TWI505298B - 導電膜形成方法及燒結促進劑 - Google Patents
導電膜形成方法及燒結促進劑 Download PDFInfo
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- TWI505298B TWI505298B TW102123239A TW102123239A TWI505298B TW I505298 B TWI505298 B TW I505298B TW 102123239 A TW102123239 A TW 102123239A TW 102123239 A TW102123239 A TW 102123239A TW I505298 B TWI505298 B TW I505298B
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- copper
- sintering
- conductive film
- sintering accelerator
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- 238000005245 sintering Methods 0.000 title claims description 101
- 238000000034 method Methods 0.000 title claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 93
- 229910052802 copper Inorganic materials 0.000 claims description 91
- 239000010949 copper Substances 0.000 claims description 91
- 239000000758 substrate Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 15
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 150000002429 hydrazines Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims 1
- 150000001880 copper compounds Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 description 40
- 239000010419 fine particle Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WKZAQTGAIQHXQM-UHFFFAOYSA-N P(=O)(O)(O)O.OCC(P(O)(O)=O)P(O)(O)=O Chemical compound P(=O)(O)(O)O.OCC(P(O)(O)=O)P(O)(O)=O WKZAQTGAIQHXQM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/008—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression characterised by the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2202/00—Treatment under specific physical conditions
- B22F2202/11—Use of irradiation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1157—Using means for chemical reduction
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
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- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Manufacturing Of Electric Cables (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
Description
本發明有關一利用光燒結(photo sintering)之導電膜形成方法、以及允許光燒結在導電膜形成方法中進行之燒結促進劑。
至今存在一印刷電路板，其中藉由光微影將一由銅箔組成之電路形成在基板上。光微影需要蝕刻銅箔的步驟，並且需要高成本來處理由蝕刻所產生的廢棄液體及其類似者。
已知一方法作為不需蝕刻的技術，其中使用包含散佈在分散媒介物中之銅微粒(銅奈米微粒)的銅微粒分散劑(銅墨水)在基板上形成導電膜(見例如專利文獻1)。根據此方法，將銅微粒分散劑的液態膜形成在基板上，並使液態膜乾燥以形成一銅微粒層。藉由光線照射而使銅微粒層進行光燒結，並從而形成具有低電阻的導電膜。
然而，在上述方法中，即使增加光燒結中所照射之光線能量，光燒結可能仍無法充分進行，且因此無法形成具有低電阻的導電膜。
專利文獻1：美國專利申請案第2008/0286488號。
本發明係用以解決上述問題，且其目的在於導電膜形成方法中利用光燒結來形成具有低電阻的導電膜。
本發明之導電膜形成方法係其中利用光燒結來形成導電膜的方法，且其特徵在於包括下列步驟：在基板上形成一由燒結促進劑所製成之層，在燒結促進劑所製成之層上形成一由銅微粒分散劑所製成之液態膜，使液態膜乾燥以形成銅微粒層，以及使銅微粒層進行光燒結。燒結促進劑係自金屬銅移除氧化銅之化合物。
在此導電膜形成方法中，燒結促進劑較佳地選自由醯胺類、亞醯胺類、酮類、氨基甲酸酯類(urethanes)、硫醚類、羧酸類、及磷酸類所組成的群組。
在此導電膜形成方法中，燒結促進劑較佳地選自由聚乙烯基吡咯啶酮(polyvinylpyrrolidone)、聚醯胺醯亞胺樹脂、聚氨基甲酸酯樹脂、聚伸苯基硫化物樹脂、及羥基亞乙基二膦酸(hydroxyethylidenediphosphonic)所組成的群組。
在此導電膜形成方法中，燒結促進劑較佳地可選自由醇類、醣類、醛類、聯氨類、醌類(quinones)、酚類、及胺類所組成的群組。
在此導電膜形成方法中，燒結促進劑較佳地可選自由聚乙烯基醇、氫醌、及矽烷耦合劑所組成的群組。
本發明之燒結促進劑係用於上述導電膜形成方法中。
根據本發明，由於燒結促進劑在光燒結中移除了銅微粒的表面氧化物膜、將已移除表面氧化物膜的銅微粒燒結、以及使銅微粒層進行結塊，且因此輕易形成具有低電阻的導電膜。
1‧‧‧基板
2‧‧‧燒結促進劑
3‧‧‧液態膜
4‧‧‧銅微粒層
5‧‧‧導電膜
21‧‧‧溶液
22‧‧‧層
31‧‧‧銅微粒
圖1(a)至1(f)係以時間先後順序顯示藉由根據本發明之實施例之導電膜形成方法來形成導電膜的橫剖面示意圖。
將參考圖1(a)至1(f)來描述根據本發明之實施例之導
電膜形成方法。如圖1(a)及1(b)所示，將包含燒結促進劑2的溶液21塗佈在基板1上。如圖1(c)所示，使溶液21的溶劑變乾以形成一由燒結促進劑2所製成之層22。
基板1係藉由將基材形成為板狀而獲得。基材的例子包括但不限於玻璃、樹脂、陶瓷、矽晶圓、及類似者。
燒結促進劑2係自金屬銅移除氧化銅之化合物。燒結促進劑2可為例如醯胺類、亞醯胺類、酮類、氨基甲酸酯類、硫醚類、羧酸類、或磷酸類，且其例子包括但不限於醯胺類之中的聚乙烯基吡咯啶酮、亞醯胺類之中的聚醯胺醯亞胺樹脂、氨基甲酸酯類之中的聚氨基甲酸酯樹脂、硫醚類之中的聚伸苯基硫化物樹脂、及磷酸類之中的羥基亞乙基二膦酸。這類燒結促進劑2被認為是藉由蝕刻而自金屬銅移除氧化銅。
燒結促進劑2可為醇類、醣類、醛類、聯氨類、醌類、酚類、或胺類，且其例子包括但不限於醇類之中的聚乙烯基醇、醌類之中的氫醌、胺類之中的矽烷耦合劑、及類似者。這類燒結促進劑2藉由使氧化銅還原而自金屬銅移除。
這些燒結促進劑2可單獨使用，或者二或更多種類的燒結促進劑可適當地混合及使用。
如圖1(d)所示，由銅微粒分散劑所製成的液態膜3係形成在燒結促進劑2的層22上。銅微粒分散劑係一液體，該液體包含散佈於其中之銅微粒31，並且銅微粒分散劑包括銅微粒31、分散媒介物、及分散劑。銅微粒31係例如具有1nm或更大且小於100nm之中微粒直徑的銅奈米微粒。分散媒介物包含銅微粒31之液態媒介物。分散劑使銅微粒31能散佈在分散媒介物之中。由於微粒表面在空氣中被氧所氧化，所以銅微粒31覆蓋有一薄表面氧化物膜。
液態膜3係例如藉由印刷方法來形成。在印刷方法中，將銅微粒分散劑係用作印刷墨水，並且將預定圖案印刷在燒結促進劑2的層22上，因而形成帶有圖案之液態膜3。由於銅微粒分散劑係用作墨水，故其亦可稱為銅墨水。燒結促進劑2由於與液態膜3接觸而溶析在液態膜3中。
接著，使液態膜3乾燥。如圖1(e)所示，藉由使液態膜3
變乾而將銅微粒31及燒結促進劑2存留在基板1上，以在基板1上形成由銅微粒31所組成之銅微粒層4。銅微粒層4中的銅微粒31的表面係與燒結促進劑2接觸。在圖1(e)中，省略了燒結促進劑2的圖示。
接著，用光線照射銅微粒層4，並且使銅微粒層4進行光燒結。光燒結在大氣下、於室溫執行。光燒結中所使用之光源係例如氙燈。雷射裝置亦可用作光源。在光燒結中，銅微粒31的表面氧化物膜被移除，並且亦將銅微粒31燒結，且銅微粒層4進行結塊。如圖1(f)所示，銅微粒層4進行結塊以形成導電膜5。
至此，銅微粒31的表面氧化物膜已被認為是由於光燒結中的光線能量而藉由光還原反應還原成銅、並隨後被移除。
然而，根據本發明之發明人執行之測試，即使光燒結中所照射的光線能量增加，但銅微粒層4仍可能未充分進行結塊，這取決於銅微粒分散劑。由於照射在銅微粒層4上的光線之過大能量可能造成銅微粒層4的損壞，因此光燒結中所照射之光線能量有一強度上的限制。本發明之發明人認為可能有一些情況僅因光線能量而使銅微粒31的表面氧化物膜未充分移除，且因此使光燒結未充分進行，從而導致銅微粒層4的未充分結塊。
本發明之發明人藉由測試已發現到藉由使用自金屬銅移除氧化銅之化合物而允許進行光燒結。在本實施例之導電膜形成方法中，燒結促進劑2係自金屬銅移除氧化銅之化合物，並移除銅微粒31的表面氧化物膜。光照射至銅微粒層4促進其中燒結促進劑2使氧化銅能自銅微粒31移除的化學反應。已移除表面氧化物膜的銅微粒31藉由光線能量而燒結，且因此銅微粒層4進行結塊作用以形成具有導電性之導電膜5。
如以上所述，根據本實施例之導電膜形成方法，由於燒結促進劑2使銅微粒31的表面氧化物膜能在光燒結中被移除、將已移除表面氧化物膜的銅微粒31燒結、以及使銅微粒層4進行結塊，且因此輕易形成具有低電阻的導電膜5。
假使燒結促進劑2實現了氧化銅的蝕刻，則藉由蝕刻來移除銅微粒31的表面氧化物膜。
假使燒結促進劑2實現了氧化銅的還原，則藉由還原來移除
銅微粒31的表面氧化物膜。
在以下範例中，利用本發明之導電膜形成方法來形成導電膜5，並量測如此形成之導電膜5的電阻。
〔範例1〕
使用無鹼性玻璃作為基板1。使用如聚乙烯基吡咯啶酮(具有630000的分子量)作為燒結促進劑2、以及使用水作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至10%。藉由旋塗法以預定厚度將此溶液塗佈在基板1上。為了使溶液中的溶劑變乾，故將覆蓋有溶液之基板1在大氣下、於100℃至250℃乾燥30分鐘，以形成由燒結促進劑所製成的層22。藉由旋塗法以預定厚度將銅微粒分散劑(ISHIHARA CHEMICAL CO.,LTD製作，商品名稱為「CJ-0104」)塗佈在由燒結促進劑所製成的層22上。使覆蓋有銅微粒分散劑之基板1在大氣下、於100℃乾燥30分鐘，並隨後利用具有氙燈之閃光照射裝置進行光燒結，以產生樣本基板。此光燒結中的光線照射係以從0.5J/cm2
到30J/cm2
的範圍內之能量強度實施0.1ms至10ms。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。該銅色為結塊銅的顏色，並且從由於光燒結的顏色變化得知銅微粒層4經過結塊作用而形成導電膜5。光線照射不需執行超過一次。測試基板上之導電膜5的片電阻顯現200mΩ/□的低數值。
〔範例2〕
使用醯胺醯亞胺類之中的聚醯胺醯亞胺樹脂作為燒結促進劑2、以及使用丙烯碳酸酯作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至10%。除了上述以外，用如同範例1中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現280mΩ/□的低數值。
〔範例3〕
使用胺類之中的矽烷耦合劑(3-胺基丙基三乙氧基矽烷)作為燒結促進劑2、以及使用水作為溶劑，從而製備一包含燒結促進劑2之溶
液。將燒結促進劑2的濃度調節至1%。除了上述以外，用如同範例2中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現200mΩ/□。
〔範例4〕
使用另一矽烷耦合劑(N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷)作為燒結促進劑2、以及使用水作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至1%。除了上述以外，用如同範例3中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現200mΩ/□。
〔範例5〕
使用醇類之中的聚乙烯基醇(具有2000的分子量)作為燒結促進劑2、以及使用水作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至10%。除了上述以外，用如同範例4中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現300mΩ/□。
〔範例6〕
使用氨基甲酸酯類之中的聚氨基甲酸酯樹脂作為燒結促進劑2、以及使用丙烯碳酸酯作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至35%。除了上述以外，用如同範例5中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現250mΩ/□。
〔範例7〕
使用硫醚類之中的聚伸苯基硫化物樹脂作為燒結促進劑2、以及使用2-丙醇作為溶劑，從而製備一包含燒結促進劑2(分散劑)之溶液。將燒結促進劑2的濃度調節至1%。除了上述以外，用如同範例6中
的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現170mΩ/□。
〔範例8〕
使用磷酸類之中的羥基亞乙基二膦酸作為燒結促進劑2、以及使用水作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至49%。除了上述以外，用如同範例7中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現150mΩ/□。
〔範例9〕
使用醌類之中的氫醌作為燒結促進劑2、以及使用丙烯碳酸酯作為溶劑，從而製備一包含燒結促進劑2之溶液。將燒結促進劑2的濃度調節至10%。除了上述以外，用如同範例8中的相同方法產生測試基板。在光燒結前，銅微粒層4呈黑色。在藉由單次光線照射之光燒結後，表面顏色變為銅色。測試基板上之導電膜5的片電阻顯現300mΩ/□。
如以上所述，使用燒結促進劑2實現了具有低電阻之導電膜5的形成。
本發明不限於上述實施例的配置，並且在不離開本發明之精神或範圍的情況下，仍可實施各種修改。例如，基板1的表面形狀不限於平面，並可為曲面或複數平面的組合。
1‧‧‧基板
2‧‧‧燒結促進劑
3‧‧‧液態膜
4‧‧‧銅微粒層
5‧‧‧導電膜
21‧‧‧溶液
22‧‧‧層
31‧‧‧銅微粒
Claims (6)
- 一種導電膜形成方法，其中利用光燒結來形成導電膜，該導電膜形成方法包含下列步驟：在基板上形成一由燒結促進劑所製成之層，在該燒結促進劑所製成之層上形成一由銅微粒分散劑所製成之液態膜；使該液態膜乾燥，以形成銅微粒層，以及使該銅微粒層進行光燒結，其中該燒結促進劑係自金屬銅移除氧化銅之化合物。
- 如申請專利範圍第1項之導電膜形成方法，其中該燒結促進劑係選自由醯胺類、亞醯胺類、酮類、氨基甲酸酯類、硫醚類、羧酸類、及磷酸類所組成的群組。
- 如申請專利範圍第1項之導電膜形成方法，其中該燒結促進劑係選自由聚乙烯基吡咯啶酮、聚醯胺醯亞胺樹脂、聚氨基甲酸酯樹脂、聚伸苯基硫化物樹脂、及羥基亞乙基二膦酸所組成的群組。
- 如申請專利範圍第1項之導電膜形成方法，其中該燒結促進劑係選自由醇類、醣類、醛類、聯氨類、醌類、酚類、及胺類所組成的群組。
- 如申請專利範圍第1項之導電膜形成方法，其中該燒結促進劑係選自由聚乙烯基醇、氫醌、及矽烷耦合劑所組成的群組。
- 一種燒結促進劑，該燒結促進劑係用於根據申請專利範圍第1至5項其中任一項之導電膜形成方法中。
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|---|---|---|---|---|
| WO2010032841A1 (ja) * | 2008-09-19 | 2010-03-25 | 旭硝子株式会社 | 導電性フィラー、導電性ペーストおよび導電膜を有する物品 |
| TW201114860A (en) * | 2009-10-26 | 2011-05-01 | Hanwha Chemical Corp | Method for manufacturing of conductive metal thin film using carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5283291B1 (ja) | 2013-09-04 |
| JP2014011412A (ja) | 2014-01-20 |
| EP2871644A1 (en) | 2015-05-13 |
| CN104303243A (zh) | 2015-01-21 |
| WO2014006933A1 (ja) | 2014-01-09 |
| EP2871644A4 (en) | 2016-06-15 |
| US20150030784A1 (en) | 2015-01-29 |
| KR20140131576A (ko) | 2014-11-13 |
| TW201405588A (zh) | 2014-02-01 |
| CN104303243B (zh) | 2018-04-17 |
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