WO2018080091A1 - Silver powder and preparation method therefor - Google Patents

Silver powder and preparation method therefor Download PDF

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Publication number
WO2018080091A1
WO2018080091A1 PCT/KR2017/011507 KR2017011507W WO2018080091A1 WO 2018080091 A1 WO2018080091 A1 WO 2018080091A1 KR 2017011507 W KR2017011507 W KR 2017011507W WO 2018080091 A1 WO2018080091 A1 WO 2018080091A1
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Prior art keywords
weight
silver
silver powder
parts
reaction solution
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PCT/KR2017/011507
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French (fr)
Korean (ko)
Inventor
강태훈
최재원
이미영
이창근
진우민
권태현
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엘에스니꼬동제련 주식회사
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Publication of WO2018080091A1 publication Critical patent/WO2018080091A1/en

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Classifications

    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic 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
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a method for producing silver powder for conductive paste used in electronic components such as solar cell electrodes, internal electrodes of multilayer capacitors, conductor patterns of circuit boards and the like.
  • Silver is widely used as an electrode material in the field of electric and electronics because of its inherent high electrical conductivity and oxidation stability.
  • conductive silver paste in which silver is powdered and processed into paste or ink.
  • Conductive silver paste using silver powder has various uses such as PDP, solar cell front side, rear electrode, touch screen as well as traditional conductive electrodes such as through hole, die bonding, and chip parts, and its usage is continuously increasing. to be.
  • the silver powder for solar cell electrodes has a wider area to receive sunlight, and reducing the gap between the electrode grids is advantageous for the power generation efficiency of solar cells.
  • internal voids, crystallite size, particle size In order to realize fine line width, in the powder side, internal voids, crystallite size, particle size, It is important to produce powders with high shrinkage characteristics through packing density or high atomic diffusivity of the surface, but there are many problems in printability when pasting due to the increase of specific surface area or the accumulation of organic matter into the internal voids. .
  • the present invention is to provide a silver powder having a large crystallite diameter, low content of residual organic matter, high shrinkage, and excellent electrical conductivity, and a method of manufacturing the same.
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a silver powder having a large crystallite diameter, a low residual organic substance content and a high shrinkage ratio.
  • the present invention provides a reaction solution preparing step (S21) for preparing a first reaction solution containing a silver ion, ammonia (NH 3 ) and phosphorus compounds and a second reaction solution containing a reducing agent and ascorbic acid and
  • It provides a silver powder manufacturing method comprising a; silver salt reduction step (S2) comprising a precipitation step (S22) of reacting the first reaction solution and the second reaction solution to obtain a silver powder.
  • the phosphorus compound is any one selected from the group consisting of pyrophosphate containing sodium pyrophosphate, sodium phosphate, phosphate containing potassium phosphate and metaphosphate. It is characterized by including a species or more.
  • the silver ion is a silver salt solution containing silver nitrate (AgNO 3 ) is included in the first reaction solution, the phosphorus compound is included in 0.05 to 0.2 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ), Ascorbic acid is characterized in that it comprises 0.1 to 1 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ).
  • the weight part of the phosphorus compound added to 100 parts by weight of the silver nitrate (AgNo 3 ) is A part by weight and the weight part of the ascorbic acid is B part by weight
  • the relationship between the addition amount of the phosphorus compound and ascorbic acid is represented by the following formulas It is characterized by being added to satisfy 3.
  • the present invention is a silver powder having an average particle size of 1.0 to 1.5 ⁇ m, has a crystallite diameter of 280 to 430 mm 3, an organic content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m 2 / g Provide powder.
  • the present invention is a conductive paste containing the silver powder, the shrinkage of the conductive film formed by baking the conductive paste 200 ⁇ m coated printing after heating at a heating rate of 50 °C / min, the final 700 °C for 1 minute in a belt-type drying furnace is 20 to 30 %, And a resistivity of 3.1 ⁇ Pa ⁇ cm or less is provided.
  • the present invention provides a solar cell comprising an electrode formed using the conductive paste.
  • the present invention can produce a silver powder having a high shrinkage while having a low content of residual organic matter by adjusting the content of phosphorus compound and ascorbic acid in the silver powder manufacturing process.
  • a silver powder having an average particle size of 1.0 to 1.5 ⁇ m, a crystallite diameter of 280 to 430 mm 3, an organic content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m 2 / g can be prepared.
  • Another silver powder in one embodiment of the present invention by reducing the content of the residual organic matter of the silver powder prepared by adjusting the content of the phosphorus compound and ascorbic acid in the manufacturing process and at the same time to increase the shrinkage during sintering, in particular comprising the silver powder It provides an effect of increasing the power generation efficiency of a solar cell comprising a front electrode manufactured using a conductive paste to.
  • Method for producing a silver powder according to an embodiment of the present invention is a silver salt manufacturing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4).
  • the production method of silver powder according to the present invention necessarily includes a silver salt reduction step (S2), other steps can be omitted.
  • Silver salt preparation step (S1) according to an embodiment of the present invention to prepare a silver salt solution containing silver ions (Ag +) by acid treatment of silver (Ag +) in the form of ingots, ribs, granules
  • the silver powder may be prepared by directly preparing a silver salt solution through this step, but a later step may be performed using a commercially available silver nitrate (AgNO 3 ), a silver salt complex, or a silver intermediate solution. .
  • the silver salt reduction step (S2) is a step of depositing silver particles by reducing silver ions by adding ammonia, a reducing agent, a phosphorus compound, and ascorbic acid to the silver salt solution.
  • reaction solution preparation step (S21) ammonia and phosphorus compounds are added to the silver salt solution containing silver ions, stirred, and dissolved to prepare a first reaction solution.
  • the silver ion is not limited as long as it is a material included in the form of a silver cation.
  • it may be silver nitrate (AgNO 3 ), a silver salt complex or a silver intermediate.
  • silver nitrate (AgNO 3 ) is used.
  • AgNO 3 silver nitrate
  • the use of silver nitrate (AgNO 3 ) containing silver ions will be described as an example.
  • Ammonia may be used in the form of an aqueous solution, and in the case of using a 25% aqueous ammonia solution, 100 to 150 parts by weight is added based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the aqueous ammonia solution is added below 100 parts by weight, the reaction pH is low, so that all of the silver ions are not reduced, or there is a problem in forming a uniform particle distribution. There is a problem that is too high.
  • the aqueous solution of 25% ammonia is added in an amount of 120 to 140 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ).
  • the ammonia includes its derivatives.
  • Phosphorus compound includes any one or more selected from the group consisting of pyrophosphate, phosphate and metaphosphate, more specifically sodium pyrophosphate, sodium phosphate potassium phosphate (Potassium) phosphate) and the like, preferably sodium pyrophosphate.
  • the phosphorus compound is added in an amount of 0.05 to 0.2 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ). If the phosphorus compound is added less than 0.015 parts by weight, the organic matter content of the silver powder is high, there is a problem of low conductivity because the carbon in the electrode remains during sintering, silver powder prepared when the phosphorus compound is added in excess of 0.2 parts by weight As the crystallite diameter of is rapidly increased, the sintering is delayed and the electrical properties are degraded as the recrystallization temperature is increased during firing of the conductive paste. More preferably, it is added at 0.1 to 0.2 parts by weight.
  • the first reaction solution containing silver ions, ammonia, and phosphorus compounds may be prepared in the form of a slurry by adding silver ions, aqueous ammonia, and phosphorus compounds to a solvent such as water, stirring, and dissolving the same. have.
  • Reaction liquid preparation step (S21) also prepares a second reaction liquid containing a reducing agent and ascorbic acid.
  • the reducing agent may be at least one selected from the group consisting of alkanolamines, hydroquinones, hydrazines and formalin, among which hydroquinones may be preferably selected.
  • the amount of the reducing agent is preferably included in an amount of 10 to 20 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) included in the first reaction solution.
  • AgNO 3 silver nitrate
  • the second reaction solution is prepared using 14 to 16 parts by weight of a reducing agent based on 100 parts by weight of silver nitrate.
  • the content of ascorbic acid is preferably included in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) included in the first reaction solution.
  • silver nitrate AgNO 3
  • the crystallite diameter of the prepared silver powder is increased, and as the recrystallization temperature is increased during firing of the conductive paste, there is a problem that the electrical properties are lowered due to sintering delay.
  • the content is high, and there is a problem that the conductivity is lowered because carbon in the electrode remains during sintering.
  • the second reaction solution is prepared using 0.2 to 0.8 parts by weight of a reducing agent based on 100 parts by weight of silver nitrate.
  • the second reaction solution containing a reducing agent and ascorbic acid may be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and stirring the solution.
  • the present invention is to control the crystallite diameter, organic matter content, specific surface area and shrinkage of the silver powder prepared by adjusting the content of the phosphorus compound contained in the first reaction solution and the ascorbic acid contained in the second reaction solution Characterized in that.
  • the phosphorus compound is added in an amount of 0.05 to 0.2 parts by weight based on 100 parts by weight of silver nitrate (AgNo 3 ), and ascorbic acid is added in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of silver nitrate (AgNo 3 ).
  • Ascorbic acid is added in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of silver nitrate (AgNo 3 ).
  • the weight part of the phosphorus compound added to 100 parts by weight of silver nitrate (AgNo 3 ) is called A part by weight and the part by weight of ascorbic acid is B part by weight
  • the relationship between the addition amount of the phosphorus compound and ascorbic acid satisfies Equation 1 below.
  • a silver powder having a crystallite diameter of 280 to 430 mm 3, having a low organic matter content of 0.5% or less, a specific surface area of 0.5 m 2 / g or less, and a shrinkage of 20% or more can be prepared.
  • the conductive film formed by satisfying the above formula 1 was formed by firing a conductive paste containing silver powder for 200 ⁇ m after printing and heating at a heating rate of 50 ° C./min for 1 minute in a belt-type drying furnace at 700 ° C. for a large shrinkage of 20 to 30%. Has That is, it is possible to produce a silver powder having a large crystallite diameter and a large shrinkage ratio.
  • the crystallite diameter decreases within the range of 280 to 430 kPa
  • the organic content increases within the range of 0.5% or less, 0.5m 2 / g or less It is possible to adjust the silver powder properties so that the specific surface area increases within the range and the shrinkage increases within the range of 20% or more.
  • the crystallite diameter increases within the range of 280 to 430 kPa, the organic content decreases within the range of 0.5% or less, and the range of 0.5 m 2 / g or less It is possible to adjust the silver powder properties so that the specific surface area is reduced within the range, and shrinkage is reduced within the range of 20% or more.
  • Precipitation step (S22) is a step of obtaining a silver powder by reacting the first reaction solution and the second reaction solution, stirring the first reaction solution prepared by the reaction solution preparation step (S21)
  • the second reaction liquid can be slowly added dropwise or added in a batch to react.
  • the mixture is further stirred for 5 to 10 minutes to grow the particles in the mixed solution in a short time, so that the reduction reaction is ended in a batch to prevent aggregation between the particles and to improve dispersibility.
  • dispersant examples include fatty acids, fatty acid salts, surfactants, organometallics, chelate formers and protective colloids.
  • the remaining organic matter content may be increased, so it is desirable to control the particle size, the remaining organic matter content, and the crystallite diameter of the silver powder without adding the dispersant.
  • Purification step (S3) is a silver salt reduction step (S2) after completing the silver particle precipitation reaction to remove and wash the silver powder dispersed in an aqueous solution or slurry using filtration and the like Step S31 is included. More specifically, after the silver particles in the silver powder dispersion are precipitated, the supernatant of the dispersion is discarded and filtered using a centrifuge, and the filter medium is washed with pure water. The washing process must be done by completely removing the wash water from which the powder has been washed. It is also possible to optionally add the aforementioned dispersants to the reaction complete solution prior to filtration to prevent aggregation of the silver powder.
  • the purification step (S3) may further comprise a drying and disintegration step (S34) after washing.
  • Surface treatment step (S4) is a step of hydrophobizing the hydrophilic surface of the silver powder, it may be made selectively. More specifically, the surface treatment agent containing a stearic acid ethanol solution can be added to the silver powder obtained after filtration, and hydrophobicity can be provided to a silver powder. After that, silver powder can be obtained through filtration, washing, drying and pulverization. When surface treatment of silver powder, the powder should be well dispersed, and the surface treatment is sufficient. If the water content is low, the dispersion efficiency is poor, so it is better to surface-treat a certain amount with water content.
  • Silver powder prepared according to the silver powder manufacturing method according to an embodiment of the present invention has an average particle size of 1.0 to 1.5 ⁇ m, a crystallite diameter of 280 to 430 ⁇ , an organic content of 0.5% or less, a specific surface area of 0.3 To 0.5 m 2 / g.
  • the present invention also provides a conductive paste comprising silver powder prepared according to one embodiment of the present invention. More specifically, the conductive paste according to the present invention may be suitably used for forming solar cell electrodes including silver powder, glass frit, and organic vehicle prepared according to the present invention.
  • the conductive paste composition according to the present invention may further include additives commonly known as necessary, for example, a dispersant, a plasticizer, a viscosity modifier, a surfactant, an oxidant, a metal oxide, a metal organic compound, and the like.
  • additives commonly known as necessary, for example, a dispersant, a plasticizer, a viscosity modifier, a surfactant, an oxidant, a metal oxide, a metal organic compound, and the like.
  • the present invention also provides a method for forming an electrode of a solar cell and a solar cell electrode produced by the method, wherein the conductive paste is coated on a substrate, dried and baked. Except for using the conductive paste containing the silver powder of the above characteristics in the method of forming a solar cell electrode of the present invention, the substrate, printing, drying and firing can be used as the method commonly used in the manufacture of solar cells as well to be.
  • the substrate may be a silicon wafer.
  • Shrinkage of the conductive film formed by firing the conductive paste containing the silver powder prepared according to the present invention by 200 ⁇ m coating printing after firing at a heating rate of 50 ° C./min and the final 700 ° C. for 1 minute in a belt-type drying furnace was 20-30%, and resistivity. It has a characteristic of 3.1 microPa * cm or less.
  • the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion
  • Silver powder was obtained in the same manner as in Example 1 except that the sodium pyrophosphate content of the first reaction solution and the ascorbic acid content of the second reaction solution were changed as shown in Table 1 below.
  • Comparative Example 1 ascorbic acid was not added to the second reaction liquid, and only a small amount of sodium pyrophosphate was added to obtain a silver powder in the same manner as in Example 1, and Comparative Example 2 was used as the sodium pyrophosphate of the first reaction liquid.
  • Silver powder was obtained in the same manner as in Example 1 except that the content and the ascorbic acid content of the second reaction solution were modified as shown in Table 1 below, and Comparative Example 3 was used to determine the sodium pyrophosphate content of the first reaction solution.
  • the silver powder was obtained by the same method as Example 1 except adding in excess as mentioned above and not adding ascorbic acid to a 2nd reaction solution.
  • Example 1 730 128 175 0.24 1000 20 One Example 2 730 128 175 0.20 1000 20 0.5 Example 3 730 128 175 0.16 1000 20 0.3 Example 4 730 128 175 0.18 1000 20 0.8 Example 5 730 128 175 0.22 1000 20 0.4 Comparative Example 1 730 128 175 0.024 1000 20 Comparative Example 2 730 128 175 0.024 1000 20 0.5 Comparative Example 3 730 128 175 0.32 1000 20
  • the silver powders prepared according to the Examples and Comparative Examples of the present invention were measured by averaging the diameters of 100 powders using a scanning electron microscope manufactured by JEOL. The results are shown in Table 3 below.
  • Powder X-ray diffraction was performed using an X-ray diffractometer X'per manufactured by PANalytical, and the crystallite diameter was calculated from the diffraction angle peak position and half width of the obtained [111] plane using the scherrer equation. The results are shown in Table 3 below.
  • TGA analysis was performed in air in a range from room temperature to 500 ° C. at an elevated temperature rate of 10 ° C./min to measure organic matter content. The results are shown in Table 3 below.
  • the specific surface area was measured using a multipoint measurement method using a specific surface area analyzer manufactured by BELSORP, Inc. using 1 hrs dried product at 100 ° C. The results are shown in Table 3 below.
  • the silver powder prepared according to the Examples and Comparative Examples of the present invention was applied to 200 ⁇ m after hand mixing in a binder mixed with 10.0 vol.% Of ETHOCELTM Std200 Ethylcellulose (The Dow Chemical Company) and 90.0 vol% of Buthyl cabitol acetate.
  • the conductive film was prepared by baking at a heating rate of 50 ° C./min at a final temperature of 700 ° C. for 1 minute in a belt-type drying furnace. The results are shown in Table 3 below.
  • Example 1 1.38 367 0.31 0.41 22.38 3.09
  • Example 2 1.32 406 0.37 0.38 21.1 3.02
  • Example 3 1.21 375 0.43 0.41 20.3 2.97
  • Example 4 1.34 358 0.47 0.45 24.02 3.08
  • Example 5 1.28 422 0.28 0.31 20.1 3.02
  • Comparative Example 1 1.32 355 0.24 0.37 15.3 3.22 Comparative Example 2 1.27 113 0.99 2.11 31.2 3.51 Comparative Example 3 1.28 725 0.07 0.35 13.1 3.47
  • Silver powders according to Examples 1 to 5 have an average particle size of 1.5 ⁇ m or less, crystallite diameter of 280 to 430 mm 3, organic matter content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m as shown in Table 3 above. 2 / g, the shrinkage is 20 to 30%, and has a specific resistance of 3.1 mu ⁇ cm or less.
  • Example 4 it can be seen that the crystallite diameter, organic matter content, specific surface area, and shrinkage rate can be adjusted by controlling the phosphorus compound and ascorbic acid content.
  • the silver powder according to Example 4 was found to have reduced crystallite diameter, increased organic matter content, specific surface area, and shrinkage as compared with the silver powder according to Examples 1 to 3, and the silver powder according to Example 5 was Compared with the silver powder according to 1 to 3, the crystallite diameter was increased, and the organic content, the specific surface area, and the shrinkage rate were found to decrease.

Abstract

The present invention relates to a method for preparing a silver powder, comprising a silver salt reduction step (S2) comprising: a reaction solution preparation step (S21) of preparing a first reaction solution containing a silver ion, ammonia (NH3), and a phosphorus compound and a second reaction solution containing a reducing agent and ascorbic acid; and a precipitation step (S22) of obtaining a silver powder by reacting the first reaction solution and the second reaction solution, and can provide: a silver powder having a large crystallite diameter, a low amount of remaining organic material, and high shrinkage by controlling the amounts of the phosphorous compound and the ascorbic acid; and a conductive paste comprising the same.

Description

은 분말 및 이의 제조방법Silver powder and preparation method thereof
본 발명은 태양전지용 전극이나 적층 콘덴서의 내부전극, 회로기판의 도체 패턴 등 전자부품에 사용되는 도전성 페이스트용 은 분말의 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing silver powder for conductive paste used in electronic components such as solar cell electrodes, internal electrodes of multilayer capacitors, conductor patterns of circuit boards and the like.
은(silver)은 그것이 가진 고유의 높은 전기전도도와 산화안정성으로 인해 전기전자 분야에서 전극재료로서 널리 사용되고 있다. 특히 최근에는 원하는 형태의 회로를 직접적으로 형성하는 인쇄전자기술의 발달에 힘입어 은을 분말화하고 이를 페이스트나 잉크형태로 가공한 도전성 은 페이스트에 관한 산업이 발달하고 있다. 은 분말이 사용되는 도전성 은 페이스트는 쓰루홀, 다이본딩, 칩부품 등의 전통적인 도전 전극뿐만 아니라 PDP, 태양전지 전면, 후면 전극, 터치스크린 등 그 사용처가 다양하고 계속해서 그 사용량이 증가되고 있는 추세이다.Silver is widely used as an electrode material in the field of electric and electronics because of its inherent high electrical conductivity and oxidation stability. In particular, with the development of printed electronic technology that directly forms a circuit of a desired form, an industry has been developed regarding conductive silver paste in which silver is powdered and processed into paste or ink. Conductive silver paste using silver powder has various uses such as PDP, solar cell front side, rear electrode, touch screen as well as traditional conductive electrodes such as through hole, die bonding, and chip parts, and its usage is continuously increasing. to be.
종래부터, 은 분말의 제조에는, 질산은 수용액과 암모니아수로 은 암민 착체 수용액을 제조하고, 이것에 유기환원제를 첨가하는 습식환원 프로세스가 채용되어왔다. 최근, 이들 은분말의 주된 용도는, 칩 부품, 플라즈마 디스플레이 패널 등의 전극이나 회로의 형성에 이용되고 있다.Conventionally, the wet reduction process which manufactures silver ammine complex aqueous solution with the silver nitrate aqueous solution and ammonia water, and adds an organic reducing agent to this has been employ | adopted for manufacture of silver powder. In recent years, the main use of these silver powders is used for formation of electrodes and circuits, such as a chip component and a plasma display panel.
태양전지 전극용 은 분말은 태양광을 받는 면적을 넓게 하고, 전극 그리드 사이의 간격을 줄이는 것이 태양광셀의 발전효율에 유리하므로 미세선폭 구현을 위하여 분말 측면에서는 소성 후 내부 공극, 결정자 크기, 입도, Packing density 또는 표면의 높은 원자확산성을 통해 높은 수축율 특성을 가지는 분말을 제조하는 것이 중요하나, 내부 공극으로의 유기물의 집적 또는 비표면적의 증가로 인하여 페이스트화 시 인쇄성에 문제를 야기하는 경우가 많다.The silver powder for solar cell electrodes has a wider area to receive sunlight, and reducing the gap between the electrode grids is advantageous for the power generation efficiency of solar cells.In order to realize fine line width, in the powder side, internal voids, crystallite size, particle size, It is important to produce powders with high shrinkage characteristics through packing density or high atomic diffusivity of the surface, but there are many problems in printability when pasting due to the increase of specific surface area or the accumulation of organic matter into the internal voids. .
종래의 일반적인 방법을 통해 은 분말을 제조하는 경우 결정자 지름을 크게 제조하기 어려웠으며, 환원제 함량 등을 조절하여 결정자 지름을 크게 제조하더라도 잔존 유기물 함량이 높아 제조되는 전극의 성능을 저하시키는 문제점이 있었고, 또한 결정자 지름을 크게 제조하는 경우 수축률이 낮아 전기전도성이 떨어지는 문제점이 있었다. In the case of preparing silver powder through a conventional general method, it was difficult to produce a large crystallite diameter, and even when the crystallite diameter was largely prepared by adjusting the reducing agent content, there was a problem of degrading the performance of the electrode produced with a high content of residual organic matter. In addition, when the crystallite diameter is large, there is a problem in that electrical conductivity is low due to a low shrinkage rate.
이에 본 발명은 결정자 지름이 크면서도 잔존 유기물 함량이 낮으며 수축률이 높아 전기전도성이 우수한 은 분말 및 이의 제조방법을 제공하고자 한다. Accordingly, the present invention is to provide a silver powder having a large crystallite diameter, low content of residual organic matter, high shrinkage, and excellent electrical conductivity, and a method of manufacturing the same.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로 결정자 지름이 크면서도, 잔존 유기물 함량이 낮고 높은 수축율을 가지는 은 분말을 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a silver powder having a large crystallite diameter, a low residual organic substance content and a high shrinkage ratio.
그러나 본 발명의 목적들은 상기에 언급된 목적으로 제한되지 않으며, 언급되지 않은 또 다른 목적들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.However, the objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명은 은 이온, 암모니아(NH3) 및 인 화합물을 포함하는 제1 반응액 및 환원제 및 아스코르빅산을 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 The present invention provides a reaction solution preparing step (S21) for preparing a first reaction solution containing a silver ion, ammonia (NH 3 ) and phosphorus compounds and a second reaction solution containing a reducing agent and ascorbic acid and
제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함하는 은 염 환원단계(S2);를 포함하는 은 분말 제조방법을 제공한다. It provides a silver powder manufacturing method comprising a; silver salt reduction step (S2) comprising a precipitation step (S22) of reacting the first reaction solution and the second reaction solution to obtain a silver powder.
또한 상기 인 화합물은 피로인산나트륨(Sodium Pyrophosphate)을 포함하는 피로인산염, 인산나트륨(sodium phosphate), 인산칼륨(Potassium phosphate)을 포함하는 인산염 및 메타인산염(metaphosphate)으로 구성되는 군에서 선택되는 어느 1종 이상을 포함하는 것을 특징으로 한다. In addition, the phosphorus compound is any one selected from the group consisting of pyrophosphate containing sodium pyrophosphate, sodium phosphate, phosphate containing potassium phosphate and metaphosphate. It is characterized by including a species or more.
또한 상기 은 이온은 질산은(AgNO3)을 포함하는 은 염 용액으로 상기 제1 반응액에 포함되며, 상기 인 화합물은 상기 질산은(AgNO3) 100 중량부에 대하여 0.05 내지 0.2 중량부로 포함되고, 상기 아스코르브산은 상기 질산은(AgNO3) 100 중량부에 대하여 0.1 내지 1 중량부로 포함되는 것을 특징으로 한다. In addition, the silver ion is a silver salt solution containing silver nitrate (AgNO 3 ) is included in the first reaction solution, the phosphorus compound is included in 0.05 to 0.2 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ), Ascorbic acid is characterized in that it comprises 0.1 to 1 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ).
또한 상기 질산은(AgNo3) 100 중량부에 대하여 첨가되는 상기 인 화합물의 중량부를 A 중량부라 하고 상기 아스코르브산의 중량부를 B 중량부라 할 때, 인 화합물과 아스코르브산의 첨가량 관계식이 하기 식 1 내지 식 3을 만족하도록 첨가되는 것을 특징으로 한다. In addition, when the weight part of the phosphorus compound added to 100 parts by weight of the silver nitrate (AgNo 3 ) is A part by weight and the weight part of the ascorbic acid is B part by weight, the relationship between the addition amount of the phosphorus compound and ascorbic acid is represented by the following formulas It is characterized by being added to satisfy 3.
[식 1][Equation 1]
Figure PCTKR2017011507-appb-I000001
Figure PCTKR2017011507-appb-I000001
[식 2][Equation 2]
Figure PCTKR2017011507-appb-I000002
Figure PCTKR2017011507-appb-I000002
(이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
[식 3][Equation 3]
Figure PCTKR2017011507-appb-I000003
Figure PCTKR2017011507-appb-I000003
(이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
또한 본 발명은 평균 입자 크기가 1.0 내지 1.5 μm 인 은 분말로서, 결정자 지름이 280 내지 430 Å 이고, 유기물 함량이 0.5% 이하이며, 비표면적이 0.3 내지 0.5 m2/g 인 것을 특징으로 하는 은 분말을 제공한다. In addition, the present invention is a silver powder having an average particle size of 1.0 to 1.5 μm, has a crystallite diameter of 280 to 430 mm 3, an organic content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m 2 / g Provide powder.
또한 본 발명은 상기 은 분말을 포함하는 도전성 페이스트로서, 상기 도전성 페이스트를 200μm 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 형성한 도전막의 수축률이 20 내지 30% 이고, 비저항이 3.1μΩ·cm 이하인 것을 특징으로 하는 도전성 페이스트를 제공한다. In addition, the present invention is a conductive paste containing the silver powder, the shrinkage of the conductive film formed by baking the conductive paste 200μm coated printing after heating at a heating rate of 50 ℃ / min, the final 700 ℃ for 1 minute in a belt-type drying furnace is 20 to 30 %, And a resistivity of 3.1 µPa · cm or less is provided.
또한 본 발명은 상기 도전성 페이스트를 이용하여 형성된 전극을 포함하는 태양전지를 제공한다.In another aspect, the present invention provides a solar cell comprising an electrode formed using the conductive paste.
본 발명은 은 분말 제조 공정에 있어서 인 화합물과 아스코빅산의 함량을 조절함으로써 잔존 유기물 함량이 낮으면서도 높은 수축율을 가지는 은 분말을 제조할 수 있다. The present invention can produce a silver powder having a high shrinkage while having a low content of residual organic matter by adjusting the content of phosphorus compound and ascorbic acid in the silver powder manufacturing process.
본 발명에 따라 평균 입자 크기가 1.0 내지 1.5μm 이며, 결정자 지름이 280 내지 430 Å 이고, 유기물 함량이 0.5% 이하이며, 비표면적이 0.3 내지 0.5 m2/g 인 은 분말을 제조할 수 있다. According to the present invention, a silver powder having an average particle size of 1.0 to 1.5 μm, a crystallite diameter of 280 to 430 mm 3, an organic content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m 2 / g can be prepared.
본 발명에 따라 제조된 은 분말을 포함하는 도전성 페이스트를 이용하여 200μm 두께로 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 형성한 도전막의 수축률이 20 내지 30% 이고, 비저항이 3.1μΩ·cm 이하인 도전성 페이스트를 제조할 수 있다. Shrinkage of the conductive film formed by firing for 1 minute in a belt-type drying furnace at a heating rate of 50 ℃ / min, the final 700 ℃ using a conductive paste containing a silver powder prepared in accordance with the present invention after printing 200μm thick % And a resistivity of 3.1 μm · cm or less can be produced.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 첨부하는 특허청구의 범위에 의해서만 한정되는 본 발명의 범위를 한정하려는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한은 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다.Prior to describing the present invention in detail below, it is understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is limited only by the scope of the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise indicated.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다.Throughout this specification and claims, unless otherwise indicated, the termcomprise, constitutes, and configure means to include the referenced article, step, or group of articles, and step, and any other article It is not intended to exclude a stage or group of things or groups of stages.
한편, 본 발명의 여러 가지 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징 및 특징들과 결합될 수 있다. 이하, 첨부된 도면을 참조하여 본 발명의 실시예 및 이에 따른 효과를 설명하기로 한다.On the other hand, various embodiments of the present invention can be combined with any other embodiment unless clearly indicated to the contrary. Any feature indicated as particularly preferred or advantageous may be combined with any other feature and features indicated as preferred or advantageous. Hereinafter, with reference to the accompanying drawings will be described an embodiment of the present invention and the effects thereof.
본 발명의 일실시예에 다른 은 분말은 제조 과정에서의 인 화합물 및 아스코르브산의 함량을 조절하여 제조되는 은 분말의 잔존 유기물 함량을 낮춤과 동시에 소결 시 수축률을 높임으로써, 특히 상기 은 분말을 포함하는 도전성 페이스트를 사용하여 제조된 전면 전극을 포함하는 태양전지의 발전 효율을 상승시키는 효과를 제공한다. Another silver powder in one embodiment of the present invention by reducing the content of the residual organic matter of the silver powder prepared by adjusting the content of the phosphorus compound and ascorbic acid in the manufacturing process and at the same time to increase the shrinkage during sintering, in particular comprising the silver powder It provides an effect of increasing the power generation efficiency of a solar cell comprising a front electrode manufactured using a conductive paste to.
본 발명의 일실시예에 따른 은 분말의 제조방법은 은 염 제조단계(S1); 은 염 환원단계(S2); 여과 및 세척 등 정제단계(S3); 및 표면처리단계(S4);를 포함하여 이루어진다. 본 발명에 따른 은 분말의 제조방법은 은 염 환원단계(S2)를 반드시 포함하고, 이외의 단계는 생략 가능하다.Method for producing a silver powder according to an embodiment of the present invention is a silver salt manufacturing step (S1); Silver salt reduction step (S2); Purification step such as filtration and washing (S3); And a surface treatment step (S4). The production method of silver powder according to the present invention necessarily includes a silver salt reduction step (S2), other steps can be omitted.
본 발명의 일실시예에 따른 은 염 제조단계(S1)는 잉곳, 립, 그래뉼 형태의 은(silver, Ag)을 산처리하여 은 이온(Ag+)을 포함하는 은 염(silver salt) 용액을 제조하는 단계로서, 본 단계를 거쳐 은 염 용액을 직접 제조하여 은 분말을 제조할 수 있으나, 시중에서 구입한 질산은(AgNO3), 은 염 착체 또는 은 중간체 용액을 이용하여 이 후 단계를 진행할 수 있다.Silver salt preparation step (S1) according to an embodiment of the present invention to prepare a silver salt solution containing silver ions (Ag +) by acid treatment of silver (Ag +) in the form of ingots, ribs, granules As a step, the silver powder may be prepared by directly preparing a silver salt solution through this step, but a later step may be performed using a commercially available silver nitrate (AgNO 3 ), a silver salt complex, or a silver intermediate solution. .
본 발명의 일실시예에 따른 은 염 환원단계(S2)는 은 염 용액에 암모니아, 환원제, 인 화합물 및 아스코르브산을 첨가하여 은 이온을 환원시켜 은 입자(silver particle)를 석출하는 단계로서, 은 이온, 암모니아 및 인 화합물을 포함하는 제1 반응액 및 환원제 및 아스코르브산을 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함한다. The silver salt reduction step (S2) according to the embodiment of the present invention is a step of depositing silver particles by reducing silver ions by adding ammonia, a reducing agent, a phosphorus compound, and ascorbic acid to the silver salt solution. Reaction solution preparation step (S21) of preparing a first reaction solution containing ions, ammonia and phosphorus compounds and a second reaction solution containing a reducing agent and ascorbic acid, and reacting the first reaction solution and the second reaction solution with silver powder It includes a precipitation step (S22) to obtain.
본 발명의 일실시예에 따른 반응액제조단계(S21)는 은 이온을 포함하는 은 염 용액에 암모니아 및 인 화합물을 첨가하고 교반하여 용해시켜 제1 반응액을 제조한다. In the reaction solution preparation step (S21) according to an embodiment of the present invention, ammonia and phosphorus compounds are added to the silver salt solution containing silver ions, stirred, and dissolved to prepare a first reaction solution.
상기 은 이온은 은 양이온의 형태로 포함되는 물질이라면 제한되지 않는다. 일례로 질산은(AgNO3), 은 염 착체 또는 은 중간체일 수 있다. 바람직하게는 질산은(AgNO3)을 사용하는 것이 좋다. 이하 은 이온을 포함하는 질산은(AgNO3)을 사용하는 것을 일 예시로 서술한다. The silver ion is not limited as long as it is a material included in the form of a silver cation. For example, it may be silver nitrate (AgNO 3 ), a silver salt complex or a silver intermediate. Preferably, silver nitrate (AgNO 3 ) is used. Hereinafter, the use of silver nitrate (AgNO 3 ) containing silver ions will be described as an example.
암모니아(NH3)는 수용액 형태로 사용될 수 있으며, 25% 암모니아 수용액을 사용하는 경우 질산은(AgNO3) 100 중량부에 대하여 100 내지 150 중량부로 첨가한다. 암모니아 수용액이 100 중량부 미만으로 첨가되는 경우 반응 pH가 낮아서 은 이온이 모두 환원되지 않거나, 균일한 입자 분포를 형성시키는데 문제가 있으며, 150 중량부를 초과하여 첨가되는 경우 제조된 은 분말 중 유기물 함량이 지나치게 높아지는 문제점이 있다. 바람직하게는 질산은(AgNO3) 100 중량부에 대하여 25% 암모니아 수용액을 120 내지 140 중량부로 첨가하는 것이 좋다. 상기 암모니아는 그 유도체를 포함한다. Ammonia (NH 3 ) may be used in the form of an aqueous solution, and in the case of using a 25% aqueous ammonia solution, 100 to 150 parts by weight is added based on 100 parts by weight of silver nitrate (AgNO 3 ). When the aqueous ammonia solution is added below 100 parts by weight, the reaction pH is low, so that all of the silver ions are not reduced, or there is a problem in forming a uniform particle distribution. There is a problem that is too high. Preferably, the aqueous solution of 25% ammonia is added in an amount of 120 to 140 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ). The ammonia includes its derivatives.
인 화합물은 피로인산염, 인산염 및 메타인산염(metaphosphate)으로 구성되는 군에서 선택되는 어느 1종 이상을 포함하며, 더욱 구체적으로는 피로인산나트륨(Sodium Pyrophosphate), 인산나트륨(sodium phosphate) 인산칼륨(Potassium phosphate) 등을 사용할 수 있고, 바람직하게는 피로인산나트륨을 사용하는 것이 좋다. Phosphorus compound includes any one or more selected from the group consisting of pyrophosphate, phosphate and metaphosphate, more specifically sodium pyrophosphate, sodium phosphate potassium phosphate (Potassium) phosphate) and the like, preferably sodium pyrophosphate.
인 화합물은 질산은(AgNO3) 100 중량부에 대하여 0.05 내지 0.2 중량부로 첨가한다. 인 화합물이 0.015 중량부 미만으로 첨가되는 경우 제조된 은 분말의 유기물 함량이 높으며, 소결 시 전극 내 탄소가 남으므로 전도성이 낮은 문제점이 있으며, 인 화합물이 0.2 중량부를 초과하여 첨가되는 경우 제조된 은 분말의 결정자 지름이 급격하게 상승하여, 도전성 페이스트 소성 시 재결정 온도가 상승함에 따라 소결이 지연되고 전기적 특성이 저하되는 문제점이 있다. 더욱 바람직하게는 0.1 내지 0.2 중량부로 첨가하는 것이 좋다. The phosphorus compound is added in an amount of 0.05 to 0.2 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ). If the phosphorus compound is added less than 0.015 parts by weight, the organic matter content of the silver powder is high, there is a problem of low conductivity because the carbon in the electrode remains during sintering, silver powder prepared when the phosphorus compound is added in excess of 0.2 parts by weight As the crystallite diameter of is rapidly increased, the sintering is delayed and the electrical properties are degraded as the recrystallization temperature is increased during firing of the conductive paste. More preferably, it is added at 0.1 to 0.2 parts by weight.
은 이온, 암모니아 및 인 화합물을 포함하는 제1 반응액은 물 등의 용제에 은 이온, 암모니아 수용액 및 인 화합물을 첨가하고 교반하여 용해시켜 수용액 상태로 제조될 수 있으며, 또한 슬러리 형태로 제조될 수 있다. The first reaction solution containing silver ions, ammonia, and phosphorus compounds may be prepared in the form of a slurry by adding silver ions, aqueous ammonia, and phosphorus compounds to a solvent such as water, stirring, and dissolving the same. have.
본 발명의 일실시예에 따른 반응액제조단계(S21)는 또한 환원제 및 아스코르브산을 포함하는 제2 반응액을 제조한다. Reaction liquid preparation step (S21) according to an embodiment of the present invention also prepares a second reaction liquid containing a reducing agent and ascorbic acid.
상기 환원제는 알칸올아민, 하이드로퀴논, 히드라진 및 포르말린으로 이루어지는 군으로부터 선택되는 1종 이상일 수 있으며, 이 중에서 하이드로퀴논을 바람직하게 선택할 수 있다. 환원제의 함량은 제1 반응액에 포함되는 질산은(AgNO3) 100 중량부에 대하여 10 내지 20 중량부로 포함되는 것이 바람직하다. 10 중량부 미만을 사용하는 경우, 은 이온이 모두 환원되지 않을 수 있고, 20 중량부를 초과하여 사용하는 경우 유기물 함량이 증가하는 문제가 있다. 바람직하게는 질산은 100 중량부에 대하여 환원제를 14 내지 16 중량부 사용하여 제2 반응액을 제조하는 것이 좋다. The reducing agent may be at least one selected from the group consisting of alkanolamines, hydroquinones, hydrazines and formalin, among which hydroquinones may be preferably selected. The amount of the reducing agent is preferably included in an amount of 10 to 20 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) included in the first reaction solution. When using less than 10 parts by weight, all of the silver ions may not be reduced, when using more than 20 parts by weight there is a problem that the organic content increases. Preferably, the second reaction solution is prepared using 14 to 16 parts by weight of a reducing agent based on 100 parts by weight of silver nitrate.
상기 아스코르브산의 함량은 제1 반응액에 포함되는 질산은(AgNO3) 100 중량부에 대하여 0.1 내지 1 중량부로 포함되는 것이 바람직하다. 0.1 중량부 미만을 사용하는 경우 제조된 은 분말의 결정자 지름이 상승하여, 도전성 페이스트 소성 시 재결정 온도가 상승함에 따라 소결 지연으로 전기적 특성이 저하되는 문제점이 있고, 1 중량부를 초과하여 사용하는 경우 유기물 함량이 높으며, 소결 시 전극 내 탄소가 남으므로 전도성이 낮아지는 문제가 있다. 바람직하게는 질산은 100 중량부에 대하여 환원제를 0.2 내지 0.8 중량부 사용하여 제2 반응액을 제조하는 것이 좋다. The content of ascorbic acid is preferably included in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of silver nitrate (AgNO 3 ) included in the first reaction solution. When using less than 0.1 parts by weight, the crystallite diameter of the prepared silver powder is increased, and as the recrystallization temperature is increased during firing of the conductive paste, there is a problem that the electrical properties are lowered due to sintering delay. The content is high, and there is a problem that the conductivity is lowered because carbon in the electrode remains during sintering. Preferably, the second reaction solution is prepared using 0.2 to 0.8 parts by weight of a reducing agent based on 100 parts by weight of silver nitrate.
아스코르브산 이외에 에리토르브산(erythorbic acie) 등의 이소아스코르브산(isoascorbic acid)을 사용한 경우에도 동일한 효과를 얻을 수 있다.In addition to ascorbic acid, the same effect can be obtained when isocorbic acid such as erythorbic acie is used.
환원제 및 아스코르브산을 포함하는 제2 반응액은 물 등의 용매에 환원제를 첨가하고 교반하여 용해시켜 수용액 상태로 제조될 수 있다. The second reaction solution containing a reducing agent and ascorbic acid may be prepared in an aqueous solution state by adding a reducing agent to a solvent such as water and stirring the solution.
다른 측면에서 볼 때, 본 발명은 제1 반응액에 포함되는 인 화합물 및 제2 반응액에 포함되는 아스코르브산의 함량을 조절함으로써 제조되는 은 분말의 결정자 지름, 유기물 함량, 비표면적 및 수축률을 조절하는 것을 특징으로 한다. In another aspect, the present invention is to control the crystallite diameter, organic matter content, specific surface area and shrinkage of the silver powder prepared by adjusting the content of the phosphorus compound contained in the first reaction solution and the ascorbic acid contained in the second reaction solution Characterized in that.
인 화합물은 질산은(AgNo3) 100 중량부에 대하여 0.05 내지 0.2 중량부로 첨가되고, 아스코르브산은 질산은(AgNo3) 100 중량부에 대하여 0.1 내지 1 중량부로 첨가된다. 상기 범위 내에서 인 화합물 및 아스코르브산을 첨가하는 경우 결정자 지름이 크면서도, 유기물 함량이 낮고, 수축률이 높은 은 분말을 제조할 수 있다.The phosphorus compound is added in an amount of 0.05 to 0.2 parts by weight based on 100 parts by weight of silver nitrate (AgNo 3 ), and ascorbic acid is added in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of silver nitrate (AgNo 3 ). When the phosphorus compound and ascorbic acid are added within the above range, a silver powder having a large crystallite diameter, a low organic matter content, and a high shrinkage ratio can be prepared.
더욱 구체적으로는 질산은(AgNo3) 100 중량부에 대하여 첨가되는 인 화합물의 중량부를 A 중량부라 하고 아스코르브산의 중량부를 B 중량부라 할 때, 인 화합물과 아스코르브산의 첨가량 관계식이 하기 식 1을 만족하는 경우에 결정자 지름이 280 내지 430 Å 로 크면서도, 유기물 함량이 0.5% 이하로 낮고, 비표면적이 0.5m2/g 이하이며 수축율이 20% 이상인 은 분말을 제조할 수 있다.More specifically, when the weight part of the phosphorus compound added to 100 parts by weight of silver nitrate (AgNo 3 ) is called A part by weight and the part by weight of ascorbic acid is B part by weight, the relationship between the addition amount of the phosphorus compound and ascorbic acid satisfies Equation 1 below. In this case, a silver powder having a crystallite diameter of 280 to 430 mm 3, having a low organic matter content of 0.5% or less, a specific surface area of 0.5 m 2 / g or less, and a shrinkage of 20% or more can be prepared.
[식 1][Equation 1]
Figure PCTKR2017011507-appb-I000004
Figure PCTKR2017011507-appb-I000004
상기 식 1을 만족하도록 제조된 은 분말을 포함하는 도전성 페이스트를 200μm 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 형성한 도전막은 20 내지 30%의 큰 수축률을 갖는다. 즉 결정자 지름이 크면서도 큰 수축률을 갖는 은 분말을 제조할 수 있다. The conductive film formed by satisfying the above formula 1 was formed by firing a conductive paste containing silver powder for 200 μm after printing and heating at a heating rate of 50 ° C./min for 1 minute in a belt-type drying furnace at 700 ° C. for a large shrinkage of 20 to 30%. Has That is, it is possible to produce a silver powder having a large crystallite diameter and a large shrinkage ratio.
한편, 인 화합물 및 아스코르브산의 첨가량을 하기 식 2를 만족하도록 첨가하는 경우 280 내지 430 Å 범위 내에서 결정자 지름이 감소하고, 0.5% 이하인 범위 내에서 유기물 함량이 증가하며, 0.5m2/g 이하인 범위 내에서 비표면적이 증가하고, 20% 이상인 범위 내에서 수축률이 증가하도록 은 분말 특성 조절이 가능하다. On the other hand, when the addition amount of the phosphorus compound and ascorbic acid to satisfy the following formula 2, the crystallite diameter decreases within the range of 280 to 430 kPa, the organic content increases within the range of 0.5% or less, 0.5m 2 / g or less It is possible to adjust the silver powder properties so that the specific surface area increases within the range and the shrinkage increases within the range of 20% or more.
[식 2][Equation 2]
Figure PCTKR2017011507-appb-I000005
Figure PCTKR2017011507-appb-I000005
(이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
또한 인 화합물 및 아스코르브산의 첨가량을 하기 식 3를 만족하도록 첨가하는 경우 280 내지 430 Å 범위 내에서 결정자 지름이 증가하고, 0.5% 이하인 범위 내에서 유기물 함량이 감소하며, 0.5m2/g 이하인 범위 내에서 비표면적이 감소하고, 20% 이상인 범위 내에서 수축률이 감소하도록 은 분말 특성 조절이 가능하다.In addition, when the addition amount of the phosphorus compound and ascorbic acid is added to satisfy the following formula 3, the crystallite diameter increases within the range of 280 to 430 kPa, the organic content decreases within the range of 0.5% or less, and the range of 0.5 m 2 / g or less It is possible to adjust the silver powder properties so that the specific surface area is reduced within the range, and shrinkage is reduced within the range of 20% or more.
[식 3][Equation 3]
Figure PCTKR2017011507-appb-I000006
Figure PCTKR2017011507-appb-I000006
(이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
본 발명의 일실시예에 따른 석출단계(S22)는 제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 단계로서, 반응액제조단계(S21)에 의해 제조된 제1 반응액을 교반하는 상태에서 제2 반응액을 천천히 적가하거나, 일괄 첨가하여 반응시킬 수 있다. 바람직하기로는 일괄 첨가한 후 5분 내지 10분간 더 교반하여 혼합액 중에서 입자를 성장시키는 것이 빠른 시간 내에 환원 반응이 일괄 종료되어 입자끼리의 응집을 방지하고 분산성을 높일 수 있어 좋다.Precipitation step (S22) according to an embodiment of the present invention is a step of obtaining a silver powder by reacting the first reaction solution and the second reaction solution, stirring the first reaction solution prepared by the reaction solution preparation step (S21) The second reaction liquid can be slowly added dropwise or added in a batch to react. Preferably, after the batch addition, the mixture is further stirred for 5 to 10 minutes to grow the particles in the mixed solution in a short time, so that the reduction reaction is ended in a batch to prevent aggregation between the particles and to improve dispersibility.
한편, 본 발명의 실시예에서는 은 입자의 분산성 향상 및 응집 방지를 위해 상기 분산제가 더 첨가되어 반응시키는 것을 권리범위에서 제외하지 않는다. 분산제의 예로는 지방산, 지방산염, 계면활성제, 유기 금속, 킬레이트 형성제 및 보호 콜로이드 등을 들 수 있다. On the other hand, in the embodiment of the present invention does not exclude the addition of the dispersant to react in order to improve the dispersibility of the silver particles and prevent aggregation. Examples of dispersants include fatty acids, fatty acid salts, surfactants, organometallics, chelate formers and protective colloids.
그러나, 상기 분산제가 첨가되는 경우, 잔존 유기물 함량이 증가하여 문제될 수 있으므로, 분산제의 첨가 없이 은 분말의 입경, 잔존 유기물 함량 및 결정자 지름을 제어하는 것이 바람직하다.However, when the dispersant is added, the remaining organic matter content may be increased, so it is desirable to control the particle size, the remaining organic matter content, and the crystallite diameter of the silver powder without adding the dispersant.
본 발명의 일실시예에 따른 정제단계(S3)는 은 염 환원단계(S2)를 통해 은 입자 석출 반응을 완료한 후 수용액 또는 슬러리 내에 분산되어 있는 은 분말을 여과 등을 이용하여 분리하고 세척하는 단계(S31)를 포함한다. 더욱 구체적으로는 은 분말 분산액 중의 은 입자를 침강시킨 후, 분산액의 상등액을 버리고 원심분리기를 이용하여 여과하고, 여재를 순수로 세정한다. 세척을 하는 과정은 분말을 세척한 세척수를 완전히 제거를 해야 이루어 진다. 선택적으로 여과 전에 반응 완료 용액에 상기 언급된 분산제를 첨가하여 은 분말의 응집을 방지하는 것도 가능하다. Purification step (S3) according to an embodiment of the present invention is a silver salt reduction step (S2) after completing the silver particle precipitation reaction to remove and wash the silver powder dispersed in an aqueous solution or slurry using filtration and the like Step S31 is included. More specifically, after the silver particles in the silver powder dispersion are precipitated, the supernatant of the dispersion is discarded and filtered using a centrifuge, and the filter medium is washed with pure water. The washing process must be done by completely removing the wash water from which the powder has been washed. It is also possible to optionally add the aforementioned dispersants to the reaction complete solution prior to filtration to prevent aggregation of the silver powder.
또한 본 발명의 일실시예에 따른 정제단계(S3)는 세척 후 건조 및 해쇄단계(S34)를 더 포함할 수 있다.In addition, the purification step (S3) according to an embodiment of the present invention may further comprise a drying and disintegration step (S34) after washing.
본 발명의 일실시예에 따른 표면처리단계(S4)는 은 분말의 친수 표면을 소수화하는 단계로서, 선택적으로 이루어질 수 있다. 더욱 구체적으로는 여과 후 얻어지는 은 분말에 스테아린산 에탄올 용액을 포함하는 표면처리제를 첨가하여 은 분말에 소수성을 부여할 수 있다. 이 후 다시 여과, 세정, 건조, 해쇄 과정을 거쳐 은 분말을 얻을 수 있다. 은 분말을 표면처리할 때 분말의 분산이 잘 되어야 표면처리가 충분히 이루어지고, 함수율이 낮으면 분산 효율이 떨어지기 때문에 일정량을 함수율을 가지고 표면처리를 하는 것이 좋다.Surface treatment step (S4) according to an embodiment of the present invention is a step of hydrophobizing the hydrophilic surface of the silver powder, it may be made selectively. More specifically, the surface treatment agent containing a stearic acid ethanol solution can be added to the silver powder obtained after filtration, and hydrophobicity can be provided to a silver powder. After that, silver powder can be obtained through filtration, washing, drying and pulverization. When surface treatment of silver powder, the powder should be well dispersed, and the surface treatment is sufficient. If the water content is low, the dispersion efficiency is poor, so it is better to surface-treat a certain amount with water content.
본 발명의 일실시예에 따른 은 분말 제조방법에 따라 제조된 은 분말은 평균 입자 크기가 1.0 내지 1.5μm 이며, 결정자 지름이 280 내지 430 Å 이고, 유기물 함량이 0.5% 이하이며, 비표면적이 0.3 내지 0.5 m2/g 이다.Silver powder prepared according to the silver powder manufacturing method according to an embodiment of the present invention has an average particle size of 1.0 to 1.5μm, a crystallite diameter of 280 to 430 Å, an organic content of 0.5% or less, a specific surface area of 0.3 To 0.5 m 2 / g.
본 발명은 또한 본 발명의 일실시예에 따라 제조되는 은 분말을 포함하는 도전성 페이스트를 제공한다. 더욱 구체적으로 본 발명에 따른 도전성 페이스트는 본 발명에 따라 제조되는 은 분말, 유리 프릿 및 유기 비히클을 포함하여 태양전지 전극 형성에 적합하게 사용될 수 있다.The present invention also provides a conductive paste comprising silver powder prepared according to one embodiment of the present invention. More specifically, the conductive paste according to the present invention may be suitably used for forming solar cell electrodes including silver powder, glass frit, and organic vehicle prepared according to the present invention.
본 발명에 의한 도전성 페이스트 조성물은 필요에 따라 통상적으로 알려져 있는 첨가제, 예를 들면, 분산제, 가소제, 점도 조정제, 계면활성제, 산화제, 금속 산화물, 금속 유기 화합물 등을 더 포함할 수 있다.The conductive paste composition according to the present invention may further include additives commonly known as necessary, for example, a dispersant, a plasticizer, a viscosity modifier, a surfactant, an oxidant, a metal oxide, a metal organic compound, and the like.
본 발명은 또한 상기 도전성 페이스트를 기재 위에 도포하고, 건조 및 소성하는 것을 특징으로 하는 태양전지의 전극 형성 방법 및 상기 방법에 의하여 제조된 태양전지 전극을 제공한다. 본 발명의 태양전지 전극 형성방법에서 상기 특성의 은 분말을 포함하는 도전성 페이스트를 사용하는 것을 제외하고, 기재, 인쇄, 건조 및 소성은 통상적으로 태양전지의 제조에 사용되는 방법들이 사용될 수 있음은 물론이다. 일예로 상기 기재는 실리콘 웨이퍼일 수 있다.The present invention also provides a method for forming an electrode of a solar cell and a solar cell electrode produced by the method, wherein the conductive paste is coated on a substrate, dried and baked. Except for using the conductive paste containing the silver powder of the above characteristics in the method of forming a solar cell electrode of the present invention, the substrate, printing, drying and firing can be used as the method commonly used in the manufacture of solar cells as well to be. For example, the substrate may be a silicon wafer.
본 발명에 따라 제조되는 은 분말을 포함하는 도전성 페이스트를 200μm 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 형성한 도전막의 수축률이 20 내지 30% 이고, 비저항이 3.1μΩ·cm 이하인 특성을 갖는다. Shrinkage of the conductive film formed by firing the conductive paste containing the silver powder prepared according to the present invention by 200μm coating printing after firing at a heating rate of 50 ° C./min and the final 700 ° C. for 1 minute in a belt-type drying furnace was 20-30%, and resistivity. It has a characteristic of 3.1 microPa * cm or less.
실시예 및 비교예 Examples and Comparative Examples
(1) 실시예 1(1) Example 1
상온의 순수 730g에 질산은 128g, 암모니아(농도25%) 175g, 피로인산나트륨 0.24g 첨가하여 제1 반응액을 조제하였다. 한편 상온의 순수 1000g에 하이드로퀴논 20g, 아스코르브산 1g을 첨가하여 제2 반응액을 조제하였다.128 g of silver nitrate, 175 g of ammonia (concentration 25%), and 0.24 g of sodium pyrophosphate were added to 730 g of pure water at room temperature to prepare a first reaction solution. On the other hand, 20 g of hydroquinone and 1 g of ascorbic acid were added to 1000 g of room temperature pure water to prepare a second reaction solution.
이어서, 제1 반응액을 교반한 상태로 하고, 이 제1 반응액에 제2 반응액을 일괄 첨가하여, 첨가 종료 후부터 5분간 더 교반하여 혼합액 중에서 입자를 성장시켰다. 그 후 교반을 멈추고, 혼합액 중의 입자를 침강시킨 후, 혼합액의 상등액을 버리고 혼합액을 원심분리기를 이용하여 여과하고, 여재를 순수로 세정하고, 건조하여, 은 분말을 얻었다.Subsequently, the 1st reaction liquid was made to stir, the 2nd reaction liquid was added to this 1st reaction liquid collectively, and further stirred for 5 minutes after completion | finish of addition, and the particle was grown in the mixed liquid. Then, stirring was stopped, the particles in the mixed solution were allowed to settle, the supernatant of the mixed solution was discarded, the mixed solution was filtered using a centrifugal separator, the media was washed with pure water, dried, and silver powder was obtained.
(2) 실시예 2 내지 5(2) Examples 2 to 5
제1 반응액의 피로인산나트륨의 함량 및 제2 반응액의 아스코르브산 함량을 하기 표 1과 같이 변경한 것 이외에는 실시예 1과 동일한 방법으로 은 분말을 얻었다. Silver powder was obtained in the same manner as in Example 1 except that the sodium pyrophosphate content of the first reaction solution and the ascorbic acid content of the second reaction solution were changed as shown in Table 1 below.
(3) 비교예 1 내지 3(3) Comparative Examples 1 to 3
비교예 1은 제2 반응액에 아스코르브산을 첨가하지 않았으며, 피로인산나트륨만 미량 첨가하여 실시예 1과 동일한 방법으로 은 분말을 얻은 것이고, 비교예 2는 제1 반응액의 피로인산나트륨의 함량 및 제2 반응액의 아스코르브산 함량을 하기 표 1과 같이 변형한 것 이외에는 실시예 1과 동일한 방법으로 은 분말을 얻은 것이며, 비교예 3은 제1 반응액의 피로인산나트륨 함량을 하기 표 1과 같이 과량으로 첨가하고, 제2 반응엑에 아스코르브산을 첨가하지 않은 것 이외에는 실시예 1과 동일한 방법으로 은 분말을 얻은 것이다.In Comparative Example 1, ascorbic acid was not added to the second reaction liquid, and only a small amount of sodium pyrophosphate was added to obtain a silver powder in the same manner as in Example 1, and Comparative Example 2 was used as the sodium pyrophosphate of the first reaction liquid. Silver powder was obtained in the same manner as in Example 1 except that the content and the ascorbic acid content of the second reaction solution were modified as shown in Table 1 below, and Comparative Example 3 was used to determine the sodium pyrophosphate content of the first reaction solution. The silver powder was obtained by the same method as Example 1 except adding in excess as mentioned above and not adding ascorbic acid to a 2nd reaction solution.
제1 반응액First reaction solution 제2 반응액Second reaction solution
순수(ml)Pure water (ml) 질산은(g)Silver nitrate (g) 암모니아(g)Ammonia (g) P.Na(g)P.Na (g) 순수(ml)Pure water (ml) 환원제(g)Reducing agent (g) 아스코르브산(g)Ascorbic acid (g)
실시예 1Example 1 730730 128128 175175 0.240.24 10001000 2020 1One
실시예 2Example 2 730730 128128 175175 0.200.20 10001000 2020 0.50.5
실시예 3Example 3 730730 128128 175175 0.160.16 10001000 2020 0.30.3
실시예 4Example 4 730730 128128 175175 0.180.18 10001000 2020 0.80.8
실시예 5Example 5 730730 128128 175175 0.220.22 10001000 2020 0.40.4
비교예 1Comparative Example 1 730730 128128 175175 0.0240.024 10001000 2020
비교예 2Comparative Example 2 730730 128128 175175 0.0240.024 10001000 2020 0.50.5
비교예 3Comparative Example 3 730730 128128 175175 0.320.32 10001000 2020
(4) 인 화합물 및 아스코르브산의 관계식(4) Relationship between phosphorus compound and ascorbic acid
질산은(AgNo3) 100 중량부에 대하여 첨가되는 인 화합물의 중량부를 A 중량부라 하고 아스코르브산의 중량부를 B 중량부라 할 때, 인 화합물과 아스코르브산의 첨가량 관계에 관한 식 1 내지 3 값을 하기 표 2에 나타내었다. When the weight part of the phosphorus compound added to 100 parts by weight of silver nitrate (AgNo 3 ) is called A part by weight and the part by weight of ascorbic acid is B part by weight, the following formulas 1 to 3 are used for the relationship between the addition amount of the phosphorus compound and ascorbic acid. 2 is shown.
질산은(g)Silver nitrate (g) P.Na(g)P.Na (g) AA A.A(g)A.A (g) BB [식 1][Equation 1] [식 2][식 3][Formula 2] [Formula 3]
실시예 1Example 1 128128 0.240.24 0.1880.188 1One 0.7810.781 1.001.00
실시예 2Example 2 128128 0.200.20 0.1560.156 0.50.5 0.3910.391 1.001.00
실시예 3Example 3 128128 0.160.16 0.1250.125 0.30.3 0.2340.234 1.001.00
실시예 4Example 4 128128 0.180.18 0.1410.141 0.80.8 0.6250.625 1.301.30 식 2 만족Expression 2 Satisfaction
실시예 5Example 5 128128 0.220.22 0.1720.172 0.40.4 0.3130.313 0.830.83 식 3 만족Expression 3 Satisfaction
비교예 1Comparative Example 1 128128 0.0240.024 0.018750.01875 3.093.09
비교예 2Comparative Example 2 128128 0.0240.024 0.018750.01875 0.50.5 0.3906250.390625 8.338.33
비교예 3Comparative Example 3 128128 0.320.32 0.250.25 0.230.23
실험예Experimental Example
(1) SEM size 측정(1) SEM size measurement
본 발명의 실시예 및 비교예에 따라 제조된 은 분말을 지올(JEOL) 회사제 주사전자현미경을 이용하여, 파우더 100개 각각의 지름 크기를 측정한 후 평균을 내어 측정하였다. 그 결과를 하기 표 3에 나타내었다. The silver powders prepared according to the Examples and Comparative Examples of the present invention were measured by averaging the diameters of 100 powders using a scanning electron microscope manufactured by JEOL. The results are shown in Table 3 below.
(2) 결정자 지름 측정(2) determination of crystallite diameter
PANalytical 회사제 X선 회절 장치 X'per를 이용하여 분말 X선 회절을 행하고, 얻어진 [111]면의 회절각 피크 위치와 반가폭으로부터 scherrer equation을 이용하여 결정자 지름을 계산하였다. 그 결과를 하기 표 3에 나타내었다.Powder X-ray diffraction was performed using an X-ray diffractometer X'per manufactured by PANalytical, and the crystallite diameter was calculated from the diffraction angle peak position and half width of the obtained [111] plane using the scherrer equation. The results are shown in Table 3 below.
(3) 유기물 함량(감열 감량, Ignition loss) 측정(3) Determination of organic matter content (heat loss, ignition loss)
세이코 인스트루먼트(Seiko instrument) 회사제 TG/DTA EXART6600을 이용하여, 공기 중, 승온 속도 10℃/min로 상온에서 500℃까지의 범위에서 TGA 분석을 행하여 유기물 함량을 측정하였다. 그 결과를 하기 표 3에 나타내었다.Using TG / DTA EXART6600 manufactured by Seiko instrument, TGA analysis was performed in air in a range from room temperature to 500 ° C. at an elevated temperature rate of 10 ° C./min to measure organic matter content. The results are shown in Table 3 below.
(4) 비표면적 측정(4) measurement of specific surface area
벨솔프(BELSORP) 회사제 비표면적 분석기를 이용하여 100℃에서 1hrs 건조품을 이용하여 멀티포인트 측정법을 이용하여 비표면적을 측정하였다. 그 결과를 하기 표 3에 나타내었다.The specific surface area was measured using a multipoint measurement method using a specific surface area analyzer manufactured by BELSORP, Inc. using 1 hrs dried product at 100 ° C. The results are shown in Table 3 below.
(5) 수축률 측정(5) shrinkage rate measurement
본 발명의 실시예 및 비교예에 따라 제조된 은 분말을 ETHOCELTM Std200 Ethylcellulose (The Dow Chemical Company) 10.0 vol.%와 Buthyl cabitol acetate (대정화금) 90.0 vol%가 혼합된 바인더에 핸드믹싱 후 200μm 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 도전막을 제조하였으며, 제조된 도전막의 소성 전, 후의 면수축률을 측정하였다. 그 결과를 하기 표 3에 나타내었다. The silver powder prepared according to the Examples and Comparative Examples of the present invention was applied to 200μm after hand mixing in a binder mixed with 10.0 vol.% Of ETHOCELTM Std200 Ethylcellulose (The Dow Chemical Company) and 90.0 vol% of Buthyl cabitol acetate. After printing, the conductive film was prepared by baking at a heating rate of 50 ° C./min at a final temperature of 700 ° C. for 1 minute in a belt-type drying furnace. The results are shown in Table 3 below.
(6) 비저항 측정(6) resistivity measurement
미츠비쉬(Mitsubishi chemical Analytech) 회사제 MCP-7700을 이용하여, 수축률 측정 시 제조한 샘플을 0.8cm * 1cm 크기로 제단 후 4점 프로브법으로 측정 하고, 표면조도계를 이용하여 표면의 두께를 측정 후 환산하였다. 그 결과를 하기 표 3에 나타내었다.Using MCP-7700 manufactured by Mitsubishi Chemical Analytech Co., Ltd., the samples prepared at the time of shrinkage measurement were cut to 0.8 cm * 1 cm and then measured by a four-point probe method, and the surface thickness was measured using a surface roughness meter. In conversion. The results are shown in Table 3 below.
SEM size(μm)SEM size (μm) 결정자 지름(Å)Crystalline diameter 유기물 함량(wt.%)Organic matter content (wt.%) 비표면적(m2/g)Specific surface area (m 2 / g) 수축률(%)Shrinkage (%) 비저항(μΩ·cm)Specific resistance (μΩcm)
실시예 1Example 1 1.381.38 367367 0.310.31 0.410.41 22.3822.38 3.093.09
실시예 2Example 2 1.321.32 406406 0.370.37 0.380.38 21.121.1 3.023.02
실시예 3Example 3 1.211.21 375375 0.430.43 0.410.41 20.320.3 2.972.97
실시예 4Example 4 1.341.34 358358 0.470.47 0.450.45 24.0224.02 3.083.08
실시예 5Example 5 1.281.28 422422 0.280.28 0.310.31 20.120.1 3.023.02
비교예 1Comparative Example 1 1.321.32 355355 0.240.24 0.370.37 15.315.3 3.223.22
비교예 2Comparative Example 2 1.271.27 113113 0.990.99 2.112.11 31.231.2 3.513.51
비교예 3Comparative Example 3 1.281.28 725725 0.070.07 0.350.35 13.113.1 3.473.47
실시예 1 내지 5에 따른 은 분말은 상기 표 3에 나타나는 것과 같이 평균 입자 크기가 1.5μm 이하이며, 결정자 지름이 280 내지 430 Å 이고, 유기물 함량이 0.5% 이하이며, 비표면적이 0.3 내지 0.5 m2/g 이고, 수축률이 20 내지 30% 이고 이고, 비저항이 3.1μΩ·cm 이하인 특성을 갖는다. Silver powders according to Examples 1 to 5 have an average particle size of 1.5 μm or less, crystallite diameter of 280 to 430 mm 3, organic matter content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m as shown in Table 3 above. 2 / g, the shrinkage is 20 to 30%, and has a specific resistance of 3.1 mu Ωcm or less.
실시예 1 내지 3에 따른 은 분말은 비교예 1에 따른 은 분말과 비교하여 비슷한 정도의 유기물 함량을 가지면서도 수축률이 3 내지 7% 상승한 것을 알 수 있다. It can be seen that the silver powders according to Examples 1 to 3 had a similar degree of organic matter content and a 3 to 7% increase in shrinkage rate compared to the silver powder according to Comparative Example 1.
또한 실시예 4 및 5에 나타나는 것과 같이 인 화합물 및 아스코르브산 함량을 조절하여 결정자 지름, 유기물 함량, 비표면적 및 수축률을 조절할 수 있음을 알 수 있다. 실시예 4에 따른 은 분말은 실시예 1 내지 3에 따른 은 분말과 비교하여 결정자 지름이 감소하고, 유기물 함량, 비표면적, 수축률이 증가한 것을 알 수 있고, 실시예 5에 따른 은 분말은 실시예 1 내지 3에 따른 은 분말과 비교하여 결정자 지름이 증가하고, 유기물 함량, 비표면적, 수축률이 감소한 것을 알 수 있다.In addition, as shown in Examples 4 and 5, it can be seen that the crystallite diameter, organic matter content, specific surface area, and shrinkage rate can be adjusted by controlling the phosphorus compound and ascorbic acid content. The silver powder according to Example 4 was found to have reduced crystallite diameter, increased organic matter content, specific surface area, and shrinkage as compared with the silver powder according to Examples 1 to 3, and the silver powder according to Example 5 was Compared with the silver powder according to 1 to 3, the crystallite diameter was increased, and the organic content, the specific surface area, and the shrinkage rate were found to decrease.
또한 비교예 2에 따라 아스코르브산만 첨가하여 제조된 은 분말의 경우 수축률 및 비표면적이 급격하게 상승한 것을 알 수 있으며, 이로 인하여 도전성 페이스트 가공 공정 시 어려움이 있으며 전기적 특성이 저하될 것임을 알 수 있다.In addition, in the case of silver powder prepared by adding only ascorbic acid according to Comparative Example 2, it can be seen that the shrinkage rate and the specific surface area are sharply increased, and thus, it is difficult to process the conductive paste and the electrical properties may be reduced.
또한 비교예 3에 따라 피로인산나트륨만을 과량으로 첨가한 경우 결정자지름이 급격하게 상승한 것을 알 수 있으며, 이로 인하여 도전성 페이스트 소성 시 재결정 온도가 상승하여 소결이 지연되고 전기적 특성이 저하될 것임을 알 수 있다. In addition, when the sodium pyrophosphate was added in an excessive amount according to Comparative Example 3, it can be seen that the crystallite diameter was sharply increased. As a result, the recrystallization temperature was increased during the firing of the conductive paste, so that the sintering was delayed and the electrical properties were reduced. .
전술한 각 실시예에서 예시된 특징, 구조, 효과 등은 실시예들이 속하는 분야의 통상의 지식을 가지는 자에 의하여 다른 실시예들에 대해서도 조합 또는 변형되어 실시 가능하다. 따라서 이러한 조합과 변형에 관계된 내용들은 본 발명의 범위에 포함되는 것으로 해석되어야 할 것이다.Features, structures, effects, and the like illustrated in the above-described embodiments may be combined or modified with respect to other embodiments by those skilled in the art to which the embodiments belong. Therefore, contents related to such combinations and modifications should be construed as being included in the scope of the present invention.

Claims (11)

  1. 은 이온, 암모니아(NH3) 및 인 화합물을 포함하는 제1 반응액 및 환원제 및 아스코르빅산을 포함하는 제2 반응액을 제조하는 반응액제조단계(S21) 및 Reaction solution preparation step (S21) for preparing a first reaction solution containing a silver ion, ammonia (NH 3 ) and phosphorus compound and a second reaction solution containing a reducing agent and ascorbic acid and
    제1 반응액 및 제2 반응액을 반응시켜 은 분말을 얻는 석출단계(S22)를 포함하는 은 염 환원단계(S2);를 포함하는 은 분말 제조방법.Silver salt reduction step (S2) comprising a precipitation step (S22) to obtain a silver powder by reacting the first reaction solution and the second reaction solution.
  2. 제1항에 있어서,The method of claim 1,
    상기 인 화합물은 피로인산나트륨(Sodium Pyrophosphate)을 포함하는 피로인산염, 인산나트륨(sodium phosphate), 인산칼륨(Potassium phosphate)을 포함하는 인산염 및 메타인산염(metaphosphate)으로 구성되는 군에서 선택되는 어느 1종 이상을 포함하는 것을 특징으로 하는 은 분말 제조방법.The phosphorus compound is any one selected from the group consisting of pyrophosphate containing sodium pyrophosphate, sodium phosphate, phosphate containing potassium phosphate and metaphosphate. Silver powder production method comprising the above.
  3. 제1항에 있어서,The method of claim 1,
    상기 은 이온은 질산은(AgNO3)을 포함하는 은 염 용액으로 상기 제1 반응액에 포함되며,The silver ion is a silver salt solution containing silver nitrate (AgNO 3 ) is included in the first reaction solution,
    상기 인 화합물은 상기 질산은(AgNO3) 100 중량부에 대하여 0.05 내지 0.2 중량부로 포함되고,The phosphorus compound is included in an amount of 0.05 to 0.2 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ),
    상기 아스코르브산은 상기 질산은(AgNO3) 100 중량부에 대하여 0.1 내지 1 중량부로 포함되는 것을 특징으로 하는 은 분말 제조방법.The ascorbic acid is a silver powder manufacturing method, characterized in that contained in 0.1 to 1 parts by weight based on 100 parts by weight of the silver nitrate (AgNO 3 ).
  4. 제3항에 있어서,The method of claim 3,
    상기 질산은(AgNo3) 100 중량부에 대하여 첨가되는 상기 인 화합물의 중량부를 A 중량부라 하고 상기 아스코르브산의 중량부를 B 중량부라 할 때, When the weight part of the phosphorus compound added to 100 parts by weight of the silver nitrate (AgNo 3 ) is called A parts by weight and the part by weight of the ascorbic acid is B parts by weight,
    인 화합물과 아스코르브산의 첨가량 관계식이 하기 식 1을 만족하도록 첨가되는 것을 특징으로 하는 은 분말 제조방법.A method for producing silver powder, characterized in that the addition amount relationship formula of the phosphorus compound and ascorbic acid is satisfied to satisfy the following formula (1).
    [식 1][Equation 1]
    Figure PCTKR2017011507-appb-I000007
    Figure PCTKR2017011507-appb-I000007
  5. 제3항에 있어서,The method of claim 3,
    상기 질산은(AgNo3) 100 중량부에 대하여 첨가되는 상기 인 화합물의 중량부를 A 중량부라 하고 상기 아스코르브산의 중량부를 B 중량부라 할 때, When the weight part of the phosphorus compound added to 100 parts by weight of the silver nitrate (AgNo 3 ) is called A parts by weight and the part by weight of the ascorbic acid is B parts by weight,
    인 화합물과 아스코르브산의 첨가량 관계식이 하기 식 2를 만족하도록 첨가되는 것을 특징으로 하는 은 분말 제조방법.A method for producing silver powder, characterized in that the addition amount relational expression of the phosphorus compound and ascorbic acid is satisfied to satisfy the following formula (2).
    [식 2][Equation 2]
    Figure PCTKR2017011507-appb-I000008
    Figure PCTKR2017011507-appb-I000008
    (이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
  6. 제3항에 있어서,The method of claim 3,
    상기 질산은(AgNo3) 100 중량부에 대하여 첨가되는 상기 인 화합물의 중량부를 A 중량부라 하고 상기 아스코르브산의 중량부를 B 중량부라 할 때, When the weight part of the phosphorus compound added to 100 parts by weight of the silver nitrate (AgNo 3 ) is called A parts by weight and the part by weight of the ascorbic acid is B parts by weight,
    인 화합물과 아스코르브산의 첨가량 관계식이 하기 식 3을 만족하도록 첨가되는 것을 특징으로 하는 은 분말 제조방법.A method for producing silver powder, characterized in that the addition amount relational expression of the phosphorus compound and ascorbic acid is satisfied to satisfy the following formula (3).
    [식 3][Equation 3]
    Figure PCTKR2017011507-appb-I000009
    Figure PCTKR2017011507-appb-I000009
    (이 때, 0.05≤A≤0.2 이고 0.1≤B≤1 이다.)(At this time, 0.05≤A≤0.2 and 0.1≤B≤1.)
  7. 제1항에 있어서,The method of claim 1,
    상기 환원제는 알칸올아민, 하이드로퀴논, 히드라진 및 포르말린으로 이루어지는 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 은 분말 제조방법.The reducing agent is a silver powder production method, characterized in that at least one member selected from the group consisting of alkanolamine, hydroquinone, hydrazine and formalin.
  8. 제1항에 있어서,The method of claim 1,
    상기 석출단계(S22)는 상기 제1 반응액을 교반하는 상태에서 상기 제2 반응액을 적가하거나 일괄 첨가하여 반응시키는 단계인 것을 특징으로 하는 은 분말 제조방법.The precipitation step (S22) is a silver powder manufacturing method, characterized in that for reacting by dropwise addition or batch addition of the second reaction solution in the state of stirring the first reaction solution.
  9. 평균 입자 크기가 1.0 내지 1.5 μm 인 은 분말로서,Silver powder with an average particle size of 1.0 to 1.5 μm,
    결정자 지름이 280 내지 430 Å 이고, 유기물 함량이 0.5% 이하이며, 비표면적이 0.3 내지 0.5 m2/g 인 것을 특징으로 하는 은 분말.A silver powder having a crystallite diameter of 280 to 430 mm 3, an organic content of 0.5% or less, and a specific surface area of 0.3 to 0.5 m 2 / g.
  10. 제8항에 따른 은 분말을 포함하는 도전성 페이스트로서,A conductive paste containing the silver powder according to claim 8,
    상기 도전성 페이스트를 200μm 도포 인쇄 후 승온속도 50℃/min, 최종 700℃에서 벨트형 건조로로 1분간 소성하여 형성한 도전막의 수축률이 20 내지 30% 이고, 비저항이 3.1μΩ·cm 이하인 것을 특징으로 하는 도전성 페이스트.Shrinkage of the conductive film formed by firing the conductive paste for 200 minutes at a heating rate of 50 ° C./min and the final 700 ° C. in a belt-type drying furnace was 20 to 30%, and the resistivity was 3.1 μm · cm or less. Conductive paste.
  11. 제10항의 도전성 페이스트를 이용하여 형성된 전극을 포함하는 태양전지.A solar cell comprising an electrode formed using the conductive paste of claim 10.
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