TWI606460B - 金屬糊及墨 - Google Patents
金屬糊及墨 Download PDFInfo
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- TWI606460B TWI606460B TW098122418A TW98122418A TWI606460B TW I606460 B TWI606460 B TW I606460B TW 098122418 A TW098122418 A TW 098122418A TW 98122418 A TW98122418 A TW 98122418A TW I606460 B TWI606460 B TW I606460B
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- 239000000976 ink Substances 0.000 title description 27
- 229910052751 metal Inorganic materials 0.000 claims description 180
- 239000002184 metal Substances 0.000 claims description 180
- 238000005245 sintering Methods 0.000 claims description 85
- 239000004020 conductor Substances 0.000 claims description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 39
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- 239000002082 metal nanoparticle Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 claims 1
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- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
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- 230000000996 additive effect Effects 0.000 description 3
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- 229910000431 copper oxide Inorganic materials 0.000 description 3
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- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- -1 aliphatic ketones Chemical class 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
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- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 101100162705 Caenorhabditis elegans ani-2 gene Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- 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
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0257—Nanoparticles
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10227—Other objects, e.g. metallic pieces
- H05K2201/10287—Metal wires as connectors or conductors
-
- 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
- H05K2203/08—Treatments involving gases
- H05K2203/087—Using a reactive gas
-
- 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
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
-
- 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
- H05K2203/1131—Sintering, i.e. fusing of metal particles to achieve or improve electrical conductivity
-
- 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
- H05K2203/14—Related to the order of processing steps
- H05K2203/1453—Applying the circuit pattern before another process, e.g. before filling of vias with conductive paste, before making printed resistors
-
- 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
- H05K3/1241—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 by ink-jet printing or drawing by dispensing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49117—Conductor or circuit manufacturing
- Y10T29/49169—Assembling electrical component directly to terminal or elongated conductor
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Powder Metallurgy (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
此申請案主張Roundhill等人的美國專利申請案第61/077,711號及Roundhill等人的美國專利申請案第61/081,539號之優先權,茲將其中之揭示全數以引用方式納入本文中。
本發明係關於可用以形成具有改良導電性的金屬導體之金屬糊和墨。
金屬糊,如同金屬墨,可以金屬奈米粒子、液態媒液、分散劑和其他添加劑調合。可含括添加劑以改變物性,如黏度、潤濕性和在選定基板上的接觸角度。相較於墨的黏度(如約5000cP),糊之較高的黏度(如約10,000cP至約60,000cP)有助於金屬奈米粒子的持續分散。金屬墨或糊之使用可基於數個因素包括印刷方法和基板。具低黏度的墨(如低於約20cP,或介於約10cP和約20cP之間)可用於噴墨印刷或氣溶膠印刷。糊過於黏稠而無法用於噴墨印刷且可藉網版印刷或適用於較高黏度的其他方法施用。
但是,一些金屬糊或墨,須要在惰性氣氛中於提高溫度加熱,這樣的條件不適用於某些應用,如,軟性電子產品(如,具聚合性基板者)。此外,一些金屬糊或墨包括一或多種具有高沸點的液態組份。當具有高沸點組份的金屬糊或墨藉緩慢熱燒結法在空氣中固化時,高沸點組份會形成非揮發性產物而留在固化的導體中。亦可在熱燒結期間內在惰性氣氛中熱分解成非揮發性產物,得到被污染的導體和相當高的電阻率。一些情況中,自液態媒液形成的有機殘渣造成導體和基板之間的黏著性降低,降低了金屬導體的品質。
調合用於低溫加工的金屬組成物(如墨和糊)適用以製造印刷電子產品,作為導電性黏著劑,或適用於包括各式各樣的電力組件電路(如電極和互連物)之製造和組合的其他應用。此金屬組成物包括金屬奈米粒子(如,銅、鎳、銀、金、鋁、鈷、鉬、鋅..等)於適用於光燒結之光學上透明的媒液中。可以根據尺寸和鈍化塗層地選擇這些組成物中的奈米粒子,且此組成物可經調配以得以準確印刷。經印刷的組成物中之奈米粒子可以在與塑膠基板相容的溫度下固化(如,光固化、熱固化或二者)成整體金屬膜或線。
文中描述的金屬組成物經調配以得到來自液體媒液的有機殘渣量降低之固化的導體。使用光燒結法,此金屬組成物可經燒結(如,低於約5毫秒,低於約2毫秒,或低於約1毫秒)以製造金屬導體。此光燒結法中,高強度光脈衝(如,約50,000、100,000或150,000勒克司或更高)被組成物中的金屬奈米粒子所吸收且於之後轉化成熱。結果是,金屬組成物可被施以短、高熱脈衝,其在有機組份驅動熱氧化反應或分解反應之前,迅速蒸發這些組份。相較於僅使用一些熱燒結法,金屬組成物(如,糊或墨)的此光燒結得到具高導電率(其可於較低溫度形成)和較低電阻率的導體。
一些體系中,文中描述的金屬組成物可經調合使得在聚合物基板上的組成物之光燒結和/或熱燒結(如,在空氣中或在形成氣中)提供具有較低電阻率的導體。例如,文中所述的銅糊製造的銅導體之電阻率介於約1x10-3歐姆‧公分和約1x10-6歐姆‧公分之間。即,銅導體的電阻率低於約1x10-3歐姆‧公分,低於約1x10-4歐姆‧公分,低於約1x10-5歐姆‧公分,或高於約1x10-6歐姆‧公分。
形成具高導電率(低電阻率)之導體的金屬組成物之製備的一個體系示於圖1。製法100可以在惰性氣氛中進行。步驟102中,製備所欲量(如,體積)的媒液。此媒液可包括,例如,芳族、脂族酮和醇、酯和它們的任何組合。如果媒液包括超過一種組份,則組份可以混在一起。步驟104中,一或多種分散液可加至媒液中,並攪拌該混合物(如,攪拌、振盪、混合、音波處理之類)以便均化。分散劑可包括,例如,短鏈聚合性胺、醇、磺酸鹽、磷酸鹽和它們的任何組合。步驟106中,金屬奈米粒子(如,奈米粉末形式)的量可加至媒液中以達到所欲的銅載量。一些體系中,奈米粉末可佔組成物之約30重量%至約70重量%,或約50重量%至約80重量%。然後攪拌此雜相混合物以形成糊。步驟108中,糊可經音波處理以形成均勻分散液。此音波處理可以低能量和短期間(如,低於約10分鐘,約2至8分鐘,或約5分鐘)達到。音波處理浴液體可經冷卻(如,至約0℃)。如果音波處理時間過長,或音波能量過高,則氣穴現象會導致局部加熱至無法接受的高溫,導致金屬奈米粒子聚集或結塊。藉由在音波處理程序期間內冷卻金屬糊(如,至約0℃)有助於抑制金屬奈米粒子聚集或結塊。金屬奈米粒子聚集或結塊會導致較大的粒子尺寸和燒結步驟中之較低的效能。聚集是銅奈米粒子的一個問題,此因會形成銅-銅化學鍵之故。這些銅-銅化學鍵不會因後續的機械作用而斷裂。步驟110中,可添加選用以調整性質(如黏度、潤濕性或接觸角度)的添加劑並與糊混合。此添加劑可為共價化合物、離子化合物或它們的任何組合。
依圖1中描述者製得的金屬糊可藉光燒結法製成導體(如,導電膜)。例如,金屬糊可藉洩降法塗佈在基板(如,KAPTON聚醯亞胺膜,DuPont供應)上。該光燒結法可包括閃光(其將金屬奈米粒子光燒結成,例如,金屬膜)之前的事先乾燥步驟。例如,該塗層可於約100℃在空氣中乾燥約60分鐘。此步驟促進揮發性組份自印刷糊中之移除。如果讓揮發性組份留在糊中,則在光燒結步驟期間內的迅速蒸發會造成金屬奈米粒子被吹離基板。乾燥之後,經乾燥的糊的電阻率可為,例如,高如100歐姆‧公分。一些體系中,可藉由使用較高溫度、於真空下進行乾燥步驟,或在紅外或微波射線下加熱,而減少乾燥時間。用於不含揮發性液態組份的銅糊,可免除乾燥步驟以減少加工時間。
經乾燥的糊可以在形成氣或在空氣中固化。例如,經乾燥的糊可在至多約10體積%的氫在氮中之混合物(如,約3-5體積%的氫在氮中)中,在約350℃中熱燒結約60分鐘。就奈米粒子在約20奈米至約200奈米範圍內的銅糊而言,熱燒結膜的電阻率可為約3x10-4歐姆‧公分。形成氣可將經乾燥的糊中的銅氧化物還原成銅。例如,如下示者,形成氣中的氫組份與銅氧化物反應而形成銅和水:
CuO+H2→Cu+H2O
和
Cu2O+H2→2Cu+H2O
此水蒸汽可在形成氣中被帶離。
熱燒結的金屬組成物可在形成氣或空氣中光燒結以降低其電阻率。光燒結包括對金屬組成物施以閃光。可以選擇閃光的強度(以電壓計)和期間(以脈衝寬度計)以減少金屬粒子自基板被吹走的情況,以降低所得導體的電阻率,及提高所得導體對基板的黏著性。實例中,熱燒結的銅導體在空氣中光燒結之後,導體厚度可為約1微米,且導體的電阻率可為約2x10-5歐姆‧公分。
金屬糊可以在空氣或在惰性氣氛中乾燥。金屬糊,或經乾燥的金屬糊,可經熱固化以形成金屬導體。經熱燒結的金屬導體可經光燒結以降低導體的電阻率。一些情況中,經乾燥的金屬糊可經光燒結但未驅動熱燒結。圖2說明用以自金屬組成物形成低電阻率導體之方法200。步驟202中,金屬糊施用於基板。步驟204中,該基板經加熱(如在爐中於約100℃約60分鐘)以乾燥該糊。步驟206中,經該燥的糊可經熱燒結。
一實例中,熱燒結可包括下列步驟。具有經乾燥的金屬糊之基板於室溫載入石英管中。石英管經抽真空(如,至約100毫托耳)。該石英管經加熱(如,至約350℃)並以形成氣(如,約4體積%氫與氮混合)滌氣直到溫度穩定。經塗佈的基板可於350℃加熱約60分鐘。在關閉形成氣和加熱器之後,該管可以惰性氣體(如氮)滌氣以冷卻該基板(如至低於100℃)。可自該石英管移出具有熱燒結導體的該基板。
步驟208中,經乾燥或熱燒結的金屬糊經光燒結。高電壓閃光氙燈可用於光燒結。可於溫度低於約100℃(如,常溫或約20℃)完成光燒結,以得到具有減低的電阻率和提高之與基板的黏著性之導體。美國專利申請公告第2008/0286488號(茲將該案以引用方式納入本文中)描述一種光燒結法。
光燒結和熱燒結之間之比較示於表1。
銅糊ANI-1和ANI+2之調合物示於表2。
圖3所示者為表1中的銅導體之電阻率(歐姆‧公分)與燒結溫度的關係圖。點300指出銅糊ANI-1在形成氣環境中熱燒結形成的導體之電阻率約3x10-4歐姆‧公分。點302指出銅糊ANI-1在形成氣環境中熱燒結(點300)及之後在空氣中於約20℃光燒結(1.2毫秒,1200伏特)形成的導電膜之電阻率約2x10-5歐姆‧公分。光燒結步驟使得電阻率降低約一個級次(order)。
點304、306和308指出銅糊ANI-1在空氣中於約100℃、約200℃和約300℃熱燒結形成的導電膜之電阻率約4.5x103歐姆‧公分。點310指出銅糊ANI-1在空氣中熱燒結(點304、306和308)及之後在空氣中於約20℃光燒結(1.2毫秒,1200伏特)形成的導電膜之電阻率約2x10-4歐姆‧公分。光燒結步驟使得電阻率降低超過7個級次。
點312、314和316指出ANI-2糊(奈米粒子尺寸200奈米,無添加劑或分散劑)在形成氣(4體積%H2在N2中)中分別於300℃、350℃、500℃熱燒結形成的導電膜之電阻率約4x102歐姆‧公分、約2x102歐姆‧公分和約2x10-4歐姆‧公分。因此,圖3指出,在某些溫度(如,在一些情況中約400℃),光燒結可用以使得電阻率比僅使用熱燒結時所達到者為低。
一些體系中,經乾燥的金屬糊可經光燒結且無居間的熱燒結步驟。就較高的熱燒結溫度所造成基板損傷而言,此具優點。因為光燒結法中含括的低溫(如,低於100℃),光燒結可用以自金屬糊或墨在基板(包括聚合物,如聚乙烯、聚酯、阻燃劑4..等)上形成電阻率約10-5歐姆‧公分或更低的導體(使用或未使用形成氣環境)且不損及基板。
金屬組成物(如,糊或墨)可用以在印刷電路板上製造互連物。圖4說明具有以經光燒結的金屬糊形成之印刷金屬互聯物402的組合品400。該組合品400可包括基板404(如,矽、陶瓷或撓性有機基板,如,聚醯亞胺、聚酯、液晶聚合物之類)和二或更多個晶片406。每一晶片406可具有一或多個金屬導線408,該導線可用以與其他晶片導線408連接。因為光燒結步驟可於低溫進行,所以此金屬互連物402可以直接連接至晶片導線408以提供組合於基板404上的晶片406間之互連。
圖5說明組合品500,其中由光燒結的金屬組成物(如,糊或墨)形成的互連物402用以填充介於晶片金屬導線408和金屬互連物402之間的貫孔502。基板404(如,矽、陶瓷或撓性有機基板,如,聚醯亞胺、聚酯、液晶聚合物之類)可包括二或多個晶片406位於其上,每一晶片具有一或多個金屬導線408。保角塗層506印在基板404上以覆蓋晶片406。可鑽鑿至金屬晶片導線408的貫孔502並以導電性銅糊填滿。之後,銅互連物402可以印在貫孔502頂部,藉此連接晶片導線408。可重複此方法以製造多層電路板。
可使用高銅載量(如約50重量%至約80重量%)製造高黏度銅糊(如約10,000cP至約60,000cP)以用於粗線印刷。具有低電阻率的粗線帶有許多電子設備須要的高電流密度。該銅糊可印成圖4或5中之所欲的互連輪廓402或用以填滿圖5中的貫孔502。銅糊的該黏度和潤濕特徵可經修飾以用於不同的互連尺寸或不同的貫孔直徑和深度。
文中描述的金屬糊可用以製造多層互連物以降低互連長度和電阻值。結果是,可形成具有較輕重量、較小真實尺寸、低雜訊和較低電力訊號耗損的高密度互連,以得到改良的晶片與晶片連接。文中描述的金屬糊亦可用以消除金屬線結合法,以提高用於晶片與寬互連物的電路設計的效能和可靠性,及移除錫晶鬚生長風險(和後續的短路),此風險情況可能因使用無鉛焊劑而引發。藉由使用可直接澱積(如,網版印刷)和光燒結的金屬糊,多層板之製備較簡單且花費較低。
一些情況中,自金屬糊或墨形成的導電突起物可用以製造介於積體電路和其他電子電路之間的界面。圖6說明電子裝置600,其中基板404承載積體電路406。該積體電路406電力連接至形成於基板404上的金屬突起物602。金屬突起物602以金屬線604連接至積體電路406。一些體系中,金屬突起物602由銅糊或墨形成,且金屬線604是銅線。
圖7說明形成圖6中之組合品之方法700。步驟702中,以根據墨或糊之性質(如黏度)選擇的方法,金屬墨或糊的液滴澱積在基板上。該基板可為聚合物,例如,聚醯亞胺。步驟704中,一部分的金屬線(如,金屬線端)插入液滴中。步驟706中,液滴602經固化(如,熱燒結、光燒結之類)。另一部分的金屬線(如,另一端點)可固定至,例如,積體電路。光燒結促進金屬氧化物之去除(藉,例如,氧化銅還原成銅)及金屬奈米粒熔入金屬整體膜中。燒結步驟之後,金屬線固定在實心的金屬突起物中,得到介於金屬線和有金屬突起物黏著的基板之間的電力連接。
圖8說明裝置800,其包括澱積在基板404上並經光燒結的金屬墨或糊形成的導線或墊802。導線或墊可為,例如,約0.1微米厚。基板404可包括聚合型材料,如KAPTON。帶結合金屬線804置於經光燒結的銅墊802上。此結合金屬線804可為,例如,直徑約25微米。金屬墨或糊的液滴(如,直徑約40-60微米)806澱積在導電墊/結合金屬線接頭808上並烘烤(如,於100℃ 30分鐘)以乾燥液滴。之後液滴經光燒結,經由金屬線接點808測定電阻值。
圖9A-9F係對應於圖8描述的方法之各階段的照片。圖9A和9C顯示在光燒結之前,銅線804插在銅液滴806中。圖9B和9D-F顯示光燒結之後的銅突起物900。
一些情況中,如圖10所示者,金屬突起物可為平順者。平順的突起物1000可藉由將平順的聚合物材料1002澱積在基板404上而形成。之後,金屬墨或糊1004澱積在聚合物材料1002上。金屬線可以插入金屬墨或糊1004中,且液滴經固化(如,經光燒結)以將金屬線固定在固化的金屬導體上。此方法可於低於100℃的溫度進行。
因數種原因,當金屬突起物製自,例如,銅,而非金時,可降低製造成本。首先,銅液滴可以準確地以選用的印刷技巧澱積(如,銅墨可經噴墨印刷)。再者,由於銅突起物可於低於100℃固化(如,經光固化),可以使用陣列較寬的基板材料且不會因高溫方法而受損。第三,由於銅突起物可於低溫固化,此燒結可發生於空氣環境(而非惰性環境),且在晶片墊和導電突起物之間結合的期間內,金屬氧化作用最小。
應瞭解已經以其細節描述本發明,前述描述用以說明但不限制本發明之範圍,本發明之範圍由所附申請專利範圍界定。其他特徵、優點和修飾屬下列申請專利範圍之範圍內。
100...製法
102...製備媒液
104...在媒液中添加分散劑並混合
106...添加金屬奈米粉末及混合以形成金屬糊
108...音波處理金屬糊
110...添加劑與金屬糊混合
200...方法
202...將金屬糊施用於基板
204...乾燥金屬糊
206...熱燒結乾金屬糊
208...光燒結經乾燥或經熱燒結的金屬糊
300...點
302...點
304...點
306...點
308...點
310...點
312...點
314...點
316...點
400...組合品
402...金屬互連物
404...基板
406...晶片
408...晶片金屬導線
500...組合品
502...貫孔
506...保角塗層
600...電子裝置
602...金屬突起物
604...金屬線
700...方法
702...將金屬糊或墨澱積在基板上
704...將一部分金屬線插入金屬糊或墨中
706...固化金屬糊或墨以將金屬線固定於金屬突化物
800...裝置
802...導線或墊
804...帶結合金屬線
806...金屬墨或糊的液滴
808...導電墊/結合金屬線接頭
1000...平順的突起物
1002...聚合物材料
1004...金屬突起物
圖1係說明金屬組成物之製備的流程圖。
圖2係說明藉包括熱燒結之方法形成金屬導體之方法的流程圖。
圖3係藉熱燒結和光燒結形成的銅導體之電阻率與加工溫度的關係圖。
圖4說明具有藉金屬組成物製得的印刷導體互連之晶片的組合品。
圖5說明具有藉金屬組成物製得的印刷導體經由貫孔互連的晶片之組合品。
圖6說明固定在光燒結的金屬突起物上的金屬線。
圖7係說明形成光燒結的金屬突起物之步驟的流程圖。
圖8說明固定在光燒結的金屬突起物之間的金屬線。
圖9A-9F顯示銅線固定於光燒結的金屬突起物的多個階段的照片。
圖10說明平順之光燒結的金屬突起物。
400...組合品
402...金屬互連物
404...基板
406...晶片
408...晶片金屬導線
Claims (36)
- 一種包含溶劑和多個金屬奈米粒子分散於其中的金屬糊,其中該金屬糊具有黏度為10,000cP至60,000cP,其中該金屬糊經調合使得該金屬糊之固化得到電阻率約5x10-4歐姆.公分或較低的金屬導體,其中該固化包含光燒結,以及其中該光燒結包含使該金屬糊經受閃光(light flash)。
- 如申請專利範圍第1項之金屬糊,其中該金屬奈米粒子包含銅。
- 如申請專利範圍第1項之金屬糊,其中該固化包含在該光燒結之前進行熱燒結。
- 如申請專利範圍第3項之金屬糊,其中該固化包含在包含氫和氮的形成氣中熱燒結。
- 如申請專利範圍第1項之金屬糊,其中該固化包含在空氣中及在周圍溫度中光燒結。
- 如申請專利範圍第3項之金屬糊,其中該金屬糊之熱燒結係在形成氣中進行。
- 如申請專利範圍第1項之金屬糊,其中該固化於約350℃或較低溫度進行。
- 如申請專利範圍第1項之金屬糊,其中該金屬糊在聚合物基板上固化。
- 如申請專利範圍第1項之金屬糊,其中該金屬奈米粒子的平均直徑約50奈米至約200奈米。
- 一種製造金屬導體之方法,包含固化金屬糊以提 供金屬導體,其中該金屬糊具有黏度為10,000cP至60,000cP,其中金屬導體的電阻率約5x10-4歐姆.公分或較低,其中該固化包含光燒結,以及其中該光燒結包含使該金屬糊經受閃光。
- 如申請專利範圍第10項之方法,其中該金屬糊包含銅奈米粒子。
- 如申請專利範圍第10項之方法,其中該固化包含在該光燒結之前於形成氣中熱燒結,以及其中該形成氣包含氫和氮。
- 如申請專利範圍第10項之方法,其中該固化包含在空氣中、在周圍溫度光燒結。
- 如申請專利範圍第10項之方法,進一步包含在光燒結之前,在形成氣中熱燒結該金屬糊。
- 如申請專利範圍第10項之方法,其中該固化發生於約350℃或較低溫度。
- 一種電力組合品,包含藉金屬導體互連的第一和第二電力組件,該金屬導體包含固化的金屬糊或墨,其中該金屬導體的電阻率約5x10-4歐姆.公分或較低,其中該固化的金屬糊或墨包含光燒結的金屬糊或墨,以及其中該光燒結包含使該金屬糊或墨經受閃光。
- 如申請專利範圍第16項之電力組合品,其中該金屬糊或墨包含銅奈米粒子。
- 如申請專利範圍第16項之電力組合品,其中該固化的金屬糊或墨包含熱燒結的金屬糊或墨。
- 如申請專利範圍第16項之電力組合品,其中該金屬導體的電阻率約2x10-5歐姆.公分或較低。
- 如申請專利範圍第16項之電力組合品,其中該金屬導體與該第一和第二電力組件直接接觸。
- 如申請專利範圍第16項之電力組合品,其中金屬導體經由充填熱燒結或光燒結的金屬糊之貫孔連接至第一和第二電力組件。
- 一種將金屬線固定至導體的方法,該方法包含:將金屬組成物的液滴澱積在基板上,該金屬組成物包含金屬奈米粒子,其中該金屬組成物具有黏度為10,000cP至60,000cP:將一部分金屬線插入該液滴中;燒結該金屬組成物;和將該金屬線固定於固化的金屬組成物,其中該燒結包含光燒結,以及其中該光燒結包含使該金屬組成物經受閃光。
- 如申請專利範圍第22項之方法,其中在該金屬組成物燒結之後,該金屬線的一部分插在金屬組成物中。
- 如申請專利範圍第22項之方法,其中該金屬奈米粒子包含銅。
- 如申請專利範圍第22項之方法,其中該燒結包含在該光燒結之前於形成氣中熱燒結,以及其中該形成氣包含氫和氮。
- 如申請專利範圍第22項之方法,其中該燒結包 含在空氣中及在周圍溫度中光燒結。
- 如申請專利範圍第22項之方法,其中該金屬組成物包含金屬奈米粒子,該金屬奈米粒子為在適用於光燒結之光學透明媒液中。
- 如申請專利範圍第22項之方法,其中該燒結發生於約350℃或較低溫度。
- 一種製造金屬導體之方法,包含固化金屬糊以提供金屬導體,其中該金屬糊具有黏度為10,000cP至60,000cP,其中金屬導體的電阻率約5x10-4歐姆.公分或較低,其中該金屬糊包含金屬奈米粒子,該金屬奈米粒子為在適用於光燒結之光學透明媒液中,以及其中該光燒結包含使該金屬糊經受閃光。
- 一種金屬糊之用途,係用於藉由一技術以形成電阻率約5x10-4歐姆.公分或較低的金屬導體,其中該技術包含光燒結,及進一步包含在光燒結之前熱燒結該金屬糊,其中該光燒結包含使該金屬糊經受閃光,且其中該金屬糊具有黏度為10,000cP至60,000cP,該金屬糊包含金屬奈米粒子,該金屬奈米粒子為在適用於光燒結之光學透明媒液中,且該奈米粒子在該金屬糊中之量為30重量%至70重量%。
- 如申請專利範圍第30項之金屬糊之用途,其中該奈米粒子在該糊中之量為50重量%至80重量%。
- 如申請專利範圍第1項之金屬糊,其中光燒結係使金屬糊中之金屬氧化物還原。
- 如申請專利範圍第10項之方法,其中光燒結係使金屬糊中之金屬氧化物還原。
- 如申請專利範圍第16項之電力組合品,其中光燒結係使金屬糊中之金屬氧化物還原。
- 如申請專利範圍第22項之方法,其中光燒結係使金屬組成物中之金屬氧化物還原。
- 如申請專利範圍第30項之金屬糊之用途,其中光燒結係使金屬糊中之金屬氧化物還原。
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-
2009
- 2009-07-01 US US12/496,453 patent/US20100000762A1/en not_active Abandoned
- 2009-07-02 EP EP09774505.3A patent/EP2301043B1/en not_active Not-in-force
- 2009-07-02 KR KR1020117002542A patent/KR101610790B1/ko active IP Right Grant
- 2009-07-02 WO PCT/US2009/049510 patent/WO2010003056A1/en active Application Filing
- 2009-07-02 CN CN201510167222.7A patent/CN104812175B/zh active Active
- 2009-07-02 TW TW098122418A patent/TWI606460B/zh active
- 2009-07-02 JP JP2011516873A patent/JP6337249B2/ja active Active
- 2009-07-02 CN CN200980125925.6A patent/CN102084435B/zh active Active
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CN102084435B (zh) | 2015-04-29 |
JP2011527089A (ja) | 2011-10-20 |
CN104812175A (zh) | 2015-07-29 |
TW201015587A (en) | 2010-04-16 |
CN102084435A (zh) | 2011-06-01 |
WO2010003056A1 (en) | 2010-01-07 |
EP2301043B1 (en) | 2017-03-08 |
CN104812175B (zh) | 2019-03-19 |
KR101610790B1 (ko) | 2016-04-12 |
US20100000762A1 (en) | 2010-01-07 |
JP6337249B2 (ja) | 2018-06-06 |
EP2301043A1 (en) | 2011-03-30 |
EP2301043A4 (en) | 2011-07-27 |
KR20110053221A (ko) | 2011-05-19 |
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