TWI566874B - 接合用糊、半導體元件與基板之接合方法 - Google Patents
接合用糊、半導體元件與基板之接合方法 Download PDFInfo
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- TWI566874B TWI566874B TW101104192A TW101104192A TWI566874B TW I566874 B TWI566874 B TW I566874B TW 101104192 A TW101104192 A TW 101104192A TW 101104192 A TW101104192 A TW 101104192A TW I566874 B TWI566874 B TW I566874B
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- Prior art keywords
- substrate
- bonding
- bonding paste
- component
- semiconductor element
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
-
- 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
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
- B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/278—Post-treatment of the layer connector
- H01L2224/27848—Thermal treatments, e.g. annealing, controlled cooling
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
- H01L2224/29001—Core members of the layer connector
- H01L2224/29005—Structure
- H01L2224/29006—Layer connector larger than the underlying bonding area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/3201—Structure
- H01L2224/32012—Structure relative to the bonding area, e.g. bond pad
- H01L2224/32013—Structure relative to the bonding area, e.g. bond pad the layer connector being larger than the bonding area, e.g. bond pad
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Description
本發明,係有關於接合用糊,以及使用此接合用糊而將半導體元件和基板作接合之方法。本發明,特別是適合於進行如同LED元件一般之並不適於進行長時間加熱的半導體元件之接合。
近年來,為了提高LED的亮度,對於LED所要求之輸出係變高。作為伴隨此LED之高輸出化的發熱之對策,一般而言,在LED元件和基板之接合中,係進行使用有含有Sn:20質量%之Au-Sn共晶合金(以下,稱作「Au20Sn」)銲錫糊的金屬擴散接合(專利文獻1、專利文獻2)。Au20Sn,係具備有約280℃之高熔點。又,在熱敏電阻、熱電元件或者是帕耳帖元件用半導體和基板間的接合中,或者是在SAW元件或水晶振動元件等之封裝的蓋之密封中,係使用有Au20Sn銲錫糊。
當使用此Au20Sn銲錫糊並藉由回焊爐等來進行加熱的情況時,係要求將溫度提升至較熔點之280℃而更高之300~310℃。於此,作為LED元件,係為耐熱溫度330℃左右者,為了進行LED元件之接合而將溫度提升至300~310℃一事,在對於LED元件之熱性損傷的觀點來看,係並不理想。進而,若是一直加熱至上述溫度,則由於LED元件和Au-Sn合金銲錫以及基板之熱膨脹係數的差異所導
致之應力,係會變大。又,銲劑(flux)殘渣係會增加,並產生需要更加注意地進行洗淨工程之問題。又,在熱敏電阻、熱電元件或者是帕耳帖元件和基板間的接合中,或者是在SAW元件或水晶振動元件等之封裝的蓋之密封等中,就算是在使用有Au20Sn銲錫糊的情況時,由熱膨脹係數之差所導致的應力亦仍會變大。又,銲劑(flux)殘渣係會增加,並產生需要更加注意地進行洗淨工程之問題,亦仍會共通性地產生。另外,在為了將熱敏電阻和基板作接合而使用有Au20Sn銲錫糊的情況時,亦會產生使熱敏電阻之電阻值改變的問題。故而,係對於熔點或者是液相線溫度為較Au20Sn銲錫糊更為低溫的接合材料有所需求。
[專利文獻1]日本特開2007-67145號公報
[專利文獻2]日本特開2007-61857號公報
本發明,係為了解決上述課題,而以提供一種:能夠以較Au-Sn合金銲錫更低之溫度來進行接合之接合用糊、以及使用有此接合用糊之半導體元件和基板之接合方法一事,作為目的。
以下,對於本發明之接合用糊以及使用有此接合用糊的半導體元件和基板之接合方法的形態作展示。
(1)一種接合用糊,其特徵為,係包含有:(A)平均粒徑100nm以下之金屬奈米粒子、和(B)沸點為50~100℃之溶劑、和(C)沸點為150~200℃之溶劑,相對於前述(B)成分和(C)成分之合計100質量部,前述(B)成分之含有量,係為10~30質量部。
(2)如上述(1)所記載之接合用糊,其中,前述(A)成分之粒徑的變動係數,係為50~65%。
(3)如前述(1)或(2)所記載之接合用糊,其中,前述(A)成分之金屬奈米粒子,相對於前述金屬奈米粒子:100質量部,係含有75質量部以上之Ag。
(4)如上述(1)~(3)中之任一項所記載之接合用糊,其中,相對於前述接合用糊:100質量部,前述(A)成分之含有量,係為60~95質量部。
(5)如前述(1)~(4)中之任一項所記載之接合用糊,其中,前述(B)成分,係為由丙酮、丁酮、異丙醇、乙酸乙酯所選擇的1種以上。
(6)如前述(1)~(5)中之任一項所記載之接合用糊,其中,前述(C)成分,係為由2-丁氧乙醇、甲基甲氧丁醇、環己酮、乙酸2-乙氧基乙酯、甲氧基乙酸以及二丙酮醇所選擇的1種以上。
(7)如前述(1)~(6)中之任一項所記載之接合用糊,其中,係被使用在半導體元件和基板之接合中。
(8)一種半導體元件和基板之接合方法,其特徵為,具備有:在基板上,塗佈如上述(1)~(7)中之任一項所記載之接合用糊,並使前述接合用糊乾燥之工程;和在前述乾燥後的接合用糊上載置半導體元件,並進行加熱之工程。
(9)如前述(8)所記載之半導體元件和基板之接合方法,其中,在前述加熱工程中,係於大氣中或是於惰性氣體氛圍中,以180~280℃之溫度而進行5~60分鐘之加熱。
(10)如前述(8)或(9)所記載之半導體元件和基板之接合方法,其中,前述半導體元件係為LED元件。
若依據上述(1)之形態,則係能夠以200℃程度之低溫來進行接合,並且在接合部處之孔隙(void)的發生係被作抑制。又,係能夠得到良好的塗佈性。故而,上述(1)之形態的接合用糊,對於如同LED元件等一般之並不適於以高溫度來進行長時間加熱的半導體元件和基板間之接合而言,係極為有用。
又,若依據上述(5)之形態,則係能夠以200℃程度之低溫來進行接合。因此,係能夠得到對於接合部之孔隙的發生作了抑制之半導體元件和基板之接合體。
以下,根據實施形態,對於本發明作具體說明。另外,代表含有量之單位「%」,只要並未作特別標示,則係
代表質量%。
本實施形態之接合用糊,係包含有:(A)平均粒徑100nm以下之金屬奈米粒子、和(B)沸點為50~100℃之溶劑、和(C)沸點為150~200℃之溶劑,相對於(B)成分和(C)成分之合計100質量部,係以10~30質量部而包含有(B)成分。
(A)成分,係為平均粒徑為100nm以下之金屬奈米粒子。作為金屬,係可列舉出由Ag、Au、Pt、Pd、Ru、Ni、Cu、Sn、In、Zn、Fe、Cr、Mn所選擇之1種以上。從在低溫下之燒結性、製造之容易性的觀點來看,係以Ag、Au等為理想,進而,從成本面之觀點來看,係以Ag為更理想。
從低溫燒結性、分散性、填充(packing)性之觀點來看,金屬奈米粒子之平均粒徑,係為100nm以下。從金屬奈米粒子之安定性、製造之容易性的觀點來看,金屬奈米粒子之平均粒徑,係以20nm以上為理想,又以25~85nm為更理想,又以25~70nm為最理想。若是平均粒徑較100nm更大,則會有使填充性變差之虞。若是平均粒徑過小,則會有使金屬奈米粒子燒結體的強度變低之虞。於此,平均粒徑,係藉由透過型電子顯微鏡(TEM)觀察來進行
測定。具體之測定方法,係於後再述。從低溫燒結性、分散性、填充(packing)性之觀點來看,金屬奈米粒子之形狀,係以球狀或者是桿狀為理想。
(A)成分之粒徑的變動係數(CV值,單位:%),係以成為50~65%為理想。上述變動係數,係以成為52~63%為更理想,又以成為55~60%為最理想。當粒徑之偏差為大的情況時,亦即是當CV值為大的情況時,接合用糊之接合強度係降低。當粒徑之偏差為小的情況時,亦即是當CV值為小的情況時,接合用糊之接合強度亦係降低。以下,針對粒徑之變動係數的測定方法作說明。首先,對於金屬奈米粒子,藉由TEM而以約50萬倍程度之倍率來進行攝影。接著,根據所得到之畫像,針對金屬奈米粒子200個而對於一次粒徑作測定,並將此一次粒徑之平均值作為平均粒徑。接著,根據上述200個的粒子之一次粒徑,來將變動係數藉由數式:{[(標準偏差)/(平均粒徑)]×100}而求取出來。
從金屬奈米粒子之安定性、分散性的觀點來看,(A)成分之金屬奈米粒子,係以藉由保護劑來進行化學修飾為理想。更理想,保護劑,係由有機分子所成,有機分子主鍊之碳骨架,係為碳數1~3。藉由此,保護劑,係能夠在低溫下分解,金屬奈米粒子係能夠以低溫來作燒結。作為保護劑,例如係可列舉出檸檬酸、蘋果酸、甘醇酸。
(B)成分,係對於接合用糊賦予塗佈時之流動性。(B)成分,由於沸點係為50~100℃,因此,在塗佈時,係殘存於接合用糊中並賦予流動性。並且,(B)成分,在乾燥後係會揮發,而對於接合用糊之流動性作抑制,而能夠防止接合用糊之滲出。又,(B)成分,係在乾燥後揮發。藉由此,而對於半導體元件和基板間之孔隙的發生作抑制,並提升接合性。較理想,(B)成分之20℃下的蒸氣壓,係為10hPa以上。藉由此,係能夠容易地進行乾燥後之揮發。
作為(B)成分,係可列舉出丙酮(沸點:56℃,蒸氣壓(20℃):233hPa)、丁酮(沸點:80℃,蒸氣壓(20℃):105hPa)、異丙醇(沸點:82℃,蒸氣壓(20℃):43hPa)、乙酸乙酯(沸點:77℃,蒸氣壓(20℃):97hPa)等。
(C)成分,係對於接合用糊賦予塗佈時之流動性和乾燥後之黏著性。(C)成分,由於沸點係為150~200℃,因此,在使接合用糊乾燥後,亦係殘存在接合用糊中。但是,在使接合糊中之金屬奈米粒子作燒結時,(C)成分係揮發。因此,係並不會變成殘渣等,而對於半導體元件和基板間之孔隙的發生作抑制。較理想,(C)成分之20℃下的蒸氣壓,係為未滿10hPa。藉由此,乾燥後之揮發係被作抑制。
作為(C)成分,係可列舉出2-丁氧乙醇(別名:丁賽路
蘇,沸點:170℃,蒸氣壓(20℃):0.8hPa)、甲基甲氧丁醇(沸點:174℃,蒸氣壓(20℃):0.67hPa)、環己酮(沸點:156℃,蒸氣壓(20℃):4.7hPa)、乙酸2-乙氧基乙酯(別名:乙酸甲賽路蘇,沸點:156℃,蒸氣壓(20℃):1.6hPa)、甲氧基乙酸(沸點:170℃,蒸氣壓(20℃):1.8hPa)、二丙酮醇(沸點:168℃,蒸氣壓(20℃):1hPa)等。
從對於接合用糊加熱所得到的金屬奈米粒子燒結體之電性傳導率、熱傳導率的觀點來看,在(A)成分中,相對於金屬奈米粒子:100質量部,Ag之含有量,係以75質量部以上、100質量部以下為較理想,又以85質量部以上、100質量部以下為更理想。
相對於接合用糊:100質量部,(A)成分之含有量,係以60~95質量部為理想,又以70~90質量部為更理想。若是(A)成分為少,則金屬奈米粒子燒結體之強度會不足,起因於此,會有使半導體元件和基板之間的接合強度降低之虞。又,會有使金屬奈米粒子燒結體之電性傳導率降低之虞。若是(A)成分為多,則會有使接合用糊之塗佈性(印刷性)降低之虞。
從接合用糊之塗佈性(印刷性)的觀點來看,相對於(B)成分和(C)成分之合計100質量部,(B)成分之含有量,係為10~30質量部。
又,接合用糊,在不會對於本實施形態之目的有所損害的範圍內,係亦可使其含有消泡劑、抗垂流劑、平滑劑、流變調整劑等之添加劑。
本實施形態之接合用糊,係能夠以低溫作接合,並對於接合部孔隙之發生作抑制,並且塗佈性亦為佳,因此,當被接合體為半導體元件和基板的情況時,係為理想,而若是半導體元件為並不適於進行長時間加熱之LED元件,則係為特別理想。
本實施形態之半導體元件和基板之接合方法,係具備有:在基板上,塗佈上述之本實施形態之接合用糊,並使其乾燥之工程;和在前述乾燥後的接合用糊上載置半導體元件,並進行加熱之工程。
圖1,係為對於本實施形態之半導體元件和基板之接合方法作說明的剖面模式圖。首先,如圖1(A)所示,準備基板1。接著,如圖1(B)所示,在基板1上塗佈接合用糊2,並使其乾燥。乾燥溫度,係以80~110℃為理想。接著,如圖1(C)所示,在接合用糊2上,搭載半導體元件3。接著,藉由進行加熱,而如圖1(D)所示,接合用糊,係成為金屬奈米粒子之燒結體20(燒結後之接合用糊),半導體元件3和基板1,係經由燒結體20而被作接合。
作為半導體元件,係可列舉出LED元件、熱敏電阻、熱電元件、帕耳帖元件用半導體等。
關於基板,雖並未特別限定,但是,作為基板,係可使用由玻璃、陶瓷、高分子材料或者是矽所成之基板的任一者,或者是使用從由玻璃、陶瓷、高分子材料以及矽所
成之群中而選擇的2種類以上之層積體。作為高分子基板,係可列舉出藉由聚醯亞胺或者是PET(聚對苯二甲酸乙二酯)等之有機聚合物所形成的基板。
針對銀奈米粒子的情況,來對於(A)成分之金屬奈米粒子的製造方法之其中一例作說明。首先,將硝酸銀溶解在去離子水等之水中,而調製金屬鹽水溶液。另一方面,將檸檬酸鈉,溶解於去離子水等之水中,而調製出濃度10~40質量%之檸檬酸鈉水溶液。於氮氣等之惰性氣體的氣流中,將粒狀或粉狀之硫酸亞鐵直接添加至此檸檬酸鈉水溶液中,並使其溶解,而調製出以3:2之莫耳比來包含有檸檬酸離子和亞鐵離子的還原劑水溶液。接著,一面在惰性氣體氣流中對還原劑水溶液作攪拌,一面在此還原劑水溶液中滴下金屬鹽水溶液並作混合。於此,較理想,係以使金屬鹽水溶液之添加量成為還原劑水溶液之量之1/10以下的方式,來對於各溶液之濃度作調整。藉由此,就算是滴下室溫之金屬鹽水溶液,反應溫度亦係被保持為30~60℃。又,以使作為還原劑所添加之亞鐵離子的當量成為金屬離子的當量之3倍的方式,來對於雙方之水溶液的混合比作調整。亦即是,以使(金屬鹽水溶液中之金屬離子的莫耳數)×(金屬離子的價數)=3×(還原劑水溶液中之亞鐵離子的莫耳數)的方式,來對於雙方之水溶液的混合比作調整。在金屬鹽水溶液之滴下結束後,進而持續進行10~300分鐘之混合液的攪拌,而調製出由金屬膠體所成之分散液。將此分散液放置於室溫中,並將作了沈降的金屬奈
米粒子之凝集物藉由傾析法或者是離心分離法等來作分離。接著,在此分離物中加入去離子水等的水並設為分散體,而藉由超過濾來進行脫鹽處理。進而,接著藉由與水相溶之有機溶劑來作置換洗淨,而將金屬(銀)之含有量設為2.5~50質量%。之後,使用離心分離機,並對於此離心分離機之離心力作調整,而將粗粒子分離。藉由此,而以使金屬奈米粒子之一次粒徑成為20~100nm之範圍內,且粒徑之變動係數成為50~65%的方式,來作調製。另外,經由使用檸檬酸鈉,銀奈米粒子,係經由檸檬酸(保護劑)而被作化學修飾。檸檬酸之有機分子主鍊的碳骨架之碳數,係為3。若是將檸檬酸鈉置換為蘋果酸鈉或者是甘醇酸鈉,則經由蘋果酸或者是甘醇酸(保護劑),銀奈米粒子係被作化學修飾。蘋果酸或甘醇酸之有機分子主鍊的碳骨架之碳數,係為2或是1。如此這般,藉由將檸檬酸鈉置換為蘋果酸鈉或者是甘醇酸鈉,係能夠將對於銀奈米粒子作化學修飾之保護劑的有機分子主鍊的碳骨架之碳數從3而設為2或者是1。
當作為構成銀奈米粒子以外之金屬奈米粒子的金屬,而使用Au、Pt、Pd、Ru、Ni、Cu、Sn、In、Zn、Fe、Cr、Mn的情況時,係將在調製金屬鹽水溶液時所使用的硝酸銀,替換為氯金酸、氯白金酸、硝酸鈀、三氯化釕、氯化鎳、硝酸亞銅、二氯化錫、硝酸銦、氯化鋅、硫酸鐵、硫酸鉻或者是硫酸錳。除此之外,係可與上述相同的而調製出分散體。
經由將所期望之成分藉由通常方法來以塗料搖擺器、球磨機、砂磨機、離心磨機、三輥磨機等作混合,而在(B)成分以及(C)成分中,使(A)成分作分散。藉由此,係能夠製造接合用糊。當然的,藉由通常之攪拌操作,亦能夠製造之。
接合用糊之塗佈,係以藉由噴霧塗佈法、滴液器塗佈法、旋轉塗佈法、刮刀塗佈法、細縫塗佈法、噴墨塗佈法、網版印刷法、平版印刷法或者是鑄模塗佈法之其中一者來進行為理想,但是,係並不被限定於此,而可利用各種之方法。
噴霧塗佈法,係將接合用糊藉由壓縮空氣而設為霧狀並塗佈在基板上、或者是對於分散體(接合用糊)自身作加壓並設為霧狀而塗佈在基板上之方法。滴液器塗佈法,例如,係將接合用糊裝入注射器內,並藉由推壓此注射器之活塞來將分散體(接合用糊)從注射器前端之細微噴嘴而吐出並塗佈在基板上的方法。旋轉塗佈法,係將接合用糊滴下至正在作旋轉之基板上,並使此作了滴下的接合用糊藉由該離心力而擴散至基板週緣的方法。刮刀塗佈法,係將與刮刀前端空出有特定之空隙的基板,以能夠在水平方向上移動的方式而作設置,並藉由此刮刀而對於上游側之基板上供給接合用糊,再使基板朝向下游側作水平移動的方法。細縫塗佈法,係為使接合用糊從狹窄的細縫而流出並塗佈在基板上的方法。噴墨塗佈法,係為將接合用糊填充於市面販賣之噴墨印表機的墨水匣內,並對於基板上作噴
墨印刷的方法。網版印刷法,係為作為圖案指示材而使用紗,並使接合用糊通過被製作於其上之版畫像來轉移至基板上的方法。平版印刷法,係為使附著在版上之接合用糊並不直接附著於基板地而先從版上來一度轉印至橡膠薄板上,之後再從橡膠薄板而轉移至基板上的印刷方法,而對於接合用糊之撥水性有所利用。鑄模塗佈法,係將被供給至鑄模內之接合用糊,藉由岐管而作分配並藉由細縫而推出至薄膜上,而塗佈於行走中之基板上的方法。在鑄模塗佈法中,係存在有槽塗佈方式或滑動塗佈方式、簾塗佈方式。
接著,將塗佈了接合用糊之基板,使用自然乾燥或乾燥機等來使其乾燥,而形成接合用糊塗膜。
在乾燥了的接合用糊塗膜上載置半導體元件之方法,係可藉由同業者所週知之方法,並可使用安裝機等。
接著,將搭載有半導體元件之具有接合用糊塗膜的基板,在大氣中或者是在氮或氬等之惰性氣體氛圍中,以180~280℃、較理想為180~230℃之溫度,而保持5~60分鐘、較理想為15~40分鐘,來進行燒成。於此,當金屬奈米粒子為Ag的情況時,從伴隨著銀奈米粒子表面之活性化的燒結性提升、保護劑之揮發性或分解性的觀點來看,係以在大氣中進行加熱(燒成)為理想。
若是燒成溫度未滿180℃,則會有並未充分進行金屬奈米粒子的燒結之虞。若是燒成溫度超過280℃,則並無法發揮所謂低溫製程之生產上的優勢。亦即是,會使製造
成本增大,並使生產性降低。又,特別當半導體元件為LED元件等一般之熱耐性較弱者的情況時,會由於燒成工程而導致半導體元件受到熱性損傷。
若是燒成時間未滿5分鐘,則並不會充分進行金屬奈米粒子的燒結。若是燒成時間超過60分鐘,則會使使製造成本產生必要以上之增大,並使生產性降低。又,會有使LED元件等之半導體元件受到熱性損傷之虞。
藉由上述工程,係能夠得到半導體元件和基板之接合體。如此這般,本實施形態之半導體元件和基板之製造方法,係能夠以200℃程度之低溫作接合,藉由此,接合部孔隙之發生係被作抑制。又,係可提供塗佈性為佳之接合用糊。本實施形態,對於像是將LED元件等之半導體元件和基板間的作接合一般之並不適於進行高溫度和長時間加熱的接合中,係為非常有用。又,在SAW元件或水晶振動元件等之封裝的蓋之密封等中,亦為有用。
以下,雖根據實施例來將本發明作詳細說明,但是本發明係並不被此些所限定。
如同下述一般,而製造出銀奈米粒子。首先,將硝酸銀溶解在去離子水中,而調製金屬鹽水溶液。另一方面,將檸檬酸鈉溶解於去離子水中,而調製出濃度20%之檸檬酸鈉水溶液。於氮氣的氣流中,將粒狀之硫酸亞鐵直接添加至此檸檬酸鈉水溶液中,並使其溶解,而調製出以3:2
之莫耳比來包含有檸檬酸離子和亞鐵離子的還原劑水溶液。接著,一面在氮氣氣流中對還原劑水溶液作攪拌,一面在此還原劑水溶液中滴下金屬鹽水溶液並作混合。於此,係以使金屬鹽水溶液之添加量成為還原劑水溶液之量之5%的方式,來對於各溶液之濃度作調整。藉由此,就算是滴下室溫之金屬鹽水溶液,反應溫度亦係成為被保持為30~60℃。又,雙方之水溶液(還原劑水溶液和金屬鹽水溶液)的混合比,係以使作為還原劑所添加之亞鐵離子的當量成為金屬離子的當量之3倍的方式,來作了調整。亦即是,以使(金屬鹽水溶液中之金屬離子的莫耳數)×(金屬離子的價數)=3×(還原劑水溶液中之亞鐵離子的莫耳數)的方式,來對於雙方之水溶液的混合比作了調整。在金屬鹽水溶液之滴下結束後,進而持續進行240分鐘之混合液的攪拌,而調製出由金屬膠體所成之分散液。將此分散液放置於室溫中,並將作了沈降的金屬奈米粒子之凝集物藉由傾析法或者是離心分離法等來作分離。接著,在此分離物中加入去離子水並設為分散體,而藉由超過濾來進行脫鹽處理。進而,接著藉由與水相溶之有機溶劑來作置換洗淨,而將金屬(銀)之含有量設為30質量%。之後,使用離心分離機,並對於此離心分離機之離心力作調整,而將粗粒子分離。藉由此,以使銀奈米粒子之一次粒徑成為20~100nm,且粒徑之變動係數成為50~65%的方式,來作了調製。詳細而言,粒徑之變動係數,係為58%。又,對於離心分離器之離心力作變更,並調製出變動係數(CV值,
單位:%)為未滿50%之銀奈米粒子和變動係數超過65%之銀奈米粒子。另外,上述3種之銀奈米粒子的平均粒徑,係均為42nm。
將如此這般所得到之銀奈米粒子,在軟膏瓶中作秤量,並添加(C)成分,而藉由研磨機等來作了混合。之後,添加(B)成分,並再度藉由研磨機等來作混合,而得到了100g之接合用糊。另外,係使相對於銀奈米粒子:80質量部而使(B)和(C)之總成分量成為20質量部的方式,來作了調整。於表1~5中,對於實施例1~18、比較例1~18之配合作展示。
將如此這般所得到之接合用糊:2.8g,在對於表面施加了Ni/Au鍍敷之Si製基板的表面上,藉由網版印刷機來作塗佈,並製作了長度:20mm、寬幅:20mm、厚度:0.5mm之塗膜。藉由目視,來對於是否有暈開或褪去等作確認,並對於印刷性作了評價。將並不存在有暈開或褪去之情況者,評價為「A(Good)」,並將存在有暈開或褪去者,評價為「B(Bad)」。在表1~5中,對於印刷性之結果作展示。另外,在印刷性之評價中,係使用包含有一次粒徑為20~100nm且粒徑之變動係數為50~65%的銀奈米粒子(平均粒徑:42nm、變動係數:58%)之接合用糊。
將長度:5mm、寬幅:5mm、厚度:5mm之藍寶石基板,作為元件之代用品而作了準備。在被塗佈於Si製基板上之接合用糊上,將元件(藍寶石基板)作載置,並在大氣中,以200℃來進行20分鐘之燒成,而得到了接合體。對於所得到之接合體的接合性,藉由目視來作了評價。將形狀為安定的情況,評價為「A(Good)」,並將形狀有所缺陷的情況,評價為「B(Bad)」。在表1~5中,對於接合性之結果作展示。另外,在接合性之評價中,係使用包含有一次粒徑為20~100nm且粒徑之變動係數為50~65%的銀奈米粒子(平均粒徑:42nm、變動係數:58%)之接合用糊。
使用DAGE JAPAN股份有限公司製之接合測試機(型號:4000系列),來如同下述一般地對於剪斷強度作了測定。對於在上述接合性之評價中所得到的接合體,將Si製基板作為下方地來作了水平固定。之後,對於將元件(藍寶石基板)藉由剪斷工具(shear tool)來從橫方向作水平推壓並使元件(藍寶石基板)和Si製基板之接合面作了破斷時的強度進行了測定。在表1~5中,對於剪斷強度之結果作展示。另外,表1~5之剪斷強度的欄之(a)、(b)、(c),係分別在(A)成分之金屬奈米粒子(銀奈米粒子)的粒徑之變動係數上有所相異。(a),係為使用了含有粒徑之變動係數未滿50%的金屬奈米粒子之接合用糊的接合體之剪斷強
度。(b),係為使用了含有粒徑之變動係數為50~65%的金屬奈米粒子之接合用糊的接合體之剪斷強度。(c),係為使用了含有粒徑之變動係數超過65%的金屬奈米粒子之接合用糊的接合體之剪斷強度。
如同由表1~5而可得知一般,在實施例1~18之全部中,印刷性以及接合性均係為良好,並且剪斷強度亦為高。特別是,當(A)成分之金屬奈米粒子的粒徑之變動係
數為50~65%的情況時(項目(b))之剪斷強度,係為39~44Mpa而為非常高。相對於此,在並不包含(B)成分之比較例1、3、5、7、9、11、13、15、17中,接合性係為差,且剪斷強度為未滿20Mpa的情況亦為多。又,相對於(B)成分和(C)成分之合計100質量部而將(B)成分以50質量部來作含有之比較例2,其印刷性係為差,且接合強度亦相較於實施例而為低。
本實施形態之接合用糊,係能夠以低溫作接合,並對於接合部孔隙之發生作抑制。進而,係能夠得到良好的塗佈性。故而,本實施形態,係能夠合適地適用在將LED元件等之不適合以高溫度來作長時間加熱之半導體元件和基板間的接合工程中。
1‧‧‧基板
2‧‧‧接合用糊
20‧‧‧燒結後之接合用糊
3‧‧‧半導體元件
[圖1]對於本實施形態之半導體元件和基板之接合方法作說明的剖面模式圖。
1‧‧‧基板
2‧‧‧接合用糊
20‧‧‧燒結後之接合用糊
3‧‧‧半導體元件
Claims (10)
- 一種接合用糊,其特徵為,係包含有:(A)平均粒徑100nm以下之金屬奈米粒子、和(B)沸點為50~100℃之溶劑、和(C)沸點為150~200℃之溶劑,相對於前述(B)成分和(C)成分之合計100質量部,前述(B)成分之含有量,係為10~30質量部。
- 如申請專利範圍第1項所記載之接合用糊,其中,前述(A)成分之粒徑的變動係數,係為50~65%。
- 如申請專利範圍第1項所記載之接合用糊,其中,前述(A)成分之金屬奈米粒子,相對於前述金屬奈米粒子:100質量部,係含有75質量部以上之Ag。
- 如申請專利範圍第1項所記載之接合用糊,其中,相對於前述接合用糊:100質量部,前述(A)成分之含有量,係為60~95質量部。
- 如申請專利範圍第1項所記載之接合用糊,其中,前述(B)成分,係為由丙酮、丁酮、異丙醇、以及乙酸乙酯所選擇的1種以上。
- 如申請專利範圍第1項所記載之接合用糊,其中,前述(C)成分,係為由2-丁氧乙醇、甲基甲氧丁醇、環己酮、乙酸2-乙氧基乙酯、甲氧基乙酸以及二丙酮醇所選擇的1種以上。
- 如申請專利範圍第1項所記載之接合用糊,其中,係被使用在半導體元件和基板之接合中。
- 一種半導體元件和基板之接合方法,其特徵為,具備有:在基板上,塗佈如申請專利範圍第1項所記載之接合用糊,並使前述接合用糊乾燥之工程;和在前述乾燥後的接合用糊上載置半導體元件,並進行加熱之工程。
- 如申請專利範圍第8項所記載之半導體元件和基板之接合方法,其中,在前述加熱工程中,係於大氣中或是於惰性氣體氛圍中,以180~280℃之溫度而作5~60分鐘之加熱。
- 如申請專利範圍第8項所記載之半導體元件和基板之接合方法,其中,前述半導體元件係為LED元件。
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