WO2015160066A1 - Conductive paste composition and semiconductor device comprising the same - Google Patents
Conductive paste composition and semiconductor device comprising the same Download PDFInfo
- Publication number
- WO2015160066A1 WO2015160066A1 PCT/KR2014/012356 KR2014012356W WO2015160066A1 WO 2015160066 A1 WO2015160066 A1 WO 2015160066A1 KR 2014012356 W KR2014012356 W KR 2014012356W WO 2015160066 A1 WO2015160066 A1 WO 2015160066A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal oxide
- oxide powder
- powder
- conductive paste
- metal
- Prior art date
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- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 238000005476 soldering Methods 0.000 description 1
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- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
Definitions
- the present invention relates to a conductive paste composition, and more particularly, to a conductive paste composition for forming a thin film pattern such as an electrode or wiring to connect electrical signals of semiconductor devices.
- the present invention relates to a semiconductor device, especially, a solar cell, having an electrode or wiring formed of the conductive paste composition.
- a conductive paste (or ink) is applied on a substrate to form a pattern for transferring an electrical signal.
- a conductive paste typically includes a conductive powder, a glass frit, and an organic medium.
- a conductive paste is printed in the form of a linear pattern or other patterns on a substrate and then fired.
- a conductive paste should be printed in a pattern having a desired line width via a desired printing process, and also, enables the resulting electrode to be attached onto a substrate while possessing durability, so as to exhibit high adhesion and low resistance.
- desired printability research has to be ongoing into compositions adapted for fine line widths and properties for printing processes corresponding thereto. To this end, the size of a conductive powder or the properties of an organic medium is regarded as important.
- desired adhesiveness research has to be carried out into stably attaching the conductive paste composition to a substrate for a long period of time. To this end, the composition of a glass frit is regarded as important.
- electrical conductivity requires studies for ohmic contact and line resistance due to a reduction in line width. To this end, the composition of a conductive powder and a frit is regarded as important.
- a conductive paste composition has to be individually characterized with regard to printability, adhesiveness and electrical conductivity depending on the end use.
- an anti-reflective film made of silicon nitride, titanium oxide or silicon oxide is formed on a semiconductor substrate to promote absorption of solar light and may thus may function as an insulator, undesirably damaging the flow of electrons to the substrate (or from the substrate).
- a conductive paste for heat generation should infiltrate the anti-reflective film during firing in order to achieve efficient electrical contact with the substrate, and also should be specifically characterized so as to form strong bonding to the substrate.
- a conductive paste for use in a flexible substrate should be developed to have a composition able to maintain adhesiveness despite flexibility of the substrate.
- a conductive powder, a glass frit and an organic medium which are technical elements for use in ensuring printability, adhesiveness and electrical conductivity of the conductive paste composition, have antagonistic influences on each other, and thus development of balanced technology for individual technical elements is required.
- Cited reference 1 Korean Patent Application Publication No. 2005-243500 discloses a conductive paste including an organic binder, a solvent, a glass frit, a conductive powder and at least one metal selected from the group consisting of Ti, Bi, Zn, Y, In and Mo or a metal compound thereof, wherein the average particle size of metal or metal compound is 0.001 to less than 0.1 ⁇ m.
- the conductive paste including ultrafine metal or a metal compound is fired, thereby forming a front electrode having stability, high electrical conductivity and superior adhesion between the conductive paste and the semiconductor through the anti-reflective layer.
- the coating film may shrink, thus increasing contact resistance.
- thermal shrinkage behavior coefficient of linear expansion
- microcracks may be created on the surface of the semiconductor substrate.
- an increase in the contact resistance may undesirably result in lowered FF and thus deteriorated conversion efficiency.
- the present invention is intended to provide a conductive paste composition having enhanced printability and electrical conductivity by improving a conductive powder.
- the present invention is intended to provide a conductive paste composition having a wide firing temperature range by use of a metal oxide powder having an appropriate glass transition temperature.
- the present invention is intended to provide a semiconductor device having increased efficiency and good durability while reducing a line width.
- An aspect of the present invention provides a conductive paste composition, comprising: a conductive powder; a metal oxide powder including a first metal oxide powder having a first glass transition temperature of a°C and a second metal oxide powder having a second glass transition temperature of b°C; an organic medium; and an additive.
- the first glass transition temperature of the first metal oxide powder may be 170 ⁇ a ⁇ 310
- the second glass transition temperature of the second metal oxide powder may be 230 ⁇ b ⁇ 320
- a and b may satisfy 10 ⁇ b-a ⁇ 60.
- the first metal oxide powder may be used in an amount of 80 ⁇ 90 wt%
- the second metal oxide powder may be used in an amount of 0.5 ⁇ 20 wt%, based on the total weight of the metal oxide powder.
- the first metal oxide powder may include 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 may include 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.
- the conductive powder may comprise a first metal powder having an average diameter of 1 ⁇ 3 ⁇ m, and a metal nanopowder agglomerate having an average diameter of 0.5 ⁇ 10 ⁇ m obtained by agglomerating a metal nanopowder having an average diameter of 100 ⁇ 200 nm.
- the additive may be used in an amount of 1 ⁇ 5 parts by weight based on 100 parts by weight of the conductive powder, and may comprise Te-X-O, Te-Y or Te-Y-Z.
- X may be at least one metal selected from the group consisting of alkali metals and alkaline earth metals
- Y and Z are at least one metal selected from the group consisting of Zn, Ag, Na, Mg and Al, provided that Y and Z may not be the same.
- the conductive paste composition according to the present invention may comprise, based on the total weight thereof, 70 ⁇ 90 wt% of the conductive powder, 0.7 ⁇ 9 wt% of the metal oxide powder, 3.5 ⁇ 18 wt% of the organic medium, and 0.7 ⁇ 4.5 wt% of the inorganic additive.
- a silicon solar cell comprising: a silicon semiconductor substrate; an emitter layer formed on the substrate; an anti-reflective film formed on the emitter layer; a front electrode connected to the emitter layer through the anti-reflective film; and a rear electrode connected to a rear side of the substrate, wherein the front electrode is formed by applying the conductive paste composition as above in a predetermined pattern on the anti-reflective film and then performing firing.
- a conductive paste composition includes a metal oxide powder comprising two or more kinds of powder having different glass transition temperatures, thus enhancing electrical conductivity and printability.
- the conductive paste composition includes metal oxides having glass transition temperatures different by 10 ⁇ 60°C from each other, so that the firing temperature range can become wide.
- an electronic device can be enhanced in printability and durability of an electrode or wiring formed with the conductive paste composition, thus increasing efficiency of a semiconductor device.
- FIG. 1 is an electron microscope image illustrating a conductive powder having projections with a size of 0.4 ⁇ 0.6 ⁇ m according to an embodiment of the present invention
- FIG. 2 is an electron microscope image illustrating a conductive powder having projections with a size of 0.1 ⁇ 0.2 ⁇ m according to an embodiment of the present invention
- FIG. 3 is an electron microscope image (MAG 2.50kx) illustrating a metal nanopowder agglomerate according to an embodiment of the present invention.
- FIG. 4 is an electron microscope image (MAG 40.0kx) illustrating a metal nanopowder agglomerate according to an embodiment of the present invention.
- a conductive paste composition comprises a conductive powder, a metal oxide powder, an organic medium and an additive.
- a conductive powder may include any organic or inorganic material having electric conductivity.
- a metal powder used as the conductive powder may include 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) and ITO (Indium tin oxide), which may be used alone or in combination of two or more.
- the conductive powder may be a metal powder comprising Ag.
- the metal powder (first metal powder) used as the conductive powder has an average diameter (D50) of 0.1 ⁇ 10 ⁇ m, preferably 0.5 ⁇ 5 ⁇ m, and more preferably 1 ⁇ 3 ⁇ m.
- average diameter (D50) refers to a powder diameter at 50% in the cumulative powder diameter distribution.
- the shape of the metal powder is not limited, a spherical powder having projections on the outer surface thereof is preferable.
- the powder may function to improve sintering properties based on a principle of an increase in the specific surface area.
- the average diameter is a size including projections, and the projections mean that the highest point of the projections is higher by 0.1 ⁇ 0.6 ⁇ m than a portion having no projection without limitation of shape or size so long as they enable the outer surface of the powder to be irregular.
- the conductive powder may further include a metal nanopowder agglomerate.
- the metal nanopowder agglomerate is obtained by agglomerating a metal nanopowder having an average diameter (D50) of 100 ⁇ 200 nm, and the average diameter (D50) of the metal nanopowder agglomerate is preferably 0.5 ⁇ 10 ⁇ m.
- the metal nanopowder having an average diameter of 100 ⁇ 200 nm plays a role in enhancing adhesion between the substrate and the electrode, it may increase line resistance due to sintering shrinkage of the electrode and may cause physical defects such as cracking after firing to thus decrease the sintering density, undesirably resulting in poor long-term reliability.
- the metal nanopowder agglomerate may be used in an amount of 0.1 ⁇ 10 parts by weight based on 100 parts by weight of the first metal powder.
- the conductive powder may further include a second metal powder having an average diameter (D50) of 0.5 ⁇ 1 ⁇ m.
- the average diameter of the second metal powder is smaller than that of the first metal powder.
- the use of the second metal powder is considered to improve a function of reducing line resistance based on a principle of an increase in the packing density.
- the second metal powder may be contained in an amount of 10 ⁇ 40 parts by weight based on 100 parts by weight of the first metal powder.
- a metal such as Cu, Ag, Au, Ni, Al, W or Zn may be used.
- a metal such as Cu, Ag, Au, Ni, Al, W or Zn may be used.
- Ag is preferably useful.
- the specific surface area of the conductive powder may be 0.05 ⁇ 5 m 2 /g. If the specific surface area thereof is less than 0.05 m 2 /g, it is impossible to form a fine line (70 ⁇ m or less) due to the large particle size. In contrast, if the specific surface area thereof exceeds 5 m 2 /g, poor workability such as a need for a large amount of solvent to adjust viscosity may result.
- the amount of the conductive powder is not particularly limited so long as it may achieve the purpose of the present invention.
- the conductive powder is used in an amount of 70 ⁇ 90 wt% based on the total weight of the conductive paste composition. If the amount of the conductive powder exceeds 90 wt%, viscosity may increase, making it difficult to form a composition in a paste phase. In contrast, if the amount thereof is less than 70 wt%, the amount of the conductive powder may be lowered, and thus electrical conductivity of the resulting front electrode and the aspect ratio of the printed pattern may decrease.
- a metal oxide powder is an X1-X2-...-Xn-O oxide powder, wherein Xn is selected from the group consisting of 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 and Nb, and n is an integer of 2 or more.
- X1-X2-...-Xn-O may be at least partially crystalline.
- the metal oxide powder has a desired powder size by mixing X1, X2, ..., and Xn oxides, followed by melting, cooling, grinding and screening.
- the average particle size (D50) of the metal oxide powder may be 0.1 ⁇ 3.0 ⁇ m.
- the metal oxide powder preferably has a melting temperature of 250 ⁇ 900°C.
- the metal oxide powder has a softening temperature of 200 ⁇ 550°C so that the conductive paste may be sintered at 600 ⁇ 950°C, appropriately wet or properly adhered to the substrate. If the softening temperature is lower than 200°C, sintering may proceed, making it impossible to sufficiently obtain the effects of the invention. In contrast, if the softening temperature is higher than 550°C, sufficient melt fluidity is not caused during firing, and thus desired adhesive strength cannot be exhibited. In some cases, liquid sintering of Ag cannot be promoted. As such, "softening temperature” refers to a softening temperature based on a fiber elongation method according to ASTM C338-57.
- the chemical composition of the metal oxide powder is not limited in the present invention, and a typical material may be used.
- the metal oxide powder may comprise a single kind of metal oxide powder, or two or more kinds of metal oxide powder having different glass transition temperatures.
- Xn may include at least two metals selected from the group consisting of Pb, Te, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P and Mn.
- the metal oxide powder essentially contains Pb, Te and Bi.
- Pb calculated in terms of oxide, PbO
- the amount of Pb is a wt% based on the total weight of the metal oxide powder, it preferably falls in the range of 0.1 ⁇ a ⁇ 20, and more preferably 1 ⁇ a ⁇ 15. Given the amount range, pn bonding reliability may be ensured under various sheet resistance values and solar cell efficiency may increase.
- the amount of Te (calculated in terms of oxide, TeO 2 ) is b wt% based on the total weight of the metal oxide powder, it preferably falls in the range of 50 ⁇ b ⁇ 80 and more preferably 60 ⁇ b ⁇ 75. If the amount of TeO 2 is less than 50 wt%, Ag solidity by TeO 2 may decrease and thus contact resistance may increase. In contrast, if the amount of TeO 2 exceeds 80 wt%, reactivity with the Si interface may become weak due to excessive addition of TeO 2 , and thus contact resistance may increase.
- a, b and c preferably satisfy both of [Relation 1] and [Relation 2] below.
- the metal oxide powder may further include Zn.
- Zn When the amount of Zn in the metal oxide powder is d wt%, it may satisfy [Relation 3] below.
- An example of the metal oxide powder may be Pb-Te-Bi-Si-B-Zn-Al-O.
- the amounts of respective metals are set in terms of oxides, including 0.5 ⁇ 15 wt% of PbO, 50 ⁇ 75 wt% of TeO 2 , 10 ⁇ 20 wt% of Bi 2 O 3 , 0.1 ⁇ 10 wt% of SiO 2 , 0.1 ⁇ 10 wt% of B 2 O 3 , 1 ⁇ 8 wt% of ZnO and 0.1 ⁇ 3 wt% of Al 2 O 3 .
- the metal oxide powder may be Pb-Te-W-Mo-Zn-Bi-Al-O.
- the amounts of respective metals are set in terms of oxides, including 0.5 ⁇ 15 wt% of PbO, 60 ⁇ 75 wt% of TeO 2 , 0.5 ⁇ 15 wt% of ZnO, 10 ⁇ 20 wt% of Bi 2 O 3 and 0.1 ⁇ 12 wt% of Al 2 O 3 .
- the sum of WO 3 and MoO 3 is 5 ⁇ 30 wt%.
- the metal oxide powder when two kinds of metal oxide powder are used, the metal oxide powder may include both of a first metal oxide powder having a first glass transition temperature of a°C and a second metal oxide powder having a second glass transition temperature of b°C.
- the first metal oxide powder preferably has a first glass transition temperature of 170 ⁇ a ⁇ 310
- the second metal oxide powder may have a second glass transition temperature of 230 ⁇ b ⁇ 320.
- a difference between the second glass transition temperature b of the second metal oxide powder and the first glass transition temperature a of the first metal oxide powder may satisfy 10 ⁇ b-a ⁇ 60. If the temperature difference is less than 10°C, an effect of widening the firing temperature range may become insignificant. In contrast, if the temperature difference exceeds 60°C, either the first or the second metal oxide powder cannot function as the metal oxide powder during the firing.
- the first metal oxide powder preferably contains 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 contains 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.
- the amount of the first metal oxide powder may be set to 80 ⁇ 90 wt%, and the amount of the second metal oxide powder may be set to 0.5 ⁇ 20 wt%.
- the amount of the metal oxide powder is not particularly limited so long as the purposes of the present invention are achieved, it may be set to 1 ⁇ 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, adhesive strength may become poor. In contrast, if the amount thereof exceeds 10 parts by weight, it is difficult to perform the subsequent soldering process attributed to glass floating or the like.
- organic medium refers to incorporation of a binder and a solvent, wherein a binder may include a solvent.
- a viscosity modifier may be further added as the additive, as necessary.
- examples of the binder may include, but are not limited to, cellulose derivatives, such as methyl cellulose, ethyl cellulose or ethyl hydroxyethyl cellulose, wood rosin, ethyl cellulose-phenol resin mixture, polymethacrylate of lower alcohol and monobutyl ether of ethyleneglycol monoacetate, acrylic resin, alkyd resin, polypropylene-based resin, polyvinylchloride-based resin, polyurethane-based resin, rosin-based resin, terpene-based resin, phenol-based resin, aliphatic petroleum resin, acrylic acid ester-based resin, xylene-based resin, Coumarone-Indene-based resin, styrene-based resin, dicyclopentadiene-based resin, polybutene-based resin, polyether-based resin, urea-based resin, melamine-based resin, vinylacetate-based resin, and polyisobutyl-based resin.
- cellulose derivatives such
- the solvent may include, but are not limited to, hexane, toluene, ester alcohol, terpene such as ⁇ - or ⁇ -terpineol, kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, benzyl alcohol, alcohol ester, diethyleneglycol diethylether, diacetonealcohol terpineol methylethylketone, ethylcellosove, cyclohexanone, butylcellosolve, and butylcellosolve acetate.
- any one or a mixture of two or more selected from the group consisting of bis(2-(2-butoxyethoxy)ethyl)adipate, dibasic ester, octyl epoxytallate, isotetradecanol and pentaerythritol ester of hydrogenated rosin may be used instead of or together with the solvent as above.
- dibasic ester may include any one or a mixture of two or more selected from the group consisting of dimethylester of adipic acid, dimethylester of glutaric acid, and dimethylester of succinic acid.
- the amount of the organic medium may be 5 ⁇ 20 parts by weight based on 100 parts by weight of the conductive powder. If the amount of the organic medium exceeds 20 parts by weight, the resulting front electrode may have lowered electrical conductivity. In contrast, if the amount of the organic medium is less than 5 parts by weight, bondability with the substrate may deteriorate.
- the conductive paste according to an embodiment of the present invention may include inorganic and organic additives.
- An inorganic additive may include any metal selected from the group consisting of Li, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Pb, Cu, Zn, Ag, Te, Zn, Na, Mg, Al, W and Fe, metal oxides, and alloys or alloy oxides thereof. Examples thereof may include PbO, CuO, ZnO, MgO and WO 3 .
- the inorganic additive may include a metal alloy or metal alloy oxide, containing Te, and preferable examples thereof include Te-X-O, Te-Y and Te-Y-Z, wherein X is at least one metal selected from the group consisting of 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 and Al, provided that Y and Z are not the same metal.
- Te-X-O is exemplified by Li 2 TeO 3 , Na 2 TeO 3 , SrTeO 3 , BeTeO 3 or MgTeO 3 , and Te-Y or Te-Y-Z may be Ag-Te, Li-Te-Zn, Te-Zn-K, or Te-Zn-Na.
- the inorganic additive according to the present invention includes a metal able to promote a solid-phase reaction via reaction with the metal contained in the conductive powder, and thus may accelerate grain growth of the metal powder, which is the conductive powder, even at low temperature. Thereby, the firing temperature range of the paste composition may become wide, thus increasing electrical conductivity.
- the particle size of the additive according to the present invention is not particularly limited.
- the average particle size may be smaller than 10 ⁇ m.
- the average particle size is 0.01 ⁇ 5 ⁇ m, and is more preferably 50 ⁇ 200 nm.
- the amount of the inorganic additive is 1 ⁇ 10 parts by weight, and preferably 1 ⁇ 5 parts by weight, based on 100 parts by weight of the conductive powder. If the amount of the inorganic additive exceeds 5 parts by weight based on 100 parts by weight of the conductive powder, the amount of the conductive powder may decrease and thus the resistance of the front electrode formed of the corresponding paste composition may increase, thereby deteriorating solar cell efficiency. In contrast, if the amount of the inorganic additive is less than 1 part by weight based on 100 parts by weight of the conductive powder, it is difficult to sufficiently exhibit the effects by the additive.
- the organic additive may include, but is not limited, to a dispersant, an antioxidant, a UV absorber, a defoaming agent, a thickener, a stabilizer, and a viscosity modifier, which may be used alone or in combination of two or more and may be mixed within a range that does not impair the effects of the present invention.
- the dispersant such as stearic acid, palmitic acid, myristic acid, oleic acid or lauric acid, may be mixed with the conductive paste.
- the dispersant is not limited to organic acid so long as it is typically useful.
- the conductive paste is prepared by mixing a conductive powder, a metal oxide powder, an organic medium, and an additive using a 3-roll kneader.
- the conductive paste according to the present invention is preferably applied on a desired portion of an electronic device via screen printing. When it is applied using such a printing process, it may have a predetermined viscosity.
- the viscosity of the conductive paste according to the present invention may be 50 ⁇ 300 PaS as measured using #14 spindle with a Brookfield HBT viscometer and using a utility cup at 10 rpm and 25°C.
- the conductive paste according to the present invention is applied via screen printing on a substrate of a semiconductor device to be manufactured, and then dried.
- the substrate coated with the conductive paste is fired at about 700 ⁇ 950°C, thus forming a conductive paste pattern.
- a conductive powder was prepared by mixing a first Ag powder having an average diameter of 2 ⁇ m with an Ag nanopowder having an average diameter of 200 nm.
- a metal oxide powder was composed of 6.5 g of MO3 having an average diameter of 2 ⁇ m (based on the total weight of the metal oxide powder, 4.1 wt% of PbO, 72.6 wt% of TeO 2 , 15.9 wt% of Bi 2 O 3 , 0.7 wt% of B 2 O 3 , 4.8 wt% of ZnO, 0.5 wt% of Cr 2 O 3 , 0.4 wt% of MnO 2 , 0.7 wt% of CuO 2 , and 0.3 wt% of Li 2 O).
- a conductive paste composition was prepared by mixing, based on 100 g of the paste composition, 70.0 g of the first Ag powder, 11.0 g of the Ag nanopowder, 6.5 g of the metal oxide powder, 10.2 g of a terpineol solution containing 20 wt% of ethylcellulose as an organic solvent, and 2.3 g of an inorganic additive ZnO.
- Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the kind of metal oxide was changed as shown in Table 1 below.
- Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the conductive powder and the kind of metal oxide powder were changed as shown in Table 1 below.
- Conductive paste compositions were prepared in the same manner as in Examples 4 to 6, with the exception that the kind of inorganic additive was changed as shown in Table 1 below.
- Conductive paste compositions were prepared in the same manner as in Example 10, with the exception that the kinds of inorganic additive and metal oxide powder were changed as shown in Table 1 below.
- Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the kind of metal oxide powder was changed as shown in Table 1 below.
- Conductive paste compositions were prepared in the same manner as in Example 4, with the exception that the kind of metal oxide powder was changed as shown in Table 1 below.
- the conductive paste compositions of the above examples and comparative examples were pre-mixed using a universal mixer, and kneaded using a 3-roll kneader, thus obtaining individual conductive pastes.
- the amounts (g) of materials used and the features thereof are shown in Table 1 below.
- the composition proportions (wt%) of the metal oxide powders MO1 ⁇ MO6 are shown in Table 2 below, and the composition proportions of MO7 ⁇ MO10 are shown in Table 3 below.
- a solar cell was manufactured using the conductive paste of each of Examples 1 to 12 and Comparative Examples 1 to 5. Specifically, a silicon substrate was prepared, and a conductive paste (Ag paste) for solder connection was applied on the rear side thereof using screen printing and then dried. Subsequently, an Al paste (PV333 made by E.I. du Pont de Nemours and Company) for a rear electrode was applied via screen printing so as to partially overlap the dried Ag paste, and then dried.
- a conductive paste Al paste for solder connection
- each paste was set to 120°C.
- the film thickness of each electrode of the rear side which is a dried film thickness
- the Al paste and the Ag paste were applied to 35 ⁇ m and 20 ⁇ m, respectively.
- the paste of the invention was applied on a light-receiving side (front side) via screen printing and then dried.
- a 1.5 inch pattern for evaluation comprising a finger line having a width of 100 ⁇ m and a bus bar having a width of 2 mm was employed, and the film thickness was 13 ⁇ m after firing.
- the paste applied on the substrate was co-fired in an IR firing furnace under conditions of a peak temperature of about 730°C and an IN-OUT time of about 5 min, thus obtaining a desired solar cell.
- the solar cell obtained using the conductive paste according to the present invention was configured such that the Ag electrode was formed on the light-receiving side (front side) and the Al electrode (first electrode) composed mainly of Al and the Ag electrode (second electrode) composed mainly of Ag were formed on the rear side.
- the electric properties (I-V properties) of the obtained solar cell substrate were evaluated by a cell tester. Using a system (NCT-M-150AA) made by NPC as a cell tester, Eff (Conversion Efficiency) (%) and FF (Fill Factor) were measured. The results are shown in Table 4 below.
- the adhesion of the obtained solar cell was measured as follows. Specifically, the surface of the front electrode formed using an electrode forming process was heated to 200°C and a SnPbAg-based solder ribbon (line width: 2 mm, indium corporation, SUNTABTM) was attached to a length of 10 cm thereto. Then, while one end of the attached portion was pulled in a 180° direction with a universal tensile tester (QC-508E, COMETECH), a force (N, newton) until the electrode and the solder ribbon were peeled from each other was measured.
- the evaluation results based on the following criteria are shown in adhesion (N) in Table 4 below.
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Abstract
Disclosed is a conductive paste composition, including: a conductive powder; a metal oxide powder including a first metal oxide powder having a first glass transition temperature of a℃ and a second metal oxide powder having a second glass transition temperature of b℃; and an organic medium.
Description
The present invention relates to a conductive paste composition, and more particularly, to a conductive paste composition for forming a thin film pattern such as an electrode or wiring to connect electrical signals of semiconductor devices. In addition, the present invention relates to a semiconductor device, especially, a solar cell, having an electrode or wiring formed of the conductive paste composition.
A conductive paste (or ink) is applied on a substrate to form a pattern for transferring an electrical signal. A conductive paste typically includes a conductive powder, a glass frit, and an organic medium. In order to form a pattern for transferring an electrical signal on a substrate, a conductive paste is printed in the form of a linear pattern or other patterns on a substrate and then fired.
Requirements of a conductive paste include printability, adhesiveness and electrical conductivity. Specifically, a conductive paste should be printed in a pattern having a desired line width via a desired printing process, and also, enables the resulting electrode to be attached onto a substrate while possessing durability, so as to exhibit high adhesion and low resistance. For desired printability, research has to be ongoing into compositions adapted for fine line widths and properties for printing processes corresponding thereto. To this end, the size of a conductive powder or the properties of an organic medium is regarded as important. For desired adhesiveness, research has to be carried out into stably attaching the conductive paste composition to a substrate for a long period of time. To this end, the composition of a glass frit is regarded as important. Also, electrical conductivity requires studies for ohmic contact and line resistance due to a reduction in line width. To this end, the composition of a conductive powder and a frit is regarded as important.
Meanwhile, a conductive paste composition has to be individually characterized with regard to printability, adhesiveness and electrical conductivity depending on the end use. For example, when it is used for an electrode for a crystalline silicon solar cell, an anti-reflective film made of silicon nitride, titanium oxide or silicon oxide is formed on a semiconductor substrate to promote absorption of solar light and may thus may function as an insulator, undesirably damaging the flow of electrons to the substrate (or from the substrate). Hence, a conductive paste for heat generation should infiltrate the anti-reflective film during firing in order to achieve efficient electrical contact with the substrate, and also should be specifically characterized so as to form strong bonding to the substrate. Furthermore, a conductive paste for use in a flexible substrate should be developed to have a composition able to maintain adhesiveness despite flexibility of the substrate.
As such, a conductive powder, a glass frit and an organic medium, which are technical elements for use in ensuring printability, adhesiveness and electrical conductivity of the conductive paste composition, have antagonistic influences on each other, and thus development of balanced technology for individual technical elements is required.
Since the conversion efficiency of a solar cell is obtained by multiplying open voltage, short current density and fill factor (FF), it may be lowered in proportion to a decrease in FF. However, the characteristics of electrodes are considered important to increase power generation in solar cells. For instance, as the resistance value of the electrode is lower, the power generation efficiency may increase. In this regard, Cited reference 1 (Korean Patent Application Publication No. 2005-243500) discloses a conductive paste including an organic binder, a solvent, a glass frit, a conductive powder and at least one metal selected from the group consisting of Ti, Bi, Zn, Y, In and Mo or a metal compound thereof, wherein the average particle size of metal or metal compound is 0.001 to less than 0.1 μm. In Cited reference 1, the conductive paste including ultrafine metal or a metal compound is fired, thereby forming a front electrode having stability, high electrical conductivity and superior adhesion between the conductive paste and the semiconductor through the anti-reflective layer. However, when the composition of the conductive paste including the ultrafine metal or the metal compound as disclosed in Cited reference 1 is printed, dried and then fired on the surface of the semiconductor substrate, the coating film (paste film) may shrink, thus increasing contact resistance. In some cases, due to a difference in thermal shrinkage behavior (coefficient of linear expansion) between the paste film and the semiconductor substrate, microcracks may be created on the surface of the semiconductor substrate. Moreover, an increase in the contact resistance may undesirably result in lowered FF and thus deteriorated conversion efficiency.
Accordingly, the present invention is intended to provide a conductive paste composition having enhanced printability and electrical conductivity by improving a conductive powder.
In addition, the present invention is intended to provide a conductive paste composition having a wide firing temperature range by use of a metal oxide powder having an appropriate glass transition temperature.
In addition, the present invention is intended to provide a semiconductor device having increased efficiency and good durability while reducing a line width.
An aspect of the present invention provides a conductive paste composition, comprising: a conductive powder; a metal oxide powder including a first metal oxide powder having a first glass transition temperature of a℃ and a second metal oxide powder having a second glass transition temperature of b℃; an organic medium; and an additive. The first glass transition temperature of the first metal oxide powder may be 170≤a≤310, and the second glass transition temperature of the second metal oxide powder may be 230≤b≤320, and a and b may satisfy 10≤b-a≤60.
In the metal oxide powder according to the present invention, the first metal oxide powder may be used in an amount of 80 ~ 90 wt%, and the second metal oxide powder may be used in an amount of 0.5 ~ 20 wt%, based on the total weight of the metal oxide powder.
In the metal oxide powder according to the present invention, the first metal oxide powder may include Te, and may further include at least one metal selected from the group consisting of Bi, Zn, B, Al, Ba, Si, W and Fe. Also, the second metal oxide powder may include 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.
In the conductive paste composition according to the present invention, the conductive powder may comprise a first metal powder having an average diameter of 1 ~ 3 μm, and a metal nanopowder agglomerate having an average diameter of 0.5 ~ 10 μm obtained by agglomerating a metal nanopowder having an average diameter of 100 ~ 200 nm.
In the conductive paste composition according to the present invention, the additive may be used in an amount of 1 ~ 5 parts by weight based on 100 parts by weight of the conductive powder, and may comprise Te-X-O, Te-Y or Te-Y-Z. As such, X may be at least one metal selected from the group consisting of alkali metals and alkaline earth metals, and Y and Z are at least one metal selected from the group consisting of Zn, Ag, Na, Mg and Al, provided that Y and Z may not be the same.
The conductive paste composition according to the present invention may comprise, based on the total weight thereof, 70 ~ 90 wt% of the conductive powder, 0.7 ~ 9 wt% of the metal oxide powder, 3.5 ~ 18 wt% of the organic medium, and 0.7 ~ 4.5 wt% of the inorganic additive.
Another aspect of the present invention provides a silicon solar cell, comprising: a silicon semiconductor substrate; an emitter layer formed on the substrate; an anti-reflective film formed on the emitter layer; a front electrode connected to the emitter layer through the anti-reflective film; and a rear electrode connected to a rear side of the substrate, wherein the front electrode is formed by applying the conductive paste composition as above in a predetermined pattern on the anti-reflective film and then performing firing.
According to the present invention, a conductive paste composition includes a metal oxide powder comprising two or more kinds of powder having different glass transition temperatures, thus enhancing electrical conductivity and printability.
Also, the conductive paste composition includes metal oxides having glass transition temperatures different by 10 ~ 60℃ from each other, so that the firing temperature range can become wide.
According to the present invention, an electronic device can be enhanced in printability and durability of an electrode or wiring formed with the conductive paste composition, thus increasing efficiency of a semiconductor device.
The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is an electron microscope image illustrating a conductive powder having projections with a size of 0.4 ~ 0.6 μm according to an embodiment of the present invention;
FIG. 2 is an electron microscope image illustrating a conductive powder having projections with a size of 0.1 ~ 0.2 μm according to an embodiment of the present invention;
FIG. 3 is an electron microscope image (MAG 2.50kx) illustrating a metal nanopowder agglomerate according to an embodiment of the present invention; and
FIG. 4 is an electron microscope image (MAG 40.0kx) illustrating a metal nanopowder agglomerate according to an embodiment of the present invention.
In the following description of the present invention, the terms used herein are merely intended to describe specific embodiments and are not construed as limiting the scope of the present invention by the appended claims. Unless otherwise defined, all of technical or scientific terms used herein have the same meanings as those typically understood by persons having ordinary knowledge in the art to which the present invention belongs.
Unless otherwise stated, the terms "comprise", "comprises" and "comprising" are used to designate the presence of an object, a step or groups of objects and steps described in the specification and claims, and should be understood so as not to exclude presence or additional probability of any other objects, steps or groups of objects or steps.
Unless otherwise noted, various embodiments of the present invention may be combined with any other embodiments. In particular, any feature which is mentioned preferably or favorably may be combined with any other features which may be mentioned preferably or favorably.
Conductive paste composition
According to an embodiment of the present invention, a conductive paste composition comprises a conductive powder, a metal oxide powder, an organic medium and an additive.
1. Conductive powder
Useful in the present invention, a conductive powder may include any organic or inorganic material having electric conductivity. Specific examples of a metal powder used as the conductive powder may include 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) and ITO (Indium tin oxide), which may be used alone or in combination of two or more. Particularly, the conductive powder may be a metal powder comprising Ag.
The metal powder (first metal powder) used as the conductive powder has an average diameter (D50) of 0.1 ~ 10 μm, preferably 0.5 ~ 5 μm, and more preferably 1 ~ 3 μm. As used herein, "average diameter (D50)" refers to a powder diameter at 50% in the cumulative powder diameter distribution.
Although the shape of the metal powder is not limited, a spherical powder having projections on the outer surface thereof is preferable. When the powder has projections on the outer surface thereof, it may function to improve sintering properties based on a principle of an increase in the specific surface area. As such, the average diameter is a size including projections, and the projections mean that the highest point of the projections is higher by 0.1 ~ 0.6 μm than a portion having no projection without limitation of shape or size so long as they enable the outer surface of the powder to be irregular.
In an embodiment of the present invention, the conductive powder may further include a metal nanopowder agglomerate. The metal nanopowder agglomerate is obtained by agglomerating a metal nanopowder having an average diameter (D50) of 100 ~ 200 nm, and the average diameter (D50) of the metal nanopowder agglomerate is preferably 0.5 ~ 10 μm. Although the metal nanopowder having an average diameter of 100 ~ 200 nm plays a role in enhancing adhesion between the substrate and the electrode, it may increase line resistance due to sintering shrinkage of the electrode and may cause physical defects such as cracking after firing to thus decrease the sintering density, undesirably resulting in poor long-term reliability. However, when the metal nanopowder is made into an agglomerate, such an agglomerate is effective at increasing sintering density and ensuring long-term reliability without cracking. The metal nanopowder agglomerate may be used in an amount of 0.1 ~ 10 parts by weight based on 100 parts by weight of the first metal powder.
In an embodiment of the present invention, the conductive powder may further include a second metal powder having an average diameter (D50) of 0.5 ~ 1 μm. The average diameter of the second metal powder is smaller than that of the first metal powder. The use of the second metal powder is considered to improve a function of reducing line resistance based on a principle of an increase in the packing density.
The second metal powder may be contained in an amount of 10 ~ 40 parts by weight based on 100 parts by weight of the first metal powder.
For the metal powder or metal nanopowder, a metal such as Cu, Ag, Au, Ni, Al, W or Zn may be used. Preferably useful is Ag.
The specific surface area of the conductive powder may be 0.05 ~ 5 m2/g. If the specific surface area thereof is less than 0.05 m2/g, it is impossible to form a fine line (70 μm or less) due to the large particle size. In contrast, if the specific surface area thereof exceeds 5 m2/g, poor workability such as a need for a large amount of solvent to adjust viscosity may result.
The amount of the conductive powder is not particularly limited so long as it may achieve the purpose of the present invention. Preferably, the conductive powder is used in an amount of 70 ~ 90 wt% based on the total weight of the conductive paste composition. If the amount of the conductive powder exceeds 90 wt%, viscosity may increase, making it difficult to form a composition in a paste phase. In contrast, if the amount thereof is less than 70 wt%, the amount of the conductive powder may be lowered, and thus electrical conductivity of the resulting front electrode and the aspect ratio of the printed pattern may decrease.
2. Metal oxide powder (X1-X2-…-
Xn
-O powder)
A metal oxide powder is an X1-X2-…-Xn-O oxide powder, wherein Xn is selected from the group consisting of 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 and Nb, and n is an integer of 2 or more. In the metal oxide powder, X1-X2-…-Xn-O may be at least partially crystalline.
The metal oxide powder has a desired powder size by mixing X1, X2, …, and Xn oxides, followed by melting, cooling, grinding and screening.
The average particle size (D50) of the metal oxide powder may be 0.1 ~ 3.0 μm. As such, the metal oxide powder preferably has a melting temperature of 250 ~ 900℃.
In the present invention, the metal oxide powder has a softening temperature of 200 ~ 550℃ so that the conductive paste may be sintered at 600 ~ 950℃, appropriately wet or properly adhered to the substrate. If the softening temperature is lower than 200℃, sintering may proceed, making it impossible to sufficiently obtain the effects of the invention. In contrast, if the softening temperature is higher than 550℃, sufficient melt fluidity is not caused during firing, and thus desired adhesive strength cannot be exhibited. In some cases, liquid sintering of Ag cannot be promoted. As such, "softening temperature" refers to a softening temperature based on a fiber elongation method according to ASTM C338-57.
The chemical composition of the metal oxide powder is not limited in the present invention, and a typical material may be used. The metal oxide powder may comprise a single kind of metal oxide powder, or two or more kinds of metal oxide powder having different glass transition temperatures.
When a single kind of metal oxide powder is used, Xn may include at least two metals selected from the group consisting of Pb, Te, W, Mo, Zn, Al, Bi, Si, B, Fe, Co, Cr, Cu, Ni, V, Li, P and Mn. In the present invention, the metal oxide powder essentially contains Pb, Te and Bi. When the amount of Pb (calculated in terms of oxide, PbO) is a wt% based on the total weight of the metal oxide powder, it preferably falls in the range of 0.1≤a≤20, and more preferably 1≤a≤15. Given the amount range, pn bonding reliability may be ensured under various sheet resistance values and solar cell efficiency may increase. Also, when the amount of Te (calculated in terms of oxide, TeO2) is b wt% based on the total weight of the metal oxide powder, it preferably falls in the range of 50≤b≤80 and more preferably 60≤b≤75. If the amount of TeO2 is less than 50 wt%, Ag solidity by TeO2 may decrease and thus contact resistance may increase. In contrast, if the amount of TeO2 exceeds 80 wt%, reactivity with the Si interface may become weak due to excessive addition of TeO2, and thus contact resistance may increase.
In the metal oxide powder essentially containing Pb, Te and Bi according to the present invention, when the amounts of Pb, Te and Bi are a wt%, b wt% and c wt%, respectively, a, b and c preferably satisfy both of [Relation 1] and [Relation 2] below.
[Relation 1]
70≤a+b+c≤90 (1≤a≤15, 60≤b≤75)
[Relation 2]
2.5≤b/c≤7.5 (60≤b≤75)
The metal oxide powder may further include Zn. When the amount of Zn in the metal oxide powder is d wt%, it may satisfy [Relation 3] below.
[Relation 3]
0.5≤d/a≤3.5 (1≤a≤15)
An example of the metal oxide powder may be Pb-Te-Bi-Si-B-Zn-Al-O. As such, the amounts of respective metals are set in terms of oxides, including 0.5 ~ 15 wt% of PbO, 50 ~ 75 wt% of TeO2, 10 ~ 20 wt% of Bi2O3, 0.1 ~ 10 wt% of SiO2, 0.1 ~ 10 wt% of B2O3, 1 ~ 8 wt% of ZnO and 0.1 ~ 3 wt% of Al2O3.
Another example of the metal oxide powder may be Pb-Te-W-Mo-Zn-Bi-Al-O. As such, the amounts of respective metals are set in terms of oxides, including 0.5 ~ 15 wt% of PbO, 60 ~ 75 wt% of TeO2, 0.5 ~ 15 wt% of ZnO, 10 ~ 20 wt% of Bi2O3 and 0.1 ~ 12 wt% of Al2O3. The sum of WO3 and MoO3 is 5 ~ 30 wt%.
In the present invention, when two kinds of metal oxide powder are used, the metal oxide powder may include both of a first metal oxide powder having a first glass transition temperature of a℃ and a second metal oxide powder having a second glass transition temperature of b℃. The first metal oxide powder preferably has a first glass transition temperature of 170≤a≤310, and the second metal oxide powder may have a second glass transition temperature of 230≤b≤320. A difference between the second glass transition temperature b of the second metal oxide powder and the first glass transition temperature a of the first metal oxide powder may satisfy 10≤b-a≤60. If the temperature difference is less than 10℃, an effect of widening the firing temperature range may become insignificant. In contrast, if the temperature difference exceeds 60℃, either the first or the second metal oxide powder cannot function as the metal oxide powder during the firing.
The first metal oxide powder preferably contains 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 contains 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.
Based on the total weight of the metal oxide powder, the amount of the first metal oxide powder may be set to 80 ~ 90 wt%, and the amount of the second metal oxide powder may be set to 0.5 ~ 20 wt%.
Although the amount of the metal oxide powder is not particularly limited so long as the purposes of the present invention are achieved, it may be set to 1 ~ 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, adhesive strength may become poor. In contrast, if the amount thereof exceeds 10 parts by weight, it is difficult to perform the subsequent soldering process attributed to glass floating or the like.
3. Organic medium
As used herein, "organic medium" refers to incorporation of a binder and a solvent, wherein a binder may include a solvent. In the present invention, when the organic medium is very viscous, a viscosity modifier may be further added as the additive, as necessary.
In the present invention, examples of the binder may include, but are not limited to, cellulose derivatives, such as methyl cellulose, ethyl cellulose or ethyl hydroxyethyl cellulose, wood rosin, ethyl cellulose-phenol resin mixture, polymethacrylate of lower alcohol and monobutyl ether of ethyleneglycol monoacetate, acrylic resin, alkyd resin, polypropylene-based resin, polyvinylchloride-based resin, polyurethane-based resin, rosin-based resin, terpene-based resin, phenol-based resin, aliphatic petroleum resin, acrylic acid ester-based resin, xylene-based resin, Coumarone-Indene-based resin, styrene-based resin, dicyclopentadiene-based resin, polybutene-based resin, polyether-based resin, urea-based resin, melamine-based resin, vinylacetate-based resin, and polyisobutyl-based resin.
Examples of the solvent may include, but are not limited to, hexane, toluene, ester alcohol, terpene such as α- or β-terpineol, kerosene, dibutyl phthalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, benzyl alcohol, alcohol ester, diethyleneglycol diethylether, diacetonealcohol terpineol methylethylketone, ethylcellosove, cyclohexanone, butylcellosolve, and butylcellosolve acetate.
In particular, any one or a mixture of two or more selected from the group consisting of bis(2-(2-butoxyethoxy)ethyl)adipate, dibasic ester, octyl epoxytallate, isotetradecanol and pentaerythritol ester of hydrogenated rosin may be used instead of or together with the solvent as above. Herein, dibasic ester may include any one or a mixture of two or more selected from the group consisting of dimethylester of adipic acid, dimethylester of glutaric acid, and dimethylester of succinic acid.
The amount of the organic medium may be 5 ~ 20 parts by weight based on 100 parts by weight of the conductive powder. If the amount of the organic medium exceeds 20 parts by weight, the resulting front electrode may have lowered electrical conductivity. In contrast, if the amount of the organic medium is less than 5 parts by weight, bondability with the substrate may deteriorate.
4. Additive
The conductive paste according to an embodiment of the present invention may include inorganic and organic additives.
An inorganic additive may include any metal selected from the group consisting of Li, K, Rb, Cs, Fr, Be, Ca, Sr, Ba, Ra, Pb, Cu, Zn, Ag, Te, Zn, Na, Mg, Al, W and Fe, metal oxides, and alloys or alloy oxides thereof. Examples thereof may include PbO, CuO, ZnO, MgO and WO3.
In the present invention, the inorganic additive may include a metal alloy or metal alloy oxide, containing Te, and preferable examples thereof include Te-X-O, Te-Y and Te-Y-Z, wherein X is at least one metal selected from the group consisting of 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 and Al, provided that Y and Z are not the same metal.
Most preferable Te-X-O is exemplified by Li2TeO3, Na2TeO3, SrTeO3, BeTeO3 or MgTeO3, and Te-Y or Te-Y-Z may be Ag-Te, Li-Te-Zn, Te-Zn-K, or Te-Zn-Na. The inorganic additive according to the present invention includes a metal able to promote a solid-phase reaction via reaction with the metal contained in the conductive powder, and thus may accelerate grain growth of the metal powder, which is the conductive powder, even at low temperature. Thereby, the firing temperature range of the paste composition may become wide, thus increasing electrical conductivity.
The particle size of the additive according to the present invention is not particularly limited. In an embodiment, the average particle size may be smaller than 10 μm. Preferably, the average particle size is 0.01 ~ 5 μm, and is more preferably 50 ~ 200 nm.
The amount of the inorganic additive is 1 ~ 10 parts by weight, and preferably 1 ~ 5 parts by weight, based on 100 parts by weight of the conductive powder. If the amount of the inorganic additive exceeds 5 parts by weight based on 100 parts by weight of the conductive powder, the amount of the conductive powder may decrease and thus the resistance of the front electrode formed of the corresponding paste composition may increase, thereby deteriorating solar cell efficiency. In contrast, if the amount of the inorganic additive is less than 1 part by weight based on 100 parts by weight of the conductive powder, it is difficult to sufficiently exhibit the effects by the additive.
The organic additive may include, but is not limited, to a dispersant, an antioxidant, a UV absorber, a defoaming agent, a thickener, a stabilizer, and a viscosity modifier, which may be used alone or in combination of two or more and may be mixed within a range that does not impair the effects of the present invention.
In particular, the dispersant, such as stearic acid, palmitic acid, myristic acid, oleic acid or lauric acid, may be mixed with the conductive paste. Furthermore, the dispersant is not limited to organic acid so long as it is typically useful.
Preparation of conductive paste composition
According to the present invention, the conductive paste is prepared by mixing a conductive powder, a metal oxide powder, an organic medium, and an additive using a 3-roll kneader. The conductive paste according to the present invention is preferably applied on a desired portion of an electronic device via screen printing. When it is applied using such a printing process, it may have a predetermined viscosity. The viscosity of the conductive paste according to the present invention may be 50 ~ 300 PaS as measured using #14 spindle with a Brookfield HBT viscometer and using a utility cup at 10 rpm and 25℃.
Manufacture of semiconductor device using conductive paste composition
The conductive paste according to the present invention is applied via screen printing on a substrate of a semiconductor device to be manufactured, and then dried. The substrate coated with the conductive paste is fired at about 700 ~ 950℃, thus forming a conductive paste pattern.
Examples
<Preparation of conductive paste composition>
Example 1
A conductive powder was prepared by mixing a first Ag powder having an average diameter of 2 μm with an Ag nanopowder having an average diameter of 200 nm.
A metal oxide powder was composed of 6.5 g of MO3 having an average diameter of 2 μm (based on the total weight of the metal oxide powder, 4.1 wt% of PbO, 72.6 wt% of TeO2, 15.9 wt% of Bi2O3, 0.7 wt% of B2O3, 4.8 wt% of ZnO, 0.5 wt% of Cr2O3, 0.4 wt% of MnO2, 0.7 wt% of CuO2, and 0.3 wt% of Li2O).
A conductive paste composition was prepared by mixing, based on 100 g of the paste composition, 70.0 g of the first Ag powder, 11.0 g of the Ag nanopowder, 6.5 g of the metal oxide powder, 10.2 g of a terpineol solution containing 20 wt% of ethylcellulose as an organic solvent, and 2.3 g of an inorganic additive ZnO.
Examples 2 and 3
Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the kind of metal oxide was changed as shown in Table 1 below.
Examples 4 to 7
Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the conductive powder and the kind of metal oxide powder were changed as shown in Table 1 below.
Examples 8 to 10
Conductive paste compositions were prepared in the same manner as in Examples 4 to 6, with the exception that the kind of inorganic additive was changed as shown in Table 1 below.
Examples 11 to 14
Conductive paste compositions were prepared in the same manner as in Example 10, with the exception that the kinds of inorganic additive and metal oxide powder were changed as shown in Table 1 below.
Comparative Examples 1 and 2
Conductive paste compositions were prepared in the same manner as in Example 1, with the exception that the kind of metal oxide powder was changed as shown in Table 1 below.
Comparative Examples 3 to 5
Conductive paste compositions were prepared in the same manner as in Example 4, with the exception that the kind of metal oxide powder was changed as shown in Table 1 below.
The conductive paste compositions of the above examples and comparative examples were pre-mixed using a universal mixer, and kneaded using a 3-roll kneader, thus obtaining individual conductive pastes. The amounts (g) of materials used and the features thereof are shown in Table 1 below. The composition proportions (wt%) of the metal oxide powders MO1 ~ MO6 are shown in Table 2 below, and the composition proportions of MO7 ~ MO10 are shown in Table 3 below.
Table 1
Composition | Conductive powder | Metal oxide | Organic medium | Inorganicadditive | |||||||||
1st Ag powder | Ag nanopowder | 2nd Ag powder | 1st metal oxide | 2nd metal oxide | |||||||||
Ex. | 1 | 70 | Projection X | 11 | Agglomerate X | - | 6.5 | MO3 | - | 10.2 | 2.3 | ZnO | |
2 | 70 | ProjectionX | 11 | Agglomerate X | - | 6.5 | MO4 | - | 10.2 | 2.3 | ZnO | ||
3 | 70 | ProjectionX | 11 | Agglomerate X | - | 6.5 | MO5 | - | 10.2 | 2.3 | ZnO | ||
4 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO3 | - | 10.2 | 2.3 | ZnO | ||
5 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO4 | - | 10.2 | 2.3 | ZnO | ||
6 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO5 | - | 10.2 | 2.3 | ZnO | ||
7 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO6 | - | 10.2 | 2.3 | ZnO | ||
8 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO3 | - | 10.2 | 2.3 | Te-Zn-Na | ||
9 | 63.5 | ProjectionO | 5 | Agglomerate | 12.5 | 6.5 | MO4 | - | 10.2 | 2.3 | Ag-Te | ||
10 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 6.5 | MO5 | - | 10.2 | 2.3 | Na2TeO3 | ||
11 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 3.3 | MO7 | 3.2 | MO7 | 10.2 | 2.3 | ZnO | |
12 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 5.2 | MO7 | 1.3 | MO7 | 10.2 | 2.3 | ZnO | |
13 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 5.2 | MO8 | 1.3 | MO8 | 10.2 | 2.3 | Te-Zn-Na | |
14 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 5.2 | MO9 | 1.3 | MO9 | 10.2 | 2.3 | BeTeO3 | |
C.Ex. | 1 | 70 | Projection X | 11 | Agglomerate X | - | 6.5 | MO1 | - | 10.2 | 2.3 | ZnO | |
2 | 70 | Projection X | 11 | Agglomerate X | - | 6.5 | MO2 | - | 10.2 | 2.3 | ZnO | ||
3 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 6.5 | MO1 | - | 10.2 | 2.3 | ZnO | ||
4 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 6.5 | MO2 | - | 10.2 | 2.3 | ZnO | ||
5 | 63.5 | Projection O | 5 | Agglomerate | 12.5 | 5.5 | MO10 | 1.0 | MO10 | 10.2 | 2.3 | ZnO |
Table 2
Metal oxide powder (wt% based on the total metal oxide powder) | Tg (℃) | |||||||||||||
Composition | 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 3
1st Metal oxide powder | 2nd Metal oxide powder | ||||||||||||
Composition (wt%) | 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 |
Test Example
<Manufacture of solar cell>
A solar cell was manufactured using the conductive paste of each of Examples 1 to 12 and Comparative Examples 1 to 5. Specifically, a silicon substrate was prepared, and a conductive paste (Ag paste) for solder connection was applied on the rear side thereof using screen printing and then dried. Subsequently, an Al paste (PV333 made by E.I. du Pont de Nemours and Company) for a rear electrode was applied via screen printing so as to partially overlap the dried Ag paste, and then dried.
The drying temperature of each paste was set to 120℃. As for the film thickness of each electrode of the rear side, which is a dried film thickness, the Al paste and the Ag paste were applied to 35 μm and 20 μm, respectively.
Also, the paste of the invention was applied on a light-receiving side (front side) via screen printing and then dried. A printer made by Price Co., and a stainless wire 250-mesh mask with an 8 inch × 10 inch frame, were used. A 1.5 inch pattern for evaluation comprising a finger line having a width of 100 μm and a bus bar having a width of 2 mm was employed, and the film thickness was 13 μm after firing. Subsequently, the paste applied on the substrate was co-fired in an IR firing furnace under conditions of a peak temperature of about 730℃ and an IN-OUT time of about 5 min, thus obtaining a desired solar cell. The solar cell obtained using the conductive paste according to the present invention was configured such that the Ag electrode was formed on the light-receiving side (front side) and the Al electrode (first electrode) composed mainly of Al and the Ag electrode (second electrode) composed mainly of Ag were formed on the rear side.
1. Measurement of light conversion efficiency and fill factor
The electric properties (I-V properties) of the obtained solar cell substrate were evaluated by a cell tester. Using a system (NCT-M-150AA) made by NPC as a cell tester, Eff (Conversion Efficiency) (%) and FF (Fill Factor) were measured. The results are shown in Table 4 below.
2. Measurement of adhesion
The adhesion of the obtained solar cell was measured as follows. Specifically, the surface of the front electrode formed using an electrode forming process was heated to 200℃ and a SnPbAg-based solder ribbon (line width: 2 mm, indium corporation, SUNTABTM) was attached to a length of 10 cm thereto. Then, while one end of the attached portion was pulled in a 180° direction with a universal tensile tester (QC-508E, COMETECH), a force (N, newton) until the electrode and the solder ribbon were peeled from each other was measured. The evaluation results based on the following criteria are shown in adhesion (N) in Table 4 below.
<Evaluation criteria>
Excellent: 3N or more
Good: 2N or more
Bad: 1N or less
The numeral values of electrical properties in Table 4 were obtained by averaging the measurement values of five solar cell samples.
Table 4
Eff(%) | FF | Adhesion | ||
Ex. | 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 | |
C.Ex. | 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 |
The features, structures, effects and so on illustrated in individual exemplary embodiments as above may be combined or modified with the other exemplary embodiments by those skilled in the art. Therefore, the contents related to such combinations or modifications should be understood to fall within the scope of the present invention.
Claims (9)
- A conductive paste composition, comprising:a conductive powder;a metal oxide powder including a first metal oxide powder having a first glass transition temperature of a℃ and a second metal oxide powder having a second glass transition temperature of b℃;an organic medium; andan additive,wherein the first glass transition temperature of the first metal oxide powder is 170≤a≤310, and the second glass transition temperature of the second metal oxide powder is 230≤b≤320, with satisfying 10≤b-a≤60, andthe additive is used in an amount of 1 ~ 5 parts by weight based on 100 parts by weight of the conductive powder, and comprises Te-Y or Te-Y-Z (wherein Y and Z are at least one metal selected from the group consisting of Zn, Ag, Na, Mg and Al, Y≠Z).
- The conductive paste composition of claim 1, wherein the first metal oxide powder is used in an amount of 80 ~ 90 wt%, and the second metal oxide powder is used in an amount of 0.5 ~ 20 wt%, based on a total weight of the metal oxide powder.
- The conductive paste composition of claim 2, wherein the first metal oxide powder includes Te.
- The conductive paste composition of claim 3, wherein the first metal oxide powder further includes at least one metal selected from the group consisting of Bi, Zn, B, Al, Ba, Si, W and Fe.
- The conductive paste composition of claim 4, wherein the second metal oxide powder includes Pb.
- The conductive paste composition of claim 5, wherein the second metal oxide powder further includes at least one metal selected from the group consisting of Li, Na, Ti, Cu, Ni, V, P, K and Sn.
- The conductive paste composition of claim 6, wherein the conductive powder comprises a first metal powder having an average diameter of 1 ~ 3 μm, and a metal nanopowder agglomerate having an average diameter of 0.5 ~ 10 μm obtained by agglomerating a metal nanopowder having an average diameter of 100 ~ 200 nm.
- The conductive paste composition of claim 6, comprising:70 ~ 90 wt% of the conductive powder;0.7 ~ 9 wt% of the metal oxide powder;3.5 ~ 18 wt% of the organic medium; and0.7 ~ 4.5 wt% of the additive.
- A silicon solar cell, comprising:a silicon semiconductor substrate;an emitter layer formed on the substrate;an anti-reflective film formed on the emitter layer;a front electrode connected to the emitter layer through the anti-reflective film; anda rear electrode connected to a rear side of the substrate,wherein the front electrode is formed by applying the conductive paste composition of any one of claims 1 to 8 in a predetermined pattern on the anti-reflective film and then performing firing.
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CN107408418A (en) * | 2015-03-27 | 2017-11-28 | 贺利氏德国有限责任两合公司 | Electrocondution slurry comprising oxide addition |
CN111499208A (en) * | 2020-04-23 | 2020-08-07 | 常州聚和新材料股份有限公司 | Glass material for front silver paste of monocrystalline silicon solar cell and preparation method and application thereof |
CN114292088A (en) * | 2021-12-30 | 2022-04-08 | 安徽大学 | Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof |
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US10804003B2 (en) * | 2017-10-03 | 2020-10-13 | Shoei Chemical Inc. | Conductive paste for forming solar cell electrode |
CN110289121B (en) * | 2019-06-19 | 2021-10-26 | 南通天盛新能源股份有限公司 | Alloy aluminum paste for back of PERC solar cell |
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JP2011119340A (en) * | 2009-12-01 | 2011-06-16 | Harima Chemicals Inc | Conductive aluminum paste |
KR20130117345A (en) * | 2012-04-17 | 2013-10-25 | 헤레우스 프레셔스 메탈즈 노스 아메리카 콘쇼호켄 엘엘씨 | Tellurium inorganic reaction systems for conductive thick film paste for solar cell contacts |
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CN111499208A (en) * | 2020-04-23 | 2020-08-07 | 常州聚和新材料股份有限公司 | Glass material for front silver paste of monocrystalline silicon solar cell and preparation method and application thereof |
CN114292088A (en) * | 2021-12-30 | 2022-04-08 | 安徽大学 | Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof |
CN114292088B (en) * | 2021-12-30 | 2022-10-11 | 安徽大学 | Tritium-neutron composite breeder lead-acid lithium eutectic ceramic spherulite and preparation method thereof |
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