TW201504389A - 異向性導電接著劑、發光裝置及異向性導電接著劑之製造方法 - Google Patents

異向性導電接著劑、發光裝置及異向性導電接著劑之製造方法 Download PDF

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TW201504389A
TW201504389A TW103105393A TW103105393A TW201504389A TW 201504389 A TW201504389 A TW 201504389A TW 103105393 A TW103105393 A TW 103105393A TW 103105393 A TW103105393 A TW 103105393A TW 201504389 A TW201504389 A TW 201504389A
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Taiwan
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weight
light
conductive adhesive
anisotropic conductive
particles
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TW103105393A
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English (en)
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TWI623604B (zh
Inventor
Hidetsugu Namiki
Shiyuki Kanisawa
Hideaki Umakoshi
Masaharu Aoki
Akira Ishigami
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Dexerials Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

提供一種射出光之強度高的發光裝置。藉由異向性導電接著劑12，將360nm以上500nm以下之範圍內具有發光光線之波峰的藍色LED晶片20接著於電極基板11。於異向性導電接著劑12所含有之導電粒子1的表面，形成有銀合金之光反射層，對於藍光之反射率高。光反射層係對濺鍍靶進行濺鍍所形成，對遷移之耐性亦高，其中該濺鍍靶以Ag、Bi、Nd之合計為100重量%時，含有0.1重量%以上3.0重量%以下之Bi，0.1重量%以上2.0重量%以下之Nd。

Description

異向性導電接著劑、發光裝置及異向性導電接著劑之製造方法
本發明係關於一種用於將LED元件異向性導電連接於電極基板之異向性導電接著劑，及以該異向性導電接著劑將LED元件構裝於電極基板而成之LED發光裝置。
近年來，使用LED之光功能元件一直受到矚目。
作為此種光功能元件，為了小型化等，一直進行將LED晶片直接構裝於配線基板上的覆晶構裝。
作為將LED晶片覆晶構裝於配線基板上之方法，如圖7(a)~(c)所示，已知以往有各種方法。
圖7(a)，係利用打線接合(wire bonding)進行之構裝方法。
於圖7(a)所示之發光裝置101，係在使LED晶片103之第1及第2電極104、105為上側(與配線基板102相反之側)的狀態下，藉由固晶接著劑110、111將LED晶片103固定在配線基板102上。
然後，藉由接線(bonding wire)106、108，分別將配線基板102上之第1及第2圖案電極107、109與LED晶片103之第1及第2電極104、105電連接。
圖7(b)，係利用導電性糊進行之構裝方法。
於圖7(b)所示之發光裝置121，係在使LED晶片103之第1及第2電極104、105朝向配線基板102側的狀態下，例如藉由銅糊等導電性糊122、123，將此等第1及第2電極104、105與配線基板102之第1及第2圖案電極124、125電連接，且藉由密封樹脂126、127將LED晶片103接著於配線基板102上。
圖7(c)，係利用異向性導電接著劑進行之構裝方法。
於圖7(c)所示之發光裝置131，係在使LED晶片103之第1及第2電極104、105朝向配線基板102側的狀態下，藉由異向性導電接著劑134中的導電性粒子135，將此等第1及第2電極104、105與設置在配線基板102之第1及第2圖案電極124、125上的凸塊(bump)132、133電連接，且藉由異向性導電接著劑134中之絕緣性接著劑樹脂136，將LED晶片103接著於配線基板102上。
然而，上述之先前技術具有各種的課題。
首先，於利用打線接合進行之構裝方法中，由金構成之接線106、108，由於例如會吸收波長為400~500nm之光，故發光效率會降低。
又，此方法之情形，由於使用烘箱使固晶接著劑110、111硬化，故硬化時間長，而難以提升生產效率。
另一方面，於使用導電性糊122、123之構裝方法，僅有導電性糊122、123的話，接著力弱，故必須使用密封樹脂126、127來補強，但此密封樹脂126、127會使得光向導電性糊122、123內擴散，或是光於導電性糊122、123內被吸收，因此而造成發光效率降低。
又，此方法之情形，由於使用烘箱使密封樹脂126、127硬化，故硬化時間長，而難以提升生產效率。
另一方面，於使用異向性導電接著劑134之構裝方法，由於異向性導電接著劑134中之導電性粒子135的顏色為茶色，故絕緣性接著劑樹脂136的顏色亦成為茶色，光於異向性導電接著劑134內被吸收，因此而造成發光效率降低。
為了解決此種問題，亦提出：提供一種異向性導電接著劑，該異向性導電接著劑係藉由使用光反射率高、電阻低之銀(Ag)形成導電層，以抑制光的吸收，而不會使發光效率降低。
然而，由於銀係化學上不穩定之材料，故會有容易氧化或硫化之問題，且具有下述問題：於熱壓合後，因通電而發生遷移(migration)，因此而會引起配線部分之斷線或接著劑劣化導致接著強度之降低。
為了解決此問題，例如專利文獻4之記載，亦提出一種反射率、耐蝕性、耐遷移性優異之Ag系薄膜合金。
若將此Ag系薄膜合金被覆在導電性粒子之表面，耐蝕性、耐遷移性雖會獲得提升，但若將此Ag系薄膜合金用於最表層，基底層例如使用鎳時，則會有下述問題：由於鎳之反射率低於Ag，故導電性粒子整體之反射率會降低。
又，於導電性粒子135的表面若露出Au或Ni，則因光的吸收而會使得發光效率降低。
專利文獻1：日本特開2005-120375號公報
專利文獻2：日本特開平5-152464號公報
專利文獻3：日本特開2003-26763號公報
專利文獻4：日本特開2008-266671號公報
本發明之課題在於提供一種360nm以上500nm以下波長之射出光強度高的發光裝置。
為了解決上述課題，本發明為一種異向性導電接著劑，含有導電粒子與接著黏合劑，將發光光線最大強度之波峰位於波長為360nm以上500nm以下之範圍內的LED元件接著在電極基板，而將該LED元件之電極與該電極基板之電極電連接，該導電粒子，具有樹脂粒子、以電鍍法形成在該樹脂粒子表面之基底層、及以濺鍍法形成在該基底層表面且含有Ag、Bi、Nd之導電性光反射層，該光反射層係對濺鍍靶進行濺鍍所形成，該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
又，本發明為一種異向性導電接著劑，該異向性導電接著劑之硬化物的反射率，於360nm以上740nm以下之波長區域中，為30%以上。
又，本發明為一種異向性導電接著劑，該基底層為鎳薄膜。
又，本發明為一種異向性導電接著劑，相對於加熱硬化絕緣性之該接著黏合劑100重量份，於1重量份以上100重量份以下之範圍含有該導電粒子。
又，本發明為一種發光裝置，LED元件與基板係以接著劑含有導電粒 子之異向性導電接著劑接著，該LED元件的發光光線最大強度之波峰位於波長為360nm以上500nm以下之範圍內，該導電粒子，具有樹脂粒子、以電鍍法形成在該樹脂粒子表面之基底層、及以濺鍍法形成在該基底層表面且含有Ag、Bi、Nd之導電性光反射層，該光反射層係對濺鍍靶進行濺鍍所形成，該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
又，本發明為一種異向性導電接著劑之製造方法，係將導電性粒子分散在接著劑，製造異向性導電接著劑，該異向性導電接著劑，係藉由電鍍法將基底層形成在樹脂粒子之表面，並對濺鍍靶進行濺鍍將光反射層形成在該基底層之表面，而形成該導電粒子，其中該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
根據本發明，異向性導電接著劑對於360nm以上500nm以下波長之光的反射率高，導電粒子之耐遷移性亦高，故可得到360nm以上500nm以下波長之發光光線強度高，可靠性亦高之發光裝置。
1‧‧‧導電粒子
2‧‧‧樹脂粒子
3‧‧‧基底層
4‧‧‧光反射層
7‧‧‧發光裝置
9‧‧‧半導體晶片
11‧‧‧電極基板
10、12、21‧‧‧異向性導電接著劑
20‧‧‧LED元件
圖1(a)：用以說明本發明之異向性導電接著劑之圖，(b)：分散在異向性導電接著劑之導電粒子的剖面圖。
圖2(a)：顯示電極基板上塗布有異向性導電接著劑之狀態的剖面圖，(b)：用以說明LED發光裝置之剖面圖。
圖3：用以說明本發明所使用之藍色LED元件之發光光線波峰之圖形。
圖4：顯示使用藍色LED元件與螢光體之本發明的發光裝置其射出光波長分布之圖形。
圖5：用以說明紅、綠、藍之LED元件發光光線波峰之圖形。
圖6：顯示本發明所使用之導電粒子與比較例形成有金薄膜之導電粒子的反射率與波長關係之圖形。
圖7(a)：用以說明利用打線接合進行之構裝方法的剖面圖，(b)：用以說明使用導電性糊之方法的剖面圖，(c)：用以說明使用異向性導電接著劑之方法的剖面圖。
首先，說明本發明之發光裝置。
參照圖2(b)，本發明之發光裝置7具有LED元件20與電極基板11，該LED元件在360nm以上500nm以下之範圍的波長區域具有發光光線強度最大值之波峰。
LED元件20具有由切斷之半導體基板形成之半導體晶片9，於半導體晶片9的內部，藉由導入之雜質(摻雜物)而形成有pn結合，於半導體晶片9之一表面上，分開設置有2個電極13。
在設置有電極13之半導體晶片9的表面上，以使電極13之至少一部份露出的方式，形成有絕緣性保護膜17。
電極基板11具有玻璃環氧製之基板本體5，在基板本體5上，分開設置有以金屬膜構成之2個連接端子15。
在基板本體5的表面上，以使連接端子15之至少一部份露出的方式， 形成有絕緣性保護膜22，並於連接端子15的露出部份，設置有上部呈平坦之凸塊6。
另，凸塊6只要形成在電極基板11之連接端子15的表面上或LED元件20之電極13的表面上至少任一者即可，即使是形成在LED元件20之電極13上的情形，凸塊6之上部亦宜為平坦。此處，在一個連接端子15的表面上，設置有一個上部平坦之凸塊6。
設置在LED元件20之2個電極13間的距離，與設置在電極基板11之2個凸塊6間的距離相同，LED元件20與電極基板11，係在未硬化之異向性導電接著劑配置於LED元件20與電極基板11之間的狀態下，以電極13與凸塊6一對一相對接觸之方式受到按壓，使未硬化之異向性導電接著劑硬化而將LED元件20固定在電極基板11。
圖1(a)之符號21，係表示硬化前之異向性導電接著劑。
此異向性導電接著劑21，於未硬化之狀態下，具有具接著性之黏合劑樹脂8與分散在黏合劑樹脂8中之導電粒子1。
黏合劑樹脂8之種類，雖然沒有特別限定，但從透明性、接著性、耐熱性、機械強度、電絕緣性優異之觀點來看，可適用含有環氧系樹脂與含有其硬化劑之組成物。
環氧系樹脂，具體而言，為脂環式環氧化合物、雜環式環氧化合物或氫化環氧化合物等。作為脂環式環氧化合物，較佳可舉出在分子內具有2個以上之環氧基者。此等可為液狀或亦可為固狀。具體而言，可列舉環氧丙基六氫雙酚A、3,4-環氧環己烯甲基-3’,4’-環氧環己烯羧酸酯等。其中，從可確保硬化物適於LED元件構裝等之透光性且速硬化性亦 優異的方面來看，可較佳使用環氧丙基六氫雙酚A、3,4-環氧環己烯甲基-3’,4’-環氧環己烯羧酸酯。
作為雜環系環氧化合物，可舉具有三環之環氧化合物，尤佳可列舉1,3,5-參(2,3-環氧丙基)-1,3,5-三-2,4,6-(1H,3H,5H)-三酮。
作為氫化環氧化合物，可使用前述之脂環式環氧化合物、雜環式環氧化合物之氫化物或其他公知的氫化環氧樹脂。
又，除了此等環氧化合物外，只要無損本發明之效果，亦可合併使用其他環氧樹脂。例如可列舉：雙酚A、雙酚F、雙酚S、四甲基雙酚A、二芳基雙酚A、對苯二酚、兒茶酚、間苯二酚、甲酚、四溴雙酚A、三羥基聯苯、二苯基酮(benzophenone)、雙間苯二酚、雙酚六氟丙酮、四甲基雙酚A、四甲基雙酚F、參(羥基苯基)甲烷、聯二甲苯酚(bixylenol)、苯酚酚醛清漆(phenol novolac)、甲酚酚醛清漆(cresol novolac)等多元酚與表氯醇反應而得之環氧丙基醚1甘油；新戊二醇、乙二醇、丙二醇、丁二醇、己二醇、聚乙二醇、聚丙二醇等脂肪族多元醇與表氯醇反應而得之聚環氧丙基醚1對羥苯甲酸；如β-羥基萘甲酸(β-oxynaphthoic acid)之羥基羧酸與表氯醇反應而得之環氧丙基醚酯1酞酸；自如甲基酞酸、異酞酸、對酞酸、四氫酞酸、內亞甲四氫酞酸、內亞甲六氫酞酸、苯偏三酸(trimellitic acid)、聚合脂肪酸之多羧酸所得到之聚環氧丙基酯1胺基苯酚；從自胺基烷基苯酚所得到之環氧丙基胺基環氧丙基醚1胺基苯甲酸得到的環氧丙基胺基環氧丙基酯1苯胺；自甲苯胺、三溴苯胺、伸二甲苯二胺(xylylenediamine)、二胺基環己烷、雙胺基甲基環己烷、4,4'-二胺基二苯 甲烷、4,4'-二胺基二苯基碸等所得到之環氧丙胺1環氧化聚烯烴等公知之環氧樹脂類。
又，作為硬化劑，可列舉：酸酐、咪唑化合物、二氰(dicyan)等。其中，可使用難以使硬化劑變色之酸酐，尤其是脂環式酸酐系硬化劑。具體而言，適合有甲基六氫酞酐等。
另，當使用脂環式環氧化合物與脂環式酸酐系硬化劑之情形時，各自之使用量，若脂環式酸酐系硬化劑過少，則未硬化環氧化合物會變多，若過多，則會有下述傾向：因剩餘硬化劑之影響而促進被接著體材料之腐蝕，因此，相對於脂環式環氧化合物100質量份，可使用80~120質量份，更適合使用95~105質量份之比例。
黏合劑樹脂8，係具有熱硬化性與絕緣性之樹脂，黏合劑樹脂8接觸於接著對象物，若異向性導電接著劑21在接著於接著對象物之狀態下受到加熱，則異向性導電接著劑21會在接著於接著對象物之狀態下硬化。
圖2(b)之符號12，係顯示經硬化之異向性導電接著劑。
即使是硬化狀態之異向性導電接著劑12，亦維持導電粒子1分散之狀態，複數個導電粒子1位於電極13與凸塊6之間。
未硬化之異向性導電接著劑21，係配置在基板本體5上，並且在該未硬化之異向性導電接著劑21上配置有LED元件20，若將LED元件20按壓在未硬化之異向性導電接著劑21，則未硬化之異向性導電接著劑21的基板本體5側之底面，與基板本體5之保護膜22及凸塊6接觸，LED元件20側之表面，與LED元件20之保護膜17及電極13接觸。
並且，未硬化之異向性導電接著劑21，藉由將LED元件20按壓在電極基板11，導電粒子1會與電極13及凸塊6兩者接觸，確實地電連接電極13與凸塊6。另，硬化之黏合劑樹脂19具有絕緣性，位於電極13與凸塊6間之外側的導電粒子1，不與其他導電粒子1接觸，不會造成電極13間及凸塊6間短路。
於LED元件20，在內部形成有pn接合。
當將連接端子15連接於電源之輸出端子，於2個連接端子15之間施加電壓使pn接合為正向偏壓的情形，電流會通過連接端子15、凸塊6、導電粒子1、電極13而流至pn接合部，使pn接合之部分發光。
LED元件20之表面中，不面對電極基板11而朝向外側之表面為發光光線之射出面，若設置透明封裝，則會在受到透明封裝保護之狀態下，於大氣中射出發光光線。
半導體晶片9及半導體晶片9上之保護膜17，具有透射發光光線之透明性，由pn接合生成之發光光線中，於射出面側行進之發光光線會通過半導體晶片9、保護膜17及透明封裝等，而射出至發光裝置7之外部。
硬化之黏合劑樹脂19對於發光光線亦是透明的，行進於與電極基板11對向之面側射入至硬化之異向性導電接著劑12的發光光線，一部份照射至導電粒子1。
如圖1(b)所示，異向性導電接著劑12、21含有之導電粒子1，具有樹脂粒子2、由以電鍍法形成在樹脂粒子2表面之金屬薄膜構成的基底層3、及以濺鍍法形成在基底層3表面的光反射層4。
樹脂粒子2並無特別限定，但從得到高導通可靠性之觀點來看，例如可使用由交聯聚苯乙烯系、苯代三聚氰胺(benzoguanamine)系、尼龍系、PMMA(聚甲基丙烯酸酯)系等構成之樹脂粒子。
樹脂粒子2的大小並無特別限定，但從得到高導通可靠性之觀點來看，可使用平均粒徑為3μm~5μm者。
此處，樹脂粒子2係丙烯酸樹脂成形為球狀而構成，基底層3係藉由電鍍法形成在樹脂粒子2表面之鎳薄膜。
光反射層4，係由在後述之含有率的範圍內含有Ag、Bi、Nd之濺鍍靶受到濺鍍氣體(稀有氣體)濺擊而形成之薄膜構成。
濺鍍法是將薄膜形成在物體的方法之一，係於真空中進行者。於濺鍍法，係在使容器內為真空之狀態下，於成膜對象物與濺鍍靶之間施加電壓產生輝光放電。藉此產生之電子或離子以高速撞擊靶，藉此濺擊出靶材料之粒子，該粒子(濺鍍粒子)附著於成膜對象物之表面而形成薄膜。
此處，作為藉由濺鍍將薄膜形成在如本發明之微小粒子的方法，可將分散成一次粒子之微粒子安裝在裝置內之容器，旋轉容器使微粒子流動。亦即，可對此種流動狀態之微粒子進行濺鍍，藉此使各微粒子之整面成為成膜面，靶材料之濺鍍粒子撞擊於成膜面，而將薄膜形成在各微粒子之整面。
又，作為適用於本發明之濺鍍法，可採用包含雙極濺鍍法、磁控濺鍍法、高頻濺鍍法、反應性濺鍍法之公知的濺鍍法。
於濺鍍時，在濺鍍粒子到達之成膜面露出有基底層3，而樹 脂粒子2之表面沒有露出。濺鍍粒子由於到達基底層3之表面，故樹脂粒子2之表面不會受到濺鍍粒子造成之損害，於導電粒子1形成有表面平坦之光反射層4。
因此，射入至導電粒子1之發光光線，會受到形成在基底層3表面之光反射層4的反射，而射向LED元件20所在之方向。
形成有光反射層4之濺鍍靶，為含有Ag、Bi、Nd之合金，靶中之Ag、Bi、Nd的含有率，於以Ag、Bi、Nd之合計為100重量%時，Bi之含有率為0.1重量%以上3.0重量%以下之值，Nd之含有率為0.1重量%以上2.0重量%以下之值。Ag之含有率為自100重量%之值減去Bi含有率與Nd含有率之值。
以此含有率含有Ag、Bi、Nd之銀合金薄膜，對於波長360nm以上740nm以下之範圍的光，光反射率高於金薄膜或Ni薄膜等不含銀之薄膜。
另一方面，本發明之發光裝置7具有之LED元件20，如圖3所示，係於波長360nm以上500nm以下之範圍內存在強度最大之波峰的LED元件，LED元件20之發光光線以高反射率被導電粒子1反射而回到LED元件20側，較被金薄膜或Ni薄膜等反射時更強之反射光通過LED元件20，自半導體晶片9之射出面射出至發光裝置7之外部。
於本發明之情形，導電性粒子1相對於加熱硬化絕緣性黏合劑樹脂8之含量，並無特別限定，但若考慮確保光反射率、耐遷移性、絕緣性，則較佳相對於100重量份之黏合劑樹脂8，含有1重量份以上100重量份以下之導電性粒子1。
於黏合劑樹脂8之內部，除了導電粒子1，亦分散有光反射 性絕緣填充物(未圖示)。本例之光反射性絕緣填充物，例如為白色SiO2，沒有射入至導電粒子1而射入至光反射性絕緣填充物之發光光線，會以低於導電粒子1之反射率受到反射，使反射光回到LED元件20側。
又，基板本體5之表面著色成白色，射入至基板本體5表面之發光光線，會以低於導電粒子1之反射率受到反射，而回到LED元件20側。
被光反射性絕緣填充物或基板本體5表面反射之反射光，亦會通過LED元件20，而自射出面射出至外部。
另，LED元件20之發光光線，並不會通過電極13、凸塊6及連接端子15。
若發光裝置7之發光時間變長，則電流流經導電粒子1之時間將會變長，若為Ag薄膜，則會發生因(電)遷移造成之斷線。以上述範圍重量%之值含有Bi與Nd的銀合金薄膜，相較於純銀之薄膜，難以發生遷移。因此，於本發明之發光裝置7，不會發生因遷移造成之斷線。
金屬薄膜之反射率的值，會因入射光之波長而變化。圖6為顯示反射率相對於入射光波長的關係之圖，該圖之曲線f，係當對下述之濺鍍靶進行濺鍍形成該導電粒子1之光反射層4時異向性導電接著劑的反射率，該濺鍍靶係在以Ag、Bi、Nd之合計重量為100重量%時，以0.7重量%之含有率含有Bi，以0.3重量%之含有率含有Nd(Ag為99重量%)。
該圖之曲線g，顯示分散有由Au層構成之光反射層露出於表面的導電粒子之異向性導電接著劑的反射率。
曲線f、g之異向性導電接著劑，除了導電粒子表面之光反射層的構成外，其餘之構成相同。
如從圖6可知，本發明之異向性導電接著劑相較於Au層之導電粒子，即使於360nm以上500nm以下之範圍，反射率亦為高達30%以上之值。
以下，若將於360nm以上500nm以下之範圍具有波峰的LED元件稱作藍色LED元件，則上述實施例之發光裝置7，雖不具有圖3所示之發光強度分布之藍色LED元件以外的LED元件，但本發明亦包含除了藉由本發明之異向性導電接著劑貼附在基板的藍色LED元件外，還一起配置360nm以上500nm以下之範圍外具有波峰的LED元件而一起射出藍色與藍色以外之發光光線的發光裝置。
圖5係發白光之發光裝置的發光光線相對強度分布之一例，為於發光光線之內部配置有發光光線為藍色、綠色、紅色之LED元件的情形。即使是此發光裝置，若藍色LED元件是藉由本發明之異向性導電接著劑貼附在基板的話，亦包含於本發明。
又，配置有藉由本發明之異向性導電接著劑貼附在基板的藍色LED元件、與照射藍色LED元件射出光之螢光體的發光裝置，其射出光成為如圖4所示之強度分布，發白光。此發光裝置，若藍色LED元件亦是藉由本發明之異向性導電接著劑貼附在基板的話，則亦包含於本發明。
另，使用於本發明之導電粒子的基底層，即使是鎳以外之金屬的薄膜，只要是以電鍍法來形成即可。
本發明之異向性導電接著劑，較佳為糊狀之異向性導電接著劑。
<導電粒子、異向性導電接著劑及發光裝置之製造步驟>
說明本發明之異向性導電接著劑的製造步驟。
首先，將平均粒徑5μm之樹脂粒子(此處係丙烯酸樹脂之粒子)浸漬在鎳鍍液內，藉由電鍍法，將0.03μm以上3.0μm以下膜厚之鎳薄膜形成在樹脂粒子的表面作為基底層。樹脂粒子之表面被基底層覆蓋，沒有露出樹脂粒子之表面。
預先於濺鍍裝置(共立公司製，粉體濺鍍裝置)之內部，配置以Ag、Bi、Nd之合計重量為100重量%時，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd的濺鍍靶，將表面形成有基底層之樹脂粒子配置在設於濺鍍裝置內部之旋轉容器內。
使濺鍍裝置之內部為真空環境，導入濺鍍氣體，於濺鍍靶施加電壓進行濺鍍，使濺鍍粒子到達基底層之表面，將由與濺鍍靶相同組成之銀合金構成的光反射層形成在基底層表面。
此時使旋轉容器旋轉，使形成有基底層之樹脂粒子於旋轉容器內部滾動，且同時使濺鍍粒子到達基底層整個表面，於基底層表面形成均勻之膜厚的光反射層，而得到沒有露出基底層之導電粒子。
由於沒有露出樹脂粒子表面，故不會發生因濺鍍粒子之衝擊而造成的樹脂粒子表面破裂。
光反射層形成為規定之厚度後，結束濺鍍，從濺鍍裝置取出導電粒子。圖1(b)為導電粒子1之剖面圖。
接著，相對於由熱硬化性樹脂構成之黏合劑樹脂100重量 份，以1重量份以上100重量份以下之範圍混合自濺鍍裝置取出之導電粒子並使之分散，而製成異向性導電接著劑。
如圖2(a)所示，將未硬化具有接著性之異向性導電接著劑10配置在電極基板11之凸塊6上，接著，如該圖(b)所示，將LED元件20放在異向性導電接著劑10上，一邊按壓一邊加熱使之硬化。
LED元件20之電極13，朝向電極基板11之表面，在導電粒子1位於電極13與凸塊6之間的狀態下一邊按壓一邊加熱，使異向性導電接著劑10硬化。
該圖(b)之符號12，表示經硬化之異向性導電接著劑。
導電粒子1被電極13與凸塊6夾住而與兩者接觸，藉由導電粒子1將電極13與凸塊6電連接，LED元件20被固定在電極基板11，而得到上述之發光裝置7。
若使電流流入LED元件20而發光，則位於LED元件20之半導體晶片9與電極基板11相對之部分的導電粒子1會反射發光光線，而使發光光線射出至發光裝置7之外部。
另，於發光裝置7之製造時，可用透明模具樹脂(mold resin)進行密封，來覆蓋LED元件20整體。
[實施例]
說明測量所使用之樣品。
首先，藉由電鍍法將鎳薄膜形成在丙烯酸樹脂粒子作為基底層。接著，對4種類之濺鍍靶進行濺鍍，使光反射層各自形成在基底層之表面，而製成4種類之導電粒子，該4種類之濺鍍靶係以Ag、Bi、Nd之合計重量為100 重量%時，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
使製成之導電粒子各自分散在黏合劑樹脂，而得到實施例1~4之異向性導電接著劑。鎳薄膜之膜厚為0.10μm，光反射層之膜厚為0.2μm。
表1之「最表面金屬」之欄中的「組成比」欄，顯示形成分散在實施例1~4及後述比較例3~5之異向性導電接著劑的導電粒子之各光反射層的濺鍍靶組成。
實施例1為Ag：Bi：Nd=99：0.7：0.3，實施例2為Ag：Bi：Nd=99.8：0.1：0.1，實施例3為Ag：Bi：Nd=95：3：2，實施例4為Ag：Bi：Nd=99：0.7：0.3。
於比較例3、4、5，使用含有率與本發明不同之濺鍍靶，以與實施例1~4相同之步驟，製成除了光反射層之組成不同外，其餘相同之構成的導電粒子，並使之分散於黏合劑樹脂，而得到比較例3~5之異向性導電接著劑。
比較例3~5之濺鍍靶的組成比，各自為純Ag；Ag：Bi：Nd=99.9：0.05：0.05；Ag：Bi：Nd=94：3：3。
於比較例1，藉由電鍍法將膜厚為0.2μm且由金(Au)薄膜構成之光反射層形成在樹脂粒子露出丙烯酸樹脂之表面，而製成導電粒子，於比較例2，則是將藉由電鍍法形成且膜厚為0.2μm之鎳薄膜構成的光反射層形成在樹脂粒子露出丙烯酸樹脂之表面，而製成導電粒子。將製成之導電粒子各自分散在黏合劑樹脂，而製成異向性導電接著劑。
實施例1~4與比較例1~5，係將20重量份之導電粒子分散於黏合劑樹脂100重量份(不包括溶劑)。又，各異向性導電接著劑之黏合劑樹脂為同一種類之樹脂，除導電粒子以外，為相同結構。
黏合劑樹脂，係使用環氧硬化系接著劑(daicel公司製CEL2021P-MeHHPA)作為主成分。
另，形成有金薄膜之露出丙烯酸樹脂表面的樹脂粒子、形成最表面之鎳薄膜作為光反射層之露出丙烯酸樹脂的樹脂粒子、及形成銀合金(包含純銀)薄膜作為反射層之表面為鎳薄膜的粒子之直徑，各自為5 μm。
<樹脂粒子的顏色>
觀察實施例1~4、比較例1~5之各異向性導電接著劑所含的樹脂粒子的顏色。將觀察結果示於表1之「粒子外觀」欄。可知比較例1、2之導電粒子有著色，發光元件之反射光會被著色反射回來。
<反射率測量>
以厚度100μm將實施例1~4、比較例1~5之各異向性導電接著劑塗布在白色板，搬入至加熱硬化裝置內使之加熱硬化後，藉由分光測色計(konicaminolta公司製CM-3600d)測量反射率。硬化係以200℃、一分鐘之加熱條件進行。
將測量結果示於表1之「反射率」欄。
<光學特性>
在設置有附Au凸塊之LED構裝用Au電極的電極基板(玻璃環氧基板)表面，塗布實施例1~4、比較例1~5之各異向性導電接著劑並裝上LED元件，而製成實施例1~4、比較例1~5之發光裝置。
LED元件之裝載，係以200℃、1kg/元件之按壓壓力、20秒之加熱壓合條件進行。
於所得之發光裝置，施加3.2V之電壓，使20mA之電流流經LED元件而使之發光。從發光裝置之射出光，係使用總光量測量裝置(大塚電子股份有限公司製造之總光束測量系統(積分球)LE-2100)，對實施例1~4、比較例1~5之各發光裝置，測量總光束量。測量條件為常溫常濕度。
測量結果示於表1之「光學特性」的「初期」欄。
又，將實施例1~4、比較例1~5之各發光裝置設置於85℃、85%RH之環境下，使發光500小時之後，藉由相同之測量裝置測量總光束量，算出初期總光束量、與500小時發光後之總光束量差之比的總光束量變化率算出。
算出結果示於表1之「總光束量變化率」欄。
Ag含有率高之比較例3、4雖然反射率高，但總光束量變化率高，經時變化性差。
<可靠性試驗>
用於測量總光束量之電極基板，拉開寬度100μm之空間平行地設置有電極，實施例1~4、比較例1~5之異向性導電接著劑，係被塗布成與電極接觸，異向性導電接著劑被填充於電極間及凸塊間。
設置在85℃、85%RH之環境下發光500小時之結果，在Ag含有率高之比較例3、4的電極間，檢測出漏電流。於表1之導通可靠性欄，比較例3、4記載有「×」。
於比較例3、4，觀察到導電粒子之變色，並確認發生遷移。
1‧‧‧導電粒子
5‧‧‧基板本體
6‧‧‧凸塊
7‧‧‧發光裝置
8‧‧‧黏合劑樹脂
9‧‧‧半導體晶片
10‧‧‧異向性導電接著劑
11‧‧‧電極基板
12‧‧‧異向性導電接著劑
13‧‧‧電極
15‧‧‧連接端子
17‧‧‧絕緣性保護膜
19‧‧‧硬化之黏合劑樹脂
20‧‧‧LED元件
22‧‧‧絕緣性保護膜

Claims (6)

  1. 一種異向性導電接著劑，含有導電粒子與接著黏合劑，將發光光線最大強度之波峰位於波長為360nm以上500nm以下之範圍內的LED元件接著在電極基板，而將該LED元件之電極與該電極基板之電極電連接，該導電粒子，具有樹脂粒子、以電鍍法形成在該樹脂粒子表面之基底層、及以濺鍍法形成在該基底層表面且含有Ag、Bi、Nd之導電性光反射層，該光反射層係對濺鍍靶進行濺鍍所形成，該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
  2. 如申請專利範圍第1項之異向性導電接著劑，其中，該異向性導電接著劑之硬化物的反射率，於360nm以上740nm以下之波長區域中，為30%以上。
  3. 如申請專利範圍第1項之異向性導電接著劑，其中，該基底層為鎳薄膜。
  4. 如申請專利範圍第1項之異向性導電接著劑，其中，相對於加熱硬化絕緣性之該接著黏合劑100重量份，於1重量份以上100重量份以下之範圍含有該導電粒子。
  5. 一種發光裝置，LED元件與基板係以接著劑含有導電粒子之異向性導電接著劑接著，該LED元件的發光光線最大強度之波峰位於波長為360nm以上500nm以下之範圍內，該導電粒子，具有樹脂粒子、以電鍍法形成在該樹脂粒子表面之基底層、及以濺鍍法形成在該基底層表面且含有Ag、Bi、Nd之導電性光反射層， 該光反射層係對濺鍍靶進行濺鍍所形成，該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
  6. 一種異向性導電接著劑之製造方法，係將導電性粒子分散在接著劑，製造異向性導電接著劑，該異向性導電接著劑，係藉由電鍍法將基底層形成在樹脂粒子之表面，並對濺鍍靶進行濺鍍將光反射層形成在該基底層之表面，而形成該導電粒子，其中該濺鍍靶以Ag、Bi、Nd之合計重量為100重量%，在Bi為0.1重量%以上3.0重量%以下、Nd為0.1重量%以上2.0重量%以下之範圍含有Ag、Bi及Nd。
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