WO2010102010A1 - Method for producing dispersed, crystalline, stable to oxidation copper particles - Google Patents

Method for producing dispersed, crystalline, stable to oxidation copper particles Download PDF

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Publication number
WO2010102010A1
WO2010102010A1 PCT/US2010/026061 US2010026061W WO2010102010A1 WO 2010102010 A1 WO2010102010 A1 WO 2010102010A1 US 2010026061 W US2010026061 W US 2010026061W WO 2010102010 A1 WO2010102010 A1 WO 2010102010A1
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solution
copper
carboxylic acid
salt
deionized water
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PCT/US2010/026061
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French (fr)
Inventor
Daniel V. Goia
Ionel Halaciuga
Sylas Laplante
Howard David Glicksman
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to JP2011553076A priority Critical patent/JP2012519779A/en
Priority to CN2010800078909A priority patent/CN102307689A/en
Publication of WO2010102010A1 publication Critical patent/WO2010102010A1/en
Anticipated expiration legal-status Critical
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    • 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

Definitions

  • Dispersed, crystalline, stable to oxidation copper particles were prepared in the absence of polymeric dispersants by rapidly reducing a Cu(I) salt with an Fe(II) carboxylic acid complex in water.
  • the resulting microns sized copper powders contain only organics which decompose at temperatures low enough not to interfere with the sintering process and the formation of conductive copper structures.
  • copper In the microelectronics industry, copper is used in many situations because it offers an excellent electrical conductivity at a fraction of the cost of noble metals such as gold and silver. For this reason, copper particles of various sizes and shapes are used in large quantities to build conductive structures incorporated in multi layer ceramic capacitors, printed circuit boards, and many other electronic devices.
  • Various methods including atomization, pyrolysis, electrolysis, radiolysis, and reduction of copper salts in reverse micelles and solutions are available for preparing dispersed copper particles. Among these, precipitation in homogeneous solutions is the most versatile approach as it offers a broad range of solvents and a large variety of reductants, dispersants, and complexing agents.
  • dispersed copper powders currently used in microelectronics have an average particle size between 0.5 and 3.0 micrometers and are prepared by precipitation techniques involving high molecular weight polymers as dispersants. As a result they contain residual organic matter that can adversely affect their processing into electronic devices.
  • US 6,875,252 (Sano, et al) describes a copper powder and process for producing copper powder. A copper powder with a narrow particle size distribution forms a pseudo-fused sintered product. This process requires ammonia to give the desired effect.
  • Disclosed is a method for the manufacture of easily dispersed, stable to oxidation, crystalline, copper powders in the absence of polymeric dispersants comprising the sequential steps of: a. forming a Cu(I) solution by dissolving a Cu(I) salt in deionized water; b. forming a Fe(II) solution by dissolving a Fe(II) salt in deionized water; c. forming a carboxylic acid solution by dissolving a carboxylic acid or a salt of a carboxylic acid in deionized water, d. forming a reducing Fe (II) carboxylic acid complex solution by adding the Fe (II) salt solution to the carboxylic acid solution e.
  • the copper salt used is cuprous chloride, cuprous acetate or cuprous bromine.
  • the Fe(II) salt is selected from ferrous sulfate, ferrous chloride, ferrous citrate and ferrous thiocyanate.
  • Figure 1 (a), 1 (b) and 1 (c) show scanning micrographs of Copper Powders.
  • Figure 1 (a) is the micrograph for Example 1 at 20 0 C.
  • Figure 1 (b) is the micrograph for Example 3 at 60 0 C.
  • Figure 1 (c) is a micrograph for the Comparative Example described at page 5, herein.
  • This invention involves the process where an Fe (II) carboxylic acid complex reduces a Cu(I) salt rapidly and completely to obtain well dispersed, crystalline, stable to oxidation copper particles in the absence of polymeric dispersants.
  • the resulting copper powders contain only organics which decompose at temperatures low enough not to interfere with the sintering process and the formation of conductive copper structures.
  • Any Fe(II) water soluble salt can be used.
  • suitable Fe(II) salts are ferrous sulfate, ferrous chloride, ferrous citrate, and ferrous thiocyanate. Insoluble ferrous salts are not suitable.
  • Any Cu(I) salt can be used in this invention provided there is enough solubility to be able to form a soluble Cu(I) complex.
  • Suitable Cu(I) salts are cuprous chloride, cuprous acetate, and cuprous bromide. It is preferred to use Cu(I) chloride.
  • Cu(II) salts are not suitable.
  • Suitable carboxylic acids include citric acid, oxalic acid, malonic acid, succinic acid and other di- and tri-acids.
  • salts of these carboxylic acids can be used such as sodium citrate or potassium citrate.
  • the preferred Fe(II) carboxylic acid complex is Fe(II) citrate complex formed from the reaction of Fe(II) chloride solution with a solution of sodium citrate.
  • the Fe(II) carboxylic acid complex as the reductant it is possible to reduce Cu(I) salts rapidly and completely and obtain well dispersed, stable to oxidation copper particles in the absence of polymeric dispersants. Consequently, the resulting particles contain only low decomposition temperature organic residue which does not interfere with their subsequent processing and the consolidation of highly conductive copper layers/structures. These copper particles are highly crystalline.
  • the size of the particles can be adjusted by changing the temperature of the reaction and/or changing the concentration. Increasing the temperature from 20 0 C to 60 0 C causes the resulting copper particles to decrease from 1.5 microns to 0.5 microns. Decreasing the concentration of the ferrous citrate solution 25% resulted in the average particle size increasing from 1.5 microns to 2 microns.
  • Example 1 A copper salt solution was prepared by adding 23.3g Cu(I)CI crystals into 376.7g deionized water in a 2 I glass beaker reaction vessel under intense mixing.
  • a sodium citrate solution was obtained by dissolving 224g Na3C6H 5 O 7 x 2H 2 O into 336g deionized water and a ferrous sulfate solution was prepared by dissolving 12Og Fe(II)SO 4 x 7 H 2 O into 28Og deionized water.
  • the reducing Fe(II) citrate solution was prepared by mixing the two solutions of sodium citrate and ferrous sulfate together for 1 hour. Both solutions were at 2O 0 C.
  • the reducing Fe(II) citrate solution was then added to the reaction vessel containing the Cu(I) solution and stirred for one hour
  • the resulting copper particles were allowed to settle and the dark green clear supernatant was removed.
  • the settled particles were washed several times with 500 ml deionized water, rinsed three times with 300 ml alcohol, separated from the solvent by filtration, and dried at 8O 0 C in vacuum for several hours.
  • the resulting copper powder had an average size of 1.5 microns as measured by a Malvern Mastersizer 2000s laser diffraction particle size distribution instrument and a crystallite size of 42 nm as measured with a Bruker D8 diffractometer.
  • the X-ray diffraction was used to confirm the absence of copper oxide.
  • the weight loss as determined by a Perkin Elmer Pyris 1 thermogravimethc analysis instrument was found to be 0.49% when heated in a mixture of 95% nitrogen and 5% hydrogen to 700 0 C.
  • Example 2 Decreasing the concentration of the sodium citrate solution and the ferrous sulfate solution produced a powder that was larger in size.
  • the copper powder was prepared similarly to Example 1 except that 168g Na 3 C 6 H 5 O 7 x2H 2 O was dissolved into 336g deionized water and 100g Fe(II)SO 4 x7H 2 O was dissolved into 28Og deionized water. It had an average size of 2.0 microns.
  • Example 3 The copper powder was prepared similarly to Example 1 except that the reaction was done at 6O 0 C instead of 2O 0 C. This copper powder had an average size of 0.5 microns with a crystallite size of 24 nm. Conditions for these examples are summarized in Table 1. Comparative Example using a Cu(II) salt: An Fe(II) solution was prepared by dissolving 98 g of Iron(ll) sulfate heptahydrate in deionized water in a 1 liter glass beaker while adjusting the final weight of the solution to 400 g.
  • a sodium citrate solution was prepared by dissolving 5 168 g of thsodium citrate dehydrate in deionized water in a 600 ml glass beaker while adjusting the final weight of the solution to 560 g.
  • the sodium citrate solution was added rapidly to the iron(ll) sulfate solution to form an iron(ll) citrate solution.
  • 29.2 g of copper(ll) sulfate pentahydrate was dissolved in deionized water while adjusting the final weight of the

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Dispersed, crystalline, stable to oxidation copper particles are prepared in the absence of polymeric dispersant's by rapidly reducing a Cu(I) salt with an Fe(II) carboxylic acid complex in water. The resulting microns sized copper powders contain only organics which decompose at temperatures low enough not to interfere with sintering processes and the formation of conductive copper structures.

Description

TITLE
METHOD FOR PRODUCING DISPERSED, CRYSTALLINE, STABLE TO OXIDATION COPPER PARTICLES
Field of the Invention
Dispersed, crystalline, stable to oxidation copper particles were prepared in the absence of polymeric dispersants by rapidly reducing a Cu(I) salt with an Fe(II) carboxylic acid complex in water. The resulting microns sized copper powders contain only organics which decompose at temperatures low enough not to interfere with the sintering process and the formation of conductive copper structures.
Technical Background of the Invention
In the microelectronics industry, copper is used in many situations because it offers an excellent electrical conductivity at a fraction of the cost of noble metals such as gold and silver. For this reason, copper particles of various sizes and shapes are used in large quantities to build conductive structures incorporated in multi layer ceramic capacitors, printed circuit boards, and many other electronic devices. Various methods including atomization, pyrolysis, electrolysis, radiolysis, and reduction of copper salts in reverse micelles and solutions are available for preparing dispersed copper particles. Among these, precipitation in homogeneous solutions is the most versatile approach as it offers a broad range of solvents and a large variety of reductants, dispersants, and complexing agents. Most dispersed copper powders currently used in microelectronics have an average particle size between 0.5 and 3.0 micrometers and are prepared by precipitation techniques involving high molecular weight polymers as dispersants. As a result they contain residual organic matter that can adversely affect their processing into electronic devices. US 6,875,252 (Sano, et al) describes a copper powder and process for producing copper powder. A copper powder with a narrow particle size distribution forms a pseudo-fused sintered product. This process requires ammonia to give the desired effect.
In US 6,451 ,433 Oba, et al , fine metal particle dispersion solutions are produced (colloidal solution with nanometer sized particles) using citrate ion and ferrous ion under an atmosphere having substantially no oxygen.
It would be desirable to manufacture copper powders that are easily dispersed, stable to oxidation and crystalline, without the presence of polymeric dispersants that could adversely affect their use in electronic devices.
Summary of the Invention
Disclosed is a method for the manufacture of easily dispersed, stable to oxidation, crystalline, copper powders in the absence of polymeric dispersants comprising the sequential steps of: a. forming a Cu(I) solution by dissolving a Cu(I) salt in deionized water; b. forming a Fe(II) solution by dissolving a Fe(II) salt in deionized water; c. forming a carboxylic acid solution by dissolving a carboxylic acid or a salt of a carboxylic acid in deionized water, d. forming a reducing Fe (II) carboxylic acid complex solution by adding the Fe (II) salt solution to the carboxylic acid solution e. rapidly adding the reducing Fe(II) carboxylic acid complex solution to the Cu(I) solution f. continuing to stir the solution until all of the copper has been precipitated and the particles have been formed; g. allowing the copper particles to settle followed by removal of the supernatant, washing the copper particles, collecting them, and then drying them.
In the above process, the copper salt used is cuprous chloride, cuprous acetate or cuprous bromine. The Fe(II) salt is selected from ferrous sulfate, ferrous chloride, ferrous citrate and ferrous thiocyanate.
Brief Description of the Figures
Figure 1 (a), 1 (b) and 1 (c) show scanning micrographs of Copper Powders.
Figure 1 (a) is the micrograph for Example 1 at 20 0C.
Figure 1 (b) is the micrograph for Example 3 at 60 0C.
Figure 1 (c) is a micrograph for the Comparative Example described at page 5, herein.
Detailed Description
This invention involves the process where an Fe (II) carboxylic acid complex reduces a Cu(I) salt rapidly and completely to obtain well dispersed, crystalline, stable to oxidation copper particles in the absence of polymeric dispersants. The resulting copper powders contain only organics which decompose at temperatures low enough not to interfere with the sintering process and the formation of conductive copper structures.
Any Fe(II) water soluble salt can be used. Examples of suitable Fe(II) salts are ferrous sulfate, ferrous chloride, ferrous citrate, and ferrous thiocyanate. Insoluble ferrous salts are not suitable. Any Cu(I) salt can be used in this invention provided there is enough solubility to be able to form a soluble Cu(I) complex. Suitable Cu(I) salts are cuprous chloride, cuprous acetate, and cuprous bromide. It is preferred to use Cu(I) chloride. Cu(II) salts are not suitable.
One can produce the Fe(II) carboxylic acid complex solution by dissolving the Fe(II) carboxylic acid complex in water or by forming the complex by reacting a dissolved Fe(II) salt with the carboxylic acid or its salt. Suitable carboxylic acids include citric acid, oxalic acid, malonic acid, succinic acid and other di- and tri-acids. In addition, salts of these carboxylic acids can be used such as sodium citrate or potassium citrate. The preferred Fe(II) carboxylic acid complex is Fe(II) citrate complex formed from the reaction of Fe(II) chloride solution with a solution of sodium citrate.
By using the Fe(II) carboxylic acid complex as the reductant it is possible to reduce Cu(I) salts rapidly and completely and obtain well dispersed, stable to oxidation copper particles in the absence of polymeric dispersants. Consequently, the resulting particles contain only low decomposition temperature organic residue which does not interfere with their subsequent processing and the consolidation of highly conductive copper layers/structures. These copper particles are highly crystalline. The size of the particles can be adjusted by changing the temperature of the reaction and/or changing the concentration. Increasing the temperature from 20 0C to 60 0C causes the resulting copper particles to decrease from 1.5 microns to 0.5 microns. Decreasing the concentration of the ferrous citrate solution 25% resulted in the average particle size increasing from 1.5 microns to 2 microns.
Examples
The following examples and discussion are offered to further illustrate, but not limit the process of the invention.
Example 1 : A copper salt solution was prepared by adding 23.3g Cu(I)CI crystals into 376.7g deionized water in a 2 I glass beaker reaction vessel under intense mixing. A sodium citrate solution was obtained by dissolving 224g Na3C6H5O7 x 2H2O into 336g deionized water and a ferrous sulfate solution was prepared by dissolving 12Og Fe(II)SO4 x 7 H2O into 28Og deionized water. The reducing Fe(II) citrate solution was prepared by mixing the two solutions of sodium citrate and ferrous sulfate together for 1 hour. Both solutions were at 2O0C. The reducing Fe(II) citrate solution was then added to the reaction vessel containing the Cu(I) solution and stirred for one hour The resulting copper particles were allowed to settle and the dark green clear supernatant was removed. The settled particles were washed several times with 500 ml deionized water, rinsed three times with 300 ml alcohol, separated from the solvent by filtration, and dried at 8O0C in vacuum for several hours. The resulting copper powder had an average size of 1.5 microns as measured by a Malvern Mastersizer 2000s laser diffraction particle size distribution instrument and a crystallite size of 42 nm as measured with a Bruker D8 diffractometer. The X-ray diffraction was used to confirm the absence of copper oxide. In addition, the weight loss as determined by a Perkin Elmer Pyris 1 thermogravimethc analysis instrument was found to be 0.49% when heated in a mixture of 95% nitrogen and 5% hydrogen to 7000C.
Example 2: Decreasing the concentration of the sodium citrate solution and the ferrous sulfate solution produced a powder that was larger in size. The copper powder was prepared similarly to Example 1 except that 168g Na3C6H5O7 x2H2O was dissolved into 336g deionized water and 100g Fe(II)SO4 x7H2O was dissolved into 28Og deionized water. It had an average size of 2.0 microns.
Example 3: The copper powder was prepared similarly to Example 1 except that the reaction was done at 6O0C instead of 2O0C. This copper powder had an average size of 0.5 microns with a crystallite size of 24 nm. Conditions for these examples are summarized in Table 1. Comparative Example using a Cu(II) salt: An Fe(II) solution was prepared by dissolving 98 g of Iron(ll) sulfate heptahydrate in deionized water in a 1 liter glass beaker while adjusting the final weight of the solution to 400 g. A sodium citrate solution was prepared by dissolving 5 168 g of thsodium citrate dehydrate in deionized water in a 600 ml glass beaker while adjusting the final weight of the solution to 560 g. The sodium citrate solution was added rapidly to the iron(ll) sulfate solution to form an iron(ll) citrate solution. 29.2 g of copper(ll) sulfate pentahydrate was dissolved in deionized water while adjusting the final weight of the
10 solution to 300 g. The iron(ll) citrate solution was then added rapidly to the copper (II) sulfate solution while mixing. Under these conditions, the reduction of the copper powder was incomplete and particles had a nodular/lumpy surface appearance.
Scanning electron microscopic picture comparison of the examples
15 with the comparative example is shown in Figure 1.
Table I
Experimental Conditions Used For The Preparation Of Copper Particles
Figure imgf000008_0001

Claims

CLAIMS What is claimed is:
1. A method for the manufacture of easily dispersed, stable to oxidation, crystalline, copper powders in the absence of polymeric dispersants comprising the sequential steps: a. forming a Cu(I) solution by dissolving a Cu(I) salt in deionized water; b. forming a Fe(II) solution by dissolving a Fe(II) salt in deionized water; c. forming a carboxylic acid solution by dissolving a carboxylic acid or a salt of a carboxylic acid in deionized water, d. forming a reducing Fe (II) carboxylic acid complex solution by adding the Fe (II) salt solution to the carboxylic acid solution e. rapidly adding the reducing Fe(II) carboxylic acid complex solution to the Cu(I) solution f. continuing to stir the solution until all of the copper has been precipitated and the particles have been formed; g. allowing the copper particles to settle followed by removal of the supernatant, washing the copper particles, collecting them, and then drying them.
2. The method of claim 1 where the copper salt used to make the copper (I) solution is selected from the group consisting of cuprous chloride, cuprous acetate and cuprous bromide.
3. The method of claim 1 wherein the Fe(II) salt is selected from the group consisting of ferrous sulfate, ferrous chloride, ferrous citrate and ferrous thiocyanate.
4. The method of claim 1 wherein the carboxylic acid solution is a deionized water solution of citric acid, oxalic acid, malonic acid, or succinic acid.
5. The method of claim 1 wherein the carboxylic acid solution is a deionized water solution of citric acid.
6. The method of claim 1 where the Fe (II) citrate solution is added to the copper (I) solution at an operating temperature between 2O0C and 6O0C.
PCT/US2010/026061 2009-03-03 2010-03-03 Method for producing dispersed, crystalline, stable to oxidation copper particles Ceased WO2010102010A1 (en)

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JP2011553076A JP2012519779A (en) 2009-03-03 2010-03-03 Method for producing dispersed crystalline and oxidation stable copper particles
CN2010800078909A CN102307689A (en) 2009-03-03 2010-03-03 Process for the preparation of dispersed crystalline oxidation-stabilized copper particles

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US12/396,792 2009-03-03

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JP6106391B2 (en) * 2012-09-14 2017-03-29 Ｄｏｗａエレクトロニクス株式会社 Plate-shaped copper powder, method for producing the same, and conductive paste
WO2014080662A1 (en) * 2012-11-26 2014-05-30 三井金属鉱業株式会社 Copper powder and method for producing same
CN102941351B (en) * 2012-11-27 2015-08-26 中国船舶重工集团公司第七一二研究所 A kind of preparation method of superfine cupper powder
JP6295876B2 (en) * 2013-10-24 2018-03-20 住友金属鉱山株式会社 Method for producing copper powder
CN113414401B (en) * 2021-06-22 2022-03-15 山东建邦胶体材料有限公司 Silver powder of crystalline silicon solar PERC cell silver paste and preparation method thereof
CN119328156B (en) * 2024-09-29 2025-12-26 中船黄冈贵金属有限公司 An ultrafine copper powder, its preparation method and application

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