TWI785399B - 接合材、接合材的製造方法及接合體 - Google Patents
接合材、接合材的製造方法及接合體 Download PDFInfo
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- TWI785399B TWI785399B TW109135723A TW109135723A TWI785399B TW I785399 B TWI785399 B TW I785399B TW 109135723 A TW109135723 A TW 109135723A TW 109135723 A TW109135723 A TW 109135723A TW I785399 B TWI785399 B TW I785399B
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- sintered body
- silver
- less
- particle group
- mass
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Abstract
本發明採用一種藉由在接合材(13)接合有導電體(12)與基板(14)之接合體(10)中,含有銀粉末經燒結固化之燒結體作為接合材(13)者,該燒結體的氣孔率為8至30%,接合面的表面粗度Ra為500nm以上3.3μm以下。
Description
本發明係關於接合材、接合材的製造方法及接合體。本申請案係根據2019年10月15日於日本提出申請之日本特願2019-188913號主張優先權,並在此援引該內容。
使用碳化矽(SiC)之功率半導體與先前使用矽之半導體相比,除了為小型且降低能量損耗之外,亦具有即使在300℃以上的高溫下亦可動作之特徵。
於高溫下使SiC功率半導體動作之情形下,動作環境下的耐熱溫度約為150℃之先前焊料不適合作為接合材。因此,正檢討使用耐熱性、電導度優異且於溶劑中分散有金屬微粒之膏(金屬微粒膏)作為取代其之接合材。
然而,在使用前述金屬微粒膏於高溫下接合基板與晶片時,於接合時溶劑揮發,而產生於接合部有較大氣孔(空孔)之問題、或是於所得到之接合體中晶片的位置產生偏離之問題。
針對上述問題,為了抑制接合部中形成較大氣孔,已提案有一邊將銀粒子加壓成型一邊製作接合材,並使用此接合材接合基板間之方法(參考專利文獻1)。
[先前技術文獻]
[專利文獻1]日本特許第4876979號公報
然而,在使用專利文獻1所記載之接合材並於高溫下接合基板與晶片時,有所得到之接合體的接合強度不充分之問題。
因此,本發明之目的係提供一種能夠製作出具有接合強度較先前更優異之接合體的接合材、該接合材的製造方法以及使用該接合材之接合體。
為了解決上述課題,本發明係採用下列構成。
亦即,本發明之第1樣態為一種接合材,其係含有銀粉末經燒結固化之燒結體,前述燒結體的氣孔率為8至30%,接合面的表面粗度Ra為500nm以上3.3μm以下。
此外,本發明之第2樣態為一種接合材的製造方法,其係具有:將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟;其中,前述分散液中之前述溶劑的含量為5質量%以上25質量%以下。
此外,本發明之第3樣態為一種接合材的製造方法,其係具有:將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟;其中,前述銀粉末含有平均粒徑相異之第1銀粒子群與第2銀粒子群,前述第1銀粒子群的平均粒徑為50nm以上且未達1000nm,前述第2銀粒子群的平均粒徑為1μm以上且未達20μm。
於第3樣態之接合材的製造方法中,前述銀粉末較佳是更含有平均粒徑為20μm以上且未達60μm之第3銀粒子群。
此外,第2或第3樣態之接合材的製造方法,於得到前述燒結體之步驟中,較佳係一邊將施加於前述塗佈膜之壓力設為5MPa以下一邊加熱前述塗佈膜。
此外,第2或第3樣態之接合材的製造方法較佳是更具有:研磨前述燒結體的表面之步驟,或是對前述燒結體的表面施予選自由銀、銅、錫、金及鎳所組成之群組之1種以上的鍍覆之步驟。
此外,本發明之第4樣態為一種接合體,其係藉由前述第1樣態之接合材接合有導電體與基板者。
根據本發明,可提供一種能夠製作出具有接合強度較先前更優異之接合體的接合材、該接合材的製造方法以及使用該接合材之接合體。
10:接合體
12:導電體
13:接合材
14:基板
圖1為顯示本發明之接合體的一實施形態之剖面圖。
圖2A為藉由掃描型電子顯微鏡所拍攝之接合材的剖面之顯微鏡影像。
圖2B為藉由掃描型電子顯微鏡所拍攝之接合材的剖面之顯微鏡影像。
圖2C為藉由掃描型電子顯微鏡所拍攝之接合材的剖面之顯微鏡影像。
圖2D為藉由掃描型電子顯微鏡所拍攝之接合材的剖面之顯微鏡影像。
圖2E為藉由掃描型電子顯微鏡所拍攝之接合材的剖面之顯微鏡影像。
圖3A為本發明之接合材與經銀鍍覆之銅板之接合部附近的顯微鏡影像。
圖3B為顯示本發明之接合體的剪切強度(shear strength)與燒結時的溫度及壓力之關係之圖表。
圖4A為本發明之接合材與未施予鍍覆之銅板之接合部附近的顯微鏡影像。
圖4B為顯示本發明之接合體的剪切強度與燒結時的溫度及壓力之關係之圖表。
圖1為顯示本發明之接合體的一實施形態之剖面圖。
圖1所示之接合體10為藉由接合材13接合有導電體12與基板14之積層體。
本實施形態之接合體10的特徵在於接合材13,其他構成可適當地適用一般所知的各種接合體。
[接合材]
本實施形態之接合材係含有銀粉末經燒結固化之燒結體,前述燒結體的氣孔率為8至30%,接合面的表面粗度Ra為500nm以上3.3μm以下。
於本說明書中所謂接合材係包含貼合兩物體者,典型而言可舉出中介存在於導電體與基板之間並將此等貼合者。
本實施形態之接合材所含有之燒結體的氣孔率為8至30%,較佳為8至20%,尤佳為9至15%。
燒結體的氣孔率位於上述範圍內時,例如可使導電體與基板之接合強度(接合體的剪切強度)變得優異。
在此,剪切強度意指藉由依據JIS Z 3198-7:2003之方法所測得者。具體的測定方法將於後述實施例中說明。
於本說明書中,燒結體的氣孔率係以下列方式測定。
首先,將燒結體沉入於水中並測定燒結體的體積,然後測定燒結體的質量。接著,根據理論上的密度算出相當於該質量之燒結體在不具有氣孔之情形下的體積。從所測定之體積與不具有氣孔之情形下之理論上的體積算出燒結體的氣孔率。
將本實施形態之接合材所含有之燒結體的氣孔率控制在上述範圍內之方法,可列舉例如:適當地選擇銀粉末的種類或粒徑之方法、適當地設定燒結時的壓力條件之方法、於使用銀粉末的分散液製造接合材時調整該分散液的溶劑量之方法等。
本實施形態之接合材在可充分地確保接合體的剪切強度下,亦可含有由銀粉末所形成之燒結體以外的物質。
本實施形態之接合材的形狀並無特別限定,例如可列舉:圓板、矩形板等平板形狀;圓筒狀、圓柱狀、多角筒狀、多角柱狀等棒狀;球狀等。
此外,為了容易接合,本實施形態之接合材可為具有1mm以下的厚層部分者。
接合材的大小並無特別限定,可因應基板及導電體的規格適當地調整。在接合材的形狀為圓板狀時,圓板的直徑較佳為0.5至50mm,尤佳為2至30mm。在接合材的形狀為矩形板狀時,長邊的長度較佳為0.5至50mm,尤佳為2至30mm。
本實施形態之接合材之接合面的表面粗度Ra為500nm以上,較佳為800nm以上,尤佳為1.06μm以上,更佳為1.4μm以上。
此外,本實施形態之接合材之接合面的表面粗度Ra為3.3μm以下,較佳為3.1μm以下,尤佳為2.9μm以下,更佳為2.8μm以下。
本實施形態之接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
表面粗度Ra之上限值及下限值的組合為500nm以上3.3μm以下,較佳為800nm以上3.3μm以下,尤佳為1.06μm以上3.3μm以下,更佳為1.4μm以上2.8μm以下。
如後述實施例所說明般,接合面的表面粗度Ra位於上述範圍內時,可使接合體的剪切強度變得優異。
於本實施形態之接合材中,燒結體的氣孔率及接合面的表面粗度Ra之數值範圍可任意地組合。
燒結體的氣孔率及接合面的表面粗度Ra之組合係氣孔率為8至30%且表面粗度Ra為500nm以上3.3μm以下,較佳係氣孔率為8至30%且表面粗度Ra為1.06μm以上3.3μm以下,尤佳係氣孔率為8至27%且表面粗度Ra為1.06μm以上2.8μm以下,更佳係氣孔率為8至27%且表面粗度Ra為1.4μm以上2.8μm以下。
表面粗度:
接合材之接合面的表面粗度可藉由下列方式測定。使用超深度彩色3D形狀測定顯微鏡(Keyence、VK-9510),對接合材表面的任意5處測定表面粗度並算出平均值。
將接合材之接合面的表面粗度Ra控制在上述範圍內之方法並無特別限定,可列舉例如:研磨燒結體的表面之方法、對燒結體的表面施予鍍覆之方法等。鍍覆種類並無特別限定,可列舉例如選自由銀、銅、錫、金及鎳所組成之群組的1種金屬或是由2種以上所構成之合金的鍍覆。鍍覆亦可為重疊有組成相異之2層以上的鍍覆者。
本實施形態之接合材在燒結體的表面經研磨時,接合材之接合面的表面粗度Ra為500nm以上,較佳為1.06μm以上,尤佳為1.5μm以上,更佳為1.7μm以上。
本實施形態之接合材在燒結體的表面經研磨時,接合材之接合面的表面粗度Ra為3.3μm以下,較佳為3.1μm以下,尤佳為2.9μm以下,更佳為2.8μm以下。
接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
本實施形態之接合材在燒結體的表面經研磨時,接合材之接合面的表面粗度Ra之上限值及下限值的組合為500nm以上3.3μm以下,較佳為1.06μm以上3.3μm以下,尤佳為1.5μm以上2.9μm以下,更佳為1.7μm以上2.8μm以下。
於本實施形態之接合材中,在燒結體的表面經研磨時,上述所規定之燒結體的氣孔率及接合面的表面粗度Ra之數值範圍可任意地組合。
本實施形態之接合材在燒結體的表面經研磨時,燒結體的氣孔率及接合面的表面粗度Ra之組合係氣孔率為8至30%且表面粗度Ra為500nm以上3.3μm以下,較佳係氣孔率為8至30%且表面粗度Ra為1.06μm以上3.3μm以下,尤佳係氣孔率為8至27%且表面粗度Ra為1.5μm以上3.1μm以下,更佳係氣孔率為8至27%且表面粗度Ra為1.7μm以上2.8μm以下。
本實施形態之接合材為燒結體的表面施予了鍍覆者時,接合材之接合面的表面粗度Ra為500nm以上,較佳為800nm以上,尤佳為1.06μm以上,更佳為1.4μm以上。本實施形態之接合材在燒結體的表面施予了鍍覆時,接合材之接合面的表面粗度Ra為3.3μm以下,較佳為2.5μm以下,尤佳為2.0μm以下,更佳為1.8μm以下。
接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
本實施形態之接合材為燒結體的表面施予了鍍覆者時,接合材之接合面的表面粗度Ra之上限值及下限值的組合為500nm以上3.3μm以下,較佳為1.06μm以上3.3μm以下,尤佳為1.06μm以上2.0μm以下,更佳為1.4μm以上1.8μm以下。
於本實施形態之接合材中,在燒結體的表面施予了鍍覆時,上述所規定之燒結體的氣孔率及接合面的表面粗度Ra之數值範圍可任意地組合。
本實施形態之接合材在燒結體的表面施予了鍍覆時,燒結體的氣孔率及接合面的表面粗度Ra之組合係氣孔率為8至30%且表面粗度Ra為500mm以上3.3μm以下,較佳係氣孔率為8至27%且表面粗度Ra為1.06μm以上3.3μm以下,尤佳係氣孔率為9至15%且表面粗度Ra為1.06μm以上2.0μm以下,更佳係氣孔率為9至13%且表面粗度Ra為1.4μm以上1.8μm以下。
以上所說明之本實施形態之接合材係含有燒結體的氣孔率為8至30%之銀粉末的燒結體,並且接合面的表面粗度Ra為500nm以上3.3μm以下。如此,由於採用接合面的表面粗度Ra位於特定範圍且具有特定氣孔率之銀粉末的燒結體,根據本實施形態之接合材,能夠製作出具有接合強度較先前更優異之接合體。
除此之外,該燒結體即使在高於銀粉末熔點之溫度下亦不會熔融。此外,藉由使用含有此燒結體之接合材,可在低於總體熔點之溫度下接合。
[接合材的製造方法]
本實施形態之接合材的製造方法係具有:將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟。
(溶劑)
本實施形態之分散液係於溶劑中分散有銀粉末者。
在此之溶劑可列舉例如:水、醇系溶劑、二醇醚系溶劑、松油醇(Terpineol)類等。
醇系溶劑可列舉出:異丙醇、1,2-丁二醇、異莰基環己醇、2,4-二乙基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇、2,5-二甲基-2,5-己二醇、2,5-二甲基-3-己炔-2,5-二醇、2,3-二甲基-2,3-丁二醇、1,1,1-三(羥基甲基)乙烷、2-乙基-2-羥基甲基-1,3-丙二醇、2,2'-氧基雙(亞甲基)雙(2-乙基-1,3-丙二醇)、2,2-雙(羥基甲基)-1,3-丙二醇、1,2,6-三羥基己烷、雙[2,2,2-三(羥基甲基)乙基]醚、1-乙炔基-1-環己醇、1,4-環己二醇、1,4-環己二甲醇、赤藻糖醇(Erythritol)、蘇糖醇(Threitol)、癒創木酚甘油醚(Guaiacol Glycerol Ether)、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇等。
二醇醚系溶劑可列舉出:二乙二醇單-2-乙基己醚、乙二醇單苯醚、2-甲基戊烷-2,4-二醇、二乙二醇單己醚、二乙二醇二丁醚、三乙二醇單丁醚等。
(銀粉末)
在此之銀粉末較佳係組合使用平均粒徑相異之銀粒子群。藉由併用平均粒徑相異者,可容易地製作出具有特定氣孔率(8至30%)之接合材。
平均粒徑:
銀粒子群的平均粒徑係採用中位徑D50之值。於本發明中,各銀粉末的中位徑D50係使用SALD-2300(島津製作所公司製)並藉由雷射繞射法所測得者(體積平均粒徑)。
平均粒徑相異之銀粒子群的較佳組合可列舉出奈米等級的銀粒子群與微米等級的銀粒子群之組合。
例如,較佳係含有平均粒徑相異之第1銀粒子群與第2銀粒子群,第1銀粒子群的平均粒徑為50nm以上且未達1000nm,第2銀粒子群的平均粒徑為1μm以上且未達20μm。
第1銀粒子群的平均粒徑為50nm以上且未達1000nm,較佳為100nm以上800nm以下,尤佳為200nm以上500nm以下。
第2銀粒子群的平均粒徑為1μm以上且未達20μm,較佳為3μm以上15μm以下,尤佳為3μm以上10μm以下。
藉由該第1銀粒子群與第2銀粒子群之併用,可容易地製作出具有特定氣孔率(8至30%)之接合材,變得容易得到接合強度經提高之接合體。
第1銀粒子群之銀粒子形狀並無特別限定,可為球狀及非球狀中任一種。非球狀的例子可列舉出:碎片狀、針狀、方角狀、樹枝狀、粒狀、不規則形狀、淚滴狀、板狀、極薄板狀、六角板狀、柱狀、棒狀、多孔狀、纖維狀、塊狀、海綿狀、傾角狀、圓緩狀等。該形狀中,較佳為球狀、柱狀。
第2銀粒子群較佳係含有碎片狀銀粒子。在此情形時,第2銀粒子群只要是銀粒子的過半數於顯微鏡下觀察到碎片狀(薄片狀或剝片狀)者即可。典型而言,意指構成第2銀粒子群之粒子(一次粒子)的51質量%以上具有碎片(薄片或剝片)形狀。在此所謂碎片狀(薄片狀或剝片狀)的粒子,意指長寬比(最長的長徑/最短的短徑)為5至300之粒子。
本實施形態之銀粉末可更含有平均粒徑為20μm以上且未達60μm之第3銀粒子群。
第3銀粒子群的平均粒徑為20μm以上且未達60μm,較佳為30μm以上50μm以下,尤佳為35μm以上45μm以下。
除了第1銀粒子群與第2銀粒子群之外更併用第3銀粒子群,藉此可更穩定地製作出具有特定氣孔率(8至30%)之接合材。
第3銀粒子群之銀粒子的形狀並無特別限定,可為球狀及非球狀中任一種。非球狀的例子可列舉出:碎片狀、針狀、方角狀、樹枝狀、粒狀、不規則形狀、淚滴狀、板狀、極薄板狀、六角板狀、柱狀、棒狀、多孔狀、纖維狀、塊狀、海綿狀、傾角狀、圓緩狀等。該形狀中,較佳為球狀、柱狀。
此外,第1銀粒子群、第2銀粒子群、第3銀粒子群可使用平均粒徑相異的2種以上作為各銀粒子群。
於本實施形態之銀粉末中,第2銀粒子群較佳係使用平均粒徑相異的2種以上。例如,第2銀粒子群較佳係組合使用平均粒徑為1μm以上且未達10μm之銀粒子群與平均粒徑為10μm以上且未達20μm之銀粒子群。
在組合使用平均粒徑相異之銀粒子群作為本實施形態之銀粉末時,第1銀粒子群的比率相對於銀粉末的合計質量(100質量%)較佳為1至50質量%,尤佳為1至30質量%,更佳為3至10質量%。
第2銀粒子群的比率相對於銀粉末的合計質量(100質量%)較佳為30至99質量%,尤佳為45至90質量%,更佳為50至90質量%。
在更併用第3銀粒子群時,第3銀粒子群的比率相對於銀粉末的合計質量(100質量%)較佳為1至70質量%,尤佳為1至50質量%,更佳為1至45質量%。惟,第1銀粒子群、第2銀粒子群、第3銀粒子群的比率之和不超過100質量%。
(分散液)
本實施形態之前述溶劑與前述銀粉末之分散液中,該分散液中之前述溶劑的含量較佳為5質量%以上25質量%以下,尤佳為5質量%以上20質量%以下,更佳為5質量%以上15質量%以下,特佳為6質量%以上10質量%以下。
藉由將分散液中之溶劑的含量設為5質量%以上25質量%以下,可容易地得到氣孔率為8至30%之燒結體。
於燒結分散液時,分散液中的溶劑揮發而在燒結體中形成氣孔。藉由將分散液中之溶劑的含量設為上述範圍內,可使燒結體的氣孔率成為8至30%。
接著,詳細地說明本實施形態之接合材的製造方法。
得到燒結體之步驟:
於本實施形態之得到燒結體之步驟中,係將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體。
首先,將上述分散液塗佈於基台上而形成塗佈膜。塗佈方法並無特別限定,可列舉出:分注塗佈、印刷塗佈、噴霧塗佈、刷毛塗佈、注入等。
基台的材料可列舉例如:玻璃、石英、矽、金屬等,惟並不限定於此。如之後實施例中所說明般,金屬例如可使用黃銅,惟並不限定於此。
在使用金屬的基台之情形,預先將潤滑脫模劑塗佈於基台時,可容易地從基台中剝離燒結體。
接著,加熱塗佈膜而得到燒結體。加熱溫度只要是可得到燒結體之溫度即可,可適當地設定,例如較佳為150℃以上300℃以下,尤佳為200℃以上250℃以下。
加熱塗佈膜之時間只要是可得到燒結體之時間即可,可適當地設定,例如較佳為15分鐘以上180分鐘以下,尤佳為30分鐘以上90分鐘以下。
於本實施形態之得到燒結體之步驟中,較佳可將施加於塗佈膜之壓力抑制在5MPa以下,亦可抑制在1MPa以下,尤其亦可設為無加壓。
接著,可因應基板及導電體的規格來切斷所得到之燒結體。燒結體的切斷所使用之器具並無特別限定,可列舉例如剪刀、金剛石刀、紙張裁切器等。於本說明書中,有將上述切換後的燒結體僅稱為燒結體之情形。
更具體而言,以上所說明之接合材的製造方法可較佳地列舉下列所示之實施形態。
實施形態(i):一種接合材的製造方法,其係具有將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟,其中,前述分散液中之前述溶劑的含量為5質量%以上25質量%以下。
根據實施形態(i),藉由將分散液中之前述溶劑的含量設為特定比率,可容易地製造出含有氣孔率8至30%的燒結體之接合材。
實施形態(ii):一種接合材的製造方法,其係具有將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟,其中,前述分散液中之前述溶劑的含量為5質量%以上25質量%以下,前述銀粉末是由平均粒徑相異之第1銀粒子群與第2銀粒子群所構成,前述第1銀粒子群的平均粒徑為50nm以上且未達1000nm,前述第2銀粒子群的平均粒徑為1μm以上且未達20μm。
前述銀粉末係例如第1銀粒子群的比率為1至50質量%,第2銀粒子群的比率為50至99質量%。
前述銀粉末係例如第1銀粒子群的比率為5至30質量%,第2銀粒子群的比率為70至95質量%。
前述銀粉末係例如第1銀粒子群的比率為5至15質量%,第2銀粒子群的比率為85至95質量%。
前述第1銀粒子群及第2銀粒子群的比率為相對於前述銀粉末的合計質量(100質量%)之比率。此外,前述第1銀粒子群及第2銀粒子群的比率之和不超過100質量%。
根據實施形態(ii),藉由組合使用具有特定的平均粒徑之銀粒子群,可容易地製造出含有氣孔率8至30%的燒結體之接合材。
實施形態(iii):一種接合材的製造方法其係具有將使用溶劑與銀粉末之分散液所形成的塗佈膜加熱而得到燒結體之步驟,其中,前述分散液中之前述溶劑的含量為5質量%以上25質量%以下,前述銀粉末是由平均粒徑相異之第1銀粒子群與第2銀粒子群與第3銀粒子群所構成,前述第1銀粒子群的平均粒徑為50nm以上且未達1000nm,前述第2銀粒子群的平均粒徑為1μm以上且未達20μm,前述第3銀粒子群的平均粒徑為20μm以上且未達60μm。
上述銀粉末係例如第1銀粒子群的比率為1至50質量%,第2銀粒子群的比率為30至98質量%,第3銀粒子群的比率為1至69質量%。
上述銀粉末係例如第1銀粒子群的比率為1至30質量%,第2銀粒子群的比率為30至90質量%,第3銀粒子群的比率為5至60質量%。
上述銀粉末係例如第1銀粒子群的比率為3至8質量%,第2銀粒子群的比率為45至72質量%,第3銀粒子群的比率為20至50質量%。
上述第1銀粒子群、第2銀粒子群及第3銀粒子群的比率為相對於銀粉末的合計質量(100質量%)之比率。此外,第1銀粒子群、第2銀粒子群及第3銀粒子群的比率之和不超過100質量%。
根據實施形態(iii),藉由組合使用具有特定平均粒徑之銀粒子群,可容易地製造出含有氣孔率8至30%的燒結體之接合材。
本實施形態之接合材的製造方法除了得到燒結體之步驟之外,亦可具有其他步驟。
例如,為了控制所得到之燒結體表面的粗度,於得到燒結體之步驟的後段側,可更具有研磨燒結體的表面之步驟,或是對燒結體的表面施予選自由銀、銅、錫、金及鎳所組成之群組之1種以上的鍍覆之步驟。
在本實施形態之接合材的製造方法具有前述研磨燒結體的表面之步驟或是前述施予鍍覆之步驟時,藉由研磨步驟或是施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra為500nm以上,較佳為800nm以上,尤佳為1.06μm以上,更佳為1.4μm以上。
另一方面,藉由研磨步驟或是施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra之上限為3.3μm以下,較佳為3.1μm以下,尤佳為2.9μm以下,更佳為2.8μm以下。
藉由研磨步驟或是施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
藉由研磨步驟或是施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra之上限值及下限值的組合為500nm以上3.3μm以下,較佳為800nm以上3.3μm以下,尤佳為1.06μm以上3.3μm以下,更佳為1.4μm以上2.8μm以下。
研磨燒結體的表面之步驟:
研磨燒結體的表面之方法並無特別限定,可列舉例如化學研磨、電解研磨、機械研磨等。如之後實施例中所說明般,藉由使用2000號的研磨紙來研磨燒結體的表面,可得到一種能夠製作出具有充分的接合強度之接合體的接合材。
在本實施形態之接合材的製造方法具有前述研磨燒結體的表面之步驟情形下,藉由研磨步驟所得到之接合材之接合面的表面粗度Ra為500nm以上,較佳為1.06μm以上,尤佳為1.5μm以上,更佳為1.7μm以上。
另一方面,藉由研磨步驟所得到之接合材之接合面的表面粗度Ra為3.3μm以下,較佳為3.1μm以下,尤佳為2.9μm以下,更佳為2.8μm以下。
藉由研磨步驟所得到之接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
藉由研磨步驟所得到之接合材之接合面的表面粗度Ra之上限值及下限值的組合為500nm以上3.3μm以下,較佳為1.06μm以上3.3μm以下,尤佳為1.5μm以上2.9μm以下,更佳為1.7μm以上2.8μm以下。
對燒結體的表面施予鍍覆之步驟:
對燒結體的表面施予鍍覆之方法並無特別限定,可列舉例如:電鍍、無電解鍍覆、真空鍍覆等。鍍覆的種類並無特別限定,可列舉出選自由銀、銅、錫、金及鎳所組成之群組的1種金屬或是由2種以上所構成之合金的鍍覆。施予鍍覆之步驟亦可為重疊有組成相異之2層以上的鍍覆進行鍍覆者。
例如,在接合對象物的一方為銅基板時,可對燒結體的表面施予銅鍍覆。藉此增強接合材與銅基板之親和性而變得容易提高接合強度。
在本實施形態之接合材的製造方法具有前述對研磨燒結體的表面施予鍍覆之步驟時,藉由施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra為500nm以上,較佳為800nm以上,尤佳為1.06μm以上,更佳為1.4μm以上。
另一方面,藉由施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra為3.3μm以下,較佳為2.5μm以下,尤佳為2.0μm以下,更佳為1.8μm以下。
藉由施予鍍覆之步驟所得到之接合材之接合面的表面粗度Ra的上限值及下限值可任意地組合。
藉由施予鍍覆之步驟所得到之接合材之接合面的表面粗度為500nm以上3.3μm以下,較佳為1.06μm以上3.3μm以下,尤佳為1.06μm以上2.0μm以下,更佳為1.4μm以上1.8μm以下。
接合材的製造方法在得到燒結體之步驟之實施形態(i)的後段側具有前述研磨燒結體的表面之步驟或是前述施予鍍覆之步驟時,所得到之接合材之係接合面的表面粗度Ra位於特定範圍,並且燒結體具有特定的氣孔率。
接合材的製造方法在得到燒結體之步驟之實施形態(ii)的後段側具有前述研磨燒結體的表面之步驟或是前述施予鍍覆之步驟時,所得到之接合材係接合面的表面粗度Ra位於特定範圍,並且可得到燒結體係具有特定的氣孔率之銀粉末的燒結體。
接合材的製造方法在得到燒結體之步驟之實施形態(iii)的後段側具有前述研磨燒結體的表面之步驟或是前述施予鍍覆之步驟時,所得到之接合材係接合
面的表面粗度Ra位於特定範圍,並且可得到燒結體係具有特定的氣孔率之銀粉末的燒結體。
[接合體]
如圖1所示,本實施形態之接合體係藉由上述接合材接合有導電體與基板。
導電體可列舉出:電容器及電阻等晶片零件,或是將電阻、電晶體、電容器及積體電路等之半導體元件形成於晶圓後,從晶圓中切出各半導體元件的區隔之Si晶片、SiC晶片、GaN等。
基板可列舉出:電路基板、玻璃纖維強化環氧系印刷配線基板或聚醯亞胺系基板、陶瓷基板、金屬基板、Cu引線架等。
接合時的溫度例如較佳為150℃以上400℃以下,尤佳為200℃以上300℃以下。
使用上述接合材來接合導電體與基板之方法可採用一般所知的方法。
接合時的壓力並無特別限定,例如可為0.1MPa以上3MPa以下。
接合時的氣體環境可在大氣中進行或是在氮中進行。
於上述本實施形態之接合體中,係適用含有氣孔率為8至30%之銀粉末的燒結體,並且接合面的表面粗度Ra為500nm以上3.3μm以下之接合材。因此,該接合體具有較先前更優異的接合強度。
[實施例]
以下,藉由實施例說明本發明,惟本發明並不限定於下列實施例。
〈所使用之原料〉
銀粉末係使用下列所示之銀粒子群。
銀粒子群1A:平均粒徑300nm
銀粒子群2A:平均粒徑4μm
銀粒子群2B:平均粒徑10μm
銀粒子群3:平均粒徑42μm
銀粒子群1B:平均粒徑50nm
銀粒子群1A、1B、2A、3之銀粒子的形狀為球狀,銀粒子群2B之銀粒子的形狀為碎片狀。
溶劑係使用乙二醇。
上述平均粒徑係採用中位徑D50之值。於本發明中,各銀粉末的中位徑D50意指使用SALD-2300(島津製作所公司製)並藉由雷射繞射法所測得者(體積平均粒徑)。
〈銀粉末之分散液的調製〉
以表1所示之組成來混合上述銀粒子群與溶劑,而調製出分散液1至9。表1中,銀粒子群的各值係表示各銀粒子群的質量相對於銀粉末的合計質量之比率(質量%)。此外,溶劑的比率係表示溶劑的質量相對於銀粉末與溶劑的合計質量之比率(質量%)。
〈接合材的製造〉
(實施例1)
使用分散液1並在黃銅的基台上製作塗佈膜。
黃銅係使用由65質量%的銅與35質量%的鋅所構成者。
得到燒結體之步驟:
將所製作之塗佈膜於200℃下以無加壓加熱30分鐘,而得到燒結體。使用剪刀將所得到之燒結體切斷為小片(縱×橫的尺寸:3mm×3mm)。
研磨步驟:
使用2000號的研磨紙(三井理化學公司製耐水研磨紙片)對所得到之小片研磨燒結體的表面,而得到接合材。
(實施例2)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與實施例1相同地施作而得到接合材。
(實施例3)
使用分散液1並在上述黃銅的基台上製作塗佈膜。
得到燒結體之步驟:
將所製作之塗佈膜於200℃下以無加壓加熱30分鐘,而得到燒結體。
施予銀鍍覆之步驟:
將所得到之燒結體浸漬於在2-乙基己胺中溶解有乙醯乙酸銀之溶液,於40℃下浸漬10分鐘。接著,從混合液中取出燒結體並乾燥。
(實施例4)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與實施例3相同地施作而得到接合材。
(實施例5)
除了將所使用之分散液變更為分散液2之外,其他與實施例1相同地施作而得到接合材。
(實施例6)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與實施例5相同地施作而得到接合材。
(實施例7)
除了將所使用之分散液變更為分散液2之外,其他與實施例3相同地施作而得到接合材。
(實施例8)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與實施例7相同地施作而得到接合材。
(實施例9)
除了將所使用之分散液變更為分散液3之外,其他與實施例2相同地施作而得到接合材。
(實施例10)
除了將所使用之分散液變更為分散液4之外,其他與實施例2相同地施作而得到接合材。
(實施例11)
除了將燒結條件變更為於250℃加熱90分鐘之外,其他與實施例5相同地施作而得到接合材。
(實施例12)
除了將所使用之分散液變更為分散液5之外,其他與實施例2相同地施作而得到接合材。
(實施例13)
除了將所使用之分散液變更為分散液6之外,其他與實施例2相同地施作而得到接合材。
(實施例14)
使用分散液2並在上述黃銅的基台上製作塗佈膜。
得到燒結體之步驟:
將所製作之塗佈膜於250℃下以無加壓加熱30分鐘,而得到燒結體。
施予銅鍍覆之步驟:
將所得到之燒結體於氮氣環境中,浸漬於在2-乙基己胺中溶解有甲酸銅(II)四水合物(和光純藥工業股份有限公司製,型號:LKJ3210,一次平均粒徑:20μm)之溶液,於140℃下浸漬10分鐘。接著,從混合液中取出燒結體並乾燥。
(比較例1)
除了將所使用之分散液變更為分散液7之外,其他與實施例1相同地施作而得到接合材。
(比較例2)
除了將燒結條件變更為於250℃下加熱30分鐘,並且於燒結時一邊以0.4MPa加壓一邊燒結之外,其他與比較例1相同地施作而得到接合材。
(比較例3)
除了於燒結時一邊以0.4MPa加壓一邊燒結之外,其他與比較例1相同地施作而得到接合材。
(比較例4)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與比較例1相同地施作而得到接合材。
(比較例5)
除了將所使用之分散液變更為分散液7,並且不研磨燒結體的表面之外,其他與實施例1相同地施作而得到接合材。
(比較例6)
除了將燒結條件變更為於250℃加熱30分鐘之外,其他與比較例5相同地施作而得到接合材。
(比較例7)
除了將所使用之分散液變更為分散液8,並且不研磨燒結體的表面之外,其他與實施例2相同地施作而得到接合材。
(比較例8)
除了將所使用之分散液變更為分散液8之外,其他與實施例2相同地施作而得到接合材。
(比較例9)
除了將所使用之分散液變更為分散液9,並且不研磨燒結體的表面之外,其他與實施例2相同地施作而得到接合材。
(比較例10)
除了將所使用之分散液變更為分散液9之外,其他與實施例2相同地施作而得到接合材。
對於在實施例1至14、比較例1至10中所得到之各接合材,係藉由下列所示之測定方法來分別測定氣孔率與表面粗度。
[氣孔率的測定]
使接合材沉入於水中並測定接合材的體積,然後測定接合材的質量。此外,根據理論上的密度來算出相當於該質量之接合材在不具有氣孔時的體積。從所測定之體積與不具有氣孔時之理論上的體積中,算出氣孔率。
[表面粗度的測定]
使用超深度色彩3D形狀測定顯微鏡(Keyence、VK-9510),對接合材表面的任意5處測定表面粗度並算出平均值。測定處的大小為1400μm×1050μm。
實施例1至14、比較例1至10中所得到之各接合材的燒結條件、氣孔率、表面粗度示於表2。
在銀粉末含有銀粒子群1與銀粒子群2,且分散液中之溶劑的含量為5質量%以上25質量%以下時,所得到之實施例1至14的接合體之燒結體的氣孔率為8至30%。
藉由樹脂來埋覆所得到之燒結體後,使用離子研磨裝置IM4000PLUS(Hitachi Hi Technologies股份有限公司製)將藉由樹脂所埋覆之燒結體切斷,而得到平滑化後的切片。使用掃描型電子顯微鏡(SEM:Scanning Electron Microscope)觀察所得到之切片,圖2顯示藉由SEM所拍攝之接合材的剖面之顯微鏡影像。
圖2A為藉由SEM所拍攝之實施例2的接合材剖面之顯微鏡影像。圖2B為藉由SEM所拍攝之實施例6的接合材剖面之顯微鏡影像。圖2C為藉由SEM所拍攝之比較例4的接合材剖面之顯微鏡影像。圖2D為藉由SEM所拍攝之實施例9的接合材剖面之顯微鏡影像。圖2E為藉由SEM所拍攝之實施例10的接合材剖面之顯微鏡影像。
其結果,與比較例4的接合材剖面相比,在實施例2、6、9、10的接合材剖面上可觀察到多量的氣孔。
〈接合體的製造〉
(實施例21至34、比較例11至20)
導電體係使用:從Si晶片側依序藉由濺鍍積層有Ti層(厚度40nm)及Ag層(厚度1000nm)之Si晶片(縱×橫的尺寸:3mm×3mm)。接合材係使用實施例1至14、比較例1至10的各接合材。各接合材的厚度為100μm。基板係使用銅基板。
以使接合材之經研磨的面成為接合面之方式依序重疊基板、接合材、導電體後,於大氣中將壓力設定為0.4MPa並在溫度250℃下施予加熱處理並藉此接合,而得到接合體。使用實施例1至14、比較例1至10的各接合材而得到實施例21至34、比較例11至20的接合體。
藉由下列所示之測定方法測定所得到之實施例21至34、比較例11至20之接合體的剪切強度。結果示於表3。
[剪切強度試驗]
實施例21至34、比較例11至20之各接合體的剪切強度(剪切強度)係以下列方式來測定。測定結果示於表3。
剪切強度試驗:
使用萬能型黏結強度試驗機NordsonDAGE Series4000(Nordson Corporation製),於室溫(25℃)條件下,藉由依據JIS Z 3198-7:2003之方法對所得到之各接合體進行Si晶片與基板之間之剪切強度(MPa)的測定。對各試樣進行5次測定並算出剪切強度(MPa)的平均值。
在使用氣孔率為8至30%之實施例1至14的接合材時,實施例21至34之接合體的剪切強度為充分。
在使用接合面的表面粗度Ra為500nm以上3.3μm以下之實施例1至14的接合材時,所得到之實施例21至34之接合體的剪切強度為充分。
在使用研磨燒結體的表面所得到之實施例1、2、5、6、9至13的接合材時,所得到之實施例21、22、25、26、29至33之接合體的剪切強度為充分。
在使用對燒結體的表面施予鍍覆所得到之實施例3、4、7、8、14的接合材時,所得到之實施例23、24、27、28、34之接合體的剪切強度為充分。
在使用於5質量%以上25質量%以下的範圍內增加分散液中之前述溶劑的含量所得到之實施例12、13的接合材時,所得到之實施例32、33之接合體的剪切強度為充分。
使用僅含有銀粒子1B之分散液所得到之比較例1至6的接合材,其燒結體的氣孔率未達8%,使用此等之比較例11至16之接合體的剪切強度不充分。
使用溶劑的含量為26%之分散液之比較例7至10的接合材,其燒結體的氣孔率大於30%,使用此等接合材之比較例17至20之接合體的剪切強度不充分。
在使用不研磨燒結體的表面且未施予鍍覆之比較例5、6、7、9的接合材時,所得到之比較例25、26、27、29之接合體的剪切強度不充分。
此外,如下述般,藉由在條件(a)及條件(b)下對比實施例的接合材與比較例的接合材,可得知下列所示者。
《條件(a):分散液中之銀粉末的組成及燒結條件為相同者之比較》
(1)實施例2的接合材與比較例8的接合材之對比
(2)實施例6的接合材與比較例10的接合材之對比
(3)實施例12的接合材與比較例10的接合材之對比
(4)實施例13的接合材與比較例10的接合材之對比
實施例2的接合材與比較例8的接合材之對比:
於製造接合材時,實施例2使用分散液1,比較例8使用分散液8,分散液中之銀粉末的組成皆為銀粒子群1A/銀粒子群2A/銀粒子群2B=10/40/50(質量%)。
燒結條件皆將燒結時的溫度、時間設為250℃、30分鐘,燒結時的壓力設定為無加壓,並研磨燒結體的表面。
接合材中之表面粗度(μm)/氣孔率(%)/接合體的剪切強度(MPa)如下列所示。
實施例2為2.79μm/10.6%/22.3MPa(實施例22)
比較例8為2.75μm/36.3%/10.6MPa(比較例18)
實施例6的接合材與比較例10的接合材之對比:
於製造接合材時,實施例6使用分散液2,比較例10使用分散液9,分散液中之銀粉末的組成皆為銀粒子群1A/銀粒子群2A/銀粒子群2B/銀粒子群3=5/20/25/50(質量%)。
燒結條件皆將燒結時的溫度、時間設為250℃、30分鐘,燒結時的壓力設定為無加壓,並研磨燒結體的表面。
接合材中之表面粗度(μm)/氣孔率(%)/接合體的剪切強度(MPa)如下列所示。
實施例6為2.36μm/13.1%/22.1MPa(實施例26)
比較例10為2.68μm/35.7%/8.6MPa(比較例20)
實施例12的接合材與比較例10的接合材之對比:
於製造接合材時,實施例12使用分散液5,比較例10使用分散液9,分散液中之銀粉末的組成皆為銀粒子群1A/銀粒子群2A/銀粒子群2B/銀粒子群3=5/20/25/50(質量%)。
燒結條件皆將燒結時的溫度、時間設為250℃、30分鐘,燒結時的壓力設定為無加壓,並研磨燒結體的表面。
接合材中之表面粗度(μm)/氣孔率(%)/接合體的剪切強度(MPa)如下列所示。
實施例12為2.76μm/17.2%/22.2MPa(實施例32)
比較例10為2.68μm/35.7%/8.6MPa(比較例20)
實施例13的接合材與比較例10的接合材之對比:
於製造接合材時,實施例13使用分散液6,比較例10使用分散液9,分散液中之銀粉末的組成皆為銀粒子群1A/銀粒子群2A/銀粒子群2B/銀粒子群3=5/20/25/50(質量%)。
燒結條件皆將燒結時的溫度、時間設為250℃、30分鐘,燒結時的壓力設定為無加壓,並研磨燒結體的表面。
接合材中之表面粗度(μm)/氣孔率(%)/接合體的剪切強度(MPa)如下列所示。
實施例13為2.61μm/26.3%/21.7MPa(實施例33)
比較例10為2.68μm/35.7%/8.6MPa(比較例20)
《條件(b):接合材的表面粗度為相同(1.06μm)者之比較》
實施例14的接合材與比較例11的接合材之對比:
接合材中之表面粗度(μm)/氣孔率(%)/接合體的剪切強度(MPa)如下列所示。
實施例14為1.06μm/11.6%/18.5MPa(實施例34)
比較例1為1.06μm/5.3%/12.5MPa(比較例11)
藉由在上述條件(a)及條件(b)下的對比,可得知即使接合面的表面粗度為同等程度,關於該表面粗度位於特定範圍(500nm以上3.3μm以下)且燒結體的氣孔率位於數值限定(8至30%)內與外之各效果,從接合體的剪切強度之點而言亦存在有顯著的差異。除此之外,關於該接合體的剪切強度,亦可得知涵蓋氣孔率之數值限定(8至30%)內的全體中,存在有顯著性。
亦即,在組合「燒結體的氣孔率8至30%」、「接合面的表面粗度Ra500nm以上3.3μm以下」時,可得知剪切強度特別顯著。
〈施予銀鍍覆之銅板與導電體之接合〉
使用實施例1的接合材,在大氣中將壓力設定為0.4MPa或1MPa,並分別在溫度200℃、250℃、300℃下對導電體與經銀鍍覆之銅板施予加熱處理並貼合,而得到接合體。
圖3A為藉由SEM,對於在大氣中將壓力設定為0.4MPa並在溫度250℃下施予加熱處理並貼合而得到之接合體的剖面進行拍攝之顯微鏡影像。圖3B為顯示接合體的剪切強度與燒結時的溫度及壓力之關係之圖表。
其結果,在大氣中可適用實施例1的接合材接合經銀鍍覆之銅板與導電體。可得知於燒結時的溫度愈高,又,於燒結時的壓力愈高,剪切強度愈高。
〈未施予鍍覆之銅板與導電體之接合〉
使用實施例14的接合材,在氮中將壓力設定為0.4MPa或1MPa,並分別在溫度200℃、250℃、300℃下對導電體與未施予鍍覆之銅板(純銅板)施予加熱處理並貼合,而得到接合體。
圖4A為藉由SEM,對於在氮中將壓力設定為0.4MPa並在溫度300℃下施予加熱處理並貼合而得到之接合體的剖面進行拍攝之影像資料。圖4B為顯示接合體的剪切強度與燒結時的溫度及壓力之關係之圖表。
其結果,在氮中可適用實施例14的接合材直接接合未施予鍍覆之銅板與導電體。可得知於燒結時的溫度愈高,又,於燒結時的壓力愈高,剪切強度愈高。
[產業上之可利用性]
根據本發明,可提供一種能夠製作出具有較先前更優異的接合強度之接合體的接合材、該接合材的製造方法以及使用該接合材之接合體。本發明之接合材可在先前的接合材所難以使用之高溫下(例如300℃以上)使用,而有用於作為具備了使用碳化矽(SiC)之功率半導體等之電子零件用的接合材。
10:接合體
12:導電體
13:接合材
14:基板
Claims (6)
- 一種接合材,係含有銀粉末經燒結固化之燒結體,其中,藉由下述[燒結體的氣孔率的測定]測定之前述燒結體的氣孔率為8至30%,接合面的表面粗度Ra為1.06μm以上3.3μm以下;[燒結體的氣孔率的測定]首先,將燒結體沉入於水中並測定燒結體的體積,然後測定燒結體的質量;接著,根據理論上的密度算出相當於該質量之燒結體在不具有氣孔之情形下的體積;從所測定之體積與不具有氣孔之情形下之理論上的體積算出燒結體的氣孔率。
- 一種接合材的製造方法,係具有:將使用溶劑與銀粉末之分散液形成的塗佈膜加熱而得到燒結體之步驟,及對前述燒結體的表面施予選自由銀、銅、錫、金及鎳所組成之群組之1種以上的鍍覆之步驟,其中,前述分散液中之前述溶劑的含量為5質量%以上25質量%以下。
- 一種接合材的製造方法,係具有:將使用溶劑與銀粉末之分散液形成的塗佈膜加熱而得到燒結體之步驟,及對前述燒結體的表面施予選自由銀、銅、錫、金及鎳所組成之群組之1種以上的鍍覆之步驟,其中,前述銀粉末含有平均粒徑相異之第1銀粒子群與第2銀粒子群;前述第1銀粒子群的平均粒徑為50nm以上且未達1000nm,前述第2銀粒子群的平均粒徑為1μm以上且未達20μm。
- 如請求項3所述之接合材的製造方法,其中,前述銀粉末更含有平均粒徑為20μm以上且未達60μm之第3銀粒子群。
- 如請求項2至4中任一項所述之接合材的製造方法,其中,於得到前述燒結體之步驟中,係一邊將施加於前述塗佈膜之壓力設為5MPa以下,一邊加熱前述塗佈膜。
- 一種接合體,係藉由請求項1所述之接合材接合有導電體與基板者。
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