WO2015083917A1 - Method of pulverizing metallic glass, pulverized metallic glass, conductive paste, and electronic device - Google Patents

Method of pulverizing metallic glass, pulverized metallic glass, conductive paste, and electronic device Download PDF

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Publication number
WO2015083917A1
WO2015083917A1 PCT/KR2014/006823 KR2014006823W WO2015083917A1 WO 2015083917 A1 WO2015083917 A1 WO 2015083917A1 KR 2014006823 W KR2014006823 W KR 2014006823W WO 2015083917 A1 WO2015083917 A1 WO 2015083917A1
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WO
WIPO (PCT)
Prior art keywords
metallic glass
pulverized
conductive paste
acetate
glycol alkylether
Prior art date
Application number
PCT/KR2014/006823
Other languages
French (fr)
Inventor
Keumhwan PARK
Jin Man Park
Eun Sung Lee
Sang Soo Jee
Suk Jun Kim
Se Yun Kim
Young-Soo Jeong
Original Assignee
Samsung Electronics Co., Ltd.
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Application filed by Samsung Electronics Co., Ltd. filed Critical Samsung Electronics Co., Ltd.
Publication of WO2015083917A1 publication Critical patent/WO2015083917A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K9/00—Arc welding or cutting
    • B23K9/04—Welding for other purposes than joining, e.g. built-up welding
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K9/00—Arc welding or cutting
    • B23K9/06—Arrangements or circuits for starting the arc, e.g. by generating ignition voltage, or for stabilising the arc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/08—Amorphous alloys with aluminium as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2200/00—Crystalline structure
    • C22C2200/02—Amorphous

Definitions

  • a method of pulverizing metallic glass, a pulverized metallic glass, a conductive paste, and an electronic device are disclosed.
  • a metallic glass is an alloy having a disordered atomic structure including two or more elements.
  • the metallic glass has a supercooled liquid region ( ⁇ ) between a glass transition temperature (Tg) and a crystalline temperature (Tx), and is sintered to have a liquid-like behavior.
  • the metallic glass When the metallic glass is sintered in the supercooled liquid region, it is easier to deform than a general metal so the process is easier, and the wettability to a lower layer is increased. Thereby, the close contacting property to the lower layer may be enhanced.
  • the metallic glass has conductivity, is sintered in the aforementioned supercooled liquid region, and closely contacts a lower layer such as a silicon wafer, and thus may be usefully applied as an electrode for an electronic device.
  • the conductivity and close contacting property of an electrode with a lower layer may be enhanced by increasing wettability of the metallic glass in the supercooled liquid region.
  • the wettability of the metallic glass is related to the size of the metallic glass powder. In other words, as the metallic glass powder has a smaller size, contact area and reactivity and thus wettability of the metallic glass are enhanced.
  • the metallic glass may have an inherent characteristic of having higher ductility when it has a smaller size. When a metallic glass is pulverized, it may be easily crystallized and thus characteristics of a metallic glass may be lost. Accordingly, the metallic glass may be difficult to pulverize into a fine powder while maintaining characteristics of a metallic glass.
  • One embodiment provides a method of pulverizing metallic glass into fine powder while maintaining the metallic glass characteristic.
  • Another embodiment provides a pulverized metallic glass according to the method.
  • Another embodiment provides a conductive paste including the pulverized metallic glass.
  • Yet another embodiment provides electronic device including an electrode formed using the conductive paste.
  • a method of pulverizing metallic glass includes preparing a slurry including a metallic glass and a solvent, supplying a region for passing compressed air with the slurry, making the metallic glass into droplets by adiabatically expanding the compressed air, and pulverizing the metallic glass droplets.
  • the pulverization of the metallic glass droplets may include at least either of collision among the metallic glass droplets or collision of the metallic glass droplets with an opposed plate.
  • Thermal energy generated during the collision among the metallic glass droplets or the metallic glass droplets with the opposed plate may be smaller than crystallization energy of the metallic glass.
  • the metallic glass and the pulverized metallic glass may include an amorphous part.
  • the metallic glass and the pulverized metallic glass may include about 80 to about 100 vol% of an amorphous part, respectively.
  • the solvent may include at least one selected from alcohol, terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid, desalted water, alkane, toluene,
  • the slurry may include about 5 to about 60 wt% of the metallic glass and about 40 to about 95 wt% of the solvent.
  • the compressed air may be sprayed with a pressure ranging from about 0.5 to about 2.0 MPa.
  • the compressed air may be at a temperature of about -60 to about 0 °C after adiabatic expansion.
  • the pulverized metallic glass may have a particle size of D 5 o ⁇ 5pm.
  • the pulverized metallic glass may have a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
  • a pulverized metallic glass having an amorphous part ranging from about 80 to about 100 vol% and a particle size of D5o ⁇ 5 pm is provided.
  • the pulverized metallic glass having a smaller particle size than about 5 pm may be in a ratio of greater than or equal to about 40 %.
  • the pulverized metallic glass may be an alloy including at least one selected from aluminum (Al), copper (Cu), zirconium (Zr), titanium (Ti), nickel (Ni), iron (Fe), gold (Au), magnesium (Mg), calcium (Ca), cerium (Ce), strontium (Sr), ytterbium (Yb), zinc (Zn), platinum (Pt), cobalt (Co), palladium (Pd), cerium (Ce), lanthanum (La), yttrium (Y), gadolinium (Gd), beryllium (Be), tantalum(Ta), gallium (Ga), hafnium (Hf), niobium (Nb), lead (Pb), platinum (Pt), silver (Ag), phosphorus (P), boron (B), silicon (Si), carbon (C), tin (Sn), zinc (Zn), lithium (Li), molybdenum (Mo), tungsten (W), manganese (Mn), erb
  • a conductive paste that includes a conductive powder, a metallic glass including the pulverized metallic glass, and an organic vehicle is provided.
  • the conductive powder may include aluminum (Al), silver (Ag), copper (Cu), nickel (Ni), an alloy thereof, or a combination thereof.
  • the conductive powder, the metallic glass, and the organic vehicle may be included in each amount of about 30 to about 99 wt%, about 0.1 to about 20 wt%, and a balance based on the total amount of the conductive paste.
  • an electronic device that includes an electrode including a sintered product of the conductive paste is provided.
  • It may provide a method of pulverizing metallic glass into fine powder while maintaining the amorphous characteristic of the metallic glass.
  • FIG. 1 is a schematic view of a method of pulverizing metallic glass according to one embodiment
  • FIG. 2 is a SEM photograph showing non-pulverized metallic glass
  • FIG. 3 is a SEM photograph showing pulverized metallic glass according to Example 1 .
  • FIG. 4 is a SEM photograph showing pulverized metallic glass according to Comparative Example 1 .
  • FIG. 5 is a TEM photograph showing the non-pulverized metallic glass
  • FIG. 6 is a TEM photograph showing pulverized metallic glass according to Example 2
  • FIG. 7 is a TEM photograph showing pulverized metallic glass according to Comparative Example 2
  • FIG. 8 is the cross-sectional view showing a solar cell according to one embodiment
  • FIGS. 9 to 12 are cross-sectional views showing a method of manufacturing a solar cell according to one embodiment.
  • FIG. 1 is a schematic view showing a method of pulverizing metallic glass according to one embodiment.
  • a slurry including a metallic glass and a solvent is prepared.
  • the metallic glass is an amorphous phased alloy having a disordered atomic structure including a plurality of elements.
  • the metallic glass may also refer to an amorphous metal.
  • the metallic glass includes an amorphous part that is formed by quenching a plurality of elements.
  • the amorphous part may be about 50 vol% to about 00 vol% of the metallic glass, specifically about 70 vol% to about 100 vol%, and more specifically about 80 vol% to about 100 vol%.
  • the metallic glass may maintain the amorphous part formed when having been in a liquid phase at a high temperature as it is, even at room temperature. Accordingly, the metallic glass has a different structure from the crystalline structure of a general alloy having a regular arrangement of elements when being quenched into a solid phase, and is also different from the structure of liquid metals present in a liquid phase at room temperature.
  • the metallic glass has low resistivity and thus high conductivity, unlike a glass such as a silicate.
  • the metallic glass may be an alloy of a transition metal, a noble metal, a rare earth element, an alkaline-earth metal, a semi-metal, and a combination thereof, and may be, for example, an alloy including at least one selected from aluminum (Al), copper (Cu), zirconium (Zr), titanium (Ti), nickel (Ni), iron (Fe), gold (Au), magnesium (Mg), calcium (Ca), cerium (Ce), strontium (Sr), ytterbium (Yb), zinc (Zn), platinum (Pt), cobalt (Co), palladium (Pd), cerium (Ce), lanthanum (La), yttrium (Y), gadolinium (Gd), beryllium (Be), tantalum (Ta), gallium (Ga), hafnium (Hf), niobium (Nb), lead (Pb), platinum (Pt), silver (Ag), phosphorus (P), boron (B), silicon (Si), carbon (
  • the metallic glass may be, for example, an aluminum-based metallic glass, a copper-based metallic glass, a zirconium-based metallic glass, a titanium-based metallic glass, a nickel-based metallic glass, an iron-based metallic glass, a cerium-based metallic glass, a strontium-based metallic glass, a gold-based metallic glass, a ytterbium-based metallic glass, a zinc-based metallic glass, a calcium-based metallic glass, a magnesium-based metallic glass, a platinum-based metallic glass, and the like, but is not limited thereto.
  • the aluminum-based metallic glass, copper-based metallic glass, zirconium-based metallic glass, titanium-based metallic glass, nickel-based metallic glass, iron-based metallic glass, cerium-based metallic glass, strontium-based metallic glass, gold-based metallic glass, ytterbium-based metallic glass, zinc-based metallic glass, calcium-based metallic glass, magnesium-based metallic glass, and platinum-based metallic glass may be each alloy including aluminum, copper, zirconium, titanium, nickel, iron, cerium, strontium, gold, ytterbium, zinc, calcium, magnesium, and platinum as a main component, and further including, for example, nickel (Ni), yttrium (Y), cobalt (Co), lanthanum (La), zirconium (Zr), iron (Fe), titanium (Ti), calcium (Ca), beryllium (Be), magnesium (Mg), sodium (Na), molybdenum (Mo), tungsten (W), tin (Sn), zinc (Zn), potassium (K), lithium (Li
  • the metallic glass is softened at more than or equal to a glass transition temperature (Tg), where it may have a liquid-like behavior.
  • Tg glass transition temperature
  • Tx crystalline temperature
  • ⁇ supercooled liquid region
  • the metallic glass may have a glass transition temperature (Tg) of less than or equal to, for example, about 800 °C, and for example about 50 to about 800 °C.
  • Tg glass transition temperature
  • ⁇ supercooled liquid region
  • the solvent may be any solvent being capable of dispersing the metallic glass, and is not particularly limited.
  • the solvent may be, for example, at least one selected from alcohol, terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl acetate, dimethylphthalic acid, diethylphthal
  • the slurry may further include various additives.
  • the slurry may include about 5 to about 60 wt% of a metallic glass and about 40 to about 95 wt% of a solvent.
  • an apparatus of pulverizing metallic glass includes a region (R1) for supplying compressed air, a region (R2) for passing the compressed air, and a region (R3) for adiabatically expanding the compressed air.
  • the region (R1) for supplying compressed air is a region where air 50 is supplied with a predetermined pressure, and for example, sprayed with a pressure of about 0.5 to about 2.0 MPa.
  • the region (R1) for supplying compressed air may include a nozzle 70 for spraying the slurry.
  • the region (R2) for passing the compressed air may be a region with a cross-section that becomes smaller and through which the air 50 is compressed and passes at a high speed.
  • the slurry may be sprayed from the nozzle 70 in the region (R2) for passing the compressed air.
  • the slurry is sprayed, for example, at a speed of about 10 ml/min to about 200 ml/min.
  • the region (R3) for adiabatically expanding the compressed air is a region with a cross-section that becomes larger and in which the compressed air is adiabatically expanded.
  • the region (R2) for passing the compressed air and the region (R3) for adiabatically expanding the compressed air may have a cross-section diameter ratio of about 1 :30, specifically, about 1 :10, and more specifically, about 1 :5.
  • the compressed air in the region (R3) for adiabatically expanding the compressed air may be adiabatically expanded and has a lower temperature, and thus may make a sprayed metallic glass slurry 60 into droplets. After the adiabatic expansion, temperature of the compressed air may decrease to about -60 to about 10 °C.
  • the metallic glass droplets 60a obtained by lowering the temperature have high mobility and collide with an opposed plate 80 positioned on a front side as well as more frequently collide with one another, and thus may be pulverized to have a smaller size.
  • thermal energy is generated but is absorbed by the metallic glass droplets 60a and thus may prevent crystallization of the metallic glass droplets.
  • the thermal energy generated when the metallic glass droplets 60a collide with one another or when the metallic glass droplets 60a collide with the opposed plate 80 may be smaller than crystallization energy of the metallic glass.
  • the pulverized metallic glass may maintain almost the same amorphous phase as that of the metallic glass before pulverization, and the metallic glass may have an amorphous part, for example, in a range of about 50 to 100 vol%, specifically, about 70 to about 100 vol%, and more specifically, about 80 to about 100 vol%.
  • the metallic glass before pulverization and the pulverized metallic glass may respectively have an amorphous part of about 80 to about 100 vol%.
  • the pulverized metallic glass may be collected.
  • the pulverized metallic glass may have a particle size D 50 ⁇ 5 pm.
  • the D 50 indicates a particle size corresponding to about 50 % relative to a maximum value in a cumulative particle distribution measured by using a particle size analyzer.
  • the pulverized metallic glass may have a smaller particle size than about 5 ⁇ ⁇ in a ratio of greater than or equal to about 40 %. Specifically, the pulverized metallic glass may have a smaller particle size than about 5 ⁇ in a ratio of about 50 % to about 99 %, and more specifically, about 50 % to about 80 % within the range. In this way, the pulverized metallic glass is formed as a fine powder in a relatively high ratio and thus may have a larger contact area and higher reactivity than the metallic glass before pulverization. Accordingly, wettability for a lower layer may be increased during heat treatment of the pulverized metallic glass.
  • a conductive paste according to one embodiment includes a conductive powder, the metallic glass, and an organic vehicle.
  • the conductive powder may include a silver (Ag)-containing metal such as silver or a silver alloy, an aluminum (Al)-containing metal such as aluminum or an aluminum alloy, a copper (Cu)-containing metal such as copper (Cu) or a copper alloy, a nickel (Ni)-containing metal such as nickel (Ni) or a nickel alloy, or a combination thereof.
  • the conductive powder is not limited thereto, and may include other metals and an additive other than the metals.
  • the conductive powder may have a size of about 1 nm to about 50 pm, and may include one or more kinds.
  • At least a part of the metallic glass may include the pulverized metallic glass, and for example, the pulverized metallic glass may have an amorphous part of about 80 to 100 vol% and a particle size of D 50 ⁇ 5 pm.
  • the pulverized metallic glass may have a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
  • the organic vehicle may include an organic compound that is mixed with the conductive powder and metallic glass and imparts appropriate viscosity to the organic vehicle, and a solvent dissolving the above components.
  • the organic compound may include, for example, at least one selected from a (meth)acrylate-based resin, a cellulose resin such as ethyl cellulose, a phenol resin, an alcohol resin, TEFLON (poly(tetrafluoroethylene)), and a combination thereof, and may further include an additive such as a dispersing agent, a surfactant, a thickener, and a stabilizer.
  • a (meth)acrylate-based resin ethyl cellulose, a phenol resin, an alcohol resin, TEFLON (poly(tetrafluoroethylene)), and a combination thereof
  • an additive such as a dispersing agent, a surfactant, a thickener, and a stabilizer.
  • the solvent may be any solvent being capable of mixing these without limitation, and may include, for example, at least one selected from terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid,
  • the conductive powder, the metallic glass, and the organic vehicle may be included in each amount of about 30 to about 99 wt%, about 0.1 to about 20 wt%, and a balance based on the total amount of the conductive paste.
  • the conductive paste may be applied using a screen printing method and the like, as an example, and may be used as an electrode of an electronic device.
  • the electronic device may be, for example, a liquid crystal display (LCD), a plasma display device (PDP), an organic light emitting diode (OLED), a solar cell, and the like, but is not limited thereto.
  • the electrode may include a sintered product of the conductive paste.
  • the electrode may have contact resistance of less than or equal to about 1 ⁇ 2 . Within the contact resistance range of the electrode, electric power loss caused by an electrode may be effectively reduced, and efficiency of an electronic device, specifically a solar cell, may be improved. Specifically, the electrode may have contact resistance of about 1 ⁇ 2 to about 20 mQcm 2 , and specifically about 1 ⁇ 2 to about 10 mQcm 2 .
  • One of the electronic devices may be a solar cell.
  • FIG. 8 a solar cell according to one embodiment is described.
  • FIG. 8 is a cross-sectional view showing a solar cell according to one embodiment.
  • a solar energy incident side of a semiconductor substrate 1 10 is termed a front side, and the opposite side is called a rear side.
  • a solar cell includes the semiconductor substrate 1 10 doped with p-type or n-type impurities.
  • the semiconductor substrate 110 may include crystalline silicon or a compound semiconductor.
  • the crystalline silicon may be, for example, a silicon wafer.
  • the p-type impurity may be a Group III element such as boron (B), and the n-type impurity may be a Group V element such as phosphorus (P).
  • the semiconductor substrate 1 10 may be subjected to a surface- texturing treatment.
  • the surface-textured semiconductor substrate 1 10 may, for example, have protrusions and depressions like a pyramid, or a pore structure like a honeycomb.
  • the surface-textured semiconductor substrate 1 10 may have an enlarged surface area to enhance a light-absorption rate and decrease reflectivity, resultantly improving efficiency of a solar cell.
  • the semiconductor substrate 1 10 may include a first doping region 1 1 1a and a second doping region 1 1 1 b on the rear side of the semiconductor substrate 1 10.
  • the first doping region 1 1 1 a may be doped with an n-type impurity
  • the second doping region 1 1 1 b may be doped with a p-type impurity.
  • the first doping region 1 1 1 a and the second doping region 1 1 1 b may be alternately disposed on the rear side of the semiconductor substrate 110.
  • An insulation layer 1 12 is formed on the semiconductor substrate 10.
  • the insulation layer 1 12 may be formed of a material that absorbs less light and has an insulating property, for example, silicon nitride (SiNx), silicon oxide (Si02), titanium oxide (Ti02), aluminum oxide (AI203), magnesium oxide (MgO), cerium oxide (Ce02), and a combination thereof, and it may be formed of a single layer or multiple layers.
  • the insulation layer 1 12 may have a thickness of about 200 to 1500 A.
  • the insulation layer 2 may be an anti-reflective coating (ARC) that decreases reflectivity of light and increases selectivity of a particular wavelength region on the surface of the solar cell, and simultaneously improves properties of silicon on the surface of the semiconductor substrate 1 10, thereby increasing efficiency of the solar cell.
  • ARC anti-reflective coating
  • a passivation layer 130a including a plurality of contact holes may be disposed on the rear side of the semiconductor substrate 1 10.
  • the passivation layer 130a may be made of a silicon oxide, a silicon nitride, aluminum oxide, and the like.
  • a first electrode 120 electrically connected to the first doping region 1 1 a and a second electrode 140 electrically connected to the second doping region 1 11 b are respectively formed on the rear side of the semiconductor substrate 1 10.
  • the first electrode 120 may contact the first doping region 1 1a through contact holes of the passivation layer 130a, while the second electrode 140 may contact the second doping region 1 1 1 b through contact holes of the passivation layer 130a.
  • the front electrode 120 and the rear electrode 140 may be alternately disposed.
  • the first electrode 120 may include a first buffer part 5a in a region contacting the first doping region 1 1 1a and a first electrode part 121 in regions other than the first buffer part 1 15a.
  • the second electrode 140 may include a second buffer part 1 15b in a region contacting the second doping region 1 1 1 b and a second electrode part 141 in regions other than the second buffer part 1 15b.
  • the first electrode 120 and the second electrode 140 may be formed of the above-described conductive paste.
  • the first and second electrodes 120 and 140 are not limited thereto, and either of the first electrode 120 and the second electrode 140 may be formed of the aforementioned conductive paste.
  • the first buffer part 1 15a and the second buffer part 1 15b may be formed of a metallic glass softened with the conductive paste and thus may have conductivity.
  • the first buffer part 115a may respectively contact the first doping region 1 1 1 a and the first electrode part 121 , and thus enlarge the area of a path through which charges move from the first doping region 1 1 1 a to the first electrode part 121 and prevent loss of the charges.
  • the second buffer part 1 15b may respectively contact the second doping region 1 1 1 b and the second electrode part 141 , and thus enlarge the area of a path through which charges move from the second doping region 1 1 1 b to the second electrode part 141 and prevent loss of the charges.
  • FIGS. 9 to 12 are cross-sectional views sequentially showing a method of manufacturing a solar cell according to one embodiment.
  • a semiconductor substrate 1 10 doped with, for example, an n-type impurity is prepared. Then, the semiconductor substrate 1 10 is surface-textured, and the insulation layer 1 12 and a passivation layer 130 are disposed on the front and rear sides of the semiconductor substrate 10, respectively.
  • the insulation layer 1 12 and the passivation layer 130 may be provided by chemical vapor deposition (CVD), for example.
  • the passivation layer 130 is patterned to provide a passivation layer 130a to expose a part of the rear side of the semiconductor substrate 1 0.
  • the first doping region 1 1 1a and the second doping region 1 1 1 b may be disposed by sequentially doping a p-type impurity and an n-type impurity at a high concentration on the rear side of the semiconductor substrate 1 10.
  • the first doping region 1 1 a and the second doping region 1 1 b may be doped with impurities with a higher concentration, for example, than the semiconductor substrate 1 10.
  • the first doping region 1 1 1a and the second doping region 1 1 1 b may be formed before formation of the passivation layer 130.
  • a conductive paste 120a for the first electrode is applied on a portion corresponding to the first doping region 11 1 a
  • a conductive paste 140a for the second electrode is applied on a portion corresponding to the second doping region 1 1 1 b on one side of the passivation layer 130a.
  • the conductive paste 120a for the first electrode and the conductive paste 140a for the second electrode may be the above-described conductive paste.
  • the conductive paste 120a for the first electrode and the conductive paste 140a for the second electrode may be formed using a screen printing method.
  • the conductive paste 120a for the first electrode and the conductive paste 40a for the second electrode may be fired together or separately.
  • the sintering process is performed at a higher temperature than the glass transition temperature (Tg) of the metallic glass in the conductive paste 120a for the first electrode and the conductive paste 140a, and thereby the metallic glass of the conductive paste undergoes plastic deformation and shows wettability.
  • Tg glass transition temperature
  • the conductive paste is applied to a back contact solar cell here, the conductive paste may be applied to all solar cells.
  • the conductive paste is applied to an electrode for a solar cell here, it is not limited thereto, and it may be applied to an electrode for all electronic devices.
  • An aluminum (Al)-nickel (Ni)-yttrium (Y)-cobalt (Co) mother alloy is manufactured by preparing aluminum (Al), nickel (Ni), yttrium (Y), and cobalt (Co) and then melting them with an arc melter or an induction melter.
  • the aluminum (Al)-nickel (Ni)-yttrium (Y)-cobalt (Co) mother alloy is charged in a crucible and mounted in an atomizer.
  • the atomizer is maintained in a vacuum state, and argon (Ar) gas is supplied into a chamber to form an argon atmosphere.
  • a powder-shaped metallic glass, AlssNisYs ⁇ is manufactured by melting the metal and spraying a high-speed and high- pressure inert gas into the molten solution.
  • a metallic glass, AI 8 3Ni 5 5 Y 6 Sii. 5 La2Co2, is manufactured according to the same method as Preparation Example 1 , except for using aluminum (Al), nickel
  • Ni nickel
  • yttrium Y
  • silicon Si
  • lanthanum La
  • Co cobalt
  • a metallic glass, AI 84 Ni5Y6Ca 2 NiCo2, is manufactured according to the same method as Preparation Example 1 , except for using aluminum (Al), nickel
  • Ni yttrium
  • Y calcium
  • Co cobalt
  • a metallic glass slurry is prepared by mixing the metallic glass according to Preparation Example 1 in a concentration of 30 wt% with an ethanol solvent.
  • the metallic glass slurry is pulverized by using a metallic glass pulverizer having the following conditions and is shown in FIG. 1.
  • a pulverized metallic glass is obtained according to the same method as Example 1 , except for using the metallic glass according to Preparation Example 2 instead of the metallic glass according to Preparation Example 1.
  • a pulverized metallic glass is obtained according to the same method as Example 1 , except for using the metallic glass according to Preparation Example 3 instead of the metallic glass according to Preparation Example 1. Comparative Example 1
  • a pulverized metallic glass is obtained by pulverizing the metallic glass according to Preparation Example 1 through air jet milling, a kind of method of dry-pulverizing metallic glass.
  • the metallic glass is supplied at 0.67 g/min, and the air spray pressure is 1.15 MPa.
  • Pulverized metallic glass is obtained according to the same method as Comparative Example 1 , except for using the metallic glass according to Preparation Example 2 instead of the metallic glass according to Preparation Example !
  • a pulverized metallic glass is obtained according to the same method as Comparative Example 1 , except for using the metallic glass according to Preparation Example 3 instead of the metallic glass according to Preparation Example 1 . Evaluation 1
  • the brittleness degree of the metallic glass is evaluated by transformation degree of the powder shape before and after pulverization.
  • FIG. 2 is a SEM photograph showing metallic glass before the pulverization
  • FIG. 3 is a SEM photograph showing pulverized metallic glass according to Example 1
  • FIG. 4 is a SEM photograph showing the pulverized metallic glass according to Comparative Example 1 .
  • the pulverized metallic glass according to Example 1 is broken into fine particles, while the pulverized metallic glass according to Comparative Example 1 is partially pulverized but mostly non- pulverized and left.
  • the particle distribution is evaluated by averaging three measurements obtained by using a particle size analyzer (LA-950 Laser Particle Size Analyzer, Horiba).
  • each pulverized metallic glass according to Examples 1 to 3 shows remarkably improved fine powders compared with each metallic glass according to Comparative Examples 1 to 3.
  • the pulverized metallic glasses according to Comparative Examples 1 to 3 are not only well pulverized, but the pulverized powder is not broken but is crushed and entangled into a chunk due to ductility during the pulverization.
  • Evaluation 3 An amorphous phase of each pulverized metallic glass according to Examples 1 to 3 is evaluated.
  • the amorphous phase is evaluated by using an X-ray diffraction (XRD) analysis method, and an overall broad peak in the XRD graph shows an amorphous phase, while at least one sharp peak shows a crystal phase.
  • XRD X-ray diffraction
  • each pulverized metallic glass according to Examples 1 to 3 maintains a similar amorphous phase to non-pulverized metallic glass, while each pulverized metallic glass according to Comparative Examples 1 to 3 is crystallized and forms a crystal phase during the pulverization.
  • FIG. 5 is a TEM photograph showing non-pulverized metallic glass
  • FIG. 6 is a TEM photograph showing the pulverized metallic glass according to Example 2
  • FIG. 7 is a TEM photograph showing the pulverized metallic glass according to Comparative Example 2.
  • the pulverized metallic glass according to Example 2 shows a similar amorphous phase to the non-pulverized metallic glass, while the pulverized metallic glass according to Comparative Example 2 shows many crystalline phases.
  • each pulverized metallic glass according to Examples 1 to 3 shows similar thermal properties to metallic glass before pulverization, while each pulverized metallic glass according to Comparative Examples 1 to 3 shows remarkably changed thermal properties.
  • the electrical characteristics are evaluated by contact resistance of an electrode sample formed of a conductive paste including pulverized metallic glass.
  • the electrode sample 1 is formed in the following method.
  • the pulverized metallic glass according to Example 1 and silver (Ag) powder are added to an organic vehicle including an ethyl cellulose binder, a surfactant, and a mixed solvent of butyl carbitol/butyl carbitol acetate.
  • the silver (Ag) powder, the pulverized metallic glass according to Example 1 , and the organic vehicle are respectively added in an amount of 82.58 wt%, 3.93 wt%, and 13.49 wt% based on the total weight of a conductive paste.
  • the conductive paste is kneaded with a 3-roll mill.
  • the conductive paste is screen-printed on a silicon wafer.
  • the coated silicon wafer is then heated to about 600 °C by using a belt furnace.
  • the wafer is then cooled, obtaining an Electrode Sample 1.
  • An Electrode Sample 2 is formed according to the same method as the Electrode Sample 1 , except for using a conductive paste including non- pulverized metallic glass instead of the pulverized metallic glass according to Example 1 .
  • An Electrode Sample 3 is formed according to the same method as the Electrode Sample 1 , except for using a conductive paste including the pulverized metallic glass according to Comparative Example 1 instead of the pulverized metallic glass according to Example 1.
  • the Electrode Sample 1 shows sharply deteriorated contact resistance compared with the Electrode Samples 2 and 3. Accordingly, the pulverized metallic glass according to Example 1 is formed as a fine powder and thus shows improved electrical characteristics. While this disclosure has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

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Abstract

A method of pulverizing metallic glass including preparing a slurry including a metallic glass and a solvent, supplying a region for passing compressed air with the slurry, making the metallic glass into droplets by adiabatically expanding the compressed air, and pulverizing the metallic glass droplets, pulverized metallic glass obtained in the same method, a conductive paste including the pulverized metallic glass, and an electronic device including an electrode formed of the conductive paste are disclosed.

Description

[DESCRIPTION]
[Invention Title]
METHOD OF PULVERIZING METALLIC GLASS, PULVERIZED METALLIC GLASS, CONDUCTIVE PASTE, AND ELECTRONIC DEVICE
[Technical Field]
A method of pulverizing metallic glass, a pulverized metallic glass, a conductive paste, and an electronic device are disclosed.
[Background Art]
A metallic glass is an alloy having a disordered atomic structure including two or more elements. The metallic glass has a supercooled liquid region (ΔΤχ) between a glass transition temperature (Tg) and a crystalline temperature (Tx), and is sintered to have a liquid-like behavior.
When the metallic glass is sintered in the supercooled liquid region, it is easier to deform than a general metal so the process is easier, and the wettability to a lower layer is increased. Thereby, the close contacting property to the lower layer may be enhanced.
On the other hand, research on using the metallic glass as an electrode for an electronic device has been undertaken. The metallic glass has conductivity, is sintered in the aforementioned supercooled liquid region, and closely contacts a lower layer such as a silicon wafer, and thus may be usefully applied as an electrode for an electronic device.
The conductivity and close contacting property of an electrode with a lower layer may be enhanced by increasing wettability of the metallic glass in the supercooled liquid region. The wettability of the metallic glass is related to the size of the metallic glass powder. In other words, as the metallic glass powder has a smaller size, contact area and reactivity and thus wettability of the metallic glass are enhanced.
[Disclosure]
[Technical Problem]
The metallic glass may have an inherent characteristic of having higher ductility when it has a smaller size. When a metallic glass is pulverized, it may be easily crystallized and thus characteristics of a metallic glass may be lost. Accordingly, the metallic glass may be difficult to pulverize into a fine powder while maintaining characteristics of a metallic glass.
[Technical Solution]
One embodiment provides a method of pulverizing metallic glass into fine powder while maintaining the metallic glass characteristic.
Another embodiment provides a pulverized metallic glass according to the method.
Another embodiment provides a conductive paste including the pulverized metallic glass.
Yet another embodiment provides electronic device including an electrode formed using the conductive paste.
According to one embodiment, a method of pulverizing metallic glass is provided, that includes preparing a slurry including a metallic glass and a solvent, supplying a region for passing compressed air with the slurry, making the metallic glass into droplets by adiabatically expanding the compressed air, and pulverizing the metallic glass droplets.
The pulverization of the metallic glass droplets may include at least either of collision among the metallic glass droplets or collision of the metallic glass droplets with an opposed plate.
Thermal energy generated during the collision among the metallic glass droplets or the metallic glass droplets with the opposed plate may be smaller than crystallization energy of the metallic glass.
The metallic glass and the pulverized metallic glass may include an amorphous part.
The metallic glass and the pulverized metallic glass may include about 80 to about 100 vol% of an amorphous part, respectively.
The solvent may include at least one selected from alcohol, terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid, desalted water, alkane, toluene, xylene, chloroform, acetone, alkyl acetate, methylalkyl ketone, ethylalkyl ketone, propylalkyl ketone, butylalkyl ketone, and cycloalkanone.
The slurry may include about 5 to about 60 wt% of the metallic glass and about 40 to about 95 wt% of the solvent.
The compressed air may be sprayed with a pressure ranging from about 0.5 to about 2.0 MPa.
The compressed air may be at a temperature of about -60 to about 0 °C after adiabatic expansion.
The pulverized metallic glass may have a particle size of D5o≤ 5pm.
The pulverized metallic glass may have a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
According to another embodiment, a pulverized metallic glass having an amorphous part ranging from about 80 to about 100 vol% and a particle size of D5o≤ 5 pm is provided.
The pulverized metallic glass having a smaller particle size than about 5 pm may be in a ratio of greater than or equal to about 40 %.
The pulverized metallic glass may be an alloy including at least one selected from aluminum (Al), copper (Cu), zirconium (Zr), titanium (Ti), nickel (Ni), iron (Fe), gold (Au), magnesium (Mg), calcium (Ca), cerium (Ce), strontium (Sr), ytterbium (Yb), zinc (Zn), platinum (Pt), cobalt (Co), palladium (Pd), cerium (Ce), lanthanum (La), yttrium (Y), gadolinium (Gd), beryllium (Be), tantalum(Ta), gallium (Ga), hafnium (Hf), niobium (Nb), lead (Pb), platinum (Pt), silver (Ag), phosphorus (P), boron (B), silicon (Si), carbon (C), tin (Sn), zinc (Zn), lithium (Li), molybdenum (Mo), tungsten (W), manganese (Mn), erbium (Er), chromium (Cr), praseodymium (Pr), thulium (Tm), and a combination thereof.
According to yet another embodiment, a conductive paste that includes a conductive powder, a metallic glass including the pulverized metallic glass, and an organic vehicle is provided.
The conductive powder may include aluminum (Al), silver (Ag), copper (Cu), nickel (Ni), an alloy thereof, or a combination thereof.
The conductive powder, the metallic glass, and the organic vehicle may be included in each amount of about 30 to about 99 wt%, about 0.1 to about 20 wt%, and a balance based on the total amount of the conductive paste.
According to still another embodiment, an electronic device that includes an electrode including a sintered product of the conductive paste is provided. [Advantageous Effects]
It may provide a method of pulverizing metallic glass into fine powder while maintaining the amorphous characteristic of the metallic glass.
[Description of Drawings]
FIG. 1 is a schematic view of a method of pulverizing metallic glass according to one embodiment,
FIG. 2 is a SEM photograph showing non-pulverized metallic glass,
FIG. 3 is a SEM photograph showing pulverized metallic glass according to Example 1 ,
FIG. 4 is a SEM photograph showing pulverized metallic glass according to Comparative Example 1 ,
FIG. 5 is a TEM photograph showing the non-pulverized metallic glass, FIG. 6 is a TEM photograph showing pulverized metallic glass according to Example 2,
FIG. 7 is a TEM photograph showing pulverized metallic glass according to Comparative Example 2, FIG. 8 is the cross-sectional view showing a solar cell according to one embodiment, and
FIGS. 9 to 12 are cross-sectional views showing a method of manufacturing a solar cell according to one embodiment.
[Best Mode]
Exemplary embodiments of the present invention will hereinafter be described in detail, and may be easily performed by those who have common knowledge in the related art. However, this disclosure may be embodied in many different forms and is not construed as limited to the exemplary embodiments set forth herein.
Hereinafter, a method of pulverizing metallic glass according to one embodiment is described referring to drawings.
FIG. 1 is a schematic view showing a method of pulverizing metallic glass according to one embodiment.
First, a slurry including a metallic glass and a solvent is prepared.
The metallic glass is an amorphous phased alloy having a disordered atomic structure including a plurality of elements. The metallic glass may also refer to an amorphous metal. The metallic glass includes an amorphous part that is formed by quenching a plurality of elements. The amorphous part may be about 50 vol% to about 00 vol% of the metallic glass, specifically about 70 vol% to about 100 vol%, and more specifically about 80 vol% to about 100 vol%.
The metallic glass may maintain the amorphous part formed when having been in a liquid phase at a high temperature as it is, even at room temperature. Accordingly, the metallic glass has a different structure from the crystalline structure of a general alloy having a regular arrangement of elements when being quenched into a solid phase, and is also different from the structure of liquid metals present in a liquid phase at room temperature. The metallic glass has low resistivity and thus high conductivity, unlike a glass such as a silicate.
The metallic glass may be an alloy of a transition metal, a noble metal, a rare earth element, an alkaline-earth metal, a semi-metal, and a combination thereof, and may be, for example, an alloy including at least one selected from aluminum (Al), copper (Cu), zirconium (Zr), titanium (Ti), nickel (Ni), iron (Fe), gold (Au), magnesium (Mg), calcium (Ca), cerium (Ce), strontium (Sr), ytterbium (Yb), zinc (Zn), platinum (Pt), cobalt (Co), palladium (Pd), cerium (Ce), lanthanum (La), yttrium (Y), gadolinium (Gd), beryllium (Be), tantalum (Ta), gallium (Ga), hafnium (Hf), niobium (Nb), lead (Pb), platinum (Pt), silver (Ag), phosphorus (P), boron (B), silicon (Si), carbon (C), tin (Sn), zinc (Zn), lithium (Li), molybdenum (Mo), tungsten (W), manganese (Mn), erbium (Er), chromium (Cr), praseodymium (Pr), thulium (Tm), and a combination thereof.
The metallic glass may be, for example, an aluminum-based metallic glass, a copper-based metallic glass, a zirconium-based metallic glass, a titanium-based metallic glass, a nickel-based metallic glass, an iron-based metallic glass, a cerium-based metallic glass, a strontium-based metallic glass, a gold-based metallic glass, a ytterbium-based metallic glass, a zinc-based metallic glass, a calcium-based metallic glass, a magnesium-based metallic glass, a platinum-based metallic glass, and the like, but is not limited thereto.
The aluminum-based metallic glass, copper-based metallic glass, zirconium-based metallic glass, titanium-based metallic glass, nickel-based metallic glass, iron-based metallic glass, cerium-based metallic glass, strontium-based metallic glass, gold-based metallic glass, ytterbium-based metallic glass, zinc-based metallic glass, calcium-based metallic glass, magnesium-based metallic glass, and platinum-based metallic glass may be each alloy including aluminum, copper, zirconium, titanium, nickel, iron, cerium, strontium, gold, ytterbium, zinc, calcium, magnesium, and platinum as a main component, and further including, for example, nickel (Ni), yttrium (Y), cobalt (Co), lanthanum (La), zirconium (Zr), iron (Fe), titanium (Ti), calcium (Ca), beryllium (Be), magnesium (Mg), sodium (Na), molybdenum (Mo), tungsten (W), tin (Sn), zinc (Zn), potassium (K), lithium (Li), phosphorus (P), palladium (Pd), platinum (Pt), rubidium (Rb), chromium (Cr), strontium (Sr), cerium (Ce), praseodymium (Pr), promethium (Pm), samarium (Sm), lutetium (Lu), neodymium (Nd), niobium (Nb), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), thulium (Th), scandium (Sc), barium (Ba), ytterbium (Yb), europium (Eu), hafnium (Hf), arsenic (As), plutonium (Pu), gallium (Ga), germanium (Ge), antimony (Sb), silicon (Si), cadmium (Cd), indium (In), platinum (Pt), manganese (Mn), niobium (Nb), osmium (Os), vanadium (V), aluminum (Al), copper (Cu), silver (Ag), and mercury (Hg). Herein, the main component has the highest mole ratio among the components of the metallic glass.
The metallic glass is softened at more than or equal to a glass transition temperature (Tg), where it may have a liquid-like behavior. The liquid-like behavior is maintained between the glass transition temperature (Tg) and the crystalline temperature (Tx) of the metallic glass, which is called a supercooled liquid region (ΔΤχ).
The metallic glass may have a glass transition temperature (Tg) of less than or equal to, for example, about 800 °C, and for example about 50 to about 800 °C. The metallic glass may have a supercooled liquid region (ΔΤχ) of about 0 K to about 200 K, and specifically about 5 K to about 200 K.
The solvent may be any solvent being capable of dispersing the metallic glass, and is not particularly limited. The solvent may be, for example, at least one selected from alcohol, terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid, desalted water, alkane, toluene, xylene, chloroform, acetone, alkyl acetate, methylalkyl ketone, ethylalkyl ketone, propylalkyl ketone, butylalkyl ketone, and cycloalkanone. Among them, the solvent may be ethanol, isopropyl alcohol, ethyl acetate, hexane, or a combination thereof.
The slurry may further include various additives.
The slurry may include about 5 to about 60 wt% of a metallic glass and about 40 to about 95 wt% of a solvent.
Referring to FIG. 1 , an apparatus of pulverizing metallic glass includes a region (R1) for supplying compressed air, a region (R2) for passing the compressed air, and a region (R3) for adiabatically expanding the compressed air.
The region (R1) for supplying compressed air is a region where air 50 is supplied with a predetermined pressure, and for example, sprayed with a pressure of about 0.5 to about 2.0 MPa. The region (R1) for supplying compressed air may include a nozzle 70 for spraying the slurry.
The region (R2) for passing the compressed air may be a region with a cross-section that becomes smaller and through which the air 50 is compressed and passes at a high speed. The slurry may be sprayed from the nozzle 70 in the region (R2) for passing the compressed air. The slurry is sprayed, for example, at a speed of about 10 ml/min to about 200 ml/min.
The region (R3) for adiabatically expanding the compressed air is a region with a cross-section that becomes larger and in which the compressed air is adiabatically expanded. Herein, the region (R2) for passing the compressed air and the region (R3) for adiabatically expanding the compressed air may have a cross-section diameter ratio of about 1 :30, specifically, about 1 :10, and more specifically, about 1 :5. The compressed air in the region (R3) for adiabatically expanding the compressed air may be adiabatically expanded and has a lower temperature, and thus may make a sprayed metallic glass slurry 60 into droplets. After the adiabatic expansion, temperature of the compressed air may decrease to about -60 to about 10 °C. The metallic glass droplets 60a obtained by lowering the temperature have high mobility and collide with an opposed plate 80 positioned on a front side as well as more frequently collide with one another, and thus may be pulverized to have a smaller size.
Herein, when the metallic glass droplets 60a collide with one another or when the metallic glass droplets 60a collide with the opposed plate 80, thermal energy is generated but is absorbed by the metallic glass droplets 60a and thus may prevent crystallization of the metallic glass droplets. For example, the thermal energy generated when the metallic glass droplets 60a collide with one another or when the metallic glass droplets 60a collide with the opposed plate 80 may be smaller than crystallization energy of the metallic glass.
Accordingly, the pulverized metallic glass may maintain almost the same amorphous phase as that of the metallic glass before pulverization, and the metallic glass may have an amorphous part, for example, in a range of about 50 to 100 vol%, specifically, about 70 to about 100 vol%, and more specifically, about 80 to about 100 vol%.
For example, the metallic glass before pulverization and the pulverized metallic glass may respectively have an amorphous part of about 80 to about 100 vol%.
The pulverized metallic glass may be collected.
The pulverized metallic glass may have a particle size D50≤ 5 pm. Herein, the D50 indicates a particle size corresponding to about 50 % relative to a maximum value in a cumulative particle distribution measured by using a particle size analyzer.
In addition, the pulverized metallic glass may have a smaller particle size than about 5 μι ι in a ratio of greater than or equal to about 40 %. Specifically, the pulverized metallic glass may have a smaller particle size than about 5 μηι in a ratio of about 50 % to about 99 %, and more specifically, about 50 % to about 80 % within the range. In this way, the pulverized metallic glass is formed as a fine powder in a relatively high ratio and thus may have a larger contact area and higher reactivity than the metallic glass before pulverization. Accordingly, wettability for a lower layer may be increased during heat treatment of the pulverized metallic glass.
Hereinafter, a conductive paste including the pulverized metallic glass is described.
A conductive paste according to one embodiment includes a conductive powder, the metallic glass, and an organic vehicle.
The conductive powder may include a silver (Ag)-containing metal such as silver or a silver alloy, an aluminum (Al)-containing metal such as aluminum or an aluminum alloy, a copper (Cu)-containing metal such as copper (Cu) or a copper alloy, a nickel (Ni)-containing metal such as nickel (Ni) or a nickel alloy, or a combination thereof. However, the conductive powder is not limited thereto, and may include other metals and an additive other than the metals.
The conductive powder may have a size of about 1 nm to about 50 pm, and may include one or more kinds.
At least a part of the metallic glass may include the pulverized metallic glass, and for example, the pulverized metallic glass may have an amorphous part of about 80 to 100 vol% and a particle size of D50≤ 5 pm. The pulverized metallic glass may have a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
The organic vehicle may include an organic compound that is mixed with the conductive powder and metallic glass and imparts appropriate viscosity to the organic vehicle, and a solvent dissolving the above components.
The organic compound may include, for example, at least one selected from a (meth)acrylate-based resin, a cellulose resin such as ethyl cellulose, a phenol resin, an alcohol resin, TEFLON (poly(tetrafluoroethylene)), and a combination thereof, and may further include an additive such as a dispersing agent, a surfactant, a thickener, and a stabilizer.
The solvent may be any solvent being capable of mixing these without limitation, and may include, for example, at least one selected from terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid, and desalted water.
The conductive powder, the metallic glass, and the organic vehicle may be included in each amount of about 30 to about 99 wt%, about 0.1 to about 20 wt%, and a balance based on the total amount of the conductive paste.
The conductive paste may be applied using a screen printing method and the like, as an example, and may be used as an electrode of an electronic device. The electronic device may be, for example, a liquid crystal display (LCD), a plasma display device (PDP), an organic light emitting diode (OLED), a solar cell, and the like, but is not limited thereto.
The electrode may include a sintered product of the conductive paste.
The electrode may have contact resistance of less than or equal to about 1 ΚΩαη2. Within the contact resistance range of the electrode, electric power loss caused by an electrode may be effectively reduced, and efficiency of an electronic device, specifically a solar cell, may be improved. Specifically, the electrode may have contact resistance of about 1 μΩαη2 to about 20 mQcm2, and specifically about 1 μΩαη2 to about 10 mQcm2.
One of the electronic devices may be a solar cell.
Referring to FIG. 8, a solar cell according to one embodiment is described.
FIG. 8 is a cross-sectional view showing a solar cell according to one embodiment.
In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like reference numerals designate like elements throughout the specification. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
Hereinafter, the spatial relationship of components will be described with respect to a semiconductor substrate 1 10 for better understanding and ease of description, but the present disclosure is not limited thereto. In addition, a solar energy incident side of a semiconductor substrate 1 10 is termed a front side, and the opposite side is called a rear side.
Referring to FIG. 8, a solar cell according to one embodiment includes the semiconductor substrate 1 10 doped with p-type or n-type impurities.
The semiconductor substrate 110 may include crystalline silicon or a compound semiconductor. The crystalline silicon may be, for example, a silicon wafer. The p-type impurity may be a Group III element such as boron (B), and the n-type impurity may be a Group V element such as phosphorus (P).
The semiconductor substrate 1 10 may be subjected to a surface- texturing treatment. The surface-textured semiconductor substrate 1 10 may, for example, have protrusions and depressions like a pyramid, or a pore structure like a honeycomb. The surface-textured semiconductor substrate 1 10 may have an enlarged surface area to enhance a light-absorption rate and decrease reflectivity, resultantly improving efficiency of a solar cell.
The semiconductor substrate 1 10 may include a first doping region 1 1 1a and a second doping region 1 1 1 b on the rear side of the semiconductor substrate 1 10. For example, the first doping region 1 1 1 a may be doped with an n-type impurity, and the second doping region 1 1 1 b may be doped with a p-type impurity. The first doping region 1 1 1 a and the second doping region 1 1 1 b may be alternately disposed on the rear side of the semiconductor substrate 110.
An insulation layer 1 12 is formed on the semiconductor substrate 10.
The insulation layer 1 12 may be formed of a material that absorbs less light and has an insulating property, for example, silicon nitride (SiNx), silicon oxide (Si02), titanium oxide (Ti02), aluminum oxide (AI203), magnesium oxide (MgO), cerium oxide (Ce02), and a combination thereof, and it may be formed of a single layer or multiple layers. The insulation layer 1 12 may have a thickness of about 200 to 1500 A.
The insulation layer 2 may be an anti-reflective coating (ARC) that decreases reflectivity of light and increases selectivity of a particular wavelength region on the surface of the solar cell, and simultaneously improves properties of silicon on the surface of the semiconductor substrate 1 10, thereby increasing efficiency of the solar cell.
A passivation layer 130a including a plurality of contact holes may be disposed on the rear side of the semiconductor substrate 1 10. The passivation layer 130a may be made of a silicon oxide, a silicon nitride, aluminum oxide, and the like.
A first electrode 120 electrically connected to the first doping region 1 1 a and a second electrode 140 electrically connected to the second doping region 1 11 b are respectively formed on the rear side of the semiconductor substrate 1 10. The first electrode 120 may contact the first doping region 1 1a through contact holes of the passivation layer 130a, while the second electrode 140 may contact the second doping region 1 1 1 b through contact holes of the passivation layer 130a. The front electrode 120 and the rear electrode 140 may be alternately disposed.
The first electrode 120 may include a first buffer part 5a in a region contacting the first doping region 1 1 1a and a first electrode part 121 in regions other than the first buffer part 1 15a. The second electrode 140 may include a second buffer part 1 15b in a region contacting the second doping region 1 1 1 b and a second electrode part 141 in regions other than the second buffer part 1 15b.
The first electrode 120 and the second electrode 140 may be formed of the above-described conductive paste. However, the first and second electrodes 120 and 140 are not limited thereto, and either of the first electrode 120 and the second electrode 140 may be formed of the aforementioned conductive paste.
The first buffer part 1 15a and the second buffer part 1 15b may be formed of a metallic glass softened with the conductive paste and thus may have conductivity. The first buffer part 115a may respectively contact the first doping region 1 1 1 a and the first electrode part 121 , and thus enlarge the area of a path through which charges move from the first doping region 1 1 1 a to the first electrode part 121 and prevent loss of the charges. Likewise, the second buffer part 1 15b may respectively contact the second doping region 1 1 1 b and the second electrode part 141 , and thus enlarge the area of a path through which charges move from the second doping region 1 1 1 b to the second electrode part 141 and prevent loss of the charges.
Hereinafter, the method of manufacturing a solar cell is described with reference to FIGS. 9 to 12.
FIGS. 9 to 12 are cross-sectional views sequentially showing a method of manufacturing a solar cell according to one embodiment.
First, referring to FIG. 9, a semiconductor substrate 1 10 doped with, for example, an n-type impurity is prepared. Then, the semiconductor substrate 1 10 is surface-textured, and the insulation layer 1 12 and a passivation layer 130 are disposed on the front and rear sides of the semiconductor substrate 10, respectively. The insulation layer 1 12 and the passivation layer 130 may be provided by chemical vapor deposition (CVD), for example.
Referring to FIG. 10, the passivation layer 130 is patterned to provide a passivation layer 130a to expose a part of the rear side of the semiconductor substrate 1 0.
Referring to FIG. 1 1 , the first doping region 1 1 1a and the second doping region 1 1 1 b may be disposed by sequentially doping a p-type impurity and an n-type impurity at a high concentration on the rear side of the semiconductor substrate 1 10. The first doping region 1 1 a and the second doping region 1 1 b may be doped with impurities with a higher concentration, for example, than the semiconductor substrate 1 10. Optionally, the first doping region 1 1 1a and the second doping region 1 1 1 b may be formed before formation of the passivation layer 130.
Referring to FIG. 12, a conductive paste 120a for the first electrode is applied on a portion corresponding to the first doping region 11 1 a, and a conductive paste 140a for the second electrode is applied on a portion corresponding to the second doping region 1 1 1 b on one side of the passivation layer 130a. The conductive paste 120a for the first electrode and the conductive paste 140a for the second electrode may be the above-described conductive paste. The conductive paste 120a for the first electrode and the conductive paste 140a for the second electrode may be formed using a screen printing method.
The conductive paste 120a for the first electrode and the conductive paste 40a for the second electrode may be fired together or separately. Herein, the sintering process is performed at a higher temperature than the glass transition temperature (Tg) of the metallic glass in the conductive paste 120a for the first electrode and the conductive paste 140a, and thereby the metallic glass of the conductive paste undergoes plastic deformation and shows wettability.
Even though it is described that the conductive paste is applied to a back contact solar cell here, the conductive paste may be applied to all solar cells.
In addition, even though it is described that the conductive paste is applied to an electrode for a solar cell here, it is not limited thereto, and it may be applied to an electrode for all electronic devices.
[Mode for Invention]
The following examples illustrate this disclosure in further detail. However, it is understood that this disclosure shall not be limited by these examples.
Preparation of Metallic Glass
Preparation Example 1
An aluminum (Al)-nickel (Ni)-yttrium (Y)-cobalt (Co) mother alloy is manufactured by preparing aluminum (Al), nickel (Ni), yttrium (Y), and cobalt (Co) and then melting them with an arc melter or an induction melter. The aluminum (Al)-nickel (Ni)-yttrium (Y)-cobalt (Co) mother alloy is charged in a crucible and mounted in an atomizer. The atomizer is maintained in a vacuum state, and argon (Ar) gas is supplied into a chamber to form an argon atmosphere. Subsequently, a powder-shaped metallic glass, AlssNisYs^, is manufactured by melting the metal and spraying a high-speed and high- pressure inert gas into the molten solution.
Preparation Example 2
A metallic glass, AI83Ni5 5Y6Sii.5La2Co2, is manufactured according to the same method as Preparation Example 1 , except for using aluminum (Al), nickel
(Ni), yttrium (Y), silicon (Si), lanthanum (La), and cobalt (Co) instead of aluminum (Al), nickel (Ni), yttrium (Y), and cobalt (Co).
Preparation Example 3
A metallic glass, AI84Ni5Y6Ca2NiCo2, is manufactured according to the same method as Preparation Example 1 , except for using aluminum (Al), nickel
(Ni), yttrium (Y), calcium (Ca), and cobalt (Co) instead of aluminum (Al), nickel
(Ni), yttrium (Y), and cobalt (Co) and melting a mother alloy with an AIN powder by adding an AIN powder thereto.
Pulverization of Metallic Glass
Example 1
A metallic glass slurry is prepared by mixing the metallic glass according to Preparation Example 1 in a concentration of 30 wt% with an ethanol solvent.
The metallic glass slurry is pulverized by using a metallic glass pulverizer having the following conditions and is shown in FIG. 1.
- Diameter of the region (R2) for passing compressed air: 2 mm
- Diameter of the region (R3) of adiabatic expansion: 7 mm
- Spray pressure of compressed air: 1 .45 MPa
- Spray speed of metallic glass slurry: 100 ml/min
- Temperature of the region (R3) for adiabatically expanding the compressed air: -40 °C
- Opposed plate: diamond
Example 2
A pulverized metallic glass is obtained according to the same method as Example 1 , except for using the metallic glass according to Preparation Example 2 instead of the metallic glass according to Preparation Example 1. Example 3
A pulverized metallic glass is obtained according to the same method as Example 1 , except for using the metallic glass according to Preparation Example 3 instead of the metallic glass according to Preparation Example 1. Comparative Example 1
A pulverized metallic glass is obtained by pulverizing the metallic glass according to Preparation Example 1 through air jet milling, a kind of method of dry-pulverizing metallic glass. Herein, the metallic glass is supplied at 0.67 g/min, and the air spray pressure is 1.15 MPa.
Comparative Example 2
Pulverized metallic glass is obtained according to the same method as Comparative Example 1 , except for using the metallic glass according to Preparation Example 2 instead of the metallic glass according to Preparation Example !
Comparative Example 3
A pulverized metallic glass is obtained according to the same method as Comparative Example 1 , except for using the metallic glass according to Preparation Example 3 instead of the metallic glass according to Preparation Example 1 . Evaluation 1
A brittleness degree of each metallic glass according to Example 1 and Comparative Example 1 is evaluated.
The brittleness degree of the metallic glass is evaluated by transformation degree of the powder shape before and after pulverization.
FIG. 2 is a SEM photograph showing metallic glass before the pulverization, FIG. 3 is a SEM photograph showing pulverized metallic glass according to Example 1 , and FIG. 4 is a SEM photograph showing the pulverized metallic glass according to Comparative Example 1 .
Referring to FIGS. 2 to 4, the pulverized metallic glass according to Example 1 is broken into fine particles, while the pulverized metallic glass according to Comparative Example 1 is partially pulverized but mostly non- pulverized and left.
Evaluation 2
Particle distribution of each pulverized metallic glass according to Examples 1 to 3 and Comparative Examples 1 to 3 is evaluated.
The particle distribution is evaluated by averaging three measurements obtained by using a particle size analyzer (LA-950 Laser Particle Size Analyzer, Horiba).
The results are provided in Tables 1 to 3.
(Table 1)
Figure imgf000025_0001
D < 5 μιη (%) D50 (pm)
Metallic glass before pulverization 3.09 21.2
Example 2 57.2 4.38
Comparative Example 2 22.4 10.0
(Table 3)
D < 5 pm (%) D50 (pm)
Metallic glass before pulverization 2.01 25.6
Example 3 58.8 4.21
Comparative Example 3 28.0 9.12
Referring to Tables 1 to 3, each pulverized metallic glass according to Examples 1 to 3 shows remarkably improved fine powders compared with each metallic glass according to Comparative Examples 1 to 3. The pulverized metallic glasses according to Comparative Examples 1 to 3 are not only well pulverized, but the pulverized powder is not broken but is crushed and entangled into a chunk due to ductility during the pulverization.
Evaluation 3 An amorphous phase of each pulverized metallic glass according to Examples 1 to 3 is evaluated.
The amorphous phase is evaluated by using an X-ray diffraction (XRD) analysis method, and an overall broad peak in the XRD graph shows an amorphous phase, while at least one sharp peak shows a crystal phase.
The results are provided in Table 4 and FIGS. 5 to 7.
(Table 4)
Figure imgf000026_0001
Referring to Table 4, each pulverized metallic glass according to Examples 1 to 3 maintains a similar amorphous phase to non-pulverized metallic glass, while each pulverized metallic glass according to Comparative Examples 1 to 3 is crystallized and forms a crystal phase during the pulverization.
FIG. 5 is a TEM photograph showing non-pulverized metallic glass, FIG. 6 is a TEM photograph showing the pulverized metallic glass according to Example 2, and FIG. 7 is a TEM photograph showing the pulverized metallic glass according to Comparative Example 2.
Referring to FIGS. 5 to 7, the pulverized metallic glass according to Example 2 shows a similar amorphous phase to the non-pulverized metallic glass, while the pulverized metallic glass according to Comparative Example 2 shows many crystalline phases.
Evaluation 4
Heat flow characteristics of each metallic glass according to Examples 1 to 3 and Comparative Examples 1 to 3 are evaluated.
The results are provided in Tables 5 to 7.
(Table 5)
Exothermic heat (AHsum) (dig)
Metallic glass before pulverization 74
Example 1 70
Comparative Example 1 33
(Table 6)
Exothermic heat (AHSUm) (J/g)
Metallic glass before pulverization 79
Example 2 76
Comparative Example 2 43
(Table 7) Exothermic heat (AHsum) (J/g)
Metallic glass before pulverization 75
Example 3 72
Comparative Example 3 44
Referring to Tables 5 to 7, each pulverized metallic glass according to Examples 1 to 3 shows similar thermal properties to metallic glass before pulverization, while each pulverized metallic glass according to Comparative Examples 1 to 3 shows remarkably changed thermal properties.
Evaluation 5
Electrical characteristics of each pulverized metallic glass according to Example 1 and Comparative Example 1 are evaluated.
The electrical characteristics are evaluated by contact resistance of an electrode sample formed of a conductive paste including pulverized metallic glass.
The electrode sample 1 is formed in the following method.
The pulverized metallic glass according to Example 1 and silver (Ag) powder are added to an organic vehicle including an ethyl cellulose binder, a surfactant, and a mixed solvent of butyl carbitol/butyl carbitol acetate. Herein, the silver (Ag) powder, the pulverized metallic glass according to Example 1 , and the organic vehicle are respectively added in an amount of 82.58 wt%, 3.93 wt%, and 13.49 wt% based on the total weight of a conductive paste. Subsequently, the conductive paste is kneaded with a 3-roll mill. Then, the conductive paste is screen-printed on a silicon wafer. The coated silicon wafer is then heated to about 600 °C by using a belt furnace. The wafer is then cooled, obtaining an Electrode Sample 1.
An Electrode Sample 2 is formed according to the same method as the Electrode Sample 1 , except for using a conductive paste including non- pulverized metallic glass instead of the pulverized metallic glass according to Example 1 .
An Electrode Sample 3 is formed according to the same method as the Electrode Sample 1 , except for using a conductive paste including the pulverized metallic glass according to Comparative Example 1 instead of the pulverized metallic glass according to Example 1.
Contact resistances of the Electrode Samples 1 to 3 are evaluated by averaging four measurements obtained in a transmission line method (TLM).
The results are provided in Table 8.
(Table 8)
Figure imgf000029_0001
Referring to Table 8, the Electrode Sample 1 shows sharply deteriorated contact resistance compared with the Electrode Samples 2 and 3. Accordingly, the pulverized metallic glass according to Example 1 is formed as a fine powder and thus shows improved electrical characteristics. While this disclosure has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

[CLAIMS]
[Claim 1 ]
A method of pulverizing metallic glass, comprising:
preparing a slurry including a metallic glass and a solvent;
supplying a region for passing compressed air with the slurry;
making the metallic glass into droplets by adiabatically expanding the compressed air; and
pulverizing the metallic glass droplets.
[Claim 2]
The method of claim 1 , wherein the pulverization of the metallic glass droplets includes at least either one of collision among the metallic glass droplets or collision of the metallic glass droplets with an opposed plate.
[Claim 3]
The method of claim 2, wherein thermal energy generated when the metallic glass droplets collide with one another or when the metallic glass droplets collide with the opposed plate is smaller than crystallization energy of the metallic glass.
[Claim 4]
The method of claim 1 , wherein the metallic glass and the pulverized metallic glass comprise an amorphous part.
[Claim 5]
The method of claim 4, wherein the metallic glass and the pulverized metallic glass comprise about 80 to about 100 vol% of an amorphous part, respectively.
[Claim 6]
The method of claim 1 , wherein the solvent comprises at least one selected from alcohol, terpineol, butylcarbitol, butylcarbitol acetate, pentanediol, dipentyne, limonene, ethylene glycol alkylether, diethylene glycol alkylether, ethylene glycol alkylether acetate diethylene glycol alkylether acetate, diethylene glycol dialkylether acetate, triethylene glycol alkylether acetate, triethylene glycol alkylether, propylene glycol alkylether, propylene glycol phenylether, dipropylene glycol alkylether, tripropylene glycol alkylether, propylene glycol alkylether acetate, dipropylene glycol alkylether acetate, tripropylene glycol alkyl ether acetate, dimethylphthalic acid, diethylphthalic acid, dibutylphthalic acid, desalted water, alkane, toluene, xylene, chloroform, acetone, alkyl acetate, methylalkyl ketone, ethylalkyl ketone, propylalkyl ketone, butylalkyl ketone, and cycloalkanone.
[Claim 7]
The method of claim 1 , wherein the slurry comprises about 5 to about 60 wt% of a metallic glass and about 40 to about 95 wt% of a solvent.
[Claim 8]
The method of claim 1 , wherein the compressed air is sprayed with a pressure of about 0.5 to about 2.0 MPa.
[Claim 9]
The method of claim 1 , wherein the temperature of the compressed air after the adiabatic expansion is in a range of about -60 to about 10 °C.
[Claim 10]
The method of claim 1 , wherein the pulverized metallic glass has a particle size of D5o≤ 5 pm.
[Claim 1 1 ]
The method of claim 1 , wherein the pulverized metallic glass has a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
[Claim 12]
The method of claim 1 , wherein the pulverized metallic glass has an amorphous part of about 80 to about 100 vol% and a particle size of D50≤ 5 pm.
[Claim 13]
The method of claim 12, wherein the pulverized metallic glass has a smaller particle size than about 5 pm in a ratio of greater than or equal to about 40 %.
[Claim 14]
The method of claim 12, wherein the pulverized metallic glass is an alloy including at least one selected from aluminum (Al), copper (Cu), zirconium (Zr), titanium (Ti), nickel (Ni), iron (Fe), gold (Au), magnesium (Mg), calcium (Ca), cerium (Ce), strontium (Sr), ytterbium (Yb), zinc (Zn), platinum (Pt), cobalt (Co), palladium (Pd), cerium (Ce), lanthanum (La), yttrium (Y), gadolinium (Gd), beryllium (Be), tantalum(Ta), gallium (Ga), hafnium (Hf), niobium (Nb), lead (Pb), platinum (Pt), silver (Ag), phosphorus (P), boron (B), silicon (Si), carbon (C), tin (Sn), zinc (Zn), lithium (Li), molybdenum (Mo), tungsten (W), manganese (Mn), erbium (Er), chromium (Cr), praseodymium (Pr), thulium (Tm), and a combination thereof.
[Claim 15]
A conductive paste, comprising
a conductive powder, a metallic glass, and an organic vehicle, wherein the metallic glass comprises the pulverized metallic glass of claim 12.
[Claim 16]
The conductive paste of claim 15, wherein the conductive powder comprises aluminum (Al), silver (Ag), copper (Cu), nickel (Ni), an alloy thereof, or a combination thereof.
[Claim 17]
The conductive paste of claim 15, wherein the conductive powder, the metallic glass, and the organic vehicle are included in each amount of about 30 to about 99 wt%, about 0.1 to about 20 wt%, and a balance based on the total amount of the conductive paste.
[Claim 18]
An electronic device comprising a sintered product of the conductive paste of claim 15.
PCT/KR2014/006823 2013-12-06 2014-07-25 Method of pulverizing metallic glass, pulverized metallic glass, conductive paste, and electronic device WO2015083917A1 (en)

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Citations (5)

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EP0127795A1 (en) * 1983-05-10 1984-12-12 Toyota Jidosha Kabushiki Kaisha Device and method for making and collecting fine metallic powder
US4523621A (en) * 1982-02-18 1985-06-18 Allied Corporation Method for making metallic glass powder
US4592302A (en) * 1984-11-07 1986-06-03 Freund Industrial Co., Ltd. Coating method and apparatus
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Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US4523621A (en) * 1982-02-18 1985-06-18 Allied Corporation Method for making metallic glass powder
EP0127795A1 (en) * 1983-05-10 1984-12-12 Toyota Jidosha Kabushiki Kaisha Device and method for making and collecting fine metallic powder
US4592302A (en) * 1984-11-07 1986-06-03 Freund Industrial Co., Ltd. Coating method and apparatus
US20110114170A1 (en) * 2009-11-11 2011-05-19 Samsung Electronics Co., Ltd. Conductive paste and solar cell
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