TW201402738A - 黏著劑組成物及使用該黏著劑組成物之半導體裝置 - Google Patents
黏著劑組成物及使用該黏著劑組成物之半導體裝置 Download PDFInfo
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Abstract
提供一種黏著劑組成物及使用該黏著劑組成物之半導體裝置,該黏著劑組成物即使是使用於其附著面是以金所形成的半導體元件的構裝時,仍具有充分高的黏著力。一種黏著劑組成物,含有包含銀原子之銀粒子及包含金屬鋅之鋅粒子,該黏著劑組成物中,相對於該黏著劑組成物的固體成分中的全部過渡金屬原子,銀原子的含量為90質量%以上,鋅原子的含量是0.01質量%以上且0.6質量%以下。
Description
本發明關於一種黏著劑組成物及使用該黏著劑組成物之半導體裝置。更詳細地說,是關於一種黏著劑組成物及使用該黏著劑組成物之半導體裝置,其中,該黏著劑組成物適合用於將功率半導體、大型積體電路(LSI)、發光二極體(LED)等的半導體元件,黏著於引線框架、陶瓷電路板、玻璃環氧電路板、聚醯亞胺電路板等的基板上。
製造半導體裝置時,作為使半導體元件與引線框架(支撐構件)互相黏著的方法,有將銀粉等的填充劑分散於環氧系樹脂、聚醯亞胺系樹脂等的樹脂中,調製成糊膏狀(例如銀膏),並將該糊膏作為黏著劑使用的方法。該方法中,使用塗佈機、印刷機、打印機等,將糊膏狀黏著劑塗佈於引線框架的晶片焊墊上後,將半導體元件進行晶片接合,藉由加熱硬化,使半導體元件與引線框架互相黏著而作成半導體裝置。
近年,隨著半導體元件的高速化,高集積化發展,為了確保半導體裝置的操作安定性,半導體元件被期待具有高散熱特性。
作為比以往藉由金屬粒子互相接觸而成的導電性黏
著劑達到更高散熱性的手段來說,提出了:高度充填熱傳導率高的銀粒子之黏著劑組成物(專利文獻1~3)、使用銲料粒子之黏著劑組成物(專利文獻4)、使用具優異燒結性且平均粒徑為0.1μm以下的金屬奈米粒子之黏著劑組成物(專利文獻5)。
又,作為比這些組成物有著更優異的熱傳導率及高溫下的連接可靠性之物,提出一種藉由使用施予特殊表面處理後的微型銀粒子,並經過於100℃以上且400℃以下狀態下的加熱,使銀粒子之間互相燒結之黏著劑組成物(專利文獻6)。在專利文獻6所提出的銀粒子之間互相燒結之黏著劑組成物中,因為銀粒子會形成金屬鍵結,因此被認為會比其他的方法有著更優異的熱傳導率及高溫下的連接可靠性。
專利文獻1:日本特開2006-73811號公報
專利文獻2:日本特開2006-302834號公報
專利文獻3:日本特開平11-66953號公報
專利文獻4:日本特開2005-93996號公報
專利文獻5:日本特開2006-83377號公報
專利文獻6:日本特許第435380號公報
然而,由防鏽的觀點來說,可將金藉由鍍敷、濺鍍
等而施予於半導體元件的附著面上。藉此,半導體元件的構裝前的性能試驗變得容易進行,又,可抑制由於形成氧化被膜所造成的黏著性的變動。
本發明人發現,若將專利文獻6中所提案的黏著劑組成物,使用於附著面以金所形成的半導體元件的構裝上,黏著力會變差。
因此,本發明的目的在於提供一種黏著劑組成物及使用該黏著劑組成物之半導體裝置,該黏著劑組成物即使是使用於其附著面是以金所形成之半導體元件的構裝時,仍能具有充分高的黏著力。
有鑒於上述情況,本發明提供一種黏著劑組成物,含有包含銀原子之銀粒子及包含金屬鋅之鋅粒子,該黏著劑組成物中,相對於該黏著劑組成物的固體含量中的全部過渡金屬原子,銀原子的含量為90質量%以上,鋅原子的含量為0.01質量%以上且0.6質量以下。
上述黏著劑組成物,較佳是進而含有分散介質。
上述黏著劑組成物,較佳是卡森(Casson)黏度為0.05Pa.s以上且2.0Pa.s以下。
上述鋅粒子的原始粒子的平均粒徑,較佳是50nm以上且150000nm以下。又,上述鋅粒子較佳是呈現片狀。此外,片狀是指,包含板狀、盤狀、鱗片狀等的形狀的概念。
上述銀粒子的原始粒子的平均粒徑,較佳是0.1μm以上且50μm以下。
上述分散介質,較佳是含有選自具有300℃以上的沸點的醇類、羧酸及酯類中的至少一種。此外,本發明中的沸點是指1大氣壓下的沸點。
將上述黏著劑組成物經過熱硬化而成的硬化物,其體積電阻率及熱傳導率,較佳是分別為1×10-4Ω.cm以下、及30W/m.K以上。
上述黏著劑組成物,較佳是在100~300℃下、5秒~10小時的條件下進行硬化,更佳是在150~300℃下、30分~5小時的條件下進行硬化,進而更佳是在150~250℃下、1~2小時的條件下進行硬化,特佳是在200℃下、1小時的條件下進行硬化。
本發明提供一種半導體裝置,其具有隔著上述的黏著劑組成物,將半導體元件與半導體元件承載(安裝)用支撐構件互相黏著的構造。
若根據本發明,即使在使用於附著面是以金所形成
之半導體元件的構裝時,仍能提供一種具有充分高的黏著力的黏著劑組成物及使用該黏著劑組成物之半導體裝置
1‧‧‧矽晶片
2‧‧‧鍍敷層
3‧‧‧鍍金層與黏著劑組成物硬化物的界面附近所發生的孔洞
4‧‧‧黏著劑組成物硬化物
5‧‧‧鍍銀的PPF-Cu引線框架的鍍銀層
6‧‧‧鍍銀的PPF-Cu引線框架的銅層
7‧‧‧鋅粒子
11‧‧‧晶片
12a、12b、12c‧‧‧引線框架
13‧‧‧黏著劑組成物
14‧‧‧引線
15‧‧‧模組樹脂
16‧‧‧基板
17‧‧‧引線框架
18‧‧‧LED晶片
19‧‧‧透光性樹脂
第1圖是實施例2的黏著劑組成物硬化物的剖面形態觀察結果,於倍率1000倍下的SEM照片。
第2圖是比較例2的黏著劑組成物硬化物的剖面形態觀察結果,於倍率1000倍下的SEM照片。
第3圖是比較例2的黏著劑組成物硬化物的剖面形態觀察結果,於倍率5000倍下的SEM照片。
第4圖是實施例2的晶片剪切強度試驗後的基板側破斷面,於倍率1000倍下的SEM照片。
第5圖是比較例1的晶片剪切強度試驗後的基板側破斷面,於倍率1000倍下的SEM照片。
第6圖是實施例7的黏著劑組成物硬化物的剖面形態觀察結果,於倍率1000倍下的SEM照片。
第7圖是比較例10的黏著劑組成物硬化物的剖面形態觀察結果,於倍率1000倍下的SEM照片。
第8圖是對使用實施例8及比較例11的黏著劑組成物所製作出來的晶片剪切強度試驗用的樣品,測定晶片剪切強度的結果的圖表。
第9圖是表示關於本實施形態的半導體裝置的一例的示意剖面圖。
第10圖是表示關於本實施形態的半導體裝置的其他例子的示意剖面圖。
本說明書中,稱為「步驟」的用語,不僅是指獨立的步驟,即使是無法與其他步驟明確區隔的狀況下,但若能達成該步驟所期待的作用,亦包含於本用語中。
又,本發明中使用「~」所表示的數值範圍,是將「~」前後所記載的數值,分別作為最大值及最小值,來表示所包含的範圍。
進而,本說明書中提及關於組成物中的各種成分的量時,組成物中相當於各種成分的物質為複數存在時,若無特別限定,則意指存在於組成物中的該複數存在物質的合計量。
<黏著劑組成物>
本實施形態的黏著劑組成物,含有銀粒子及鋅離子。而本實施形態的黏著劑組成物,亦可進而含有分散介質。
本實施形態的黏著劑組成物中,銀原子的含量,相對於固體成分中的全部過渡金屬原子,是90質量%以上,更佳是95質量%以上。藉此,可展現充分的高度黏著力。
本實施形態的黏著劑組成物中,鋅原子的含量,相對於固體成分中的全部過渡金屬原子,是0.01質量%以上,較佳是0.05質量%以上,更佳是0.08質量%以上,進而更佳是0.1質量%以上。又,本實施形態的黏著劑組成物中,鋅原子的含量,相對於固體成分中的全部過渡金屬原子,為0.6質量%以下,較佳是0.5質量%以下。
若鋅原子的含量為上述範圍內,在抑制下述的集中存在於黏著界面附近的孔洞的同時,亦可抑制過剩的鋅粒子在燒結後以原本狀態殘留所造成的黏著力低下,而可防止黏著力的低下。
黏著劑組成物中的銀原子及鋅原子的含量,可藉由X光繞射(XRD)、掃描式電子顯微鏡-能量色散X射線分析(SEM-EDX)、螢光X射線測定來進行測定。將銀原子及鋅原子的含量,藉由SEM-EDX進行測定的方法之例子,如下所示。
首先,將黏著劑組成物在盤子(schale)上延伸成厚度在
1mm以下,並藉由減壓乾燥機,以70℃、100Pa以下、40小時以上的條件進行乾燥,而獲得乾燥黏著劑組成物。將乾燥黏著劑組成物置於SEM試驗平台上,以2μm以上的厚度,使之平坦成形來作為SEM用樣品。將該SEM用樣品,按照以後述SEM-EDX所實行的定量方法的例子,來進行定量分析,藉此得到黏著劑組成物中的各過渡金屬原子的比例。
又,關於硬化後的黏著劑組成物,因為銀原子及鋅原子不會揮發,該等的含量實質上不會產生變化,測定關於硬化後的黏著劑組成物的銀原子與鋅原子的含量,亦可將該數值作為黏著劑組成物的銀原子及鋅原子的含量。具體來說,藉由於玻璃板上以0.1~0.5mm的厚度,均勻地塗佈黏著劑組成物之外,於大氣壓力中,以200~300℃,進行1小時的硬化處理,而關於硬化後的黏著劑組成物,利用後述的方法所測定的銀原子及鋅原子的含量,亦可作為黏著劑組成物的含量。
本實施態樣的黏著劑組成物中,固體成分中亦可含有銀原子及鋅原子以外之過渡金屬原子,但該過渡金屬的含量,相對於固體成分中的全部過渡金屬原子,舉例來說,較佳是未滿10質量%,更佳是未滿5質量%。
(銀粒子)
銀粒子是含有銀原子之粒子,更佳是含有銀原子作為主成分(例如,固體成分中的銀含量在90質量%以上,以下亦同)之粒子。就將銀原子作為主成分的組成來說,可舉例如金屬銀、氧化銀,而較佳是金屬銀。
就銀粒子的形狀來說,可舉例如,球狀、塊狀、針狀、片狀。銀粒子的原始粒子的平均粒徑,較佳是0.001μm以上且500μm以下,更佳是0.01μm以上且100μm以下,進而更佳是0.1μm以上且50μm以下。
銀粒子的原始粒子的平均粒徑(體積平均粒徑),可藉由雷射散射法粒度分布測定裝置來測定。測定方法的其中一例如下所示。
將銀粒子0.01g與十二烷基苯磺酸鈉(和光純藥工業股份有限公司製)0.1g、蒸餾水(和光純藥工業股份有限公司製)99.9g互相混合,並以超音波洗淨機處理5分鐘,而得到水性分散液。使用雷射散射法粒度分布測定裝置LS13 320(Beckman Coulter股份有限公司製),其裝設具有超音波分散裝置之廣用液態組件(Universal liquid module),為了安定光源,啟動主機電源後靜置30分鐘。接著,將蒸餾水藉由測定程式中的清洗指令,導入液態組件中,並進行測定程式中的De-bubble,Measure Offset,Align,Measure Background。繼而,進行測定程式中的Measure Loading指令,將該水性分散液振動混合成均勻狀態時,使用滴液吸管(spuit)將其添加至液態組件中,加至測定程式中的樣品量由低(Low)變成OK為止。之後,進行測定程式中的Measure指令,得到粒度分布。作為雷射散射法粒度分布測定裝置的設定,是設定為Pump Speed:70%、Include PIDS data:ON、Run Length:90 seconds、分散介質折射率:1.332、分散質折射率:0.23。
藉由該測定,通常,除了原始粒子,可得到具有複數個尖
峰的粒度分布,而其中包含聚合體的尖峰,但將一個最低粒徑的尖峰作為處理範圍,而可得到原始粒子的平均粒徑。
此外,後述的鋅粒子的原始粒子的平均粒徑,亦可藉由同樣的方法來進行測定。
(鋅粒子)
鋅粒子,是含有金屬鋅之粒子,較佳是含有以金屬鋅作為主成分之粒子。例如,可使用:金屬鋅粒子、粒子核為金屬鋅且表面具有氧化鋅層之鋅粒子、粒子核為金屬鋅且具有有機保護膜之鋅粒子、粒子核為金屬鋅且表面具有金屬銀層之鋅粒子。
鋅粒子,就獲得與導體層、基板等的無機材料之間的接觸面積的觀點來看,原始粒子的平均粒徑較佳是在150000nm以下,更佳是在50000nm以下,進而更佳是在15000nm以下。
另一方面,鋅容易被氧化,而氧化鋅則無法獲得上述的效果。此處,鋅粒子的原始粒子的平均粒徑,就防止氧化的觀點來看,較佳是在50nm以上。
作為鋅粒子的形狀,可舉例如,球狀、塊狀、針狀、片狀。其中,由燒結時融入銀中的觀點來看,較佳是比表面積為大者。又,由降低上述氧化所造成的影響的觀點來看,更佳是片狀的粒子。
(分散介質)
分散介質不論是有機或無機皆可,但就塗佈步驟上防止乾燥的觀點來看,較佳是具有200℃以上的沸點的分散介質,
更佳是具有300℃以上的沸點的分散介質。又,於燒結後為了不使分散介質殘留,較佳是有400℃以下的沸點的分散介質。
又,作為分散介質,較佳是使用選自具有300℃以上的沸點的醇類、羧酸及酯類其中的1種以上,更佳是併用選自具有300℃以上且400℃以下的沸點的醇類、羧酸及酯類其中的1種以上,與沸點在100℃以上,未滿300℃的揮發性成分。
作為具有300℃以上的沸點的醇、羧酸或是酯,可舉出例如:棕櫚酸、硬脂酸、二十酸、對苯二甲酸、油酸等的脂肪族羧酸,苯均四酸、鄰苯氧苯甲酸等的芳香族羧酸;十六醇、異莰基環己醇、四伸乙甘醇等的脂肪族醇;對苯基苯酚等的芳香族醇;辛酸辛酯、十四酸乙酯、亞油酸甲酯、檸檬酸三丁酯、苯甲酸苄酯等的酯類。其中,較佳是碳數在6~20的脂肪族的醇或是羧酸。
作為沸點在100℃以上,未滿300℃的揮發性成分,可舉出例如:戊醇、己醇、庚醇、辛醇、癸醇、乙二醇、二乙二醇、丙二醇、丁二醇、α-萜品醇等的一價及多價醇類;乙二醇丁基醚、乙二醇苯基醚、二乙二醇甲基醚、二乙二醇乙基醚、二乙二醇丁基醚、二乙二醇異丁基醚、二乙二醇己基醚、三乙二醇甲基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丁基醚、二乙二醇丁基甲基醚、二乙二醇異丙基甲基醚、三乙二醇二甲基醚、三乙二醇丁基甲基醚、丙二醇丙基醚、二丙二醇甲基醚、二丙二醇乙基醚、二丙二醇丙基醚、二丙二醇丁基醚、二丙二醇二甲基醚、三丙二醇
甲基醚、三丙二醇二甲基醚等的醚類;乙二醇乙基醚乙酸酯、乙二醇丁基醚乙酸酯、二乙二醇乙基醚乙酸酯、二乙二醇丁基醚乙酸酯、二丙二醇甲基醚乙酸酯、乳酸乙酯、乳酸丁酯、γ-丁內酯等的酯類;N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等的醯胺,環己酮、辛烷、壬烷、癸烷、十一烷等的脂肪族烴,甲苯、二甲苯等的芳香族烴,適當的硫醇是含有1至18的碳原子,例如像是乙基、n-丙基、i-丙基、n-丁基、i-丁基、t-丁基、戊基、己基及十二基硫醇的硫醇,或是環烷基硫醇是含有5至7的碳原子,像是環戊基、環己基、環庚基硫醇的硫醇類。其中,較佳是沸點在150℃以上的揮發性成分,更佳是碳數在4~12的醇、酯、醚類。
上述的分散介質,可單獨使用1種,或是混合2種以上使用。分散介質的含量,將黏著劑組成物的總量設為100質量份時,較佳是為0.1質量份~20質量份。
上述的銀粒子、鋅粒子及分散介質的合計含量,將黏著劑組成物的總量設為100質量份時,較佳是90質量份以上,更佳是95質量份以上,進而更佳的是98質量份以上。
本實施態樣的黏著劑組成物中,亦可含有燒結添加劑、可濕性改良劑及消泡劑中的1種以上。此外,本實施態樣的黏著劑組成物,亦可含有列舉於此以外的成分。
本實施態樣的黏著劑組成物中,依照需求,更可適當地添加氧化鈣、氧化鎂等的吸濕劑,非離子系界面活性劑,氟化物系界面活性劑等的可濕性改良劑,矽油等的消泡劑,無機離子交換體等的離子捕獲劑、聚合抑制劑等。
上述黏著劑組成物,可依照需求,適宜地組合攪拌器、擂潰機、三輥機、行星式攪拌機等的分散/溶解裝置,來將上述的成分一併或是分開地,進行加熱、混合、溶解、分解混練或是分散,使其變成均一的糊膏狀來使用。
黏著劑組成物,較佳是成形時呈現適合各種印刷、塗佈方法的黏度,25℃下的卡森(Casson)黏度,較佳是0.05Pa.s~2.0Pa.s,更佳是0.06Pa.s~1.0Pa.s。
黏著劑組成物的卡森黏度的測定,可藉由黏彈性測定裝置(Physica MCR-501,Anton Paar股份有限公司製)來進行。裝設角度為1°,直徑50mm的圓錐形測定治具(CP50-1),於測定位置,注入黏著劑組成物於測定裝置中,直到黏著劑組成物要從測定治具滿出的程度,於測定治具移至測定位置時,去除溢出的黏著劑組成物後,進行測定。測定是在25℃下,連續進行以下的2個步驟,並於第2個步驟時紀錄剪切速度與剪切應力。(1)剪切速度0s-1、600秒,(2)剪切速度0~100s-1、剪切速度增加率100/60s-1/step、測定間隔1秒、測定點數目60點。
由所得到的剪切速度與剪切應力,以周知文獻(技術情報協會:流體的測定與控制一問一答集-測量流體,將流體物性忠實呈現,東京,技術情報協會,2010,p39-46)中記載的方法,計算出卡森黏度。具體來說,分別計算出所得到的剪切速度及剪切應力的平方根,藉由從相對於(剪切速度)^(1/2)的(剪切應力)^(1/2),以最小平方法算出趨勢線的斜度。將該斜度平方後之數值作為卡森黏度。
上述黏著劑組成物,例如,可藉由在100~300℃下,加熱5秒~10小時,使其硬化。如上所述,銀原子及鋅原子的含量,在加熱前後,並沒有實質上的變化。
硬化的黏著劑組成物中的全部過渡金屬原子中,所佔的銀原子及鋅原子的含量,可藉由硬化的黏著劑組成物的SEM-EDX、穿透式電子顯微鏡-能量色散X射線分析(TEM-EDX)、歐傑電子能譜分析(Auger electron spectroscopy)來定量。
藉由SEM-EDX的定量方法的例示如下。
將具有厚度為3μm以上的黏著劑組成物硬化物層的之品,以環氧鑄型樹脂將其周圍固定。使用研磨裝置,削裁出與黏著劑組成物硬化物層垂直相交的斷面,並將該斷面修飾至平滑。於斷面上,使用濺鍍裝置或蒸鍍裝置,藉由10nm左右的貴金屬來形成帶電防止層,製作出SEM用的樣品。
將該SEM用樣品裝設於SEM-EDX裝置上(例如,ESEM XL,Philip股份有限公司製),以5,000~10,000倍程度的倍率來觀察。黏著劑組成物硬化物的中央部份上,以試料傾斜角度:0°、加速電壓25kV、Ev/Chan:10、Amp.Time:50μS、Choose Preset:LiveTime 300 secs的條件,來計算EDX點分析,而分析條件是以Matrix:ZAF、SEC(Standardless Element Coefficient):EDAX、定量法:None的條件進行定量分析,可得到硬化後黏著劑組成物中的各過渡金屬原子的比率。
硬化後的黏著劑組成物的體積電阻率,較佳是1×10-4Ω.cm以下;熱傳導率,較佳是30W/m.K以上。
<半導體裝置的製造方法>
(半導體元件與半導體元件承載用支撐構件)
作為與本發明相關的半導體元件與半導體元件承載用支撐構件,其附著體表面為金屬。作為可適用於本發明的附著體表面的金屬,舉例如金、銀、銅、鎳等。又,亦可於基材上以上述中複數個材料來形成圖案。
藉由本發明的黏著劑組成物所製成的半導體裝置的製造方法,至少具有以下的步驟。
(A)將黏著劑組成物附著於半導體元件或是半導體元件承載用支撐構件,將半導體元件與半導體元件承載用支撐構件互相貼合的步驟(以下,稱為步驟(A));
(B)使黏著劑組成物硬化,黏合半導體元件與半導體元件承載用支撐構件的步驟(以下,稱為步驟(B))。
進而,步驟(A)中,將黏著劑組成物附著後,亦可具有乾燥步驟。
(步驟(A))-黏著劑組成物的附著步驟-
[黏著劑組成物的調製]
黏著劑組成物,可於分散介質中,混合上述的銀粒子、鋅粒子及任意成分來調製。混合後,亦可進行攪拌處理。又,亦可藉由過濾來調整分散液的最大粒徑。
攪拌處理,可使用攪拌機來進行。作為這樣的攪拌機,可舉出例如,自轉公轉型攪拌裝置、擂潰機、雙軸混練機、三輥機、行星式攪拌機、薄層剪切分散機。
過濾可使用過濾裝置來進行。作為過濾用的過濾
器,可舉出例如,金屬篩網、金屬過濾器、尼龍篩網。
[黏著劑組成物的附著]
藉由將黏著劑組成物附著於基板或是半導體元件上,來形成黏著劑組成物層。作為附著方法,可舉出如塗佈或是印刷的方法。
作為黏著劑組成物的塗佈方法,例如,可使用浸漬法、噴霧塗佈法、刮條塗佈法、模嘴塗佈法、缺角輪塗佈法、狹縫塗佈法、灑施器。
作為印刷黏著劑組成物的印刷方法,例如,可使用分注器、板印刷、凹版印刷、網版印刷、針型分注器、噴嘴分注器法。
藉由黏著劑組成物的附著所形成的黏著劑組成物層,由抑制硬化時的流動及孔洞發生的觀點來看,可適當地使黏著劑組成物層乾燥。
乾燥方法,可使用藉由放置於室溫下乾燥、加熱乾燥,或是減壓乾燥。加熱乾燥或是減壓乾燥中,可使用加熱板、溫風乾燥機、溫風加熱爐、氮氣乾燥機、紅外線乾燥機、紅外線加熱爐、遠紅外線加熱爐、微波加熱裝置、雷射加熱裝置、電磁加熱裝置、加熱器加熱裝置、蒸氣加熱爐、加熱板加壓裝置等。
用來乾燥的溫度及時間。較佳是配合所使用的分散介質的種類及份量來適度地調整。例如,較佳是於50~180℃下,乾燥1~120分鐘。
黏著劑組成物層的形成後,將半導體元件與半導體
元件承載用支撐構件,藉由黏著劑組成物來互相貼合。具有乾燥步驟時,乾燥步驟可於貼合步驟之前或是之後的階段進行。
(步驟(B))-硬化處理-
接著,對於黏著劑處理層進行硬化處理。硬化處理可藉由加熱處理進行,亦可藉由加熱加壓處理進行。加熱處理,可使用加熱板、溫風乾燥機、溫風加熱爐、氮氣乾燥機、紅外線乾燥機、紅外線加熱爐、遠紅外線加熱爐、微波加熱裝置、雷射加熱裝置、電磁加熱裝置、加熱器加熱裝置、蒸氣加熱爐等。又,加熱加壓處理,可以使用加熱板加壓裝置等,亦可邊放置重物加壓,邊進行上述的加熱處理。
藉由以上本發明的黏著劑組成物的製造方法,可製造出,將半導體元件與半導體元件承載用支撐構件,以具有優異高熱傳導性及高耐熱性的黏著劑組成物硬化物來接合而成的半導體裝置。
<半導體裝置>
半導體裝置可使用在電力模組、發信器、增幅器、LED模組等,其中,電力模組是由二極管、整流器、閘流體、金氧半導體(MOS,Metal Oxide Semiconductor)閘極驅動器、電力開關、功率金氧半場效電晶體(Power MOSFET)、絕緣柵雙極電晶體(IGBT,Insulated gate bipolar transistor)、肖特基二極體、第一回復二極體(First recovery diode)等而構成。所得到的電力模組、發信器、增幅器、LED模組,其半導體元件與半導體元件承載用支撐構件之間,具有高黏著性、高熱傳
導性、高導電性及高耐熱性。
第9圖,是表示使用本實施態樣的黏著劑組成物所製造而成的半導體裝置的其中一例的示意剖面圖。第9圖所示的半導體裝置,是由三個引線框架(散熱體)12a、12b、12c、與晶片(發熱體)11、及將該等製模的模組樹脂15所組合而成;其中,晶片11,是於引線框架12a上,藉由本實施態樣的黏著劑組成物13所連接而成的晶片。晶片11,是藉由2條引線14,分別與引線框架12b、12c相連。
第10圖,是表示使用本實施態樣的黏著劑組成物所製造而成的半導體裝置的其他例子的示意剖面圖。第10圖所示的半導體裝置,是由基板16、圍繞著基板16所形成的2個引線框架17、LED晶片18,與密封該等的透光性樹脂19所組合而成;其中,LED晶片18,是藉由本實施態樣的黏著劑組成物13連接於引線框架17上。LED晶片18,是藉由引線14與引線框架17相連。
以下,藉由實施例將本發明更具體地說明,但本發明並不限定於以下的實施例。
各實施例中的各種特性的測定,是以下述的方式實施。
(1)粒子的平均粒徑
混合鋅粒子0.1g與十二烷基苯磺酸鈉(和光純藥工業股份有限公司製)0.01g、蒸餾水(和光純藥工業股份有限公司製)9.99g,並以超音波洗淨機處理5分鐘,得到水性分散液。使用雷射散射法粒度分布測定裝置LS13 320(Beckman
Coulter股份有限公司製),其裝設具有超音波分散裝置之廣用液態組件(Universal liquid module),為了安定光源,啟動主機電源後靜置30分鐘。接著,將蒸餾水藉由測定程式中的清洗指令,導入液態組件中,並進行測定程式中的De-bubble,Measure Offset,Align,Measure Background。繼而,進行測定程式中的Measure Loading指令,將該水性分散液振動混合成均勻狀態時,使用滴液吸管將其添加至液態組件,加至測定程式中的樣品量由Low變成OK為止。之後,進行測定程式中的Measure指令,得到粒度分布。作為雷射散射法粒度分布測定裝置的設定,是設定為Pump Speed:70%、Include PIDS data:ON、Run Length:90 seconds、分散介質折射率:1.332、分散質折射率:0.23。
(2)晶片剪切強度
於鍍銀的PPF-Cu引線框架(接地部份:10×5mm)上,使用尖端尖銳的鑷子,藉由精密天秤,以使重量為0.1mg的方式來塗佈黏著劑組成物。於塗佈後的黏著劑組成物上,依序進行鍍鈦、鍍鎳以及鍍金,而於1×1mm2的附著面上載置鍍金的矽晶片(鍍金的厚度0.1μm,晶片厚度:400μm),再以鑷子輕押。將該物擺設於不鏽鋼托盤中,於設定為200℃的潔淨烘箱(PVHC-210,TABAIESPEC CORP.製)中,進行1小時處理,使引線框架與矽晶片藉由黏著劑組成物黏合。
黏著劑組成物硬化物的黏著強度,是藉由晶片剪切強度來評價。使用裝設50N的負載元件的萬用型黏結強度試驗機(4000系列,DAGE股份有限公司製),以測定速度500μm/s,
測定高度100μm的條件下,將附著面為鍍金的矽晶片水平方向推,來測定黏著劑組成物硬化物的晶片剪切強度。將12次測定的平均值作為晶片剪切強度。
(3)熱傳導率
將黏著劑組成物,藉由使用潔淨烘箱(PVHC-210,TABAIESPEC CORP.製),於200℃下進行加熱處理1小時,可得10mm×10mm×1mm的黏著劑組成物硬化物。將該黏著劑組成物硬化物的熱擴散率,以雷射閃光測定法(NETZSCH股份有限公司製,LFA 447,25℃)進行測定。進而,將該熱擴散率,與以微差掃描熱量測定裝置(Pyris1,珀金埃爾默股份有限公司製)所得到的比熱、及由阿基米德原理所得到的比重,藉由三者相乘所得之積,來算出於25℃下黏著劑組成物的熱傳導率(W/m.K)。
(4)體積電阻率
於玻璃板上,貼上2條間隔約1mm,長度為50mm的美拉帶(日東電工股份有限公司製),而拉帶之間的間隙,則使用刮漿板塗佈黏著劑組成物。
將黏著劑組成物,使用潔淨烘箱(PVHC-210,TABAIESPEC CORP.製),於200℃下進行加熱處理1小時,可得於玻璃板上大小為1×50×0.03mm的黏著劑組成物硬化物。於該黏著劑組成物硬化物的兩端,使用定流電源(Model5964,METRONIX股份有限公司製),並施以1mA的電流,再將與萬用電表(R687E DIGTAL MULTIMETER,愛德萬測試股份有限公司製)連接的探測針,以10mm的間隔接觸
黏著劑組成物硬化物,來測定電壓。使用數位線性定規(Digital linear gauge)(DG-525H,小野測器股份有限公司製),來測定黏著劑組成物硬化物的膜厚度,作為玻璃基板的厚度,與玻璃基板及黏著劑組成物硬化物的合計厚度之間的差,並將測量4點的平均值,作為黏著劑組成物硬化物的厚度。黏著劑組成物硬化物的寬度,則使用光學顯微鏡測量裝置(Measurescope UM-2日本光學股份有限公司製)來測定,並將測量4點的平均值,作為黏著劑組成物硬化物的寬度。將上述的黏著劑組成物硬化物的電壓、電流(1mA)、電壓測定間隔(10mm)、膜厚及寬度的數值,代入四探針法的下述數式(1)中,求得體積電阻率。該測定是對於黏著劑組成物硬化物的相異的四個點進行,並將測定的平均值作為黏著劑組成物硬化物的體積電阻率。
[數式1]體積電阻率=(電壓/電流)×(寬度×厚度/電壓測定間隔)..(1)
(5)剖面型態觀察
將晶片與基板以黏著劑組成物黏著的樣品,於杯內以樣品夾(Samplklip I,Buehler股份有限公司製)來固定,並於周圍注入環氧鑄模樹脂(EPOMAUNNTO,Refinetec股份有限公司製),直到使樣品整個沒入為止,再靜置於真空乾燥器內,並於1分鐘內減壓使其除氣。之後,藉由60℃的恆溫機,於2小時內使環氧鑄模樹脂硬化。
藉由附有防水研磨紙(CA-BOMAKKUPAPER,Refinetec股份有限公司製)的研磨裝置(Regine Polisher HV,Refinetec
股份有限公司製),使削至黏著部份的剖面出現。之後,藉由設置有沾滿拋光劑的拋光研磨布之研磨裝置,將剖面修飾至平滑。於剖面上使用濺鍍裝置(ION SPUTTER,日立先端科技股份有限公司製),將Pt以10nm的厚度進行濺鍍,作為SEM用的樣品。該SEM用樣品藉由SEM裝置(ESEM XL30,飛利浦股份有限公司製),將黏著劑組成物硬化物的剖面,以外加電壓10kV,1000倍的條件下來觀察。
[實施例1~4、比較例1~3]
(黏著劑組成物的調製)
將作為分散介質的異莰基環己醇(TERUSORUBU MTPH,NIPPON TERPENE CHEMICALS股份有限公司製)、與二丙二醇甲醚醋酸酯(DPMA,DAICEL化學股份有限公司製)、及作為粒子表面處理劑的硬脂酸(新日本理化股份有限公司製),於聚乙烯瓶內混合,再將瓶口栓緊,以50℃的水浴加熱,不時搖晃混合使其成為透明均勻的溶液。於該溶液中,添加作為鋅粒子的鱗片狀鋅粒子(製品編號13789,Alfa Aesar,A Johnson Matthey Company製)、作為銀粒子的鱗片狀銀粒子(AGC239,福田金屬箔粉工業股份有限公司製)、及球狀銀粒子(K-0082P,METALOR股份有限公司製),以刮勺混拌至乾燥粉末消失。進而,將其密封栓緊後,使用自轉公轉型攪拌裝置(Planetary Vacuum Mixer ARV-310,THINKY股份有限公司製),以2000rpm攪拌1分鐘,而得黏著劑組成物。此時,各成分的添加量如表1所示。
此外,鱗片狀鋅粒子的平均粒徑為23μm,鱗片狀銀粒
子的平均粒徑為5.42μm,球狀銀粒子的平均粒徑為1.64μm。
關於實施例2及比較例3的黏著劑組成物,以「(2)晶片剪切強度」所記載的方法,得到將引線框架與矽晶片以黏著劑組成物黏著的樣品。關於該樣品,則藉由「(5)剖面型態觀察」所記載的方法進行剖面型態觀察。第1圖,是實施例2的黏著劑組成物硬化物的剖面型態觀察結果,於倍率1000倍下的SEM照片;第2圖、第3圖,分別是比較例2的黏著劑組成物硬化物的剖面型態觀察結果於倍率1000倍下、5000倍下的SEM照片。
第1~3圖中的符號分別是,符號1:矽晶片、符號2:鍍敷層、符號3:鍍金層與黏著劑組成物硬化物的界面附近所出現的孔洞、符號4:黏著劑組成物硬化物、符號5:鍍銀的PPF-Cu引線框架的鍍銀層、符號6:鍍銀的PPF-Cu引線框架的銅層、符號7:個別表示的鋅粒子。此外,這些符號,於第4~7圖中亦相同。
由第1圖可清楚得知,使用實施例2的黏著劑組成物時,黏著劑組成物硬化物4中因燒結而出現的孔洞,是平均地存在,並未發現集中存在的孔洞等。另一方面,由第2圖及第3圖則可清楚得知,使用比較例3的黏著劑組成物時,與鍍金層之間的連接界面附近,有大量的孔洞集中存在,而該現象被認為是造成黏著力低下的原因。
關於實施例2及比較例1的黏著劑組成物,將晶片剪切強度試驗後的基板側切面,於1000倍的倍率下以SEM進行觀察。第4圖,是實施例2的晶片剪切強度試驗後的基
板側切面,於倍率1000倍的SEM照片;第5圖是比較例1的晶片剪切強度試驗後的基板側切面,於倍率1000倍的SEM照片。
由第4圖可清楚得知,使用實施例2的黏著劑組成物時,只發現了燒結成網狀的金屬,所添加的鱗片狀鋅粒子並未被發現。此現象,推測是因為鋅粒子融入黏著劑組成物硬化物4中所造成。
另一方面,由第5圖可清楚得知,使用比較例的黏著劑組成物時,於燒結的金屬中發現了鱗片狀的鋅粒子7。
該鱗片狀的鋅粒子7,是所添加的鋅粒子的一部分,未融入黏著劑組成物硬化物4中而殘留下來之物,看起來與周圍的金屬並未融合。推測由於混入這樣的粒子而使得黏著力低下。
[表1]
[實施例5、6]
(黏著劑組成物的調製)
將異莰基環己醇1.112g,與二丙二醇甲醚醋酸酯1.112g、及硬脂酸0.132g,於聚乙烯瓶內混合,再將瓶口栓緊,以50℃的水浴加熱,不時搖晃混合使其成為透明均勻的溶液。於該溶液中,添加鋅粒子0.0176g(相對於固體成分中的全部過渡金屬元素為0.1質量%)、鱗片狀銀粒子8.791g、及球狀銀粒子8.791g,以刮勺混拌至乾燥粉末消失。進而,將其密封栓緊後,藉由自轉公轉型攪拌裝置(Planetary Vacuum Mixer ARV-310,THINKY股份有限公司製),以2000rpm攪拌1分鐘,得到黏著劑組成物。此外,作為鋅粒子,是使用表2所記載之物,關於其他的原料,則使用與實施例1等相同的原
料。
[比較例4~9]
除了使用表3所記載的添加粒子取代鋅粒子之外,其餘皆與實施例5、6相同,而得到黏著劑組成物。
[實施例7]
(黏著劑組成物的調製)
與實施2相同的方式調製黏著劑組成物。
(晶片與基板的熱壓接)
於鋁基板的銅電極表面上施予鍍銀的銅板,而在附有上述
銅板的鋁基板上,使用具有10mm×10mm的正方形開口的不鏽鋼板,將黏著劑組成物進行板印刷。於印刷的黏著劑組成物上,依序進行鍍鈦、鍍鎳及鍍金,而1×1mm2的附著面載置鍍金的矽晶片(鍍金的厚度為0.1μm、晶片厚:400μm),經過設定為90℃的潔淨烘箱處理30分鐘後,以熱壓接試驗裝置(TESTER產業股份有限公司製),於300℃,10MPa,10分鐘的條件下進行熱壓接,使基板與晶片藉由黏著劑組成物相黏著。
關於所得到的樣品,藉由「(5)剖面型態觀察」所記載的方法,進行剖面型態觀察。第6圖,是實施例7的黏著劑組成硬化物的斷面型態觀察結果,於倍率1000倍下的SEM照片。由第6圖可清楚得知,關於實施例7的黏著劑組成物硬化物,因燒結而產生的孔洞為平均存在,孔洞集結等現象並沒有被發現。
[比較例10]
(黏著劑組成物的調製)
將異莰基環己醇1.370g,與二丙二醇甲醚醋酸酯1.370g、及硬脂酸0.270g,於聚乙烯瓶內混合,將瓶口栓緊,以50℃的水浴加熱,不時搖晃混合使其成為透明均勻的溶液。於該溶液中,添加鱗片狀銀粒子27g,並以刮勺混拌至乾燥粉末消失。進而,將其密封栓緊後,藉由自轉公轉型攪拌裝置(Planetary Vacuum Mixer ARV-310,THINKY股份有限公司製),於2000rpm下攪拌1分鐘,得到黏著劑組成物。
(晶片與基板的熱壓接)
關於所得到的黏著劑組成物,以與實施例7同樣的方式進行晶片與基板的熱壓接,至於所得到的樣品,則藉由「(5)剖面型態觀察」所記載的方法進行剖面型態觀察。第7圖,是比較例10的黏著劑組成硬化物的斷面型態觀察結果,於倍率1000倍下的SEM照片。由第7圖可清楚得知,關於比較例10的黏著劑組成物硬化物,與鍍金層之間的連接界面附近,集中存在著比其他部分多的孔洞3。
[實施例8]
以與實施例1同樣的方式調製黏著劑組成物,將晶片剪切強度用的樣品,以一組12個樣品的方式,分別製作3組。將這3組的晶片剪切強度用的樣品,於加熱至200℃的加熱板上,分別保持2、5、10小時來進行熱處理。將恢復至室溫並經過熱處理的晶片剪切強度用的樣品,測定其晶片剪切強度。結果如第8圖所示。
[比較例11]
除了使用與比較1相同的方法所調製的黏著劑組成物之外,亦藉由與實施例8同樣的方法,製作晶片剪切強度用的樣品,並測定晶片剪切強度。結果如第8圖所示。
由第8圖可清楚得知,相較於比較例11,實施例8中,保持於200℃下時,可使晶片剪切強度的低下率變小,並可保持高溫下的黏著性。
Claims (9)
- 一種黏著劑組成物,含有包含銀原子之銀粒子及包含金屬鋅之鋅粒子,該黏著劑組成物中,相對於該黏著劑組成物的固體成分中的全部過渡金屬原子,銀原子的含量是90質量%以上,鋅原子的含量是0.01質量%以上且0.6質量%以下。
- 如請求項1所述之黏著劑組成物,其中,進而含有分散介質。
- 如請求項1或2所述之黏著劑組成物,其中,卡森(Casson)黏度為0.05Pa.s以上且2.0Pa.s以下。
- 如請求項1至3中的任一項所述之黏著劑組成物,其中,前述鋅粒子的原始粒子的平均粒徑是50nm以上且150000nm以下。
- 如請求項1至4中的任一項所述之黏著劑組成物,其中,前述鋅粒子為片狀。
- 如請求項1至5中的任一項所述之黏著劑組成物,其中,前述銀粒子的原始粒子的平均粒徑是0.1μm以上且50μm以下。
- 如請求項2至6中的任一項所述之黏著劑組成物,其中, 前述分散介質含有選自具有300℃以上的沸點的醇、羧酸及酯中的至少一種。
- 如請求項1至7中的任一項所述之黏著劑組成物,其中,將前述黏著劑組成物進行熱硬化而成的硬化物的體積電阻率及熱傳導率,分別是1×10-4Ω.cm以下、30W/m.K以上。
- 一種半導體裝置,其具有隔著請求項1至8中的任一項所述之黏著劑組成物,將半導體元件與半導體元件承載用支撐構件互相黏著的構造。
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KR101940363B1 (ko) | 2019-01-18 |
TWI592454B (zh) | 2017-07-21 |
EP2862910B1 (en) | 2017-03-15 |
KR20170048614A (ko) | 2017-05-08 |
WO2013187518A1 (ja) | 2013-12-19 |
CN104379689B (zh) | 2017-12-19 |
US20150137347A1 (en) | 2015-05-21 |
US10174226B2 (en) | 2019-01-08 |
JP5880300B2 (ja) | 2016-03-08 |
MY168936A (en) | 2019-01-10 |
KR20150013717A (ko) | 2015-02-05 |
EP2862910A4 (en) | 2016-01-27 |
JP2013258122A (ja) | 2013-12-26 |
EP2862910A1 (en) | 2015-04-22 |
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