JP2020029579A - Conductor formation method - Google Patents
Conductor formation method Download PDFInfo
- Publication number
- JP2020029579A JP2020029579A JP2018154648A JP2018154648A JP2020029579A JP 2020029579 A JP2020029579 A JP 2020029579A JP 2018154648 A JP2018154648 A JP 2018154648A JP 2018154648 A JP2018154648 A JP 2018154648A JP 2020029579 A JP2020029579 A JP 2020029579A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- conductor
- particles
- forming
- containing particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004020 conductor Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 title abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 179
- 229910052802 copper Inorganic materials 0.000 claims abstract description 178
- 239000010949 copper Substances 0.000 claims abstract description 178
- 239000002245 particle Substances 0.000 claims abstract description 173
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000002612 dispersion medium Substances 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000011247 coating layer Substances 0.000 claims description 14
- 239000007771 core particle Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- 230000009974 thixotropic effect Effects 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 39
- 229930195729 fatty acid Natural products 0.000 description 39
- 239000000194 fatty acid Substances 0.000 description 39
- 150000004665 fatty acids Chemical class 0.000 description 37
- 150000001875 compounds Chemical class 0.000 description 32
- 230000001603 reducing effect Effects 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 17
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- -1 specifically Substances 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 150000004671 saturated fatty acids Chemical class 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- 150000002443 hydroxylamines Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000003441 saturated fatty acids Nutrition 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 3
- 239000005750 Copper hydroxide Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000002508 contact lithography Methods 0.000 description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000012691 Cu precursor Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- YVZACCLFRNQBNO-UHFFFAOYSA-N pentylhydrazine Chemical compound CCCCCNN YVZACCLFRNQBNO-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- AREWWPRVYOZSFA-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;propane-1,2,3-triol Chemical compound OCC(O)CO.OCC(CO)(CO)CO AREWWPRVYOZSFA-UHFFFAOYSA-N 0.000 description 1
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KDWGEPODFRBACT-UHFFFAOYSA-N 2-[hydroxy(2-sulfoethyl)amino]ethanesulfonic acid Chemical compound OS(=O)(=O)CCN(O)CCS(O)(=O)=O KDWGEPODFRBACT-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 1
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 description 1
- VJHLHGFTPAGQSG-UHFFFAOYSA-N 2-methylbutan-2-ylhydrazine Chemical compound CCC(C)(C)NN VJHLHGFTPAGQSG-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- NGSOWKPBNFOQCR-UHFFFAOYSA-N 2-methylpropylhydrazine Chemical compound CC(C)CNN NGSOWKPBNFOQCR-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- GOKVSLADUAKALT-UHFFFAOYSA-N 3-[2-carboxyethyl(hydroxy)amino]propanoic acid Chemical compound OC(=O)CCN(O)CCC(O)=O GOKVSLADUAKALT-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- LVJAZWNACGZVRQ-UHFFFAOYSA-N 3-methylbutylhydrazine Chemical compound CC(C)CCNN LVJAZWNACGZVRQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- GWCJHEZFIYINAN-UHFFFAOYSA-N 4-methylpentylhydrazine Chemical compound CC(C)CCCNN GWCJHEZFIYINAN-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- RMUCZJUITONUFY-UHFFFAOYSA-N Phenelzine Chemical compound NNCCC1=CC=CC=C1 RMUCZJUITONUFY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NHOWLEZFTHYCTP-UHFFFAOYSA-N benzylhydrazine Chemical compound NNCC1=CC=CC=C1 NHOWLEZFTHYCTP-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- SFSUYFSIKDDLOL-UHFFFAOYSA-N butan-2-ylhydrazine Chemical compound CCC(C)NN SFSUYFSIKDDLOL-UHFFFAOYSA-N 0.000 description 1
- XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical compound CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- LHQRDAIAWDPZGH-UHFFFAOYSA-N cyclohexylhydrazine Chemical compound NNC1CCCCC1 LHQRDAIAWDPZGH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- QQEWMMRFXYVLQU-UHFFFAOYSA-N decylhydrazine Chemical compound CCCCCCCCCCNN QQEWMMRFXYVLQU-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- OKMQERWDFNIGLL-UHFFFAOYSA-N dodecylhydrazine Chemical compound CCCCCCCCCCCCNN OKMQERWDFNIGLL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- AETGYOWKOXPRCB-UHFFFAOYSA-N heptylhydrazine Chemical compound CCCCCCCNN AETGYOWKOXPRCB-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- VKYBUEJAQKBUFU-UHFFFAOYSA-N hexylhydrazine Chemical compound CCCCCCNN VKYBUEJAQKBUFU-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- MDKQJOKKKZNQDG-UHFFFAOYSA-N n,n'-dimethylhexane-1,6-diamine Chemical compound CNCCCCCCNC MDKQJOKKKZNQDG-UHFFFAOYSA-N 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- VDUIPQNXOQMTBF-UHFFFAOYSA-N n-ethylhydroxylamine Chemical compound CCNO VDUIPQNXOQMTBF-UHFFFAOYSA-N 0.000 description 1
- ICVFPLUSMYSIFO-UHFFFAOYSA-N n-ethylpentan-1-amine Chemical compound CCCCCNCC ICVFPLUSMYSIFO-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- IDIXOSREORKJTN-UHFFFAOYSA-N nonylhydrazine Chemical compound CCCCCCCCCNN IDIXOSREORKJTN-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- WSLDIBCXIOECNX-UHFFFAOYSA-N octylhydrazine Chemical compound CCCCCCCCNN WSLDIBCXIOECNX-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 229960000964 phenelzine Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KJAQRHMKLVGSCG-UHFFFAOYSA-N propan-2-ylhydrazine Chemical compound CC(C)NN KJAQRHMKLVGSCG-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UKPBXIFLSVLDPA-UHFFFAOYSA-N propylhydrazine Chemical compound CCCNN UKPBXIFLSVLDPA-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- YHTQKJJDMAPMSS-UHFFFAOYSA-N undecylhydrazine Chemical compound CCCCCCCCCCCNN YHTQKJJDMAPMSS-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Images
Abstract
Description
本発明は、導体の形成方法に関する。 The present invention relates to a method for forming a conductor.
半導体製造分野において、金属のバンプ、ピラー、ピン、又はフィン等は、多くの用途に利用されている。用途としては、例えば、半導体を正常動作させるため、半導体に溜まった熱を放出させるヒートシンクや、シリコンチップを基板に接合するフリップチップ実装におけるはんだバンプなどがある。 In the semiconductor manufacturing field, metal bumps, pillars, pins, fins, and the like are used for many applications. For example, there are a heat sink for releasing heat accumulated in the semiconductor and a solder bump in flip chip mounting for bonding a silicon chip to a substrate in order to normally operate the semiconductor.
ヒートシンクは、半導体からの熱を効率よく放出するために、銅やアルミニウム等の金属製のピラー、ピン、又はフィンが多数立てられ、表面積が大きい構造を有している。ヒートシンクの製造方法としては、押出成形や圧造によって作製された金属製のピラー、ピン、又はフィンを、基材にロウ付けする方法や、金属製の基材を押出成形、切削、又は金型成形することにより、基材と一体のピラー、ピン、又はフィンを形成する方法がある。 The heat sink has a large surface area in which a large number of pillars, pins, or fins made of metal such as copper or aluminum are erected to efficiently release heat from the semiconductor. As a method of manufacturing a heat sink, a method of brazing a metal pillar, pin, or fin made by extrusion or forging to a base material, or extruding, cutting, or molding a metal base material Then, there is a method of forming a pillar, a pin, or a fin integrated with the base material.
上記の方法には、ロウ付けする手間や熱移動ロスがあること、押出成形では作製可能な形状に制限があること、金型成形では少量多品種では高コストになること、切削では材料の無駄が多いこと等の問題がある。 The above-mentioned methods have the trouble of brazing and heat transfer loss, the shape that can be produced by extrusion molding is limited, the cost is high in small lots and many kinds in die molding, and the waste of material in cutting. There is a problem that there are many.
フリップ実装においては、近年、更なる省スペース化のため、はんだバンプに代わって銅ピラーが注目されている。チップ上に銅ピラーを形成する方法としては、めっきを使用する方法がある。まず、チップ上にレジストを塗布する。続いて、露光、現像によって円柱状の穴が開いた形状にレジスト層を加工する。めっきによって穴部分に銅層を充填させる。最後にレジストを除去することで、フリップチップ実装用の円柱状の銅ピラーが形成される。この方法は、レジストを形成してからめっきを行うため、工程数が多く、長時間を要する問題がある。 In flip mounting, copper pillars have recently attracted attention in place of solder bumps for further space saving. As a method of forming a copper pillar on a chip, there is a method of using plating. First, a resist is applied on the chip. Subsequently, the resist layer is processed into a shape having a cylindrical hole by exposure and development. A hole is filled with a copper layer by plating. Finally, by removing the resist, a cylindrical copper pillar for flip-chip mounting is formed. This method has a problem that the number of steps is large and a long time is required because plating is performed after forming a resist.
ところで、金属パターンの形成方法として、銅等の金属粒子を含むインク、ペースト等の導電材料を、インクジェット印刷、ディスペンサ印刷、スクリーン印刷等により基材上に付与する工程と、導電材料を加熱して金属粒子を融着させ、導電性を発現させる導体化工程とを含む、いわゆるプリンテッドエレクトロニクス法が知られている（例えば、下記特許文献１、２を参照）。 By the way, as a method of forming a metal pattern, a step of applying a conductive material such as an ink containing a metal particle such as copper, a paste, or the like onto a substrate by inkjet printing, dispenser printing, screen printing, or the like, and heating the conductive material. A so-called printed electronics method including a step of fusing metal particles to form a conductor for expressing conductivity is known (for example, see Patent Documents 1 and 2 below).
印刷方法に関しては、ペーストを液滴状にして吐出するジェットディスペンサ等の印刷装置が近年開発されている。ジェットディスペンサはペーストを吐出するため、塗布対象物から離れた位置から塗布可能である。このような非接触型の印刷装置は、印刷時間において改善が期待できる。 Regarding the printing method, a printing apparatus such as a jet dispenser that discharges the paste in the form of droplets has recently been developed. Since the jet dispenser discharges the paste, it can be applied from a position distant from the application target. Such a non-contact printing apparatus can be expected to improve printing time.
上述したように、金属のバンプ、ピラー、ピン、又はフィン等の形成方法には、工程の簡略化、時間の短縮化などの要求がある。非接触型の印刷装置を用いて高アスペクト比のピラー等を形成する場合、塗布後のピラーへの接触を防ぐために形成するピラーよりも高い位置からペーストを吐出する必要があるが、対象物から離す距離が大きくなる程正確な塗布は困難になる。また、塗布後のペーストのだれによるパターン倒れや形状変化も問題となる。 As described above, there is a demand for a method of forming a metal bump, pillar, pin, fin, or the like to simplify a process and to shorten time. When forming a high aspect ratio pillar or the like using a non-contact printing device, it is necessary to discharge the paste from a position higher than the pillar to be formed in order to prevent contact with the pillar after application. Accurate application becomes more difficult as the separation distance increases. In addition, pattern collapse and shape change due to dripping of the paste after application also poses a problem.
本発明は、上記事情に鑑み、基材上に基材から突出する所望の形状を有する導体を、簡便且つ短時間で形成することができる導体の形成方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has as its object to provide a conductor forming method capable of forming a conductor having a desired shape projecting from a substrate on a substrate in a simple and short time.
本発明は、基材上に該基材から突出する形状を有する導体を形成する方法であって、基材から０．０５ｍｍ〜１０．０ｍｍの距離の位置から液滴状の導体形成用組成物を吐出することにより基材上に導体形成用組成物を積み上げる工程を備え、導体形成用組成物は、銅を含有する銅含有粒子と、銅含有粒子を分散させる分散媒とを含み、２５℃における粘度が１〜８００Ｐａ・ｓであり、ＪＩＳ Ｚ３２８４に従って測定されるチキソトロピーインデックスが０．５０〜０．９０である導体の形成方法を提供する。 The present invention relates to a method for forming a conductor having a shape protruding from a substrate on a substrate, wherein the composition for forming a conductor in the form of a droplet is formed at a distance of 0.05 mm to 10.0 mm from the substrate. A step of stacking the composition for forming a conductor on a substrate by discharging the composition, the composition for forming a conductor includes copper-containing particles containing copper, and a dispersion medium for dispersing the copper-containing particles, and 25 ° C. The present invention provides a method for forming a conductor, the viscosity of which is 1 to 800 Pa · s and the thixotropic index measured according to JIS Z3284 is 0.50 to 0.90.
導体の導電性又は熱伝導性の観点から、上記導体形成用組成物に含まれる銅含有粒子の含有量が、銅含有粒子及び分散媒の合計量１００質量部に対して、５０〜９０質量部であることが好ましい。 From the viewpoint of conductivity or heat conductivity of the conductor, the content of the copper-containing particles contained in the composition for forming a conductor is 50 to 90 parts by mass, based on 100 parts by mass of the total amount of the copper-containing particles and the dispersion medium. It is preferred that
低温焼結性、導電性又は熱伝導性の観点から、上記銅含有粒子が、銅を含むコア粒子と、コア粒子の表面の少なくとも一部を被覆する有機被覆層とを有する被覆銅粒子であることが好ましい。 From the viewpoint of low-temperature sinterability, electrical conductivity or thermal conductivity, the copper-containing particles are coated copper particles having a copper-containing core particle and an organic coating layer that covers at least a part of the surface of the core particle. Is preferred.
低温焼結性の観点から、上記銅含有粒子の平均粒径が５０μｍ以下であることが好ましい。 From the viewpoint of low-temperature sinterability, the average particle diameter of the copper-containing particles is preferably 50 μm or less.
本発明の導体の形成方法は、基材上に積み上げた前記導体形成用組成物を、２５０℃以下で加熱することにより焼結する工程を更に備えていてもよい。 The method for forming a conductor according to the present invention may further include a step of sintering the conductor-forming composition stacked on the substrate by heating the composition at 250 ° C. or lower.
本発明によれば、基材上に基材から突出する所望の形状を有する導体を、簡便且つ短時間で形成することができる導体の形成方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the conductor formation method which can form the conductor which has a desired shape protruding from a base material on a base material easily and in a short time can be provided.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合、原理的に明らかに必須であると考えられる場合等を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified, and unless it is deemed essential in principle. The same applies to numerical values and their ranges, and does not limit the present invention.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、本用語に含まれる。本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計量を意味する。本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 In the present specification, the term “step” is included in the term as well as an independent step, even if it cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In this specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. In the present specification, the content of each component in the composition, if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity. In the present specification, the particle diameter of each component in the composition, when there are a plurality of particles corresponding to each component in the composition, unless otherwise specified, a mixture of the plurality of particles present in the composition Means the value of
本明細書において「導体化」とは、金属含有粒子を焼成して導体に変化させることをいう。「導体」とは、導電性を有する物体をいい、より具体的には体積抵抗率が３００μΩ・ｃｍ以下である物体をいう。 In the present specification, “conducting” means firing metal-containing particles to convert them into conductors. The “conductor” refers to an object having conductivity, more specifically, an object having a volume resistivity of 300 μΩ · cm or less.
＜導体の形成方法＞
本実施形態の導体の形成方法は、基材から所定の距離の位置から液滴状の導体形成用組成物を吐出することにより基材上に導体形成用組成物を積み上げた堆積体を設ける工程（以下、「堆積工程」という場合もある）と、堆積体を加熱する工程（以下、「加熱工程」という場合もある）とを備える。
<Method of forming conductor>
The method for forming a conductor according to the present embodiment includes a step of providing a deposit formed by stacking the conductor-forming composition on the substrate by discharging the droplet-shaped conductor-forming composition from a position at a predetermined distance from the substrate. (Hereinafter, also referred to as a “deposition step”) and a step of heating the deposited body (hereinafter, also referred to as a “heating step”).
図１は、本実施形態の導体の形成方法を説明するための模式断面図である。図１の（ａ）及び（ｂ）は、堆積工程を示しており、基材１０上に、導体形成用組成物の液滴２０をジェットディスペンサのノズル３０から吐出し、堆積体４０を設けている。図中のＬは、基材１０とノズル３０との距離を示す。堆積工程によって、基材１０と、基材１０から突出する形状を有する堆積体４０とを備える堆積体付基材１００が得られる（図１の（ｂ））。図１の（ｃ）は、上記加熱工程を経て得られる導体付基材２００を示し、導体付基材２００は、基材１０と、基材１０から突出する形状を有する導体５０とを備える。
FIG. 1 is a schematic cross-sectional view for describing a method for forming a conductor according to the present embodiment. FIGS. 1A and 1B show a deposition process, in which a
本実施形態の方法によれば、上記工程を経て、基材上に、基材から突出する形状を有する導体を形成することができる。以下、各工程について説明する。 According to the method of the present embodiment, a conductor having a shape protruding from the base material can be formed on the base material through the above steps. Hereinafter, each step will be described.
基材の材質は、特に制限されず、導電性を有していても有していなくてもよい。基材としては、具体的には、Ｃｕ、Ａｕ、Ｐｔ、Ｐｄ、Ａｇ、Ｚｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｓｎ等の金属、これら金属の合金、ＩＴＯ、ＺｎＯ、ＳｎＯ、Ｓｉ、ＳｉＣ等の半導体、ガラス、黒鉛、グラファイト等のカーボン材料、樹脂、紙、これらの組み合わせなどを挙げることができる。 The material of the substrate is not particularly limited, and may or may not have conductivity. As the base material, specifically, metals such as Cu, Au, Pt, Pd, Ag, Zn, Ni, Co, Fe, Al, Sn, alloys of these metals, ITO, ZnO, SnO, Si, SiC, etc. Semiconductor, glass, graphite, carbon material such as graphite, resin, paper, combinations thereof, and the like.
樹脂としては、熱可塑性樹脂及び熱硬化性樹脂を用いることができ、具体的には、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン樹脂、ポリカーボネート樹脂、液晶ポリマー樹脂、ポリアミド、ポリアラミド、ポリエーテルエーテルケトン、ポリフェニルスルホン、ポリエーテルスルホン、ポリアミドイミド、ポリイミドなどが挙げられる。 As the resin, a thermoplastic resin and a thermosetting resin can be used.Specifically, polyethylene, polypropylene, polyolefin resin such as polymethylpentene, polycarbonate resin, liquid crystal polymer resin, polyamide, polyaramid, polyetheretherketone , Polyphenylsulfone, polyethersulfone, polyamideimide, polyimide and the like.
基材の形状は、特に制限されず、板状、棒状、ロール状、フィルム状、球状、立方体状、直方体状等であってよい。また、これらを二つ以上組み合わせ形状、あるいはどれにも属さないような複雑な立体形状であってよい。 The shape of the substrate is not particularly limited, and may be plate-like, rod-like, roll-like, film-like, spherical, cubic, rectangular, or the like. Further, the shape may be a combination of two or more of them, or a complicated three-dimensional shape that does not belong to any of them.
基材は、導体との密着性の観点から、基材の表面にプライマー層を有していてよい。プライマー層は、例えば、シランカップリング剤を含む層や樹脂組成物等の高分子化合物を含む層で形成されている。 The substrate may have a primer layer on the surface of the substrate from the viewpoint of adhesion to the conductor. The primer layer is formed of, for example, a layer containing a silane coupling agent or a layer containing a polymer compound such as a resin composition.
導体形成用組成物は、銅を含有する銅含有粒子と、銅含有粒子を分散させる分散媒とを含むことができる。 The composition for forming a conductor can include copper-containing particles containing copper and a dispersion medium for dispersing the copper-containing particles.
銅含有粒子は、主として金属銅から形成された銅粒子であってもよいし、主として金属銅から形成された銅粒子であるコア粒子とコア粒子の表面の一部又は全部を覆う有機被覆層とを有する被覆銅粒子であってもよい。銅粒子と被覆銅粒子とを組み合わせてもよい。被覆銅粒子の有機被覆層は、通常、導体形成用組成物の堆積体を焼結する際の加熱により熱分解して消失する。 The copper-containing particles may be copper particles mainly formed from metallic copper, and an organic coating layer covering part or all of the surface of the core particles and the core particles, which are mainly copper particles formed from metallic copper. May be coated copper particles having Copper particles and coated copper particles may be combined. The organic coating layer of the coated copper particles is usually thermally decomposed and disappears by heating during sintering the deposit of the composition for forming a conductor.
被覆銅粒子は、低温（例えば１８０℃以下）の加熱により融着して、導体を形成し易い。有機被覆層がコア粒子である銅粒子の保護材として機能し、コア粒子の酸化が抑制される。このため、大気中での長期保存後も低温での良好な融着性が維持され易い。例えば、ある実施態様では、被覆銅粒子中の酸化物の含有率が５質量％以下である。銅含有粒子中の酸化物の含有率は、例えばＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ、Ｘ線回折）によって測定される。 The coated copper particles are easily fused by heating at a low temperature (for example, 180 ° C. or lower) to easily form a conductor. The organic coating layer functions as a protective material for the copper particles as the core particles, and the oxidation of the core particles is suppressed. For this reason, even after long-term storage in the air, good fusibility at low temperatures is easily maintained. For example, in one embodiment, the content of the oxide in the coated copper particles is 5% by mass or less. The content of the oxide in the copper-containing particles is measured, for example, by XRD (X-ray diffraction, X-ray diffraction).
銅粒子又はコア粒子は、銅及び銅を含む合金からなる群より選択される少なくとも一種を含むことができる。また、銅粒子又はコア粒子は、金属銅以外の少量の他の成分を含むことができる。金属銅以外の成分の例としては、金、銀、白金、錫及びニッケル等の金属又はこれらの金属元素を含む金属化合物、酸化銅、塩化銅、並びに有機物が挙げられる。有機物は、後述の脂肪酸銅、還元性化合物又は脂肪族アミンに由来する物質であってもよい。導電性に優れる導体を形成する観点からは、銅粒子中の金属銅の含有率は、銅粒子の質量を基準として５０〜１００質量％、６０〜１００質量％、又は７０〜１００質量％であってもよい。 The copper particles or the core particles may include at least one selected from the group consisting of copper and an alloy containing copper. Also, the copper particles or core particles can include small amounts of other components other than metallic copper. Examples of components other than metal copper include metals such as gold, silver, platinum, tin, and nickel or metal compounds containing these metal elements, copper oxide, copper chloride, and organic substances. The organic substance may be a substance derived from a fatty acid copper, a reducing compound or an aliphatic amine described below. From the viewpoint of forming a conductor having excellent conductivity, the content of metallic copper in the copper particles is 50 to 100% by mass, 60 to 100% by mass, or 70 to 100% by mass based on the mass of the copper particles. You may.
銅含有粒子の形状は、例えば、球状、長粒状、扁平状、又は繊維状であってもよい。導体形成用組成物の印刷性の観点から、銅含有粒子が球状又は長粒状であってもよい。導体の導電性の観点からは、銅含有粒子が長粒状、扁平状又は繊維状であってもよい。異なる２種以上の形状の銅含有粒子を組み合わせてもよい。 The shape of the copper-containing particles may be, for example, spherical, long, flat, or fibrous. From the viewpoint of printability of the composition for forming a conductor, the copper-containing particles may be spherical or long. From the viewpoint of the conductivity of the conductor, the copper-containing particles may be long, flat, or fibrous. Two or more different types of copper-containing particles may be combined.
銅含有粒子の長軸の長さと短軸の長さの比（長軸／短軸）であるアスペクト比が、１．０〜１０．０の範囲から選択されてよい。導体形成用組成物の粘度の調整を容易する上では、銅含有粒子のアスペクト比が１．５〜８．０であってもよい。本明細書において、「長軸の長さ」とは、銅含有粒子に外接し、互いの距離が最大となるように選ばれる２つの平面間の距離を意味する。「短軸の長さ」とは、銅含有粒子に外接し、互いの距離が最小となるように選ばれる２つの平面間の距離を意味する。 The aspect ratio, which is the ratio of the major axis length to the minor axis length (major axis / minor axis) of the copper-containing particles, may be selected from the range of 1.0 to 10.0. In order to easily adjust the viscosity of the conductor-forming composition, the copper-containing particles may have an aspect ratio of 1.5 to 8.0. In the present specification, the “length of the major axis” means a distance between two planes circumscribing the copper-containing particles and selected so that a distance between the two planes is maximized. By "length of the minor axis" is meant the distance between two planes circumscribing the copper-containing particles and selected to minimize the distance between each other.
銅含有粒子のアスペクト比の平均値が、１．０〜８．０、１．１〜６．０、又は１．２〜３．０であってもよい。銅含有粒子のアスペクト比の平均値は、無作為に選択される２００個の銅含有粒子について、長軸の長さの算術平均値及び短軸の長さの算術平均値をそれぞれ求め、得られた長軸の長さの算術平均値を短軸の長さの算術平均値で除して得られる値である。銅含有粒子のアスペクト比の調整は、例えば、後述する銅含有粒子の製造方法において使用される脂肪酸の炭素数等の条件を調節することによって行われる。 The average value of the aspect ratio of the copper-containing particles may be 1.0 to 8.0, 1.1 to 6.0, or 1.2 to 3.0. The average value of the aspect ratio of the copper-containing particles was obtained by calculating the arithmetic average value of the length of the major axis and the arithmetic average value of the length of the minor axis, respectively, for 200 copper-containing particles selected at random. It is a value obtained by dividing the arithmetic average of the length of the major axis by the arithmetic average of the length of the minor axis. The adjustment of the aspect ratio of the copper-containing particles is performed, for example, by adjusting conditions such as the carbon number of the fatty acid used in the method for producing the copper-containing particles described below.
導体形成用組成物に含まれる銅含有粒子の全数のうち、長軸の長さが５０ｎｍ以下である粒子（以下「小径粒子」ともいう。）の個数の割合が、５５％以下であってもよい。小径粒子の個数の割合は、無作為に選択される２００個の銅含有粒子中に占める小径粒子の個数の割合であることができる。例えば、銅含有粒子２００個中に小径粒子が１１０個存在する場合、小径粒子の個数の割合は５５％である。小径粒子の個数の割合が５５％以下であると、銅含有粒子が低温の加熱により融着して良好な導電性を有する導体をより形成し易い。その傾向は、特に有機被覆層を有する被覆銅粒子の場合に顕著である。同様の観点から、小径粒子の個数の割合は、５０％以下、３５％以下、又は２０％以下であってもよい。 Even when the proportion of the number of particles having a major axis of 50 nm or less (hereinafter also referred to as “small-diameter particles”) is 55% or less in the total number of copper-containing particles contained in the conductor-forming composition. Good. The ratio of the number of small-diameter particles can be the ratio of the number of small-diameter particles to 200 randomly selected copper-containing particles. For example, when 110 small-diameter particles are present in 200 copper-containing particles, the ratio of the number of small-diameter particles is 55%. When the proportion of the number of the small-diameter particles is 55% or less, the copper-containing particles are fused by heating at a low temperature, so that a conductor having good conductivity is more easily formed. This tendency is particularly remarkable in the case of coated copper particles having an organic coating layer. From the same viewpoint, the ratio of the number of small-diameter particles may be 50% or less, 35% or less, or 20% or less.
なお、上記の条件で銅含有粒子が低温で融着しやすくなる理由は明らかではないが、本発明者らは次のように考えている。銅含有粒子は本来、小さいほど溶融しやすい傾向にあるが、同時に粒子表面の触媒活性が高すぎて酸化しやすくなる。粒子が銅から酸化銅に酸化されると融着性は悪くなってしまう。一方、長軸の長さが５０ｎｍを超える銅含有粒子では、粒子表面の有機物が脱離しにくく酸化の影響を受けにくい、粒子表面の触媒活性が高すぎず溶融を妨げる物質を生成しにくい、粒子の比表面積が大きくならず酸化の影響を受けにくい、等の何らかの要因により、長軸の長さが小径粒子よりも大きいことで溶融しやすい場合がある。酸化等の表面変化が生じにくい点で、小径粒子の個数の割合が上記の範囲である銅含有粒子は、低温での融着性に優れる傾向にあると考えられる。 The reason why the copper-containing particles easily fuse at a low temperature under the above conditions is not clear, but the present inventors consider as follows. Originally, the smaller the copper-containing particles, the smaller the tendency to melt. However, at the same time, the catalytic activity on the surface of the particles is too high to easily oxidize. When the particles are oxidized from copper to copper oxide, the fusibility deteriorates. On the other hand, in the case of copper-containing particles having a major axis length of more than 50 nm, organic substances on the particle surface are less likely to be desorbed and are less susceptible to oxidation. Due to some factors such as the specific surface area of the particles is not large and is not easily affected by oxidation, the particles may be easily melted because the major axis is longer than the small diameter particles. It is considered that the copper-containing particles in which the ratio of the number of small-diameter particles is in the above-mentioned range tends to have excellent low-temperature fusion property because the surface change such as oxidation hardly occurs.
特許文献１及び特許文献２には、平均粒径が５０ｎｍ以下、又は平均粒径が２０ｎｍの銅粒子が記載されている。特許文献２には、銅粒子中に粒子径が１０ｎｍ以下の銅粒子と、粒子径が１００〜２００ｎｍの銅粒子とが混在していたことも記載されている。しかしながら、いずれの特許文献にも、銅粒子全体に占める小径粒子の割合に関する具体的な記載はなく、小径粒子の割合と融着性との関連性も示唆されない。 Patent Literature 1 and Patent Literature 2 describe copper particles having an average particle size of 50 nm or less or an average particle size of 20 nm. Patent Document 2 also describes that copper particles having a particle size of 10 nm or less and copper particles having a particle size of 100 to 200 nm were mixed in the copper particles. However, none of the patent documents describes a specific ratio of the small-diameter particles to the entire copper particles, and does not suggest a relationship between the ratio of the small-diameter particles and the fusibility.
低温での融着性の観点からは、導体形成用組成物に含まれる銅含有粒子の全数のうち、長軸の長さが７０ｎｍ以上である粒子の個数の割合が、３０％以上、５０％以上、又は６０％以上であってもよい。本明細書において、長軸の長さが７０ｎｍ以上である粒子の個数の割合は、無作為に選択される２００個の銅含有粒子中に占める当該粒子の個数の割合であることができる。 From the viewpoint of low-temperature fusibility, the ratio of the number of particles having a major axis length of 70 nm or more to the total number of copper-containing particles contained in the conductor-forming composition is 30% or more and 50% or more. Or more than 60%. In the present specification, the ratio of the number of particles having a major axis length of 70 nm or more can be the ratio of the number of particles in 200 randomly selected copper-containing particles.
低温での融着性の観点からは、銅含有粒子の長軸の長さの平均値が、５５ｎｍ以上、７０ｎｍ以上、又は９０ｎｍ以上であてもよい。低温での融着性の観点からは、銅含有粒子の長軸の長さの平均値が、５００ｎｍ以下、３００ｎｍ以下、又は２００ｎｍ以下であってもよい。本明細書において、長軸の長さの平均値とは、無作為に選択される２００個の銅含有粒子について測定した長軸の長さの算術平均値である。 From the viewpoint of the low-temperature fusion property, the average value of the major axis length of the copper-containing particles may be 55 nm or more, 70 nm or more, or 90 nm or more. From the viewpoint of low-temperature fusibility, the average value of the major axis lengths of the copper-containing particles may be 500 nm or less, 300 nm or less, or 200 nm or less. In this specification, the average value of the length of the major axis is the arithmetic average value of the length of the major axis measured for 200 copper-containing particles selected at random.
導体の強度の観点からは、導体形成用組成物に含まれる銅含有粒子の全数のうち、長軸の長さが１μｍ以上である銅含有粒子の個数の割合が、０．０５％以上、３％以上、又は５％以上であってもよい。 From the viewpoint of the strength of the conductor, the proportion of the number of copper-containing particles having a major axis length of 1 μm or more to the total number of copper-containing particles contained in the conductor-forming composition is 0.05% or more and 3% or more. % Or 5% or more.
低温での融着性の観点からは、銅含有粒子の長軸の長さの最大値が、３５０ｎｍ以下、３００ｎｍ以下、又は２５０ｎｍ以下であってもよい。本明細書において銅含有粒子の長長軸の長さの最大値とは、無作為に選択される２００個の銅含有粒子中で、長軸の長さが最長である銅含有粒子の長軸の長さである。 From the viewpoint of low-temperature fusibility, the maximum value of the major axis length of the copper-containing particles may be 350 nm or less, 300 nm or less, or 250 nm or less. In the present specification, the maximum value of the length of the major axis of the copper-containing particles refers to the major axis of the copper-containing particles having the longest major axis in 200 randomly selected copper-containing particles. Is the length of
低温での融着性の観点からは、銅含有粒子の長軸の長さの最小値が、５ｎｍ以上、８ｎｍ以上、又は１０ｎｍ以上であってもよい。本明細書において銅含有粒子の長軸の長さの最小値は、無作為に選択される２００個の銅含有粒子中で長軸の長さが最小である銅含有粒子の長軸の長さである。 From the viewpoint of low-temperature fusibility, the minimum value of the major axis length of the copper-containing particles may be 5 nm or more, 8 nm or more, or 10 nm or more. In this specification, the minimum value of the major axis length of the copper-containing particle is the major axis length of the copper-containing particle having the minimum major axis length among 200 randomly selected copper-containing particles. It is.
導体形成組成物の吐出性の観点からは、銅含有粒子の平均粒径が、５０μｍ以下、２０μｍ以下、１０μｍ以下、又は５μｍ以下であってもよい。銅含有粒子の平均粒径が適度に小さいと、導体形成組成物を吐出するディスペンサ等の装置のノズルが、銅含有粒子で詰まりにくい。詰まり抑制の観点からは、銅含有粒子の平均粒径が、導体形成用組成物が吐出されるノズルの内径の１／１０以下であってもよい。ここで、「銅含有粒子の平均粒径」は、複数の銅含有粒子を含む凝集体（二次粒子）が形成されている場合はその凝集体の粒径（長軸の長さ）を銅含有粒子の粒径とみなして求められる値である。銅含有粒子の平均粒径は、例えば、走査型電子顕微鏡（ＳＥＭ）で観察することで測定することができる。あるいは、銅含有粒子を分散媒に分散させた分散液を光散乱法粒度分布測定装置で測定する方法により、銅含有粒子の平均粒径を測定することもできる。光散乱法粒度分布測定装置を用いる場合、分散媒としてはヘキサン、トルエン、テルピネオール等を用いることができる。 From the viewpoint of the dischargeability of the conductor-forming composition, the average particle size of the copper-containing particles may be 50 μm or less, 20 μm or less, 10 μm or less, or 5 μm or less. If the average particle size of the copper-containing particles is appropriately small, the nozzle of a device such as a dispenser that discharges the conductor-forming composition is less likely to be clogged with the copper-containing particles. From the viewpoint of suppressing clogging, the average particle size of the copper-containing particles may be 1/10 or less of the inner diameter of the nozzle from which the conductor-forming composition is discharged. Here, the “average particle size of the copper-containing particles” refers to the particle size (length of the long axis) of the aggregate when the aggregate (secondary particle) including a plurality of copper-containing particles is formed. It is a value determined assuming the particle size of the contained particles. The average particle size of the copper-containing particles can be measured, for example, by observing with a scanning electron microscope (SEM). Alternatively, the average particle size of the copper-containing particles can be measured by a method in which a dispersion in which the copper-containing particles are dispersed in a dispersion medium is measured by a light scattering particle size distribution analyzer. When using a light scattering particle size distribution analyzer, hexane, toluene, terpineol or the like can be used as a dispersion medium.
銅含有粒子の長軸の長さ、アスペクト比、平均粒径、及び後述する表面の凹凸の有無は、電子顕微鏡による観察等の通常の方法により測定することができる。電子顕微鏡で観察する場合の倍率は特に制限されないが、例えば２０倍〜５００００倍である。粒子径が３．０ｎｍ未満の銅含有粒子は、通常、測定の対象から除外される。 The length of the major axis of the copper-containing particles, the aspect ratio, the average particle diameter, and the presence / absence of surface irregularities described later can be measured by ordinary methods such as observation with an electron microscope. The magnification for observation with an electron microscope is not particularly limited, but is, for example, 20 to 50,000 times. Copper-containing particles having a particle size of less than 3.0 nm are usually excluded from measurement.
市販の銅粒子等の銅含有粒子から、所望の長軸の長さを有する銅含有粒子を選択してもよい。有機被覆銅粒子の場合、後述する製造方法における原材料の種類、原材料を混合する際の温度、反応時間、反応温度、洗浄工程、洗浄溶媒等の条件を調節することによって、長軸の長さを調節することができる。 Copper-containing particles having a desired major axis length may be selected from commercially available copper-containing particles such as copper particles. In the case of organic-coated copper particles, the length of the major axis is adjusted by adjusting the conditions of the type of raw materials in the production method described below, the temperature at which the raw materials are mixed, the reaction time, the reaction temperature, the washing step, the washing solvent, and the like. Can be adjusted.
低温での融着を促進する観点からは、銅含有粒子が、凹凸表面を有する粒子を含んでいてもよい。凹凸表面を有する銅含有粒子は、例えば０．７０〜０．９９の円形度を有する粒子である。本明細書において粒子の円形度とは、４π×Ｓ／（周囲長さ）２で表される値である。Ｓは粒子の表面積である。円形度は、画像処理ソフトを用いて電子顕微鏡像を解析することにより求めることができる。電子顕微鏡で観察する場合の倍率は特に制限されないが、例えば２０倍〜５００００倍である。粒子径が３．０ｎｍ未満の銅含有粒子は、測定の対象から除外される。 From the viewpoint of promoting fusion at a low temperature, the copper-containing particles may include particles having an uneven surface. The copper-containing particles having the uneven surface are, for example, particles having a circularity of 0.70 to 0.99. In the present specification, the circularity of a particle is a value represented by 4π × S / (perimeter) 2 . S is the surface area of the particle. The circularity can be determined by analyzing an electron microscope image using image processing software. The magnification for observation with an electron microscope is not particularly limited, but is, for example, 20 to 50,000 times. Copper-containing particles having a particle size of less than 3.0 nm are excluded from measurement.
なお、銅含有粒子が表面に凹凸を有する銅含有粒子を含むことで低温での融着が促進される理由は明らかではないが、銅含有粒子の表面に凹凸が存在することにより、いわゆるナノサイズ効果による融点低下が生じ、低温での融着性が促進されると推測される。 The reason why the low-temperature fusion is promoted when the copper-containing particles include the copper-containing particles having irregularities on the surface is not clear, but the presence of the irregularities on the surface of the copper-containing particles causes the so-called nano-size. It is presumed that the melting point decreases due to the effect, and that the fusibility at low temperatures is promoted.
被覆銅粒子において、コア粒子の表面を覆う有機被覆層の割合は、コア粒子及び有機被覆層の合計質量を基準として０．１〜２０質量％であってもよい。有機被覆層の割合が０．１質量％以上であると、充分な耐酸化性が得られ易い傾向がある。有機被覆層の割合が２０質量％以下であると、被覆銅粒子の低温での融着性がより良好となる傾向にある。同様の観点から、コア粒子及び有機被覆層の合計質量を基準とする有機被覆層の割合は、０．３〜１０質量％、又は０．５〜５質量％であってもよい。 In the coated copper particles, the ratio of the organic coating layer covering the surface of the core particles may be 0.1 to 20% by mass based on the total mass of the core particles and the organic coating layer. When the proportion of the organic coating layer is 0.1% by mass or more, sufficient oxidation resistance tends to be easily obtained. When the proportion of the organic coating layer is 20% by mass or less, the adhesion of the coated copper particles at a low temperature tends to be better. From a similar viewpoint, the ratio of the organic coating layer based on the total weight of the core particles and the organic coating layer may be 0.3 to 10% by mass, or 0.5 to 5% by mass.
被覆銅粒子は、例えば、脂肪酸銅、還元性化合物、及び脂肪族アミンを含む混合物を加熱する工程を含む方法によって製造される。この方法は、必要に応じて、加熱工程後の遠心分離、洗浄等の工程を有していてもよい。 The coated copper particles are produced, for example, by a method including a step of heating a mixture containing copper fatty acid, a reducing compound, and an aliphatic amine. This method may have, if necessary, steps such as centrifugation and washing after the heating step.
上記方法において、脂肪酸銅は、銅前駆体として用いられる。これにより、銅前駆体としてシュウ酸銀等を用いる特許文献１に記載の方法と比較して、より沸点の低い（すなわち、分子量の小さい）脂肪族アミンを反応媒として使用することができる。沸点の低い脂肪族アミンを用いると、得られる被覆銅粒子の有機被覆層が、より熱分解又は揮発し易くなり、それにより、良好な導電性を有する導体をより低温での焼結により形成できると考えられる。 In the above method, fatty acid copper is used as a copper precursor. Thereby, an aliphatic amine having a lower boiling point (that is, a smaller molecular weight) can be used as a reaction medium as compared with the method described in Patent Document 1 using silver oxalate or the like as a copper precursor. When an aliphatic amine having a low boiling point is used, the organic coating layer of the obtained coated copper particles is more easily thermally decomposed or volatilized, whereby a conductor having good conductivity can be formed by sintering at a lower temperature. it is conceivable that.
脂肪酸銅を構成する脂肪酸は、ＲＣＯＯＨ（Ｒは直鎖状又は分岐状の炭化水素基を示す。）で表される１価のカルボン酸である。脂肪酸は、飽和脂肪酸又は不飽和脂肪酸のいずれであってもよい。コア粒子を効率的に被覆して酸化を抑制する観点からは、脂肪酸は直鎖状の飽和脂肪酸であってもよい。脂肪酸は１種のみでも、２種以上であってもよい。 The fatty acid constituting the fatty acid copper is a monovalent carboxylic acid represented by RCOOH (R represents a linear or branched hydrocarbon group). Fatty acids may be either saturated or unsaturated fatty acids. From the viewpoint of efficiently covering the core particles and suppressing oxidation, the fatty acid may be a linear saturated fatty acid. The fatty acids may be only one kind or two or more kinds.
脂肪酸の炭素数は、２０以下であってもよく、９以下であってもよい。炭素数が２０以下である飽和脂肪酸の例としては、デカン酸（炭素数１０）、ラウリン酸（炭素数１２）、ミリスチン酸（炭素数１４）、パルミチン酸（炭素数１６）、ステアリン酸（炭素数１７）、オレイン酸（炭素数１８）、及びアラキジン酸（炭素数２０）が挙げられる。炭素数が９以下である飽和脂肪酸の例としては、酢酸（炭素数２）、プロピオン酸（炭素数３）、酪酸及びイソ酪酸（炭素数４）、吉草酸及びイソ吉草酸（炭素数５）、カプロン酸（炭素数６）、エナント酸及びイソエナント酸（炭素数７）、カプリル酸及びイソカプリル酸及びイソカプロン酸（炭素数８）、並びに、ノナン酸及びイソノナン酸（炭素数９）が挙げられる。炭素数が９以下である不飽和脂肪酸の例としては、上記の飽和脂肪酸の炭化水素基中に１つ以上の二重結合を有するものが挙げられる。 The carbon number of the fatty acid may be 20 or less, or 9 or less. Examples of saturated fatty acids having 20 or less carbon atoms include decanoic acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), stearic acid (carbon (17), oleic acid (18 carbon atoms), and arachidic acid (20 carbon atoms). Examples of saturated fatty acids having 9 or less carbon atoms include acetic acid (2 carbon atoms), propionic acid (3 carbon atoms), butyric acid and isobutyric acid (4 carbon atoms), valeric acid and isovaleric acid (5 carbon atoms) , Caproic acid (C6), enanthic acid and isoenanthic acid (C7), caprylic acid and isocaprylic acid and isocaproic acid (C8), and nonanoic acid and isononanoic acid (C9). Examples of unsaturated fatty acids having 9 or less carbon atoms include those having one or more double bonds in the hydrocarbon group of the above-mentioned saturated fatty acids.
脂肪酸の種類は、被覆銅粒子の分散媒への分散性、融着性等の性質に影響し得る。粒子形状の均一化の観点からは、炭素数が５〜９である脂肪酸と、炭素数が４以下である脂肪酸とを併用してもよい。例えば、炭素数が９であるノナン酸と、炭素数が２である酢酸とを併用してもよい。炭素数が５〜９である脂肪酸と炭素数が４以下である脂肪酸とを併用する場合のそれらの比率は、特に制限されない。 The type of the fatty acid can affect properties such as dispersibility of the coated copper particles in the dispersion medium and fusion properties. From the viewpoint of uniformizing the particle shape, a fatty acid having 5 to 9 carbon atoms and a fatty acid having 4 or less carbon atoms may be used in combination. For example, nonanoic acid having 9 carbon atoms and acetic acid having 2 carbon atoms may be used in combination. When a fatty acid having 5 to 9 carbon atoms and a fatty acid having 4 or less carbon atoms are used together, their ratio is not particularly limited.
脂肪酸銅を得る方法は特に制限されず、例えば、水酸化銅と脂肪酸とを溶媒中で反応せせる方法により得てもよい。市販の脂肪酸銅を用いてもよい。あるいは、水酸化銅、脂肪酸及び還元性化合物を溶媒中で混合することで、脂肪酸銅の生成と、脂肪酸銅と還元性化合物との間で形成される錯体の生成とを同じ工程中で行ってもよい。 The method for obtaining fatty acid copper is not particularly limited, and may be obtained, for example, by a method in which copper hydroxide and a fatty acid are reacted in a solvent. Commercially available copper fatty acids may be used. Alternatively, by mixing copper hydroxide, a fatty acid and a reducing compound in a solvent, the formation of the fatty acid copper and the formation of the complex formed between the fatty acid copper and the reducing compound are performed in the same step. Is also good.
還元性化合物は、脂肪酸銅と反応して錯体等の複合化合物を形成すると考えられる。還元性化合物が脂肪酸銅中の銅イオンに対する電子のドナーとして機能し、それにより銅イオンが還元され易くなると考えられる。そのため、複合化合物を形成している脂肪酸銅は、複合化合物を形成していない状態の脂肪酸銅の場合と比較して、自発的な熱分解による銅原子の遊離を生じさせ易いと考えられる。 It is considered that the reducing compound reacts with the fatty acid copper to form a complex compound such as a complex. It is considered that the reducing compound functions as an electron donor for copper ions in the fatty acid copper, and thereby the copper ions are easily reduced. Therefore, it is considered that the fatty acid copper forming the composite compound is more likely to cause the release of copper atoms by spontaneous thermal decomposition than the case of the fatty acid copper not forming the composite compound.
還元性化合物は１種を単独で用いても、２種以上を併用してもよい。還元性化合物の例としては、ヒドラジン、ヒドラジン誘導体、塩酸ヒドラジン、硫酸ヒドラジン、及び抱水ヒドラジン等のヒドラジン化合物；ヒドロキシルアミン、及びヒドロキシルアミン誘導体等のヒドロキシルアミン化合物；並びに、水素化ホウ素ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、及び次亜リン酸ナトリウム等のナトリウム化合物を挙げることができる。 One reducing compound may be used alone, or two or more reducing compounds may be used in combination. Examples of the reducing compound include hydrazine compounds such as hydrazine, hydrazine derivatives, hydrazine hydrochloride, hydrazine sulfate, and hydrazine hydrate; hydroxylamine compounds such as hydroxylamine and hydroxylamine derivatives; and sodium borohydride and sodium sulfite. , Sodium hydrogen sulfite, sodium thiosulfate, and sodium hypophosphite.
脂肪酸銅の構造を維持した状態で錯体を形成しやすい等の観点から、アミノ基を有する還元性化合物を用いてもよい。アミノ基を有する還元性化合物は、例えば、ヒドラジン及びその誘導体、並びに、ヒドロキシルアミン及びその誘導体から選ばれる化合物であってもよい。これらの還元性化合物は、窒素原子が銅原子との配位結合を形成することにより錯体を形成することができる。これらの還元性化合物は一般に脂肪族アミンと比較して還元力が強いため、生成した錯体が比較的穏和な条件で自発的な分解を生じ、銅原子の還元及び遊離が生じる傾向にある。そのため、脂肪酸銅、還元性化合物及び脂肪族アミンを含む混合物を加熱する工程における加熱温度を、例えば、脂肪族アミンの蒸発又は分解を生じない低い温度（例えば１５０℃以下）とすることができる。 From the viewpoint of easily forming a complex while maintaining the structure of the fatty acid copper, a reducing compound having an amino group may be used. The reducing compound having an amino group may be, for example, a compound selected from hydrazine and its derivatives, and hydroxylamine and its derivatives. These reducing compounds can form a complex by forming a coordination bond between a nitrogen atom and a copper atom. Since these reducing compounds generally have a stronger reducing power than aliphatic amines, the resulting complexes tend to undergo spontaneous decomposition under relatively mild conditions, resulting in the reduction and release of copper atoms. Therefore, the heating temperature in the step of heating the mixture containing the fatty acid copper, the reducing compound, and the aliphatic amine can be, for example, a low temperature (for example, 150 ° C. or lower) at which the aliphatic amine does not evaporate or decompose.
ヒドラジン誘導体及びヒドロキシルアミン誘導体を用いることにより、脂肪酸銅との反応性を調節して、所望の条件で自発分解を生じる錯体を生成させることができる。ヒドラジン誘導体の例としては、メチルヒドラジン、エチルヒドラジン、ｎ−プロピルヒドラジン、イソプロピルヒドラジン、ｎ−ブチルヒドラジン、イソブチルヒドラジン、ｓｅｃ−ブチルヒドラジン、ｔ−ブチルヒドラジン、ｎ−ペンチルヒドラジン、イソペンチルヒドラジン、ｎｅｏ−ペンチルヒドラジン、ｔ−ペンチルヒドラジン、ｎ−ヘキシルヒドラジン、イソヘキシルヒドラジン、ｎ−ヘプチルヒドラジン、ｎ−オクチルヒドラジン、ｎ−ノニルヒドラジン、ｎ−デシルヒドラジン、ｎ−ウンデシルヒドラジン、ｎ−ドデシルヒドラジン、シクロヘキシルヒドラジン、フェニルヒドラジン、４−メチルフェニルヒドラジン、ベンジルヒドラジン、２−フェニルエチルヒドラジン、２−ヒドラジノエタノール、及びアセトヒドラジンが挙げられる。ヒドロキシルアミンの誘導体の例としては、Ｎ，Ｎ−ジ（スルホエチル）ヒドロキシルアミン、モノメチルヒドロキシルアミン、ジメチルヒドロキシルアミン、モノエチルヒドロキシルアミン、ジエチルヒドロキシルアミン、及びＮ，Ｎ−ジ（カルボキシエチル）ヒドロキシルアミンが挙げられる。 By using the hydrazine derivative and the hydroxylamine derivative, the reactivity with the fatty acid copper can be adjusted to generate a complex that undergoes spontaneous decomposition under desired conditions. Examples of the hydrazine derivative include methylhydrazine, ethylhydrazine, n-propylhydrazine, isopropylhydrazine, n-butylhydrazine, isobutylhydrazine, sec-butylhydrazine, t-butylhydrazine, n-pentylhydrazine, isopentylhydrazine, and neo-hydrazine. Pentylhydrazine, t-pentylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine , Phenylhydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, and acetohydrazide And the like. Examples of hydroxylamine derivatives include N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, and N, N-di (carboxyethyl) hydroxylamine. No.
脂肪酸銅に含まれる銅と還元性化合物の比率は、所望の錯体が形成される条件であれば特に制限されない。例えば、銅：還元性化合物のモル比が１：１〜１：４、１：１〜１：３、又は１：１〜１：２であってもよい。 The ratio of copper to the reducing compound contained in the fatty acid copper is not particularly limited as long as a desired complex is formed. For example, the molar ratio of copper: reducing compound may be 1: 1 to 1: 4, 1: 1 to 1: 3, or 1: 1 to 1: 2.
脂肪族アミンは、脂肪酸銅と還元性化合物とから形成される錯体の分解反応の反応媒として機能すると考えられる。脂肪族アミンは、更に、還元性化合物の還元作用によって生じるプロトンを捕捉し、反応溶液が酸性に傾いて銅原子が酸化されることを抑制すると考えられる。 The aliphatic amine is considered to function as a reaction medium for a decomposition reaction of a complex formed from the fatty acid copper and the reducing compound. It is considered that the aliphatic amine further captures a proton generated by the reducing action of the reducing compound, and suppresses the oxidation of the copper atom due to the acidity of the reaction solution.
脂肪族アミンは、ＲＮＨ２（Ｒは置換基を有していてもよい直鎖状、分岐状又は環状の脂肪族基を示す。）で表される１級アミン、Ｒ１Ｒ２ＮＨ（Ｒ１及びＲ２はそれぞれ独立に置換基を有していてもよい直鎖状、分岐状又は環状の脂肪族基を示す。）で表される２級アミン、脂肪族基及びこれを置換する２つのアミノ基を有するアルキレンジアミン、又はこれらの組み合わせであってもよい。脂肪族アミンは、１つ以上の二重結合を含む脂肪族基を有していてもよく、酸素、ケイ素、窒素、イオウ、リン等の原子を含む置換基を有していてもよい。脂肪族アミンは、１種のみであっても２種以上であってもよい。 The aliphatic amine is a primary amine represented by RNH 2 (R represents a linear, branched or cyclic aliphatic group which may have a substituent), and R 1 R 2 NH (R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group which may have a substituent.), An aliphatic group, and 2 It may be an alkylenediamine having two amino groups, or a combination thereof. The aliphatic amine may have an aliphatic group containing one or more double bonds, and may have a substituent containing an atom such as oxygen, silicon, nitrogen, sulfur, and phosphorus. The aliphatic amine may be only one kind or two or more kinds.
１級アミンの例としては、エチルアミン、２−エトキシエチルアミン、プロピルアミン、ブチルアミン、イソブチルアミン、ペンチルアミン、イソペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ドデシルアミン、ヘキサデシルアミン、オレイルアミン、３−メトキシプロピルアミン、及び３−エトキシプロピルアミンが挙げられる。 Examples of primary amines include ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, hexa Decylamine, oleylamine, 3-methoxypropylamine, and 3-ethoxypropylamine.
２級アミンの例としては、ジエチルアミン、ジプロピルアミン、ジブチルアミン、エチルプロピルアミン、エチルペンチルアミン、ジブチルアミン、ジペンチルアミン、及びジヘキシルアミンが挙げられる。 Examples of secondary amines include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, ethylpentylamine, dibutylamine, dipentylamine, and dihexylamine.
アルキレンジアミンの例としては、エチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、１，３−プロパンジアミン、２，２−ジメチル−１，３−プロパンジアミン、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ’−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ−ジエチル−１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノ−２−メチルペンタン、１，６−ジアミノへキサン、Ｎ，Ｎ’−ジメチル−１，６−ジアミノへキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、及び１，１２−ジアミノドデカンが挙げられる。 Examples of the alkylenediamine include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, 2,2- Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, , 4-Diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N′-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -Diaminooctane, 1,9-diaminononane, and 1,12-diaminododecane.
脂肪族アミンの脂肪族基の炭素数は、７以下であってもよい。脂肪族アミンの脂肪族基の炭素数が７以下であると、脂肪族アミンが熱分解し易いため、低温での焼結により良好な導電性を有する導体が形成され易い傾向がある。脂肪族アミンの脂肪族基の炭素数は６以下であってもよく、３以上であってもよい。炭素数７以下の脂肪族基を有する脂肪族アミンと、炭素数８以上の脂肪族基を有する脂肪族アミンと併用してもよい。その場合、脂肪族アミン全体に占める炭素数７以下の脂肪族基を有する脂肪族アミンの割合が５０質量％以上、６０質量％以上、又は７０質量％以上であってもよい。 The carbon number of the aliphatic group of the aliphatic amine may be 7 or less. If the aliphatic amine has 7 or less carbon atoms in the aliphatic group, the aliphatic amine is liable to be thermally decomposed, so that a conductor having good conductivity tends to be easily formed by sintering at a low temperature. The number of carbon atoms of the aliphatic group of the aliphatic amine may be 6 or less, or 3 or more. An aliphatic amine having an aliphatic group having 7 or less carbon atoms and an aliphatic amine having an aliphatic group having 8 or more carbon atoms may be used in combination. In that case, the proportion of the aliphatic amine having an aliphatic group having 7 or less carbon atoms in the entire aliphatic amine may be 50% by mass or more, 60% by mass or more, or 70% by mass or more.
脂肪酸銅に含まれる銅と脂肪族アミンとの比率は、特に制限されない。例えば、銅：脂肪族アミンのモル比が１：１〜１：８、１：１〜１：６、又は１：１〜１：４であってもよい。 The ratio of copper to the aliphatic amine contained in the fatty acid copper is not particularly limited. For example, the molar ratio of copper: aliphatic amine may be 1: 1 to 1: 8, 1: 1 to 1: 6, or 1: 1 to 1: 4.
脂肪酸銅、還元性化合物及び脂肪族アミンを含む、被覆金属粒子を形成するための混合物は、溶媒を更に含んでもよい。脂肪酸銅と還元性化合物による錯体の形成を促進する観点からは、混合物が極性溶媒を含んでいてもよい。ここで極性溶媒とは、２５℃で水に溶解する溶媒を意味する。極性溶媒がアルコールであってもよい。アルコールを用いることで錯体の形成が促進される傾向にある。その理由は明らかではないが、固体である脂肪酸銅を溶解させながら水溶性である還元性化合物との接触が促進されるためと考えられる。溶媒は１種を単独で用いても、２種以上を併用してもよい。 The mixture for forming the coated metal particles, including the fatty acid copper, the reducing compound, and the aliphatic amine, may further include a solvent. From the viewpoint of promoting the formation of a complex between the fatty acid copper and the reducing compound, the mixture may contain a polar solvent. Here, the polar solvent means a solvent that dissolves in water at 25 ° C. The polar solvent may be an alcohol. The use of alcohol tends to promote complex formation. Although the reason is not clear, it is considered that the contact with the water-soluble reducing compound is promoted while dissolving the solid fatty acid copper. One type of solvent may be used alone, or two or more types may be used in combination.
２５℃で水に溶解するアルコールは、例えば、炭素数が１〜８で水酸基を１つ有するアルコールであってもよい。このようなアルコールの例としては、直鎖状のアルキルアルコール、フェノール、２以上の炭化水素基及びこれらを結合するエーテル結合と水酸基とを有する化合物が挙げられる。より強い極性を発現する観点からは、２以上の水酸基を有するアルコールを用いてもよい。また、イオウ原子、リン原子、ケイ素原子等を含むアルコールを用いてもよい。 The alcohol soluble in water at 25 ° C. may be, for example, an alcohol having 1 to 8 carbon atoms and having one hydroxyl group. Examples of such alcohols include linear alkyl alcohols, phenols, two or more hydrocarbon groups, and compounds having an ether bond and a hydroxyl group connecting them. From the viewpoint of developing stronger polarity, an alcohol having two or more hydroxyl groups may be used. Further, an alcohol containing a sulfur atom, a phosphorus atom, a silicon atom, or the like may be used.
アルコールの例としては、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、アリルアルコール、ベンジルアルコール、ピナコール、プロピレングリコール、メントール、カテコール、ヒドロキノン、サリチルアルコール、グリセリン、ペンタエリスリトール、スクロース、グルコース、キシリトール、メトキシエタノール、トリエチレングリコールモノメチルエーテル、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、及びペンタエチレングリコールが挙げられる。アルコールは、メタノール、エタノール、１−プロパノール及び２−プロパノール、又は、１−プロパノール及び２−プロパノールから選択してもよく、１−プロパノールを選択してもよい。 Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, salicyl alcohol, glycerin Pentaerythritol, sucrose, glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, ethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol. The alcohol may be selected from methanol, ethanol, 1-propanol and 2-propanol, or 1-propanol and 2-propanol, or 1-propanol.
脂肪酸銅、還元性化合物及び脂肪族アミンを含む混合物を加熱する工程を実施するための方法は特に制限されない。その例としては、脂肪酸銅及び還元性化合物を溶媒と混合し、得られた混合物に脂肪族アミンを更に添加して、混合物を加熱する方法、脂肪酸銅及び脂肪族アミンを溶媒と混合し、得られた混合物に還元性化合物を更に添加して、混合物を加熱する方法、水酸化銅、脂肪酸、還元性化合物及び脂肪族アミンを溶媒と混合し、得られた混合物を加熱する方法が挙げられる。 The method for performing the step of heating the mixture containing the fatty acid copper, the reducing compound, and the aliphatic amine is not particularly limited. For example, a method of mixing a fatty acid copper and a reducing compound with a solvent, further adding an aliphatic amine to the obtained mixture, and heating the mixture, mixing the fatty acid copper and the aliphatic amine with a solvent, A method in which a reducing compound is further added to the obtained mixture and the mixture is heated, and a method in which copper hydroxide, a fatty acid, a reducing compound and an aliphatic amine are mixed with a solvent and the resulting mixture is heated.
加熱温度は、例えば、１５０℃以下、１３０℃以下、又は１００℃以下であってもよい。炭素数が９以下である脂肪酸銅を用いることにより、比較的低温で被覆金属粒子を形成することができる。 The heating temperature may be, for example, 150 ° C or lower, 130 ° C or lower, or 100 ° C or lower. By using a fatty acid copper having 9 or less carbon atoms, coated metal particles can be formed at a relatively low temperature.
導体形成用組成物は、銅含有粒子以外の金属粒子を含んでいてもよい。金属粒子を構成する金属成分としては、例えば、銀、ニッケル、ベリリウム、白金、コバルト、アンチモン、ゲルマニウム、タリウム、イリジウム、亜鉛、ニオブ、金、パラジウム、カドミウム、ルテニウム、チタン、インジウム、タングステン、モリブデン、アルミニウム、鉛、ビスマス、ロジウム、クロム、スズ、鉄、バナジウム、マンガン等の導電性を有する金属成分、又はこれらの金属成分を含む合金を挙げることができる。金属成分は、導電性の観点から、金及び銀並びにこれらの金属を含む合金からなる群より選択される少なくとも一種を用いることができ、耐酸化性の観点から、金及び銀、並びにこれらの金属を含む合金からなる群より選択される少なくとも一種を用いることができる。 The conductor-forming composition may include metal particles other than the copper-containing particles. As the metal component constituting the metal particles, for example, silver, nickel, beryllium, platinum, cobalt, antimony, germanium, thallium, iridium, zinc, niobium, gold, palladium, cadmium, ruthenium, titanium, indium, tungsten, molybdenum, Examples thereof include conductive metal components such as aluminum, lead, bismuth, rhodium, chromium, tin, iron, vanadium, and manganese, and alloys containing these metal components. As the metal component, from the viewpoint of conductivity, at least one selected from the group consisting of gold and silver and an alloy containing these metals can be used.From the viewpoint of oxidation resistance, gold and silver, and these metals At least one selected from the group consisting of alloys containing
導体形成用組成物に含まれる分散媒の種類は特に制限されず、導体形成用組成物の用途に応じて一般に用いられる有機溶媒から１種又は２種以上を選択できる。導体形成用組成物の粘度及びＴＩ値の制御の観点から、分散媒は、テルピネオール、シクロヘキサノン、イソボルニルシクロヘキサノール、トリブチリン、ジヒドロターピネオール及びジヒドロターピネオールアセテートからなる群より選択される少なくとも１種を含んでいてもよい。低温での融着を促進する観点からは、還元性のある分散媒を選択してもよく、その例としては、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、グリセリン、ジグリセリン、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテルが挙げられる。 The type of the dispersion medium contained in the conductor-forming composition is not particularly limited, and one or more kinds can be selected from generally used organic solvents according to the use of the conductor-forming composition. From the viewpoint of controlling the viscosity and the TI value of the conductor-forming composition, the dispersion medium contains at least one selected from the group consisting of terpineol, cyclohexanone, isobornylcyclohexanol, tributyrin, dihydroterpineol, and dihydroterpineol acetate. You may go out. From the viewpoint of promoting fusion at a low temperature, a reducing dispersion medium may be selected, and examples thereof include ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and ethylene. Glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, glycerin, diglycerin, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether.
導体形成用組成物は、必要に応じて銅含有粒子及び分散媒以外の成分を含んでもよい。このような成分としては、シランカップリング剤、高分子化合物、ラジカル開始剤、還元剤、粘度調整剤、レベリング剤及びチキソ調整剤が挙げられる。 The composition for forming a conductor may contain components other than the copper-containing particles and the dispersion medium as necessary. Examples of such components include a silane coupling agent, a polymer compound, a radical initiator, a reducing agent, a viscosity modifier, a leveling agent, and a thixotropic agent.
導体形成用組成物の２５℃における粘度は、１〜８００Ｐａ・ｓであってもよい。導体形成用組成物の２５℃における粘度が１Ｐａ・ｓ以上であると、導体形成用組成物が濡れ広がりにくく、液滴状の導体形成用組成物を高く積み重ねやすくなり、形成される堆積体が大径化することを抑制しやすくなる。導体形成用組成物の２５℃における粘度が８００Ｐａ・ｓ以下であると、液滴状の導体形成用組成物の液滴を比較的小さい圧力で吐出し易いため、導体形成用組成物が吐出される位置と基材との距離が大きい場合であっても、吐出された導体形成組成物が飛び散りにくくなる傾向がある。同様の観点から、導体形成用組成物の２５℃における粘度が、５Ｐａ・ｓ以上、又は１０Ｐａ・ｓ以上であってもよく、３００Ｐａ・ｓ以下、又は１００Ｐａ・ｓ以下であってもよい。 The viscosity at 25 ° C. of the composition for forming a conductor may be 1 to 800 Pa · s. When the viscosity at 25 ° C. of the conductor-forming composition is 1 Pa · s or more, the conductor-forming composition is hardly wetted and spread, and the droplet-shaped conductor-forming composition is easily stacked high, and the formed deposit is formed. It is easy to suppress an increase in diameter. When the viscosity at 25 ° C. of the conductor-forming composition is 800 Pa · s or less, the conductor-forming composition is discharged because the droplets of the conductor-forming composition are easily discharged at a relatively small pressure. Even when the distance between the position and the substrate is large, the discharged conductor-forming composition tends to be less likely to scatter. From the same viewpoint, the viscosity at 25 ° C. of the composition for forming a conductor may be 5 Pa · s or more, or 10 Pa · s or more, 300 Pa · s or less, or 100 Pa · s or less.
本明細書において、導体形成用組成物の粘度は、Ｅ型粘度計により２５℃で回転数２．５ｒｐｍの条件で測定される値である。Ｅ型粘度計として、例えば東機産業株式会社製、製品名：ＶＩＳＣＯＭＥＴＥＲ−ＴＶ３３（適用コーンプレート型ロータ：ＳＰＰ、３°×Ｒ１４）を用いることができる。測定用冶具として、例えば、コーンプレートを適用できる。 In the present specification, the viscosity of the composition for forming a conductor is a value measured by an E-type viscometer at 25 ° C. and a rotation speed of 2.5 rpm. As the E type viscometer, for example, a product name: VISCOMMETER-TV33 (applicable cone plate type rotor: SPP, 3 ° × R14) manufactured by Toki Sangyo Co., Ltd. can be used. As a measuring jig, for example, a cone plate can be applied.
導体形成用組成物のチキソトロピーインデックス（以下「ＴＩ値」ということがある。）は、０．５０〜０．９０であってもよい。導体形成用組成物のＴＩ値がこの範囲内にあると、吐出のためのせん断力によって導体形成用組成物が低粘度化するため、導体形成用組成物を吐出しやすく、また、導体形成用組成物が基材に着弾後は静置によって粘度が回復して、堆積体の過度な濡れ広がりを抑えることができる。同様の観点から、導体形成用組成物のＴＩ値は、０．６５以上であってもよく、０．８０以下であってもよい。本明細書において、ＴＩ値は、ＪＩＳ Ｚ３２８４に従って測定される値を意味する。より具体的には、Ｅ型粘度計を用いて、２５℃で回転数２．５ｒｐｍの条件で測定された粘度がμ２．５で、２５℃で回転数１０ｒｐｍの条件で測定される粘度がμ１０であるときに、ＴＩ値は、次式で算出される。
ＴＩ値＝｛ｌｏｇ（μ２．５／μ１０）｝／ｌｏｇ（１０／２．５）
The thixotropic index (hereinafter sometimes referred to as “TI value”) of the conductor-forming composition may be 0.50 to 0.90. When the TI value of the composition for forming a conductor is within this range, the composition for forming a conductor is reduced in viscosity due to shearing force for discharging, so that the composition for forming a conductor is easily discharged. After the composition lands on the substrate, the viscosity is restored by standing, and excessive wetting and spreading of the deposit can be suppressed. From the same viewpoint, the TI value of the conductor-forming composition may be 0.65 or more, or 0.80 or less. In the present specification, the TI value means a value measured according to JIS Z3284. More specifically, using an E-type viscometer, the viscosity measured at 25 ° C. under the condition of the number of rotations of 2.5 rpm is μ2.5, and the viscosity measured at 25 ° C. under the condition of the number of rotations of 10 rpm is μ2.5. when a mu 10, TI value is calculated by the following equation.
TI value = {log (μ 2.5 / μ 10 )} / log (10 / 2.5)
導体形成用組成物における銅含有粒子の含有量は、銅含有粒子及び分散媒の合計量１００質量部に対して、５０〜９０質量部であってもよい。銅含有粒子の含有量がこの範囲にあると、導体形成用組成物が充分な吐出性と上述の範囲内にある粘度及びＴＩ値とを有し易く、また、銅粒子が緻密に融着し良好な導電性を有する導電層が形成され易い。同様の観点から、銅含有粒子の含有量が、銅含有粒子及び分散媒の合計量１００質量部に対して、６０〜８５質量部であってもよく、又は７０〜８０質量部であってもよい。 The content of the copper-containing particles in the composition for forming a conductor may be 50 to 90 parts by mass based on 100 parts by mass of the total amount of the copper-containing particles and the dispersion medium. When the content of the copper-containing particles is in this range, the composition for forming a conductor is likely to have a sufficient ejection property and a viscosity and a TI value within the above-described ranges, and the copper particles are densely fused. A conductive layer having good conductivity is easily formed. From the same viewpoint, the content of the copper-containing particles may be 60 to 85 parts by mass, or 70 to 80 parts by mass, based on 100 parts by mass of the total amount of the copper-containing particles and the dispersion medium. Good.
本実施形態に係る導体形成用組成物は、導電塗料、導電ペースト、導電インク等の態様であってもよい。 The conductor-forming composition according to this embodiment may be in the form of a conductive paint, a conductive paste, a conductive ink, or the like.
基材から所定の距離の位置から液滴状の導体形成用組成物を吐出する手段としては、ピエゾジェットディスペンサー及びメカニカルジェットディスペンサ等のジェットディスペンサ、及びエアロゾルジェットなどの非接触式印刷装置が挙げられる。 As means for discharging the droplet-shaped conductor-forming composition from a position at a predetermined distance from the base material, a jet dispenser such as a piezo jet dispenser and a mechanical jet dispenser, and a non-contact printing device such as an aerosol jet are exemplified. .
基材から距離Ｌ（基材の表面と吐出口との距離）は、０．０５ｍｍ〜１０．０ｍｍとすることができる。距離Ｌは、実装用のバンプ等の導体を形成する場合は、０．０５ｍｍ〜５．０ｍｍとすることができ、ヒートシンク用のピラー等の導体を形成する場合は、１．０ｍｍ〜１０．０ｍｍとすることができる。 The distance L from the substrate (the distance between the surface of the substrate and the discharge port) can be 0.05 mm to 10.0 mm. The distance L can be 0.05 mm to 5.0 mm when a conductor such as a bump for mounting is formed, and 1.0 mm to 10.0 mm when a conductor such as a pillar for a heat sink is formed. It can be.
本実施形態に係る堆積工程によれば、基材上に高精度で導体形成用組成物を積み上げることができ、基材から突出する所望の形状を有する堆積体を得ることができる。 According to the deposition step according to the present embodiment, the conductor-forming composition can be stacked on the base material with high accuracy, and a deposited body having a desired shape protruding from the base material can be obtained.
導体は、例えば、上記堆積体を加熱して焼結することにより形成される。導体形成用組成物の焼結により、有機物が熱分解し、かつ、銅含有粒子同士が融着して、それにより導体形成用組成物が導体化する。焼結のための加熱温度は、例えば、３００℃以下、２５０℃以下、２３０℃以下であってもよく、１００℃以上、１２０℃以上、又は１４０℃以上であってもよい。このような低温での焼結であれば、基材の耐熱性が高くない場合であっても、基材の損傷を伴わずに導体を形成することができる。焼結のための加熱温度は、通常、１００℃以上である。特に、銅含有粒子が有機被覆層を有する被覆銅粒子である場合、低温での導体化が可能であるため、導体を形成するための加熱温度は、２５０℃以下、又は２３０℃以下であってもよい。 The conductor is formed, for example, by heating and sintering the deposit. By sintering the conductor-forming composition, the organic substance is thermally decomposed, and the copper-containing particles are fused together, whereby the conductor-forming composition becomes a conductor. The heating temperature for sintering may be, for example, 300 ° C or lower, 250 ° C or lower, 230 ° C or lower, or 100 ° C or higher, 120 ° C or higher, or 140 ° C or higher. With such low-temperature sintering, even when the heat resistance of the base material is not high, the conductor can be formed without damaging the base material. The heating temperature for sintering is usually 100 ° C. or higher. In particular, when the copper-containing particles are coated copper particles having an organic coating layer, it is possible to conduct the conductor at a low temperature, so the heating temperature for forming the conductor is 250 ° C. or lower, or 230 ° C. or lower. Is also good.
焼結のための加熱温度は、一定でも、規則的又は不規則に変化してもよい。加熱の時間は特に制限されず、加熱温度、加熱雰囲気、銅含有粒子の量等を考慮して選択できる。加熱方法は、特に制限されないが、例えば、熱板、赤外ヒータ、光照射、又はパルスレーザによる加熱であってもよい。 The heating temperature for sintering may be constant or may vary regularly or irregularly. The heating time is not particularly limited, and can be selected in consideration of the heating temperature, the heating atmosphere, the amount of the copper-containing particles, and the like. Although the heating method is not particularly limited, for example, heating by a hot plate, an infrared heater, light irradiation, or pulse laser may be used.
堆積体が加熱される雰囲気は、特に制限されないが、窒素、アルゴン等を含む不活性雰囲気であってもよく、水素、ギ酸等の還元性物質を含む還元雰囲気であってもよい。圧力は特に制限されないが、減圧雰囲気で堆積体を加熱することでより、低温での導体化が促進される傾向がある。 The atmosphere in which the deposit is heated is not particularly limited, but may be an inert atmosphere containing nitrogen, argon, or the like, or a reducing atmosphere containing a reducing substance such as hydrogen or formic acid. Although the pressure is not particularly limited, heating the deposit in a reduced-pressure atmosphere tends to promote the formation of a conductor at a low temperature.
導体の体積抵抗率は、３００μΩ・ｃｍ以下であってもよく、１００μΩ・ｃｍ以下であってもよく、３０μΩ・ｃｍ以下であってもよく、２０μΩ・ｃｍ以下であってもよい。 The volume resistivity of the conductor may be 300 μΩ · cm or less, 100 μΩ · cm or less, 30 μΩ · cm or less, or 20 μΩ · cm or less.
導体は基材から突出する形状を有しており、例えば、バンプ、ピラー、ピン、又はフィンの形状を有していてもよい。これらは、円錐状、多角推状、半球状、円柱状、多角柱状、板状、及び直方体状、並びに、これら形状の端部若しくは側面に丸み若しくは凹凸を帯びた形状のうちの１種又は２種以上を組み合わせたものであってもよい。 The conductor has a shape projecting from the base material, and may have, for example, a shape of a bump, a pillar, a pin, or a fin. These are one or two of a conical shape, a polygonal protruding shape, a hemispherical shape, a columnar shape, a polygonal columnar shape, a plate shape, and a rectangular parallelepiped shape, and a shape having a rounded or uneven shape at the end or side surface of the shape. A combination of more than one species may be used.
本実施形態の導体の形成方法によれば、基材上に高アスペクト比の堆積体を設けることができ、これにより基材上に高アスペクト比の導体を形成することができる。アスペクト比としては、堆積体及び導体の高さ／幅が、０．０１〜１０の範囲であってもよく、０．１〜６の範囲であってもよい。本明細書において、「堆積体又は導体の高さ」とは、互いの距離が最大となるように選ばれる、基材と堆積体又は導体とが接する面と、堆積体又は導体に外接する平面との間の距離を意味する。「堆積体又は導体の幅」とは、堆積体又は導体に外接し、互いの距離が最小となるように選ばれる２つの平面間の距離を意味する。 According to the conductor forming method of the present embodiment, a deposit having a high aspect ratio can be provided on a substrate, and thereby a conductor having a high aspect ratio can be formed on the substrate. As the aspect ratio, the height / width of the deposit and the conductor may be in the range of 0.01 to 10, or may be in the range of 0.1 to 6. In the present specification, the “height of the deposit or the conductor” is a plane which is selected so that a distance from each other is largest, and which is in contact with the base material and the deposit or the conductor, and a plane which circumscribes the deposit or the conductor. Means the distance between By "the width of the stack or conductor" is meant the distance between two planes circumscribing the stack or conductor and selected to minimize the distance between each other.
導体の形成方法は、必要に応じてその他の工程を更に有していてもよい。その他の工程としては、堆積体の焼結のための加熱の前に、乾燥により堆積体中の揮発成分の少なくとも一部を除去する工程、堆積体を焼結した後、形成された導体を還元雰囲気下で更に加熱して、導体に含まれる酸化銅を還元する工程、導体の光焼成により、導体中の残存成分を除去する工程、及び、導体に対して荷重を印加する工程等が挙げられる。 The method of forming the conductor may further include other steps as necessary. Other steps include, before heating for sintering the deposit, a step of removing at least a part of volatile components in the deposit by drying, and after sintering the deposit, reducing the formed conductor A step of further heating under an atmosphere to reduce copper oxide contained in the conductor, a step of removing residual components in the conductor by light firing of the conductor, and a step of applying a load to the conductor. .
本実施形態の導体の形成方法は、種々の電子部品の接合部、放熱部、配線、被膜等の形成に適用することができる。本実施形態の導体の形成方法は、導体形成用組成物が銅含有粒子を含んでおり、例えば、円柱状の銅ピラーなどを形成することができることから、フリップチップ実装における銅ピラーの形成やヒートシンクの製造等に好適である。 The method for forming a conductor according to the present embodiment can be applied to the formation of a joint, a heat radiator, a wiring, a coating, and the like of various electronic components. In the method for forming a conductor according to the present embodiment, the conductor-forming composition contains copper-containing particles and, for example, can form a columnar copper pillar or the like. And the like.
フリップチップ実装の用途において、現状のめっきで銅ピラーを作製する方法では銅ピラー作製後に続けてはんだ層をめっきで形成している。このはんだ層が接合材として働くため基板へ実装できる。本実施形態の導体の形成方法によれば、導体として銅ピラーを形成した後にめっきを施すことで銅ピラーにはんだ層を形成することができる。これ以外にも、ピラー状に設けた堆積体、乾燥後の堆積体又は焼成後の堆積体の上にはんだペーストを塗布することもできる。また、図１の（ｂ）に示されるような堆積体付基材は、堆積体が接合材としても働くため、堆積体付基材と別の被着体とを重ねて焼成することで、はんだ層無しで接合することができる。 In the flip chip mounting application, in the current method of producing a copper pillar by plating, a solder layer is formed by plating after the production of the copper pillar. Since this solder layer functions as a bonding material, it can be mounted on a substrate. According to the conductor forming method of the present embodiment, a solder layer can be formed on a copper pillar by plating after forming a copper pillar as a conductor. In addition, a solder paste can be applied on a pillar-shaped deposit, a dried deposit, or a fired deposit. Further, in the base material with a deposit as shown in FIG. 1B, since the deposit also functions as a bonding material, the base material with the deposit and another adherend are fired by being overlapped. It can be joined without a solder layer.
本実施形態の導体の形成方法で形成される導体及び導体付基材は、種々の装置に用いることができる。導体及び導体付基材は、具体的には、電磁波シールド、積層板、太陽電池パネル、照明、ディスプレイ、トランジスタ、半導体パッケージ、積層セラミックコンデンサ、センサ等の電子部品に使用される。また、上記電子部品を内蔵する電子機器、家電、産業用機械、輸送用機械等も本実施形態に係る導体又は導体付基材を備える装置に含まれる。 The conductor and the base material with a conductor formed by the method for forming a conductor of the present embodiment can be used for various devices. The conductor and the substrate with a conductor are specifically used for electronic components such as an electromagnetic wave shield, a laminated plate, a solar cell panel, a lighting, a display, a transistor, a semiconductor package, a laminated ceramic capacitor, and a sensor. Further, an electronic device, a home appliance, an industrial machine, a transport machine, and the like incorporating the above electronic component are also included in the apparatus including the conductor or the base material with a conductor according to the present embodiment.
以下、実施例及び比較例によって、本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
１．銅含有粒子の準備
三井金属鉱業株式会社製の以下の型番の銅粒子を準備した。
・ＣＨ−０２００（球形銅粒子、メジアン径：０．３４μｍ）
・１０５０ＹＦ（扁平状銅粒子、メジアン径：１．４μｍ）
1. Preparation of Copper-Containing Particles Copper particles of the following model number manufactured by Mitsui Kinzoku Mining Co., Ltd. were prepared.
CH-0200 (spherical copper particles, median diameter: 0.34 μm)
・ 1050YF (flat copper particles, median diameter: 1.4 μm)
なお、銅含有粒子の粒径は、サブミクロン粒子アナライザＮ５ ＰＬＵＳ（ベックマンコールター製）を用いて光子相関法により測定し、得られた粒径の累積分布から、メジアン径を算出した。 The particle diameter of the copper-containing particles was measured by a photon correlation method using a submicron particle analyzer N5 PLUS (manufactured by Beckman Coulter), and the median diameter was calculated from the cumulative distribution of the obtained particle diameters.
２．導体形成用組成物
銅含有粒子と、表１に示す分散媒とを、表１に示す配合比で混合して、実施例及び比較例の導体形成用組成物を調製した。２種の銅粒子の質量比は、ＣＨ−０２００：１０５０ＹＦ＝７：３とした。なお、表中の分散媒の詳細は以下のとおりである。
テルピネオール：テルピネオール（異性体混合物）（和光純薬工業株式会社製）
テルソルブＭＴＰＨ：イソボルニルシクロヘキサノール（商品名：テルソルブＭＴＰＨ、日本テルペン化学株式会社製）
エタノール（和光純薬工業株式会社製）
2. Conductor-Forming Composition Copper-containing particles and the dispersion media shown in Table 1 were mixed at the compounding ratio shown in Table 1 to prepare conductor-forming compositions of Examples and Comparative Examples. The mass ratio of the two types of copper particles was CH-0200: 1050YF = 7: 3. The details of the dispersion medium in the table are as follows.
Terpineol: Terpineol (isomer mixture) (manufactured by Wako Pure Chemical Industries, Ltd.)
Tersolve MTPH: isobornyl cyclohexanol (trade name: Tersolve MTPH, manufactured by Nippon Terpene Chemical Co., Ltd.)
Ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)
３．評価
３−１．粘度
Ｅ型粘度計（東機産業株式会社製、製品名：ＶＩＳＣＯＭＥＴＥＲ−ＴＶ３３）を用いて、導体形成用組成物の２５℃における粘度を測定した。測定用冶具として、コーンプレート型ロータＳＳＰまたは３°×Ｒ１４を用い、回転数を２．５ｒｐｍとした。
3. Evaluation 3-1. Viscosity The viscosity at 25 ° C of the composition for forming a conductor was measured using an E-type viscometer (product name: VISCOMMETER-TV33, manufactured by Toki Sangyo Co., Ltd.). As a measurement jig, a cone plate type rotor SSP or 3 ° × R14 was used, and the rotation speed was 2.5 rpm.
３−２．チキソトロピーインデックス（ＴＩ値）
ＴＩ値を、ＪＩＳ Ｚ３２８４に従って測定した。より具体的には、Ｅ型粘度計（東機産業株式会社製、製品名：ＶＩＳＣＯＭＥＴＥＲ−ＴＶ３３）を用いて、２５℃で回転数２．５ｒｐｍ及び回転数１０ｒｐｍの条件で粘度を測定した。回転数２．５ｒｐｍの粘度μ２．５、及び回転数１０ｒｐｍの粘度μ１０から、下記式によりＴＩ値を算出した。
ＴＩ値＝｛ｌｏｇ（μ２．５／μ１０）｝／ｌｏｇ（２０／５）
3-2. Thixotropy index (TI value)
The TI value was measured according to JIS Z3284. More specifically, the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: VISCOMMETER-TV33) at 25 ° C. under the conditions of 2.5 rpm and 10 rpm. The viscosity of the rotational speed 2.5 rpm mu 2.5, and the viscosity mu 10 rpm 10 rpm, was calculated TI value by the following equation.
TI value = {log (μ 2.5 / μ 10 )} / log (20/5)
３−３．導体の形成
銅板上の一点に、各導体形成用組成物を、ジェットディスペンサ（ＨＯＴＭＥＬＴ ＳＵＰＥＲ ＪＥＴ ＭＪＥＴ−Ｓ−ＨＭ、武蔵エンジニアリング株式会社製）を用いて、１秒間吐出し、堆積させた。ジェットディスペンサのノズルと銅板の表面との距離は、３．０ｍｍであった。このときの吐出性及び堆積体の形状保持性を以下の方法で評価した。その後、堆積体を加熱することにより焼結し、導体を形成した。導体の加熱は、１００％水素雰囲気中、昇温速度７℃／分で２２５℃まで昇温し、２２５℃で６０分間保持することにより行った。導体の導電性を以下の方法で評価した。
3-3. Formation of Conductor Each conductor-forming composition was ejected and deposited at one point on a copper plate using a jet dispenser (HOTMELT SUPER JET MJET-S-HM, manufactured by Musashi Engineering Co., Ltd.) for 1 second. The distance between the nozzle of the jet dispenser and the surface of the copper plate was 3.0 mm. At this time, the dischargeability and the shape retention of the deposited body were evaluated by the following methods. Thereafter, the deposit was heated and sintered to form a conductor. Heating of the conductor was performed in a 100% hydrogen atmosphere by increasing the temperature to 225 ° C. at a rate of 7 ° C./min and maintaining the temperature at 225 ° C. for 60 minutes. The conductivity of the conductor was evaluated by the following method.
（吐出性）
導体形成用組成物の液滴がノズル先端に溜まることなく、あるいはノズル詰まりなく吐出できた場合は「Ａ」、吐出できなかった場合は「Ｆ」として吐出性を評価した。
(Dischargeability)
The dischargeability was evaluated as “A” when droplets of the conductor-forming composition could be discharged without accumulating at the nozzle tip or without nozzle clogging, and as “F” when discharge was not possible.
（形状保持性）
堆積体の高さＨと幅Ｗとのアスペクト比Ｈ／Ｗを測定し、以下の基準により、形状保持性を評価した。
Ａ：アスペクト比Ｈ／Ｗが１．０以上
Ｂ：アスペクト比Ｈ／Ｗが０．５０以上１．０未満
Ｃ：アスペクト比Ｈ／Ｗが０．２０以上０．５未満
Ｄ：アスペクト比Ｈ／Ｗが０．２未満
(Shape retention)
The aspect ratio H / W between the height H and the width W of the deposit was measured, and the shape retention was evaluated according to the following criteria.
A: Aspect ratio H / W is 1.0 or more B: Aspect ratio H / W is 0.50 or more and less than 1.0 C: Aspect ratio H / W is 0.20 or more and less than 0.5 D: Aspect ratio H / W is less than 0.2
（導電性）
各導体形成用組成物を長さ１０ｍｍの直線形状に塗布し、これを焼成し、導体を形成した。なお、導体の加熱は、１００％水素雰囲気中、昇温速度７℃／分で２２５℃まで昇温し、２２５℃で６０分間保持することにより行った。形成された導体の体積抵抗率を、４端針面抵抗測定器で測定した面抵抗値と、非接触表面・層断面形状計測システム（ＶｅｒｔＳｃａｎ、三菱ケミカルシステム株式会社製）で測定した膜厚とから計算した。体積抵抗効率の値に基づく以下の基準により、導体の導電性を判定した。一般に、体積抵抗率が１００μΩ・ｃｍ未満であれば、導電性に優れるといえる。
Ａ：１０μΩ・ｃｍ未満
Ｂ：１０μΩ・ｃｍ以上３０μΩ・ｃｍ未満
Ｃ：３０μΩ・ｃｍ以上１００μΩ・ｃｍ未満
Ｄ：１００μΩ・ｃｍ以上
(Conductivity)
Each conductor-forming composition was applied in a linear shape having a length of 10 mm, which was fired to form a conductor. The conductor was heated in a 100% hydrogen atmosphere by increasing the temperature to 225 ° C. at a rate of 7 ° C./min and maintaining the temperature at 225 ° C. for 60 minutes. The volume resistivity of the formed conductor was measured with a sheet resistance value measured with a four-end needle surface resistance measuring device and a film thickness measured with a non-contact surface / layer cross-sectional shape measurement system (VertScan, manufactured by Mitsubishi Chemical System Corporation). Calculated from The conductivity of the conductor was determined according to the following criteria based on the value of the volume resistivity efficiency. Generally, if the volume resistivity is less than 100 μΩ · cm, it can be said that the conductivity is excellent.
A: less than 10 μΩ · cm B: 10 μΩ · cm or more and less than 30 μΩ · cm C: 30 μΩ · cm or more and less than 100 μΩ ·
表１に示すように、特定の粘度及びＴＩ値を有する実施例１〜８の導体形成用組成物は、充分な吐出性を示し、銅板から離れた位置から吐出しても堆積体が高いアスペクト比を有する形状を充分保持することができることが分かった。また、堆積体は加熱されることによって充分な導電性及び高いアスペクト比を保持した導体となることが確認された。 As shown in Table 1, the compositions for forming conductors of Examples 1 to 8 having specific viscosities and TI values show sufficient dischargeability, and have a high aspect ratio even when discharged from a position away from the copper plate. It has been found that a shape having a ratio can be sufficiently maintained. Further, it was confirmed that the deposited body became a conductor having sufficient conductivity and a high aspect ratio when heated.
１０…基材、２０…液滴（液滴状の導体形成用組成物）、３０…ノズル、４０…堆積体、５０…導体、１００…堆積体付基材、２００…導体付基材。
DESCRIPTION OF
Claims (5)
前記基材から０．０５ｍｍ〜１０．０ｍｍの距離の位置から液滴状の導体形成用組成物を吐出することにより前記基材上に前記導体形成用組成物を積み上げる工程を備え、
前記導体形成用組成物は、銅を含有する銅含有粒子と、前記銅含有粒子を分散させる分散媒と、を含み、２５℃における粘度が１〜８００Ｐａ・ｓであり、ＪＩＳ Ｚ３２８４に従って測定されるチキソトロピーインデックスが０．５０〜０．９０である、導体の形成方法。 A method of forming a conductor having a shape projecting from the base material on the base material,
Stacking the conductor-forming composition on the base material by discharging a droplet-shaped conductor-forming composition from a position at a distance of 0.05 mm to 10.0 mm from the base material,
The conductor-forming composition contains copper-containing particles containing copper and a dispersion medium for dispersing the copper-containing particles, and has a viscosity at 25 ° C of 1 to 800 Pa · s, which is measured according to JIS Z3284. A method for forming a conductor, wherein the thixotropic index is 0.50 to 0.90.
The method for forming a conductor according to any one of claims 1 to 4, further comprising a step of sintering the conductor-forming composition stacked on the substrate by heating the composition at 250 ° C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018154648A JP7225603B2 (en) | 2018-08-21 | 2018-08-21 | Conductor forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018154648A JP7225603B2 (en) | 2018-08-21 | 2018-08-21 | Conductor forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020029579A true JP2020029579A (en) | 2020-02-27 |
| JP7225603B2 JP7225603B2 (en) | 2023-02-21 |
Family
ID=69623897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018154648A Active JP7225603B2 (en) | 2018-08-21 | 2018-08-21 | Conductor forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7225603B2 (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009113033A (en) * | 2007-10-17 | 2009-05-28 | Hitachi Chem Co Ltd | Apparatus for forming circuit on resin molded article having three-dimensional shape |
| JP2010265420A (en) * | 2009-05-18 | 2010-11-25 | Konica Minolta Holdings Inc | Inkjet ink and method for forming electroconductive pattern |
| JP2012072418A (en) * | 2010-09-27 | 2012-04-12 | Yamagata Univ | Fine coated copper particles and method for producing the same |
| JP2012253031A (en) * | 2003-09-26 | 2012-12-20 | Hitachi Chem Co Ltd | Conductive paste |
| JP2014003175A (en) * | 2012-06-19 | 2014-01-09 | Hitachi Chemical Co Ltd | Method of manufacturing solar cell element, solar cell element, and solar cell |
| JP2014148732A (en) * | 2013-02-04 | 2014-08-21 | Yamagata Univ | Novel coated copper fine particle and production method thereof |
| JP2015047614A (en) * | 2013-08-30 | 2015-03-16 | 株式会社タムラ製作所 | Solder composition for fine pattern application |
| JP2015062230A (en) * | 2010-03-02 | 2015-04-02 | 株式会社トクヤマ | Composition for formation of wiring pattern |
| JP2015213098A (en) * | 2014-05-01 | 2015-11-26 | 住友ベークライト株式会社 | Semiconductor device manufacturing method and adhesive composition |
| WO2016024586A1 (en) * | 2014-08-13 | 2016-02-18 | 国立研究開発法人産業技術総合研究所 | Processing device for metal material |
| JP2016146291A (en) * | 2015-02-09 | 2016-08-12 | 日立化成株式会社 | Method for producing conductive film, conductor obtained thereby, and device produced using the conductive film |
| WO2017047323A1 (en) * | 2015-09-18 | 2017-03-23 | コニカミノルタ株式会社 | Wiring laminated structural body forming method |
-
2018
- 2018-08-21 JP JP2018154648A patent/JP7225603B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012253031A (en) * | 2003-09-26 | 2012-12-20 | Hitachi Chem Co Ltd | Conductive paste |
| JP2009113033A (en) * | 2007-10-17 | 2009-05-28 | Hitachi Chem Co Ltd | Apparatus for forming circuit on resin molded article having three-dimensional shape |
| JP2010265420A (en) * | 2009-05-18 | 2010-11-25 | Konica Minolta Holdings Inc | Inkjet ink and method for forming electroconductive pattern |
| JP2015062230A (en) * | 2010-03-02 | 2015-04-02 | 株式会社トクヤマ | Composition for formation of wiring pattern |
| JP2012072418A (en) * | 2010-09-27 | 2012-04-12 | Yamagata Univ | Fine coated copper particles and method for producing the same |
| JP2014003175A (en) * | 2012-06-19 | 2014-01-09 | Hitachi Chemical Co Ltd | Method of manufacturing solar cell element, solar cell element, and solar cell |
| JP2014148732A (en) * | 2013-02-04 | 2014-08-21 | Yamagata Univ | Novel coated copper fine particle and production method thereof |
| JP2015047614A (en) * | 2013-08-30 | 2015-03-16 | 株式会社タムラ製作所 | Solder composition for fine pattern application |
| JP2015213098A (en) * | 2014-05-01 | 2015-11-26 | 住友ベークライト株式会社 | Semiconductor device manufacturing method and adhesive composition |
| WO2016024586A1 (en) * | 2014-08-13 | 2016-02-18 | 国立研究開発法人産業技術総合研究所 | Processing device for metal material |
| JP2016146291A (en) * | 2015-02-09 | 2016-08-12 | 日立化成株式会社 | Method for producing conductive film, conductor obtained thereby, and device produced using the conductive film |
| WO2017047323A1 (en) * | 2015-09-18 | 2017-03-23 | コニカミノルタ株式会社 | Wiring laminated structural body forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7225603B2 (en) | 2023-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101867978B1 (en) | Metal nanoparticle paste, electronic component assembly using metal nanoparticle paste, led module, and method for forming circuit for printed wiring board | |
| US7956103B2 (en) | Ink composition and metallic material | |
| TWI651149B (en) | Metal bonding composition | |
| JP5011225B2 (en) | Metal member bonding agent, metal member bonded body manufacturing method, metal member bonded body, and electric circuit connecting bump manufacturing method | |
| CN111482596B (en) | Copper-containing particle, conductor-forming composition, method for producing conductor, and device | |
| CN111906321B (en) | Metal nanoparticle dispersion liquid for solder paste, method for producing same, and solder paste and method for producing same | |
| JP2012119611A (en) | Manufacturing method of through hole electrode substrate | |
| TW201542731A (en) | Bonding composition and metal bonded article using the same | |
| TWI744372B (en) | Bonding composition and production method thereof, bonding laminate, and cladded silver nanoparticle | |
| JP2020029579A (en) | Conductor formation method | |
| WO2019098195A1 (en) | Article and production method therefor | |
| JP2017101307A (en) | Copper-containing particle, conductor forming composition, method for producing conductor, conductor and electronic component | |
| JP7172224B2 (en) | COMPOSITION FOR CONDUCTOR-FORMING AND METHOD FOR MANUFACTURING ARTICLE HAVING CONDUCTOR LAYER | |
| JP6669420B2 (en) | Bonding composition | |
| JP7143685B2 (en) | METHOD FOR MANUFACTURING CONDUCTIVE LAMINATED BODY, CONDUCTIVE LAMINATED BODY, AND 2-PART CONDUCTIVE FILM FORMING AGENT | |
| JP6267835B1 (en) | Bonding composition and method for producing the same | |
| JP7333164B2 (en) | COMPOSITION FOR CONDUCTOR-FORMING AND METHOD FOR MANUFACTURING ARTICLE HAVING CONDUCTOR LAYER | |
| JP2016160456A (en) | Copper-containing particle, conductor forming composition, method for producing conductor, conductor and device | |
| JP2021015907A (en) | Method of manufacturing article having conductor layer | |
| JP2016157708A (en) | Light-emitting device arranged by use of silver nanoparticles, and manufacturing method thereof | |
| JP7187835B2 (en) | COMPOSITION FOR CONDUCTOR-FORMING AND MANUFACTURING METHOD THEREOF, AND ARTICLE HAVING CONDUCTOR LAYER AND MANUFACTURING METHOD THEREOF | |
| JP7477581B2 (en) | Dispersion, method for producing conductive patterned structure using same, and conductive patterned structure | |
| KR102658275B1 (en) | Compositions, conductors and methods of making the same, and structures | |
| JP2017128782A (en) | Nickel fine particle-containing composition and joining material | |
| JP2017204371A (en) | Conductor-forming composition, method for producing conductor, method for producing plating layer, conductor, laminate, and device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210721 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220614 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220705 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220830 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230110 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230123 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 7225603 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |