분말은 X1-X2-…-Xn-O는 적어도 부분적으로 결정질일 수 있다. The metal oxide powder is formed by X1-X2-. As a -Xn-O oxide powder, 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.
금속산화물 분말은 X1, X2,…, Xn의 산화물들을 혼합하여 용융시킨 후 냉각시켜 분쇄하고, 분쇄된 물질을 스크리닝하여 원하는 분말 크기로 제조한다. 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.
금속산화물 분말의 평균입경(D50)은 0.1 내지 3.0㎛이 바람직하다. 이 때, 금속산화물 분말은 녹는점이 250 내지 900℃인 것을 사용하는 것이 바람직하다. The average particle diameter (D50) of the metal oxide powder is preferably 0.1 to 3.0 µm. At this time, it is preferable to use a metal oxide powder having a melting point of 250 to 900 ° C.
본 발명에서 금속산화물분말은, 전도성 페이스트가 600 내지 950 ℃에서 소결되고 적절히 습윤되고 적절히 기판에 접착될 수 있도록, 200 내지 550 ℃의 연화점을 갖는다. 연화점이 200 ℃보다 낮으면, 소결이 진행되어 본 발명의 효과를 충분히 얻을 수 없는 경우가 있다. 연화점이 550 ℃보다 높으면 소성 동안에 충분한 용융 유동이 야기되지 않기 때문에, 충분한 접착 강도가 발현하지 않고, 또한 몇몇 경우에는 은의 액상 소결을 촉진시킬 수 없는 경우가 있다. 여기서 "연화점"이란, ASTM C338-57의 섬유 신장법(fiber elongation method)에 의해 얻어지는 연화점이다.In the present invention, 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.
금속산화물분말의 화학 조성은 본 발명에서 제한되지 않고 통상이 재료가 사용가능하나, 금속산화물분말은 1종의 금속산화물분말이 사용되거나, 유리전이온도가 2종 이상의 서로 다른 분말이 사용될 수 있다. 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.
1 종의 금속산화물 분말을 사용하는 경우 Xn은 Pb, Te, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, Mn으로 구성되는 군에서 선택되는 적어도 2종 이상의 금속이 될 수 있다. 본 발명에 있어서, 금속산화물 분말은 Pb, Te 및 Bi를 필수적으로 포함하는 것이 바람직하며, 금속산화물분말 전체 중량 대비 Pb의 함량(산화물 환산, PbO)을 a중량%이라고 할 때, 0.1≤a≤20인 것이 바람직할 수 있고, 보다 바람직하게는 1≤a≤15 일 수 있다. 상기 범위에서, 다양한 면저항 하에서 pn 접합 안정성을 확보할 수 있고 태양전지 효율을 높일 수 있기 때문이다. 또한, 금속산화물분말 전체 중량 대비 Te의 함량(산화물 환산, TeO2)을 b중량%라고 할 때, 50≤b≤80인 것이 바람직할 수 있으며, 60≤b≤75인 것이 보다 더 바람직 할 수 있다. TeO2가 50 중량% 미만인 경우, TeO2에 의한 Ag 고형도가 작아져서 접촉저항이 증가할 수 있다. TeO2가 80 중량% 초과인 경우, TeO2 과량 투입에 의해 실리콘 계면과의 반응성이 약해져서 접촉저항이 증가할 수 있기 때문이다. When using one kind of metal oxide powder, 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. In the present invention, 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. In addition, when 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. When 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.
본 발명의 Pb, Te 및 Bi를 필수적으로 포함하는 금속산화물분말에 있어서 Pb의 함량을 a중량%, Te의 함량을 b중량%, Bi의 함량을 c중량%라고 할 때, 상기 a, b 및 c의 관계는 하기 [식 1] 및 [식2]를 모두 만족하는 것이 바람직하다.  In the metal oxide powder comprising essentially Pb, Te and Bi of the present invention, when the content of Pb is a weight%, the content of Te is b% by weight, and 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].
[식 1][Equation 1]
70≤a+b+c≤90 (이 때, 1≤a≤15, 60≤b≤75)70≤a + b + c≤90 (where 1≤a≤15, 60≤b≤75)
[식 2][Equation 2]
2.5≤b/c≤7.5 (이 때, 60≤b≤75)2.5≤b / c≤7.5 (at this time 60≤b≤75)
상기 금속산화물분말은 Zn을 추가적으로 더 포함할 수 있으며, 금속산화물분말 중 Zn의 함량을 d중량% 라고 할 때 하기 [식 3]을 만족하는 것이 바람직 할 수 있다. 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].
[식 3][Equation 3]
0.5≤d/a≤3.5 (이 때, 1≤a≤15)0.5≤d / a≤3.5 (where 1≤a≤15)
금속산화물 분말의 일 예는 Pb-Te-Bi-Si-B-Zn-Al-O 일수 있다. 이 때, 각 금속의 함유량은 산화물환산으로 PbO 0.5~15 중량%, TeO2 50~75 중량%, Bi2O3 10~20 중량%, SiO2 0.1~10 중량%, B2O3 0.1~10 중량%, ZnO 1~8 중량% 및 Al2O3 0.1~3 중량%를 포함한다.One example of the metal oxide powder may be Pb-Te-Bi-Si-B-Zn-Al-O. At this time, 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%.
금속산화물 분말의 또 다른 예는 Pb-Te-W-Mo-Zn-Bi-Al-O 일수 있다. 이 때, 각 금속의 함유량은 산화물환산으로 PbO 0.5~15 중량%, TeO2 60~75 중량%, ZnO 0.5~15 중량%, Bi2O3 10~20 중량% 및 Al2O3 0.1~12 중량%를 포함한다. WO3과 MoO3는 합계하여 5~30 중량%이다. Another example of the metal oxide powder may be Pb-Te-W-Mo-Zn-Bi-Al-O. In this case, 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. Contains weight percent. WO 3 and MoO 3 are 5-30% by weight in total.
본 발명에 있어서 2종의 금속산화물분말을 사용하는 경우, 금속산화물분말은 제1유리전이온도 a℃를 갖는 제1금속산화물분말과 제2유리전이온도 b℃를 갖는 제2금속산화물분말을 동시에 포함할 수 있다. 이 때, 제1금속산화물분말은 제1유리전이온도가 170≤a≤310이고, 상기 제2금속산화물분말은 제2유리전이온도가 230≤b≤320인 것이 바람직하며, 제2금속산화물분말의 제2유리전이온도 b와 제1금속산화물분말의 제1유리전이온도 a의 차가 10≤b-a≤60를 만족시키는 것이 보다 바람직하다. 이는, 상기 온도 차이가 10℃ 미만이면 소성 온도 범위를 넓히는 효과가 미미할 수 있으며, 온도 차이가 60℃를 초과하면 소성과정에서 제1 및 제2 금속산화물분말 중 어느 하나가 금속산화물분말 역할을 실질적으로 수행하지 못하게 되기 때문이다. In the case of using two kinds of metal oxide powders in the present invention, 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. In this case, the first metal oxide powder has a first glass transition temperature of 170 ≦ a ≦ 310, and the second metal oxide powder has a second glass transition temperature of 230 ≦ b ≦ 320, and 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. If the temperature difference is less than 10 ° C., the effect of widening the firing temperature range may be insignificant. If the temperature difference is more than 60 ° C., 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.
상기 제1금속산화물분말은 Te를 포함하는 것이 바람직하며, Bi, Zn, B, Al, Ba, Si, W, Fe로 구성되는 군에서 선택되는 적어도 1종 이상의 금속을 추가로 포함할 수 있다. 상기 제2금속산화물분말은 Pb를 포함하는 것이 바람직하며, Li, Na, Ti, Cu, Ni, V, P, K, Sn로 구성되는 군에서 선택되는 적어도 1종 이상의 금속을 추가로 포함할 수 있다.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.
금속산화물분말 전체 중량에 대비하여 상기 제1금속산화물분말은 80 내지 90 중량%, 상기 제2금속산화물분말은 0.5 내지 20 중량%로 포함하는 것이 바람직하다.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.
금속산화물분말은 본 발명의 목적을 달성할 수 있는 양이면 특별히 한정되지 않지만, 전도성 분말 100 중량부에 대해서 1 내지 10중량부로 포함되는 것이 바람직하다. 금속산화물분말의 양이 1 중량부보다 적으면 접착 강도가 불충분해지는 경우가 있고, 10 중량부를 초과하면 유리 부유 등에 의해 후속 공정인 땜납에 지장을 초래하는 경우가 있다.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.
3. 유기 매질3. Organic Medium
본 명세서에서 "유기매질"은 바인더와 용제를 포함하는 개념으로 바인더 중에는 용제가 포함되어 있을 수도 있다. 본 발명에서는 유기매질은 점도가 높은 경우, 필요에 따라서 첨가제로 후술할 점도 조절제를 별도로 첨가할 수 있다.As used herein, the term "organic medium" includes a binder and a solvent, and a solvent may be included in the binder. In the present invention, when the organic medium has a high viscosity, a viscosity modifier to be described later may be separately added as an additive if necessary.
본 발명에서는 바인더로는 메틸 셀룰로오스, 에틸 셀룰로오스, 에틸 히드록시에틸셀룰로오스(hydroxyethyl cellulose) 등의 셀룰로오스 유도체, 우드로진, 에틸셀룰로스(ethyl cellulose)와 페놀 수지(phenol resin)와의 혼합물, 저급 알코올(lower alcohol)의 폴리메타크릴레이트(methacrylate) 및 에틸렌글리콜모노 아세테이트(acetate)의 모노부틸(monobutyl) 에테르(ether), 아크릴수지, 알키드 수지, 폴리프로필렌계 수지, 폴리염화비닐계 수지, 폴리우레탄계 수지, 로진계 수지, 테르펜계 수지, 페놀계 수지, 지방족계 석유 수지, 아크릴산 에스테르계 수지, 크실렌계 수지, 쿠마론인덴(Coumarone-Indene)계 수지, 스틸렌계 수지, 디시클로펜타디엔계 수지, 폴리부텐계 수지, 폴리에테르계 수지, 요소계 수지, 멜라민계 수지, 초산비닐계 수지, 폴리이소부틸계 수지를 들 수 있지만, 이들로 한정되는 것은 아니다. In the present invention, 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.
또한, 예시적인 용제로서는 헥산, 톨루엔, 에스테르(ester) 알코올(alcohol) 및 α－또는 β－테르피네올(terpineol) 등의 테르펜(terpene), 등유, 디부틸(dibutyl) 프탈레이트(phthalate), 부틸 카르비톨, 부틸 카르비톨 아세테이트(acetate), 헥시렌 글리콜 (glycol), 벤질알코올, 알코올(alcohol) 에스테르(ester), 디에틸렌글리콜디에틸에테르, 디아세톤알콜타피네올메틸에틸케톤, 에틸셀로솔브, 시클로헥사논, 부틸셀로솔브, 부틸셀로솔브 아세테이트 등의 용제를 들 수 있지만, 이들로 한정되는 것은 아니다.Exemplary solvents include terpenes such as hexane, toluene, ester alcohols and α- or β-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.
특히 전술한 용제 대용으로 또는 용제와 함께 비스(2－(2부톡시(butoxy)(butoxy) 에톡시(ethoxy)) 에틸) 아디페이트(adipate), 디베이식 에스테르(Dibasic ester), 옥틸에폭시탈레이트(Octyl Epoxy Talate), 이소테트라데카놀(isotetradecanol) 및 수소화 로진의 펜타에리트리톨 (pentaerythritol) 에스테르(ester)로 이루어지는 군으로부터 선택되는 1개 또는 복수의 성분을 포함할 수 있다. 이 때, 디베이식 에스테르(Dibasic ester)는 아디프산(adipic acid)의 디메틸에스테르(dimethylester), 글루타르산(glutaricacid)의 디메틸에스테르(dimethylester) 및 호박산(succinic acid)의 디메틸에스테르(dimethylester)로 이루어지는 군으로부터 선택되는 1개 또는 복수의 화합물이 사용될 수 있다. In particular bis (2- (butoxy ethoxy) ethyl) adipate, dibasic ester, octylepoxytalate as a substitute for or with solvent (Octyl Epoxy Talate), isotetracananol, and pentaerythritol esters of hydrogenated rosin. At this time, 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.
유기매질의 함량은 바람직하게는, 전도성 분말 100 중량부에 대해서 5 내지 20 중량부일 수 있다. 유기매질이 20 중량부를 초과하여 포함되면 제조된 전면전극의 전기전도도가 낮아질 수 있으며, 유기매질이 5 중량부 미만으로 포함되면 기판과의 접합특성이 저하될 수 있다.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. 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. 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.
4. 첨가제4. Additive
본 발명의 일측면에 따른 전도성 페이스트에는 무기 및 유기 첨가제가 포함될 수 있다. The conductive paste according to one aspect of the present invention may include inorganic and organic additives.
무기첨가제로는 Li, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Pb, Cu, Zn, Ag, Te, Zn, Na, Mg, Al, W, Fe로 구성되는 군에서 선택되는 금속, 금속산화물 및 이들의 합금 또는 합금산화물 일 수 있다. 예를 들며, PbO, CuO, ZnO, MgO, WO3 등이 있다.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.
본 발명에서는 무기첨가제로 텔루륨(Te)을 포함하는 금속합금 또는 금속합금산화물이 포함되는 것이 바람직할 수 있으며, 더욱 바람직하게는 Te-X-O, Te-Y 또는 Te-Y-Z인 것이고, 이 때 X는 알칼리금속 또는 알칼리토금속 중 선택된 적어도 하나 이상의 금속이고, Y 및 Z는 Zn, Ag, Na, Mg, Al로 구성되는 군에서 선택되는 적어도 하나 이상의 금속이다. Y와 Z는 같은 금속을 사용하지 않는다. In the present invention, it may be preferable to include 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.
가장 바람직하게는 Te-X-O는 Li2TeO3, Na2TeO3, SrTeO3, BeTeO3 또는 MgTeO3인 것이며, Te-Y 또는 Te-Y-Z는 Ag-Te, Li-Te-Zn, Te-Zn-K, 또는 Te-Zn-Na인 것이다. 본 발명의 무기첨가제는 전도성 분말로 포함된 금속과 반응하여 고상 반응을 촉진할 수 있는 금속을 포함하므로, 저온에서도 전도성 분말인 금속분말의 결정립 성장을 촉진할 수 있으며, 이에 의해 페이스트 조성물의 소성 온도 범위를 넓힐 수 있어 전기 전도도를 향상할 수 있다. Most preferably 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. Since 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.
본 발명의 첨가제의 입자 크기는 어떠한 특정 제한도 받지 않는다. 일 실시예에 있어 평균 입자 크기는 10 ㎛보다 작은 평균 입자 크기를 가질 수 있다. 바람직하게는 평균 입자 크기는 0.01 내지 5 ㎛일 수 있다. 보다 바람직하게는 50 내지 200 ㎚일 수 있다.The particle size of the additives of the invention is not subject to any particular limitation. In one embodiment, the average particle size may have an average particle size of less than 10 μm. Preferably the average particle size may be 0.01 to 5 μm. More preferably, it may be 50-200 nm.
무기첨가제의 함량은 전도성 분말 100 중량부에 대해서 1 내지 10 중량부 일 수 있으며, 바람직하게는 1 내지 5 중량부로 포함될 수 있다. 무기첨가제의 함량이 전도성 분말 100 중량부에 대해서 5 중량부를 초과하여 포함되면 전도성 분말의 양이 적어져서 이 페이스트 조성물을 이용하여 제조된 전면전극의 저항이 커질 수 있으며 이에 의해 태양 전지의 효율이 저하될 수 있다. 반면, 무기첨가제의 함량이 전도성 분말 100 중량부에 대해서 1 미만으로 포함되면 첨가제에 의한 효과를 충분히 기대하기 어려울 수 있다.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. When the content of the inorganic additive is 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. On the other hand, when 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.
유기첨가제로는 분산제, 산화방지제, 자외선흡수제, 소포제, 증점제, 안정화제, 분산제, 점도 조절제 등이 있으며, 반드시 이에 제한되는 것은 아니다. 이들은 단독 또는 2종 이상 혼합하여 사용될 수 있으며 본 발명의 효과를 방해하지 않는 범위에서 배합할 수 있다.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 | blended in the range which does not prevent the effect of this invention.
특히 분산제는 스테아린산, 팔미트산, 미리스틴(myristin)산, 올레인산, 라우린산 등의 분산제를 도전성 페이스트에 배합할 수 있다. 또한, 분산제는 일반적인 것이라면, 유기산으로 한정되지는 않는다.In particular, 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. In addition, a dispersing agent is not limited to an organic acid as long as it is a general thing.
전도성 페이스트 조성물의 제조Preparation of Conductive Paste Composition
본 발명의 전도성 페이스트는 전도성분말, 금속산화물 분말, 유기매질, 첨가제를 3-롤 혼련기로 혼합함으로써 제조된다. 본 발명의 전도성 페이스트는, 바람직하게는 스크린 인쇄로 전자장치의 원하는 부위에 도포되지만, 이러한 인쇄로 도포되는 경우, 소정의 범위의 점도를 갖는 것이 바람직하다. 본 발명의 전도성 페이스트의 점도는 바람직하게는, 브룩필드(Brookfield) HBT 점도계로 #14 스핀들을 사용하고 10 rpm 및 25 ℃에서 유틸리티 컵을 사용하여 측정하는 경우에 50 내지 300 PaS이다.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.
전도성 페이스트 조성물을 사용한 반도체장치의 제조Fabrication of Semiconductor Device Using Conductive Paste Composition
본 발명의 전도성 페이스트를 제조하고자 하는 반도체장치의 기판에 스크린 인쇄 등에 의해 도포하고 건조시킨다. 전도성 페이스트가 도포된 기판을 약 700 내지 약 950 ℃의 온도에서 소성하여 전도성 페이스트 패턴을 형성한다. 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.
실시예Example
<전도성 페이스트 조성물의 제조><Production of Conductive Paste Composition>
실시예 1Example 1
전도성 분말로는 평균직경이 2㎛인 제1은분말과 평균직경이 200nm인 나노은분말을 혼합하여 사용하였다. As the conductive powder, a first silver powder having an average diameter of 2 μm and a nano silver powder having an average diameter of 200 nm were mixed and used.
금속산화물분말은 평균직경이 2㎛로 MO3(금속산화물 분말 전체중량 대비 4.1 중량%의 PbO, 72.6 중량%의 TeO2, 15.9 중량%의 Bi2O3, 0.7 중량%의 B2O3, 4.8 중량%의 ZnO, 0.5 중량%의 Cr2O3, 0.4 중량%의 MnO2, 0.7 중량%의 CuO2, 0.3 중량%의 Li2O) 6.5g을 사용하였다. The metal oxide powder has an average diameter of 2 μm, 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.
페이스트 조성물 100g에 대하여 제1은분말이 70.0g, 나노은분말이 11.0g, 금속산화물분말이 6.5g, 유기용매로 에틸셀룰로오스를 20 중량％ 함유하는 테르피네올 용액 10.2g, 무기 첨가제 ZnO 2.3g을 첨가하여 전도성 페이스트 조성물을 제조하였다.To 100 g of the paste composition, 10.0 g of the first silver powder, 11.0 g of the nano silver powder, 6.5 g of the metal oxide powder, 10.2 g of the terpineol solution containing 20% by weight of ethyl cellulose in an organic solvent, and 2.3 g of the inorganic additive ZnO were added. To prepare a conductive paste composition.
실시예 2 내지 실시예 3Examples 2 to 3
사용하는 금속산화물분말의 종류를 표 1에 따르는 것으로 변경한 것 이외에는, 실시예 1과 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
실시예 4 내지 실시예 7 Examples 4-7
사용하는 전도성 분말을 표1에서 나타내는 바와 같이 변경하고, 금속산화물 분말의 종류를 표1에 따르는 것으로 변경한 것 이외에는 실시예 1과 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
실시예 8 내지 실시예 10 Examples 8-10
사용하는 무기첨가제의 종류를 표1에 나타내는 성분으로 변경한 것 이외에는 실시예 4 내지 6과 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
실시예 11 내지 실시예 14Examples 11-14
사용하는 무기첨가제 및 금속산화물분말의 종류를 표 1에 따르는 것으로 변경한 것 이외에는 실시예 10과 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
비교예 1 내지 비교예 2Comparative Example 1 to Comparative Example 2
사용하는 금속산화물분말의 종류를 표 1에 나타내는 바와 같이 변경한 것을 제외하고는 실시예 1과 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
비교예 3 내지 비교예 5 Comparative Examples 3 to 5
사용하는 금속산화물분말의 종류를 표 1에 나타내는 바와 같이 변경한 것을 제외하고는 실시예 4와 동일하게 하여 전도성 페이스트 조성물을 제조하였다. 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.
전술한 각 실시예와 비교예들을 만능 혼합기로 예비 혼합하고, 3롤 혼련기로 혼련하여, 전도성 페이스트를 얻었다. 사용한 재료의 함량(g) 및 특징은 표 1에 나타내었으며, 사용한 금속산화물분말인 MO1 내지 MO6의 조성비(중량%)는 표 2에 나타내고 MO7 내지 MO10의 조성비는 표 3에 나타내었다.Each of the above-described examples and comparative examples were premixed with a universal mixer and kneaded with a three-roll kneader to obtain a conductive paste. The content (g) and the characteristics of the used material are shown in Table 1, and the composition ratios (wt%) of the used metal oxide powders MO1 to MO6 are shown in Table 2 and the composition ratios of MO7 to MO10 are shown in Table 3.
표 1
성분 전도성 분말 금속산화물 유기매질 무기첨가제
제1은분말 나노은분말 제2은분말 제1금속산화물 제2금속산화물
실시예1 70 돌기X 11 응집체X - 6.5 MO3 - 10.2 2.3 ZnO
실시예2 70 돌기X 11 응집체X - 6.5 MO4 - 10.2 2.3 ZnO
실시예3 70 돌기X 11 응집체X - 6.5 MO5 - 10.2 2.3 ZnO
실시예4 63.5 돌기O 5 응집체 12.5 6.5 MO3 - 10.2 2.3 ZnO
실시예5 63.5 돌기O 5 응집체 12.5 6.5 MO4 - 10.2 2.3 ZnO
실시예6 63.5 돌기O 5 응집체 12.5 6.5 MO5 - 10.2 2.3 ZnO
실시예7 63.5 돌기O 5 응집체 12.5 6.5 MO6 - 10.2 2.3 ZnO
실시예8 63.5 돌기O 5 응집체 12.5 6.5 MO3 - 10.2 2.3 Te-Zn-Na
실시예9 63.5 돌기O 5 응집체 12.5 6.5 MO4 - 10.2 2.3 Ag-Te
실시예10 63.5 돌기O 5 응집체 12.5 6.5 MO5 - 10.2 2.3 Na2TeO3
실시예11 63.5 돌기O 5 응집체 12.5 3.3 MO7 3.2 MO7 10.2 2.3 ZnO
실시예12 63.5 돌기O 5 응집체 12.5 5.2 MO7 1.3 MO7 10.2 2.3 ZnO
실시예13 63.5 돌기O 5 응집체 12.5 5.2 MO8 1.3 MO8 10.2 2.3 Te-Zn-Na
실시예14 63.5 돌기O 5 응집체 12.5 5.2 MO9 1.3 MO9 10.2 2.3 BeTeO3
비교예1 70 돌기X 11 응집체X - 6.5 MO1 - 10.2 2.3 ZnO
비교예2 70 돌기X 11 응집체X - 6.5 MO2 - 10.2 2.3 ZnO
비교예3 63.5 돌기O 5 응집체 12.5 6.5 MO1 - 10.2 2.3 ZnO
비교예4 63.5 돌기O 5 응집체 12.5 6.5 MO2 - 10.2 2.3 ZnO
비교예5 63.5 돌기O 5 응집체 12.5 5.5 MO10 1.0 MO10 10.2 2.3 ZnO
Table 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 Turning O 5 Aggregate 12.5 6.5 MO4 - 10.2 2.3 Ag-Te
Example 10 63.5 Turning O 5 Aggregate 12.5 6.5 MO5 - 10.2 2.3 Na 2 TeO 3
Example 11 63.5 Turning O 5 Aggregate 12.5 3.3 MO7 3.2 MO7 10.2 2.3 ZnO
Example 12 63.5 Turning O 5 Aggregate 12.5 5.2 MO7 1.3 MO7 10.2 2.3 ZnO
Example 13 63.5 Turning O 5 Aggregate 12.5 5.2 MO8 1.3 MO8 10.2 2.3 Te-Zn-Na
Example 14 63.5 Turning O 5 Aggregate 12.5 5.2 MO9 1.3 MO9 10.2 2.3 BeTeO 3
Comparative Example 1 70 Turning X 11 Aggregate X - 6.5 MO1 - 10.2 2.3 ZnO
Comparative Example 2 70 Turning X 11 Aggregate X - 6.5 MO2 - 10.2 2.3 ZnO
Comparative Example 3 63.5 Turning O 5 Aggregate 12.5 6.5 MO1 - 10.2 2.3 ZnO
Comparative Example 4 63.5 Turning O 5 Aggregate 12.5 6.5 MO2 - 10.2 2.3 ZnO
Comparative Example 5 63.5 Turning O 5 Aggregate 12.5 5.5 MO10 1.0 MO10 10.2 2.3 ZnO
표 2
금속산화물분말(전체 금속산화물분말에 대한 중량%) 유리전이온도(Tg,℃)
성분 PbO TeO2 Bi2O3 SiO2 B2O3 Al2O3 ZnO Fe2O3 Cr2O3 Co2O3 MnO2 CuO2 Li2O
MO1 78.0 - - 11.5 7.5 0.5 1.0 0.5 0.5 0.1 0.4 - - 186
MO2 33.8 41.1 20.6 - - - 3.3 1.2 - - - - 420
MO3 4.1 72.6 15.9 - 0.7 - 4.8 - 0.5 - 0.4 0.7 0.3 286
MO4 2.6 69.0 19.8 0.5 - - 6.0 0.4 - - - 0.7 1.0 275
MO5 1.8 69.5 14.3 3.2 4.1 1.8 5.3 - - - - - - 312
MO6 9.2 68.0 11.8 - - 2.8 4.3 1.9 - - - 0.8 1.2 283
TABLE 2
Metal oxide powder (% by weight of total metal oxide powder) Glass transition temperature (Tg, ℃)
ingredient PbO TeO 2 Bi 2 O 3 SiO 2 B 2 O 3 Al 2 O 3 ZnO Fe 2 O 3 Cr 2 O 3 Co 2 O 3 MnO 2 CuO 2 Li 2 O
MO1 78.0 - - 11.5 7.5 0.5 1.0 0.5 0.5 0.1 0.4 - - 186
MO2 33.8 41.1 20.6 - - - 3.3 1.2 - - - - 420
MO3 4.1 72.6 15.9 - 0.7 - 4.8 - 0.5 - 0.4 0.7 0.3 286
MO4 2.6 69.0 19.8 0.5 - - 6.0 0.4 - - - 0.7 1.0 275
MO5 1.8 69.5 14.3 3.2 4.1 1.8 5.3 - - - - - - 312
MO6 9.2 68.0 11.8 - - 2.8 4.3 1.9 - - - 0.8 1.2 283
표 3
제1 금속산화분말 제2 금속산화분말
성분(중량%) TeO2 Bi2O3 ZnO WO3 Fe2O3 Tg(℃) PbO Li2O Ni2O3 CuO2 V2O5 P2O5 Tg(℃)
MO7 77.2 17.0 5.4 - 0.4 263 74.6 14.9 - 10.5 - - 288
MO8 79.8 14.4 5.0 0.8 - 226 54.4 14.3 7.3 16.8 5.4 1.8 300
MO9 67.5 24.4 6.7 1.4 - 287 48.4 30.3 2.1 11.7 4.6 2.9 312
MO10 30.2 39.4 12.6 9.2 8.6 413 36.2 31.2 12.8 - 11.4 8.4 464
TABLE 3
First metal oxide powder Second Metal Oxidized Powder
Ingredient (% by weight) TeO 2 Bi 2 O 3 ZnO WO 3 Fe 2 O 3 Tg (℃) PbO Li 2 O Ni 2 O 3 CuO 2 V 2 O 5 P 2 O 5 Tg (℃)
MO7 77.2 17.0 5.4 - 0.4 263 74.6 14.9 - 10.5 - - 288
MO8 79.8 14.4 5.0 0.8 - 226 54.4 14.3 7.3 16.8 5.4 1.8 300
MO9 67.5 24.4 6.7 1.4 - 287 48.4 30.3 2.1 11.7 4.6 2.9 312
MO10 30.2 39.4 12.6 9.2 8.6 413 36.2 31.2 12.8 - 11.4 8.4 464
실험예Experimental Example
<태양전지의 제조><Manufacture of Solar Cell>
실시예 1 내지 14 및 비교예 1 내지 5의 전도성 페이스트를 사용하여 태양 전지를 제조하였다. 먼저, 실리콘 기판을 준비하고, 후면측에 땜납 접속용의 전도성 페이스트(은 페이스트)를 스크린 인쇄에 의해 도포하고 건조시켰다. 이어서, 건조시킨 은 페이스트와 일부 중첩되도록 후면 전극용 알루미늄 페이스트(PV333(이 아이 듀퐁 디 네모아 앤드캄파니(E.I. du Pont de Nemours and Company) 제조)를 스크린 인쇄에 의해 도포하고 건조시켰다. Solar cells were prepared using the conductive pastes of Examples 1-14 and Comparative Examples 1-5. First, 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. Subsequently, 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.
각 페이스트의 건조 온도는 120 ℃로 하였다. 또한, 이면의 각 전극의 막 두께는 건조 후 막 두께로, 알루미늄 페이스트 35 ㎛, 및 은 페이스트 20 ㎛가 되도록 도포하였다.The drying temperature of each paste was 120 degreeC. In addition, the film thickness of each electrode of the back surface was apply | coated so that it might be set to the film thickness after drying, 35 micrometers of aluminum pastes, and 20 micrometers of silver pastes.
또한, 본 발명의 페이스트를 수광측 면(전면) 상에 스크린 인쇄에 의해 도포하고 건조시켰다. 프라이스사(Price Co.)에 의해 제조된 인쇄기, 및 8 인치×10 인치 프레임 및 스테인레스 와이어 250 메쉬의 마스크를 사용하였다. 폭이 100 ㎛인 핑거(finger) 라인과 폭이 2 mm인 버스 바(bus bar)로 구성되는 1.5 인치의 평가용 패턴이 사용되었고, 막 두께는 소성 후 13 ㎛이었다. 이어서, 얻어진 기판에 대해서, 적외선 소성로에서 피크 온도 약 730 ℃ 및 내부-외부(IN-OUT) 약 5 분의 조건으로, 도포된 페이스트를 동시에 소성하여, 목적으로 하는 태양 전지를 얻었다. 본 발명의 전도성 페이스트를 사용하여 얻어지는 태양 전지는, 수광면 (전면)측에 Ag 전극을 갖고, 이면측에 Al을 주성분으로 하는 Al 전극(제1 전극) 및 Ag을 주성분으로 하는 은 전극(제2 전극) 를 갖는다.Furthermore, the paste of this invention was apply | coated by screen printing and dried on the light receiving side surface (front surface). A printing machine manufactured by Price Co., and a mask of 8 inches by 10 inches frame and stainless wire 250 mesh was used. A 1.5 inch evaluation pattern consisting of a finger line 100 μm wide and a bus bar 2 mm wide was used and the film thickness was 13 μm after firing. Subsequently, 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).
1. 광변환 효율 및 곡선인자 측정1. Measurement of light conversion efficiency and curve factor
얻어진 태양 전지 기판의 전기 특성(I-V 특성)을 전지 시험기에 의해 평가하였다. 전지 시험기는 NPC사에 의해 제조된 장비(NCT-M-150AA)를 사용하여, Eff: 전환 효율(％) 및 FF: 곡선인자(Fill Factor)를 측정하여 결과를 표 4에 나타내었다. 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.
2. 부착력 측정2. Adhesion Measurement
수득한 태양전지의 부착력은 상기의 전극형성공정으로부터 형성된 전면전극의 표면에 SnPbAg계 솔더리본(solder ribbon, 2mm선폭, indium corporation, SUNTABTM)을 이용하여 200℃의 온도로 가온하여 10cm길이로 부착시키고, 부착된 부분의 한쪽 끝을 잡고 만능시험인장력평가기(COMETECH사 QC-508E)와 180°방향으로 잡아 당기면서 전극과 솔더리본이 박리될 때까지의 힘(N, newton)을 기준으로 측정하고, 하기 기준에 의거하여 평가한 결과를 하기 표 4의 부착력(N)으로 나타내었다. 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.
<평가기준><Evaluation Criteria>
Excellent : 3N이상. Excellent: more than 3N.
Good : 2N이상.Good: More than 2N.
Bad : 1N이하.Bad: 1N or less.
표 4에 나타내는 각 전기 특성의 수치는 5매의 태양 전지 기판 샘플의 측정값의 평균값으로 나타내었다. The numerical value of each electrical characteristic shown in Table 4 was shown as the average value of the measured value of five solar cell substrate samples.
표 4
Eff(%) FF 부착력
실시예 1 17.51 74.1 Excellent
2 17.72 74.8 Excellent
3 17.64 75.0 Excellent
4 18.13 76.6 Excellent
5 18.63 76.2 Excellent
6 18.85 77.1 Excellent
7 18.69 76.4 Good
8 19.14 78.5 Excellent
9 19.42 78.2 Excellent
10 19.43 79.4 Excellent
11 19.70 79.5 Good
12 19.77 79.8 Excellent
13 19.92 80.6 Excellent
14 19.84 79.8 Excellent
비교예 1 15.61 70.2 bad
2 16.20 70.8 Good
3 16.02 70.2 bad
4 16.30 70.4 Good
5 15.72 69.2 bad
Table 4
Eff (%) FF Adhesion
Example One 17.51 74.1 Excellent
2 17.72 74.8 Excellent
3 17.64 75.0 Excellent
4 18.13 76.6 Excellent
5 18.63 76.2 Excellent
6 18.85 77.1 Excellent
7 18.69 76.4 Good
8 19.14 78.5 Excellent
9 19.42 78.2 Excellent
10 19.43 79.4 Excellent
11 19.70 79.5 Good
12 19.77 79.8 Excellent
13 19.92 80.6 Excellent
14 19.84 79.8 Excellent
Comparative example One 15.61 70.2 bad
2 16.20 70.8 Good
3 16.02 70.2 bad
4 16.30 70.4 Good
5 15.72 69.2 bad
전술한 각 실시예에서 예시된 특징, 구조, 효과 등은 실시예들이 속하는 분야의 통상의 지식을 가지는 자에 의하여 다른 실시예들에 대해서도 조합 또는 변형되어 실시 가능하다. 따라서 이러한 조합과 변형에 관계된 내용들은 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.Features, structures, effects, and the like illustrated in the above-described embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (7)

  1. 전도성 분말; Conductive powder;
    X1-X2-…-Xn-O(Xn은 Pb, Te, Bi, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P, Mn으로 이루어진 군에서 선택되는 금속으로서 Pb, Te 및 Bi를 필수적으로 포함, n은 3 이상의 정수)의 금속산화물분말; X1-X2-. -Xn-O (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 Metal oxide powder of essentially Pb, Te and Bi as the metal, n is an integer of 3 or more);
    유기매질; 및Organic medium; And
    첨가제를 포함하며,Contains additives,
    상기 금속산화물분말은 연화점이 200 내지 550℃이고, The metal oxide powder has a softening point of 200 to 550 ° C.,
    상기 금속산화물분말에서 Pb의 함량을 a중량%, Te의 함량을 b중량%, Bi의 함량을 c중량%, Zn의 함량을 d중량% 라고 할 때 하기 [식 1], [식 2] 및 [식 3]을 모두 만족하는 전도성 페이스트 조성물.In the metal oxide powder, when the content of Pb is a weight%, the content of Te is b% by weight, the content of Bi is c% by weight, and the content of Zn is d% by weight [Formula 1], [Formula 2] and A conductive paste composition that satisfies all of [Formula 3].
    [식 1][Equation 1]
    70≤a+b+c≤90 (이 때, 1≤a≤15, 60≤b≤75)70≤a + b + c≤90 (where 1≤a≤15, 60≤b≤75)
    [식 2][Equation 2]
    2.5≤b/c≤7.5 (이 때, 60≤b≤75)2.5≤b / c≤7.5 (at this time 60≤b≤75)
    [식 3][Equation 3]
    0.5≤d/a≤3.5 (이 때, 1≤a≤15)0.5≤d / a≤3.5 (where 1≤a≤15)
  2. 제1항에 있어서,The method of claim 1,
    상기 금속산화물분말은 Pb-Te-Bi-Si-B-Zn-Al-O이며, The metal oxide powder is Pb-Te-Bi-Si-B-Zn-Al-O,
    상기 금속산화물 분말의 각 금속의 함유량은 금속산화물 전체 중량 대비 산화물환산으로 PbO 0.5~15 중량%, TeO2 50~75 중량%, Bi2O3 10~20 중량%, SiO2 0.1~10 중량%, B2O3 0.1~10 중량%, ZnO 1~8 중량% 및 Al2O3 0.1~3 중량%인 전도성 페이스트 조성물.The content of each metal of the metal oxide powder is PbO 0.5-15 wt%, TeO 2 50-75 wt%, Bi 2 O 3 10-20 wt%, SiO 2 0.1-10 wt% , 0.1-10% by weight of B 2 O 3 , 1-8% by weight of ZnO and 0.1-3% by weight of Al 2 O 3 .
  3. 제1항에 있어서,The method of claim 1,
    상기 금속산화물분말은 Pb-Te-W-Mo-Zn-Bi-Al-O인 전도성 페이스트 조성물.The metal oxide powder is Pb-Te-W-Mo-Zn-Bi-Al-O conductive paste composition.
  4. 제1항에 있어서,The method of claim 1,
    상기 전도성분말은 평균직경이 1 내지 3㎛ 제1금속분말, 및 평균직경이 100 내지 200nm인 금속나노분말이 응집하여 이루어지는 0.5 내지 10㎛인 금속나노분말의 응집체를 포함하는 전도성 페이스트 조성물.The conductive powder is a conductive paste composition comprising an aggregate of 0.5 to 10 μm of metal nanopowder formed by agglomeration of a first metal powder having an average diameter of 1 to 3 μm and a metal nano powder having an average diameter of 100 to 200 nm.
  5. 제1항에 있어서,The method of claim 1,
    상기 첨가제는 전도성 분말 100 중량부에 대해서 1 내지 5 중량부로 포함되며, Te-X-O, Te-Y 또는 Te-Y-Z(X는 알칼리금속 또는 알칼리토금속 중 선택된 적어도 하나 이상의 금속, Y 및 Z는 Zn, Ag, Na, Mg, Al로 구성되는 군에서 선택되는 적어도 하나 이상의 금속, Y≠Z)를 포함하는 전도성 페이스트 조성물.The additive is included in 1 to 5 parts by weight based on 100 parts by weight of the conductive powder, Te-XO, Te-Y or Te-YZ (X is at least one metal selected from alkali metal or alkaline earth metal, Y and Z is Zn, A conductive paste composition comprising at least one metal selected from the group consisting of Ag, Na, Mg, Al, Y ≠ Z).
  6. 제1항에 있어서,The method of claim 1,
    상기 전도성 분말 70 내지 90 중량%, 70 to 90% by weight of the conductive powder,
    상기 금속산화물분말 0.7 내지 9 중량%, 0.7 to 9 wt% of the metal oxide powder,
    상기 유기매질 3.5 내지 18 중량%, 및3.5 to 18% by weight of the organic medium, and
    상기 첨가제 0.7 내지 4.5 중량%를 포함하는 것을 특징으로 하는 전도성 페이스트 조성물.Conductive paste composition comprising 0.7 to 4.5% by weight of the additive.
  7. 실리콘 반도체 기판; Silicon semiconductor substrates;
    상기 기판 상부에 형성되는 에미터층; An emitter layer formed on the substrate;
    상기 에미터층 상에 형성된 반사방지막; An anti-reflection film formed on the emitter layer;
    상기 반사방지막을 관통하여 상기 에미터층에 접속된 전면 전극; 및 A front electrode penetrating the antireflection film and connected to the emitter layer; And
    상기 기판의 배면에 접속된 후면 전극을 포함하는 실리콘 태양전지로서,A silicon solar cell comprising a back electrode connected to a rear surface of the substrate,
    상기 전면 전극은 제1항 내지 제6항 중 어느 한 항에 따른 전도성 페이스트 조성물을 상기 반사방지막 상에 소정의 패턴으로 도포하고 소성시켜 형성되는 것을 특징으로 하는 실리콘 태양전지.The front electrode is formed by applying the conductive paste composition according to any one of claims 1 to 6 on the anti-reflection film in a predetermined pattern and firing.
PCT/KR2015/001359 2014-04-15 2015-02-12 Conductive paste composition, and semiconductor device comprising same WO2015160078A1 (en)

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JP2011119340A (en) * 2009-12-01 2011-06-16 Harima Chemicals Inc Conductive aluminum paste
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KR20130117344A (en) * 2012-04-17 2013-10-25 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 Conductive thick film paste for solar cell contacts

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