TWI717502B - 接合材及使用其之接合方法 - Google Patents

接合材及使用其之接合方法 Download PDF

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Publication number
TWI717502B
TWI717502B TW106113939A TW106113939A TWI717502B TW I717502 B TWI717502 B TW I717502B TW 106113939 A TW106113939 A TW 106113939A TW 106113939 A TW106113939 A TW 106113939A TW I717502 B TWI717502 B TW I717502B
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Taiwan
Prior art keywords
bonding material
silver
mass
solvent
bonding
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TW106113939A
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English (en)
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TW201807715A (zh
Inventor
栗田哲
堀達朗
遠藤圭一
三好宏昌
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日商同和電子科技有限公司
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Publication of TW201807715A publication Critical patent/TW201807715A/zh
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20Conductive material dispersed in non-conductive organic material
    • H01B1/22Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/052Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
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    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
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    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102Metallic powder coated with organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B22F7/00Manufacture 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
    • B22F7/06Manufacture 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
    • B22F7/062Manufacture 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 involving the connection or repairing of preformed parts
    • B22F7/064Manufacture 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 involving the connection or repairing of preformed parts using an intermediate powder layer
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Abstract

本發明提供一種即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡從而防止銀接合層產生孔隙的接合材及使用其之接合方法。前述接合材係由包含銀微粒子、溶劑及添加劑之銀糊所構成,其中溶劑包含由辛二醇等二元醇構成之第1溶劑及由表面張力較該第1溶劑低之極性溶劑構成的第2溶劑(以選自於由二丁基二甘醇、己基二甘醇、癸醇及十二醇所構成群組中之1種以上為佳),且添加劑為三元醇。

Description

接合材及使用其之接合方法
本發明係關於接合材及使用其之接合方法,特別是關於一種由含銀微粒子之銀糊構成的接合材及使用該接合材於銅基板等金屬基板上接合Si晶片等電子零件的方法。
近年來,有人提出使用含銀微粒子之銀糊作為接合材,藉由於被接合物間中介接合材且進行加熱,使接合材中之銀燒結而將被接合物彼此接合(參照例如,專利文獻1~2)。
使用如此之接合材於銅基板等金屬基板上固定Si晶片等電子零件時,於基板上塗布溶劑中分散有銀微粒子之銀糊後,藉由加熱去除溶劑,於基板上形成預備乾燥膜,於該預備乾燥膜上配置電子零件後,藉由一面對電子零件施加壓力一面加熱,即可透過銀接合層將電子零件接合於基板。 先前技術文獻 專利文獻
專利文獻1:日本專利特開2011-80147號公報(段落編號0014-0020) 專利文獻2:日本專利特開2016-8332號公報(段落編號0009-0012)
發明概要 發明欲解決之課題 但,若是利用金屬掩模與金屬刮漿板將如專利文獻1~2之接合材這類由含銀微粒子之銀糊構成的習知接合材於基板上印刷150mm以上之厚度而形成較厚塗布膜,印刷時銀糊於金屬掩模與金屬刮漿板間旋轉(rolling),將產生夾泡(空氣等氣體混入以致不成均勻狀態),塗布膜中容易捲入氣泡,並因形成於該塗布膜之氣泡,使預備乾燥膜表面形成凹凸、容易於預備乾燥膜產生裂縫或剝離,從而因如此之預備乾燥膜表面的凹凸或預備乾燥膜之裂縫等導致銀接合層容易產生孔隙,且接合材之可靠性或放熱性變得容易下降。特別是,將要求高溫可靠性之SiC裝置接合於基板上時,有時為確保高溫可靠性需要充分增厚接合層,為增厚接合層而加厚塗布膜以增厚預備乾燥膜時,預備乾燥膜之收縮將變大,變得更容易產生預備乾燥膜表面之凹凸或預備乾燥膜之裂縫或剝離。
因此,有鑑於如此之習知問題,本發明目的即在於提供一種即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡從而防止銀接合層產生孔隙的接合材及使用其之接合方法。 用以解決課題之手段
本發明人等致力研究以解決前述課題,結果發現可提供如下述之接合材及使用其之接合方法,該接合材係由包含銀微粒子、溶劑及添加劑之銀糊所構成,溶劑係使用由二元醇構成之第1溶劑與由表面張力較該第1溶劑低之極性溶劑構成的第2溶劑,並使用三元醇作為添加劑,藉此,即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡,從而防止於銀接合層產生孔隙,臻至完成本發明。
換言之,本發明之接合材的特徵在於:由包含銀微粒子、溶劑及添加劑之銀糊所構成,其中溶劑包含由二元醇構成之第1溶劑及由表面張力較該第1溶劑低之極性溶劑構成的第2溶劑,且添加劑為三元醇。
該接合材中,第1溶劑以辛二醇為佳。又,第2溶劑以選自於由二烷基二醇醚、乙二醇系醚及單醇所構成群組中之1種以上為佳,且以選自於由二丁基二甘醇、己基二甘醇及癸醇所構成群組中之1種以上更佳。又,銀微粒子之平均一次粒徑以1~100nm為佳,接合材中之銀微粒子含量以60~90質量%為佳。又,接合材亦含有平均粒徑0.2~10mm之銀粒子。此時,接合材中平均粒徑0.2~10mm之銀粒子含量宜為30質量%以下,且銀微粒子含量與平均粒徑0.2~10mm之銀粒子含量的合計宜為60~90質量%。又,銀微粒子宜被碳數8以下之有機化合物被覆,且有機化合物以山梨酸為佳。又,接合材中之第1溶劑含量以5~20質量%為佳,第2溶劑含量以0.5~15質量%為佳,添加劑含量以0.5~10質量%為佳。又,接合材亦可含燒結助劑。此時,燒結助劑以縮二羥乙酸或丙二酸為佳,且接合材中之燒結助劑含量以0.001~0.1質量%為佳。
又,本發明之接合方法的特徵在於:藉由於被接合物間中介前述接合材且進行加熱,使接合材中之銀燒結而形成銀接合層,並經由該銀接合層將被接合物彼此接合。
再者,本說明書中,「銀微粒子之平均一次粒徑」係指藉由銀微粒子之掃描型電子顯微鏡(SEM)或透射型電子顯微鏡照片(TEM像)求得之一次粒徑平均值。 發明效果
依據本發明,可提供一種即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡從而防止銀接合層產生孔隙的接合材及使用其之接合方法。
用以實施發明之形態 本發明之接合材的實施形態中,就包含銀微粒子、溶劑及添加劑之銀糊所構成的接合材而言,溶劑係包含由二元醇構成之第1溶劑與由表面張力較該第1溶劑低之極性溶劑構成的第2溶劑,且添加劑為三元醇。如此一來,藉由添加由表面張力較第1溶劑低之極性溶劑構成的第2溶劑作為消泡劑,使溶劑之表面張力下降,並添加三元醇,即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡,從而防止於銀接合層產生孔隙。
本發明之接合方法的實施形態係藉由於被接合物間中介前述接合材且進行加熱,使接合材中之銀燒結而形成銀接合層,並經由該銀接合層將被接合物彼此接合。例如,預備乾燥於銅基板上塗布前述接合材後所得之塗布膜,並於所得之預備乾燥膜的接合材上配置電子零件後,藉由一面對該電子零件施加壓力一面加熱,使銀糊中之銀燒結後形成銀接合層,透過該銀接合層將電子零件接合於銅基板。只要使用前述接合材,於基板上形成200mm左右之較厚塗布膜時可防止夾雜氣泡,並防止預備乾燥膜之裂縫或剝離,即使一面施加5MPa左右之低壓一面加熱,仍可防止銀接合層產生孔隙,可以較高接合力將被接合物彼此接合。
前述接合材之實施形態中,第1溶劑係(具2個羥基之)二元醇,於加熱接合材使銀糊中之銀燒結形成銀接合層時,以可藉由蒸發或分解等不會殘留於銀接合層中之溶劑為佳。又,為了可以200~300℃(以210~290℃為佳)之低溫加熱接合材中之銀微粒子使銀燒結後形成銀接合層,第1溶劑之沸點以200~300℃為佳,且210~290℃更佳。又,第1溶劑之表面張力以其平均值為31.4~37.4dyne/cm為佳。再者,表面張力可藉由例如,全自動表面張力計(協和界面化學股份有限公司製之CBVP-Z)等測量。又,為了可藉由將第1溶劑與第2溶劑及添加劑一同添加至銀微粒子中的銀糊來形成150mm以上之較厚塗布膜,第1溶劑之黏度宜在25℃下為1~300mPa×s,且50~200mPa×s更佳。如此之第1溶劑以使用碳數3~10之二元醇為佳,且使用碳數3~8之二元醇更佳。又,如此之第1溶劑以具分枝之二元醇為佳。
如此之第1溶劑,具體而言,以使用辛二醇(ODO)(2-乙基-1,3-己二醇、沸點243.0±8.0℃、黏度(25℃)178mPa×s、表面張力(25℃)34.4±3.0dyne/cm(平均值34.4dyne/cm))為佳。再者,第1溶劑可使用1種二元醇亦可使用2種以上之二元醇。接合材中之第1溶劑含量以5~20質量%為佳,且7~18質量%更佳。
第2溶劑係表面張力較第1溶劑低之極性溶劑。藉由添加如此表面張力較第1溶劑低之極性溶劑,可使溶劑全體之表面張力下降,因此相較於僅使用第1溶劑的情形,即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡,從而防止銀接合層產生孔隙。又,可作為第2溶劑使用之極性溶劑以與第1溶劑具有某程度之相溶性的極性為佳。又,第2溶劑可使用具羥基、醚鍵、胺基、羧基之極性溶劑,以使用具羥基或醚鍵之極性溶劑為佳。再者,第2溶劑係具有羥基之極性溶劑時,以使用二元醇或三元醇以外之(具1或4以上之羥基之)極性溶劑為佳。
又,第2溶劑宜與第1溶劑同樣在加熱接合材使銀糊中之銀燒結形成銀接合層時,會藉由蒸發或分解等而不殘留於銀接合層中。又,為可在200~300℃之低溫下加熱接合材中之銀微粒子使銀燒結而形成銀接合層,第2溶劑之沸點以200~300℃為佳。又,第2溶劑之表面張力相較於第1溶劑之表面張力,其平均值宜低2.0dyne/cm以上。又,為了可利用將第2溶劑與第1溶劑及添加劑一同添加至銀微粒子中的銀糊來形成150mm以上之較厚塗布膜,第2溶劑之黏度宜在25℃下為1~200mPa×s,且1~100mPa×s更佳。如此之第2溶劑宜使用二烷基二醇醚或乙二醇系醚等之二醇醚或單醇,且使用碳數8~12之二醇醚或單醇更佳。
如此之第2溶劑,具體而言,可使用二丁基二甘醇(DBDG)(沸點254.6℃、黏度(25℃)2.4mPa×s、表面張力(25℃)28.7±3.0dyne/cm(平均值28.7dyne/cm))、己基二甘醇(HeDG)(沸點260℃、黏度(25℃)8.6mPa×s、表面張力(25℃)32.3±3.0dyne/cm(平均值32.3dyne/cm))、1-癸醇(沸點227.8±3.0℃、黏度(25℃)1.38mPa×s、表面張力(25℃)29.9±3.0dyne/cm(平均值29.9dyne/cm))、1-十二醇(沸點258℃、黏度(25℃)18~20mPa×s、表面張力(25℃)30.4±3.0dyne/cm(平均值30.4dyne/cm))等,以使用二丁基二甘醇(DBDG)、己基二甘醇(HeDG)或1-癸醇為佳。再者,第2溶劑可使用1種表面張力較第1溶劑低之極性溶劑,亦可使用2種以上。接合材中第之2溶劑含量以0.5~15質量%為佳,且0.7~12質量%更佳。
作為添加劑使用之三元醇因具有3個羥基,故與第1溶劑及第2溶劑的分散性良好,藉由與第1溶劑及第2溶劑一同添加至銀微粒子中的銀糊,即使增厚塗布膜仍可防止形成塗布膜時夾雜氣泡,從而防止銀接合層產生孔隙。
又,作為添加劑使用之三元醇,宜與第1溶劑及第2溶劑同樣在加熱接合材使銀糊中之銀燒結形成銀接合層時,會藉由蒸發或分解等而不殘留於銀接合層中。又,為可在200~300℃之低溫下加熱接合材中之銀微粒子使銀燒結而形成銀接合層,第2溶劑之沸點以200~300℃為佳。又,為不使溶劑之表面張力增高,作為添加劑使用之三元醇的表面張力平均值以30~50dyne/cm為佳,且30~40dyne/cm更佳。又,為可藉由將作為添加劑使用之三元醇與第2溶劑及第1溶劑一同添加至銀微粒子中的銀糊來形成150mm以上之較厚塗布膜,三元醇之黏度宜在25℃下為2000~10000mPa×s,且4000~10000mPa×s更佳。如此之三元醇以使用碳數3~8之三元醇為佳,且使用碳數3~6之三元醇更佳。又,為提升與第1溶劑之相溶性,如此之三元醇以具有分枝之三元醇為佳。再者,該分枝可藉由烴基形成,亦可藉由羥基形成。
如此之三元醇,具體而言,可使用2-甲基-丁烷-2,3,4-三元醇(異戊二烯三元醇A(IPTL-A))(沸點255.5℃、黏度(25℃)5420mPa×s、表面張力(25℃)38.7dyne/cm)、或2-甲基-丁烷-1,3,4-三元醇(異戊二烯三元醇B(IPTL-B))(沸點278~282℃、黏度(25℃)4050mPa×s、表面張力(25℃)47.5±1.0dyne/cm(平均值47.5dyne/cm))等,以使用2-甲基-丁烷-2,3,4-三元醇(異戊二烯三元醇A(IPTL-A))為佳。再者,添加劑可使用1種三元醇,亦可使用2種以上三元醇。作為接合材中之添加劑的三元醇含量以0.5~10質量%為佳,且1~7質量%更佳。
又,接合材亦可含燒結助劑。該燒結助劑以碳數2~6之二羧酸為佳,且縮二羥乙酸或丙二酸更佳。接合材中之燒結助劑含量以0.001~0.1質量%為佳,且0.005~0.05質量%更佳。
為了以200~300℃之低溫加熱接合材中之銀微粒子使銀燒結後形成銀接合層,銀微粒子之平均一次粒徑以1~100nm為佳,且40~100nm更佳。又,接合材中之銀微粒子含量以60~90質量%為佳,且75~90質量%更佳。
又,接合材亦可含有平均粒徑0.2~10μm、宜為0.3~1μm之銀粒子。如此微型之銀粒子若以200~300℃之低溫加熱接合材中之銀微粒子使銀燒結,則可藉由熔化後之銀微粒子互相連結而全體形成銀接合層。此時,接合材中之平均粒徑0.2~10μm之銀粒子含量宜為30質量%以下,且銀微粒子含量與平均粒徑0.2~10μm之銀粒子含量的合計以60~90質量%為佳。
為防止接合材中之凝集,銀微粒子以被碳數8以下之有機化合物(例如,碳數8以下之脂肪酸或胺)被覆為佳。如此之有機化合物可使用山梨酸或己酸,為使第1溶劑及第2溶劑之分散性良好,以使用山梨酸為佳。
再者,銀微粒子之平均一次粒徑可由以下算出,例如,藉由掃描型電子顯微鏡(SEM)(日立High-Technologies股份有限公司製之S-4700)或透射型電子顯微鏡(TEM)(日本電子股份有限公司製之JEM-1011)以預定之倍率(例如,粒徑20nm以下時藉由TEM以180,000倍、大於20nm且30nm以下時藉由SEM以80,000倍、大於30nm且100nm以下時藉由SEM以50,000倍)觀察銀微粒子後的像(SEM像或TEM像)中100個以上任何銀微粒子之一次粒徑。該銀微粒子之平均一次粒徑之算出可藉由例如,影像解析軟體(旭化成Engineering股份有限公司製之A像君(登錄商標))進行。
又,接合材於25℃下測得之5rpm黏度以10~30Pa×s為佳,且10~20Pa×s更佳。又,於25℃下測量接合材之1rpm(3.1[1/S])黏度相對於5rpm黏度的比值(1rpm黏度/5rpm黏度)(Ti值)以3.0~5.0為佳。 [實施例]
以下,詳細地說明使用本發明之接合材及使用其之接合方法的實施例。
[實施例1] 於300mL燒杯中加入純水180.0g,添加硝酸銀(東洋化學股份有限公司製)33.6g後使其溶解,藉此調製作為原料液之硝酸銀水溶液。
又,於5L燒杯中加入3322.0g之純水,一面於該純水內通氮氣30分鐘去除溶氧,一面升溫至40℃。於該純水中添加(銀微粒子被覆用之)作為有機化合物之山梨酸(和光純藥工業股份有限公司製)44.8g後,添加作為穩定化劑之28%之氨水(和光純藥工業股份有限公司製)7.1g。
一面攪拌添加該氨水後之水溶液,一面自添加氨水時(反應開始時)經過5分鐘後,添加作為還原劑之純度80%的含水肼(大塚化學股份有限公司製)14.91g,調製作為還原液之含還原劑之水溶液。自反應開始時經過9分鐘後,一口氣將液溫調整至40℃之原料液(硝酸銀水溶液) 添加至還原液(含還原劑之水溶液)使其反應,更攪拌80分鐘,之後,以升溫速度1℃/分使液溫自40℃升溫至60℃後結束攪拌。
如此形成被覆有山梨酸之銀微粒子(銀奈米粒子)的凝集體後,以No.5C之濾紙過濾包含該銀微粒子之凝集體的液體,以純水洗淨經該過濾之回收物後,得到銀微粒子的凝集體。將該銀微粒子之凝集體於真空乾燥機中以80℃乾燥12小時,得到銀微粒子之凝集體的乾燥粉末。壓碎如此所得之銀微粒子之凝集體的乾燥粉末,調整成2次凝集體的大小。再者,藉由掃描型電子顯微鏡(SEM)求出該銀微粒子之平均一次粒徑係85nm。
接著,混合如此調整成2次凝集體大小的(被覆有山梨酸之)銀微粒子之凝集體的乾燥粉末(銀粒子1)86.0g、作為第1溶劑(溶劑1)之辛二醇(ODO)(協和發酵化學股份有限公司製之2-乙基-1,3-己二醇、沸點243.0±8.0℃、黏度(25℃)178mPa×s、表面張力(25℃)34.4±3.0dyne/cm(平均值34.4dyne/cm))9.89g、作為第2溶劑(溶劑2)之二丁基二甘醇(DBDG)(日本乳化劑股份有限公司製、沸點254.6℃、黏度(25℃)2.4mPa×s、表面張力(25℃)28.7±3.0dyne/cm(平均值28.7dyne/cm))1.10g、作為添加劑之2-甲基-丁烷-2,3,4-三元醇(異戊二烯三元醇A(IPTL-A))(日本萜烯化學股份有限公司製、沸點255.5℃、黏度(25℃)5420mPa×s、表面張力(25℃)38.7dyne/cm)3.0g、及作為燒結助劑(燒結促進劑)之氧二乙酸(縮二羥乙酸(DGA))(綠化學股份有限公司製)0.01g。利用混練消泡機(股份有限公司EME社製之V-mini300型)以公轉速度1400rpm、自轉速度700rpm混練該混合物30秒鐘。以混合溶劑(日本醇販售股份有限公司製之SOLMIX AP-7)稀釋該混練物後攪拌,再利用濕式噴射磨機裝置(RiX股份有限公司製之RM-L1000EP)壓碎,藉由真空攪拌消泡攪伴器真空消泡,使所有的混合溶劑(SOLMIX AP-7)蒸發後,添加作為稀釋溶劑之辛二醇(ODO)5.80g與二丁基二甘醇(DBDG)0.64g,得到由包含80.8質量%之銀粒子1、14.73質量%之ODO、1.64質量%之DBDG、2.82質量%之IPTL-A及0.01質量%之DGA之銀糊所構成的接合材。
利用流變計(黏彈性測量裝置)(Thermo社製之HAAKE Rheostress 600、使用錐體:C35/2°)求算該接合材的黏度,得出於25℃且5rpm(15.7[1/S])下為15(Pa×s),且於25℃下測量1rpm(3.1[1/S])黏度相對於5rpm黏度的比值(1rpm黏度/5rpm黏度)(Ti值)為3.6。該黏度之測量係藉由下述方式進行:使剪切速度變化成1.6[1/S]、3.1[1/S]、6.3[1/S]、15.7[1/S]、31.3[1/S]、62.7[1/S]、156.7[1/S],並測量成為各剪切速度時起20秒後的黏度。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度係79.6質量%。
如以下地藉由粒度測定儀(BYK社之50μm不鏽鋼)評價該接合材(銀糊)中所含之銀粒子的粒度。首先,以醇溶劑(SOLMIX)清潔粒度測定儀並充分地乾燥後,於粒度測定儀之深溝測(50μm側)放置5~10g左右的銀糊,以兩手之拇指與其他指頭夾住刮刀,使刮刀之長邊與粒度測定儀之寬度方向平行且刀鋒與粒度測定儀深溝的前端接觸地放置刮刀,一面保持刮刀與粒度測定儀表面垂直,一面相對於溝之長邊呈直角地以均等之速度拉粒度測定儀1~2秒至溝之深度0後,於3秒以內照著光以容易看見銀糊之模樣,自相對於溝之長邊為直角方向且相對於粒度測定儀表面為20~30°之角度的方向觀察銀糊上開始出現清楚之線的部分,得到沿著溝之第1條出現的線(1st刮痕、最大粒徑Dmax)與第4條出現的線(4th刮痕)之粒度,並以均勻出現10條以上之線的粒度得到平均粒徑D50。再者,忽略在開始出現顯著之線前的稀疏的線,因粒度測定儀係左右各1條,故將該2條所示之值的平均值作為測量結果。結果,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。
接著,於30mm×30mm×1mm之銅基板(C1020)上配置厚度200μm的金屬掩模,使用網版印刷機(國際FSengineering股份有限公司製之SP18P-L),利用金屬刮漿板將前述接合材(銀糊)於銅基板上塗布成10mm×10mm之大小、厚度(印刷膜厚度)200μm。以3D形狀測量機(股份有限公司KEYENCE製之顯微鏡VR-3200)觀察該塗布膜後,未於塗布膜觀察到氣泡。
之後,將塗布有接合材之銅基板放在金屬墊片,並設置於烘箱(YAMATO科學股份有限公司製)內,於大氣環境氣體中藉以120℃加熱20分鐘預備乾燥,可去除接合材中之溶劑形成預備乾燥膜。以3D形狀測量機(股份有限公司KEYENCE製之顯微鏡VR-3200)觀察該預備乾燥膜後,未於預備乾燥膜觀察到裂縫或剝離。
接著,將形成有預備乾燥膜之銅基板冷卻至25℃後,於預備乾燥膜上配置施行有厚度0.3mm之鍍銀的(8mm×8mm大小的)SiC晶片,再設置於熱壓機(DOWA電子社製),一面於大氣環境氣體中施加5.0MPa之負載,一面約花約120秒鐘升溫至290℃,到達290℃後進行維持90秒鐘的正式燒製,使銀糊中之銀燒結形成銀接合層,得到藉由該銀接合層於銅基板接合有SiC晶片的接合體。
對如此所得之接合體藉由超音波顯微鏡(C-SAM SONOSCAN社製)觀察銀接合層有無孔隙後,並未觀察到孔隙。
[實施例2] 除了作為溶劑1之ODO添加量為9.34g、作為溶劑2之DBDG添加量為1.65g、作為稀釋溶劑之ODO及DBDG添加量分別為6.91g及1.22g以外,藉由與實施例1相同之方法,得到包含79.5質量%之銀粒子1、15.06質量%之ODO、2.66質量%之DBDG、2.77質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.7。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例3] 除了作為溶劑1之ODO添加量為8.79g、作為溶劑2之DBDG添加量為2.20g、作為稀釋溶劑之ODO及DBDG添加量分別為6.88g及1.72g以外,藉由與實施例1相同之方法,得到包含79.2質量%之銀粒子1、14.42質量%之ODO、3.61質量%之DBDG、2.76質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.3質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.8。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例4] 除了作為溶劑1之ODO添加量為8.09g、作為溶劑2之DBDG添加量為0.90g、作為添加劑之IPTL-A添加量為5.0g、作為稀釋溶劑之ODO及DBDG添加量分別為5.56g及0.62g以外,藉由與實施例1相同之方法,得到包含81.0質量%之銀粒子1、12.85質量%之ODO、1.43質量%之DBDG、4.71質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.8質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.7。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例5] 除了作為溶劑1之ODO添加量為11.24g、作為溶劑2之DBDG添加量為1.25g、作為添加劑之IPTL-A添加量為1.5g、作為稀釋溶劑之ODO及DBDG添加量分別為6.41g及0.71g以外,藉由與實施例1相同之方法,得到包含80.3質量%之銀粒子1、16.46質量%之ODO、1.83質量%之DBDG、1.40質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.1質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.4。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例6] 除了添加己基二甘醇(HeDG)(日本乳化劑股份有限公司製、沸點260℃、黏度(25℃)8.6mPa×s、表面張力(25℃)32.3±3.0dyne/cm(平均值32.3dyne/cm))1.10g取代DBDG作為溶劑2、添加ODO5.93g及HeDG0.66g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例1相同之方法,得到包含80.7質量%之銀粒子1、14.83質量%之ODO、1.65質量%之HeDG、2.81質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.5。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例7] 除了添加1-癸醇(和光純藥工業股份有限公司製、沸點227.8±3.0℃、黏度(25℃)1.38mPa×s、表面張力(25℃)29.9±3.0dyne/cm(平均值29.9dyne/cm))1.10g取代DBDG作為溶劑2、添加ODO5.33g及1-癸醇0.59g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例1相同之方法,得到包含81.2質量%之銀粒子1、14.36質量%之ODO、1.60質量%之1-癸醇、2.83質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為80.0質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.5。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例8] 除了作為溶劑1之ODO添加量為8.79g(8.79質量%)、添加1-癸醇(和光純藥工業股份有限公司製)2.20g取代DBDG作為溶劑2、添加ODO4.84g及1-癸醇1.21g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例1相同之方法,得到包含81.1質量%之銀粒子1、12.85質量%之ODO、3.21質量%之1-癸醇、2.83質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.9質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.6。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例9] 藉於300mL燒杯裝入純水180.0g並添加硝酸銀(東洋化學股份有限公司製)33.6g後使其溶解,調製硝酸銀水溶液作為原料液。
又,於5L燒杯裝入3322.0g之純水,一面使該純水內通氮氣30分鐘去除溶氧,一面升溫至60℃。於該純水(銀微粒子被覆用之)添加作為有機化合物之山梨酸(和光純藥工業股份有限公司製)44.8g後,添加作為穩定化劑之28%之氨水(和光純藥工業股份有限公司製)7.1g。
一面攪拌該添加有氨水後之水溶液,一面自添加氨水時(反應開始時)經過5分鐘後,添加作為還原劑之純度80%之含水肼(大塚化學股份有限公司製)14.9g,調製作為還原液之含還原劑之水溶液。自反應開始時經過9分鐘後,將液溫調整至60℃之原料液(硝酸銀水溶液)全加進還原液(含還原劑之水溶液)使其反應。自反應開始時經過25分後結束攪拌。
如此使被覆有山梨酸之銀微粒子(銀奈米粒子)的凝集體形成後,以No.5C之濾紙過濾包含該銀微粒子之凝集體的溶液,以純水洗淨該過濾後之回收物,得到銀微粒子之凝集體。於真空乾燥機中以80℃乾燥將該銀微粒子之凝集體12小時,得到銀微粒子之凝集體的乾燥粉末。壓碎如此所得之銀微粒子之凝集體的乾燥粉末,調整至2次凝集體大小。再者,藉由掃描型電子顯微鏡(SEM)求出該銀微粒子之平均一次粒徑係60nm。
接著,除了將如此經調整之2次凝集體的(經山梨酸被覆之)銀微粒子之凝集體的乾燥粉末(銀粒子2)21.5g,與藉與實施例1相同之方法所得的平均一次粒徑85nm之(經山梨酸被覆之)銀微粒子之凝集體的乾燥粉末(銀粒子1)64.5g作為銀微粒子之凝集體的乾燥粉末使用、作為稀釋溶劑之ODO及DBDG添加量分別為7.19g及0.80g以外,藉由與實施例1相同之方法,得到包含59.7質量%之銀粒子1、19.9質量%之銀粒子2、15.85質量%之ODO、1.76質量%之DBDG、2.78質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.2質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.7。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例10] 除了使用丙二酸0.01g取代氧二乙酸(縮二羥乙酸)作為燒結助劑、作為稀釋溶劑之ODO及DBDG添加量分別為7.44g及0.83g以外,藉由與實施例9相同之方法,得到包含58.5質量%之銀粒子1、19.5質量%之銀粒子2、17.34質量%之ODO、1.93質量%之DBDG、2.72質量%之IPTL-A及0.01質量%之丙二酸的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.0質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.8。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例11] 藉由與實施例9相同之方法得到(經山梨酸被覆)銀微粒子之凝集體的乾燥粉末後,使用該銀微粒子之凝集體的乾燥粉末(銀粒子2)61.5g、微型之銀粒子AG2-1C(DOWA ELECTRONICS社製,平均粒徑(利用SEM像所得之平均一次粒徑)0.3μm)(銀粒子3)20.5g取代實施例1之銀微粒子之凝集體的乾燥粉末(銀粒子1),除了作為溶劑1之ODO添加量為8.25g、作為溶劑2之DBDG添加量為8.25g、作為添加劑之IPTL-A添加量為1.5g、作為稀釋溶劑之ODO及DBDG添加量分別為1.98g及1.98g,且未添加作為燒結助劑之氧二乙酸(縮二羥乙酸)以外,藉由與實施例1相同之方法,得到包含59.2質量%之銀粒子2、19.7質量%之銀粒子3、9.83質量%之ODO、9.83質量%之DBDG及1.44質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.2質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.9。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例12] 除了作為溶劑1之ODO添加量為9.90g、作為溶劑2之DBDG添加量為6.60g、作為稀釋溶劑之ODO及DBDG添加量分別為2.14g及1.43g以外,藉由與實施例11相同之方法,得到包含59.4質量%之銀粒子2、19.8質量%之銀粒子3、11.61質量%之ODO、7.74質量%之DBDG及1.45質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.9。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例13] 除了作為溶劑1之ODO添加量為11.55g、作為溶劑2之DBDG添加量為4.95g、作為稀釋溶劑之ODO及DBDG添加量分別為2.13g及0.91g以外,藉由與實施例11相同之方法,得到包含59.7質量%之銀粒子2、19.9質量%之銀粒子3、13.26質量%之ODO、5.68質量%之DBDG及1.46質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.9質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.9。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例14] 除了作為溶劑1之ODO添加量為13.20g、作為溶劑2之DBDG添加量為3.30g、作為稀釋溶劑之ODO及DBDG添加量分別為2.02g及0.50g以外,藉由與實施例11相同之方法,得到包含60.0質量%之銀粒子2、20.0質量%之銀粒子3、14.83質量%之ODO、3.71質量%之DBDG及1.46質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.3質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.9。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例15] 除了作為溶劑1之ODO添加量為14.85g、作為溶劑2之DBDG添加量為1.65g、作為稀釋溶劑之ODO及DBDG添加量分別為1.81g及0.20g以外,藉由與實施例11相同之方法,得到包含60.3質量%之銀粒子2、20.1質量%之銀粒子3、16.32質量%之ODO、1.81質量%之DBDG及1.47質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.7質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.9。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例16] 除了添加1-癸醇(和光純藥工業股份有限公司製)8.25g取代DBDG作為溶劑2、添加ODO2.19g及1-癸醇2.19g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例11相同之方法,得到包含58.9質量%之銀粒子2、19.6質量%之銀粒子3、10.03質量%之ODO、10.03質量%之1-癸醇及1.44質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.0質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.3。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例17] 除了添加1-癸醇(和光純藥工業股份有限公司製)6.60g取代DBDG作為溶劑2、添加ODO2.30g及1-癸醇1.54g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例12相同之方法,得到包含59.2質量%之銀粒子2、19.7質量%之銀粒子3、11.79質量%之ODO、7.86質量%之1-癸醇及1.45質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.4質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.3。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例18] 除了添加1-癸醇(和光純藥工業股份有限公司製)4.95g取代DBDG作為溶劑2、添加ODO2.32g及1-癸醇0.99g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例13相同之方法,得到包含59.5質量%之銀粒子2、19.8質量%之銀粒子3、13.47質量%之ODO、5.77質量%之1-癸醇及1.46質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.8質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.2。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例19] 除了添加1-癸醇(和光純藥工業股份有限公司製)3.30g取代DBDG作為溶劑2、添加ODO2.23g及1-癸醇0.56g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例14相同之方法,得到包含59.8質量%之銀粒子2、19.9質量%之銀粒子3、15.07質量%之ODO、3.77質量%之1-癸醇及1.46質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.2質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.2。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例20] 除了添加1-癸醇(和光純藥工業股份有限公司製)1.65g取代DBDG作為溶劑2、添加ODO2.05g及1-癸醇0.23g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例15相同之方法,得到包含60.1質量%之銀粒子2、20.0質量%之銀粒子3、16.59質量%之ODO、1.84質量%之1-癸醇及1.47質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.6質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.1。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例21] 除了添加己基二甘醇(HeDG)(日本乳化劑股份有限公司製)8.25g取代DBDG作為溶劑2、添加ODO1.99g及HeDG1.99g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例11相同之方法,得到包含59.1質量%之銀粒子2、19.7質量%之銀粒子3、9.88質量%之ODO、9.88質量%之HeDG及1.44質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.2質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.1。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例22] 除了作為溶劑1之ODO添加量為7.50g、作為溶劑2之DBDG添加量為7.50g、作為添加劑之IPTL-A添加量為3.0g、作為稀釋溶劑之ODO及DBDG添加量分別為1.65g及1.65g以外,藉由與實施例11相同之方法,得到包含59.5質量%之銀粒子2、19.8質量%之銀粒子3、8.90質量%之ODO、8.90質量%之DBDG及2.90質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.3質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.1。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例23] 除了作為溶劑1之ODO添加量為8.00g、作為溶劑2之DBDG添加量為8.00g、作為添加劑之IPTL-A添加量為2.0g、作為稀釋溶劑之ODO及DBDG添加量分別為1.92g及1.92g以外,藉由與實施例11相同之方法,得到包含59.2質量%之銀粒子2、19.7質量%之銀粒子3、9.59質量%之ODO、9.59質量%之DBDG及1.92質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為78.0質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.2。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例24] 藉由與實施例9相同之方法(經山梨酸被覆之)得到銀微粒子之凝集體的乾燥粉末後,使用該銀微粒子之凝集體的乾燥粉末(銀粒子2)72.0g、微型之銀粒子AG2-1C(DOWA ELECTRONICS社製、平均粒徑0.3μm)(銀粒子3)10.0g取代實施例1之銀微粒子之凝集體的乾燥粉末(銀粒子1),除了作為溶劑1之ODO添加量為8.25g、作為溶劑2之DBDG添加量為8.25g、作為添加劑之IPTL-A添加量為1.5g、作為稀釋溶劑之ODO及DBDG添加量分別為2.75g及2.75g,且未添加作為燒結助劑之氧二乙酸(縮二羥乙酸)以外,藉由與實施例1相同之方法,得到包含68.3質量%之銀粒子2、9.5質量%之銀粒子3、10.40質量%之ODO、10.40質量%之DBDG及1.40質量%之IPTL-A的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為76.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.4。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[實施例25] 除了添加2-甲基-丁烷-1,3,4-三元醇(異戊二烯三元醇B(IPTL-B))(沸點278~282℃、黏度(25℃)4050mPa×s、表面張力(25℃)47.5±1.0dyne/cm(平均值47.5dyne/cm))3.00g取代作為添加劑之IPTL-A、作為稀釋溶劑之ODO及DBDG添加量分別為2.84g及0.32g以外,藉由與實施例1相同之方法,得到包含83.4質量%之銀粒子1、12.34質量%之ODO、1.37質量%之DBDG、2.92質量%之IPTL-B及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為82.8質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.4。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜未觀察到氣泡,於預備乾燥膜未觀察到裂縫或剝離,於接合體之銀接合層未觀察到孔隙。
[比較例1] 除了將作為溶劑1之ODO添加量設為17.49g、未添加作為溶劑2之DBDG、添加ODO5.67g取代ODO及DBDG作為稀釋溶劑以外,藉由與實施例1相同之方法,得到包含81.4質量%之銀粒子1、15.80質量%之ODO、2.79質量%之IPTL-A及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為79.9質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為3.3。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜形成氣泡,且於預備乾燥膜產生裂縫,但並未觀察到預備乾燥膜之剝離。又,於接合體之銀接合層觀察到成為預備乾燥膜裂縫之起點的孔隙。
[比較例2] 除了添加二元醇(IPDL-EtHex)(日本萜烯化學股份有限公司製、沸點287.8℃、黏度(25℃)90.2mPa×s、表面張力(25℃)30.3dyne/cm)3.0g取代作為添加劑之IPTL-A、作為稀釋溶劑之ODO及DBDG添加量分別為8.36g及0.93g以外,藉由與實施例1相同之方法,得到包含78.6質量%之銀粒子1、16.55質量%之ODO、1.84質量%之DBDG、2.74質量%之IPDL-EtHex及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為77.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.5。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜形成氣泡,且於預備乾燥膜產生裂縫或剝離,但並未觀察到預備乾燥膜之剝離。又,於接合體之銀接合層觀察到成為預備乾燥膜裂縫之起點的孔隙。
[比較例3] 除了添加二元醇(IPDL-C8)(日本萜烯化學股份有限公司製、沸點308.1℃、黏度(25℃)65mPa×s、表面張力(25℃)30.86dyne/cm)3.0g取代作為添加劑之IPTL-A、作為稀釋溶劑之ODO及DBDG添加量分別為8.13g及0.90g以外,藉由與實施例1相同之方法,得到包含78.9質量%之銀粒子1、16.28質量%之ODO、1.81質量%之DBDG、2.75質量%之IPDL-C8及0.01質量%之DGA的接合材(銀糊)。再者,以熱減量法求算銀糊中之Ag濃度,得出Ag濃度為77.5質量%。
藉由與實施例1相同之方法評價該接合材(銀糊)中所含之銀粒子的粒度,1st刮痕小於20μm、4th刮痕小於10μm、平均粒徑D50 小於5μm。又,藉由與實施例1相同之方法求算該接合材(銀糊)之黏度與Ti值,得出於25℃且5rpm(15.7[1/S])下黏度為15(Pa×s),Ti值為4.5。
藉由與實施例1相同之方法使用該接合材製作塗布膜、預備乾燥膜及接合體後觀察,於塗布膜形成氣泡,且於預備乾燥膜產生裂縫或剝離。又,於接合體之銀接合層觀察到成為預備乾燥膜裂縫之起點的孔隙。
[比較例4] 除了添加十六烷(和光純藥工業股份有限公司、沸點286.6±3.0℃、黏度(25℃)3mPa×s、表面張力(25℃)27.3±3.0dyne/cm(平均值27.3dyne/cm)、非極性)1.10g取代DBDG作為溶劑2、未添加ODO及DBDG作為稀釋溶劑以外,藉由與實施例1相同之方法,試著製作接合材(銀糊),但因於添加作為稀釋溶劑之ODO及十六烷前產生分離,故各成分分散不良未能製作銀糊。
於表1~表2顯示該等實施例及比較例之接合材的製造條件及特性。
[表1]
Figure 02_image001
[表2]
Figure 02_image003

Claims (16)

  1. 一種接合材,特徵在於:由包含銀微粒子、溶劑及添加劑之銀糊所構成,其中溶劑包含:由二元醇構成之第1溶劑、及由表面張力較該第1溶劑低之極性溶劑構成的第2溶劑;第2溶劑係由碳數8~12之二醇醚或單醇構成,且添加劑為三元醇。
  2. 如請求項1之接合材,其中前述第1溶劑係辛二醇。
  3. 如請求項1之接合材,其中前述第2溶劑為選自於由二丁基二甘醇、己基二甘醇及癸醇所構成群組中之1種以上。
  4. 如請求項1之接合材,其中前述銀微粒子之平均一次粒徑係1~100nm。
  5. 如請求項1之接合材,其中前述接合材中之前述銀微粒子含量係60~90質量%。
  6. 如請求項1之接合材,其中前述接合材含有平均粒徑0.2~10μm之銀粒子。
  7. 如請求項6之接合材,其中前述接合材中前述平均粒徑0.2~10μm之銀粒子含量係30質量%以下,且前述銀微粒子含量與前述平均粒徑0.2~10μm之銀粒子含量的合計係60~90質量%。
  8. 如請求項1之接合材,其中前述銀微粒子被碳數8以下之有機化合物被覆。
  9. 如請求項8之接合材,其中前述有機化合 物係山梨酸。
  10. 如請求項1之接合材,其中前述接合材中之前述第1溶劑含量係5~20質量%。
  11. 如請求項1之接合材,其中前述接合材中之前述第2溶劑含量係0.5~15質量%。
  12. 如請求項1之接合材,其中前述接合材中之前述添加劑含量係0.5~10質量%。
  13. 如請求項1之接合材,其中前述接合材包含燒結助劑。
  14. 如請求項13之接合材,其中前述燒結助劑為縮二羥乙酸或丙二酸。
  15. 如請求項13之接合材,其中前述接合材中之前述燒結助劑含量係0.001~0.1質量%。
  16. 一種接合方法,特徵在於:藉由於被接合物間中介如請求項1之接合材且進行加熱,使接合材中之銀燒結而形成銀接合層,並經由該銀接合層將被接合物彼此接合。
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