TWI523828B - A bonding material and a joining structure - Google Patents

A bonding material and a joining structure Download PDF

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Publication number
TWI523828B
TWI523828B TW103101816A TW103101816A TWI523828B TW I523828 B TWI523828 B TW I523828B TW 103101816 A TW103101816 A TW 103101816A TW 103101816 A TW103101816 A TW 103101816A TW I523828 B TWI523828 B TW I523828B
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Taiwan
Prior art keywords
metal
glass
substrate
oxide
bonding
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TW103101816A
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English (en)
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TW201500327A (zh
Inventor
Motomune Kodama
Takashi Naito
Tadashi Fujieda
Yuichi Sawai
Takuya Aoyagi
Masanori Miyagi
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Hitachi Ltd
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Publication of TW201500327A publication Critical patent/TW201500327A/zh
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Publication of TWI523828B publication Critical patent/TWI523828B/zh

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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21C—NUCLEAR REACTORS
    • G21C19/00—Arrangements for treating, for handling, or for facilitating the handling of, fuel or other materials which are used within the reactor, e.g. within its pressure vessel
    • G21C19/20—Arrangements for introducing objects into the pressure vessel; Arrangements for handling objects within the pressure vessel; Arrangements for removing objects from the pressure vessel
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • G21C7/00—Control of nuclear reaction
    • G21C7/06—Control of nuclear reaction by application of neutron-absorbing material, i.e. material with absorption cross-section very much in excess of reflection cross-section
    • G21C7/08—Control of nuclear reaction by application of neutron-absorbing material, i.e. material with absorption cross-section very much in excess of reflection cross-section by displacement of solid control elements, e.g. control rods
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Description

接合材、接合構造體
本發明係有關接合材，例如可運用於將陶瓷、半導體、玻璃之基材與其他基材接合而成之接合構造體。
電氣電子零件、LED照明、半導體模組中，存在有陶瓷、玻璃、金屬、半導體晶片的接合處，該接合處有時會兼作為熱流或電流路徑。
在這樣的接合處，該些基材彼此通常會藉由銲料材或硬銲材來接合。
專利文獻1中揭示，用來將半導體裝置接合至陶瓷基材之銀玻璃膏，其燒成溫度為300~420℃。基本的玻璃組成為氧化鉛與氧化釩。
[先前技術文獻] [專利文獻]
[專利文獻1]日本特開平04-270140號公報
使用銲料材將陶瓷、半導體、玻璃等接合時，必須有金屬化(metalizing)處理，除了工程變複雜之外，還必須有廢液處理。另一方面，若是含有Ti(鈦)、Al(鋁)等活性金屬之硬銲材，則不需金屬化處理便可與陶瓷接合，但必須在800℃的高溫下處理。因此，需要一種不需金屬化處理，而能將陶瓷、半導體、玻璃等在300℃左右的低溫下接合之技術。
本發明之目的在於提供一種不需金屬化處理，而能將陶瓷、半導體、玻璃等基材在銲料材程度的處理溫度下接合之技術。
本發明中，若要簡單說明代表性之物的概要，則如下所述。
也就是說，接合構造體，係為複數個基材透過接合層而接合，且至少其中一方的基材為陶瓷、半導體、玻璃任一者之基材，接合材層中含有金屬與氧化物，氧化物含有V與Te，氧化物存在於金屬與基材之間。
按照本發明，能夠不需金屬化處理，而能將陶瓷、半導體、玻璃等基材在銲料材程度的處理溫度下接合。
1‧‧‧一方的基材
2‧‧‧接合材層
3‧‧‧另一方的基材
4‧‧‧陶瓷、半導體、玻璃任一者之基材
5‧‧‧另外一方的基材
6‧‧‧金屬
71‧‧‧含有V、Te之氧化物(存在於金屬與基材之間)
72‧‧‧含有V、Te之氧化物(分散於金屬中)
8‧‧‧空隙
9‧‧‧龜裂
10‧‧‧藉由前處理而形成於氮化物基板表面之氧化物層
12‧‧‧Sn的氧化物
13‧‧‧金屬箔
14‧‧‧含有V、Te之玻璃粒子
15‧‧‧含有V、Te之玻璃層
16‧‧‧附有鰭片的基底基板
17‧‧‧基底基板與絕緣基板之間的接合材層
18‧‧‧絕緣基板
19‧‧‧絕緣基板與金屬配線之間的接合材層
20‧‧‧金屬配線
21‧‧‧金屬配線與半導體晶片之間的接合材層
22‧‧‧半導體晶片
[圖1]玻璃組成物的代表性DTA曲線示意圖。
[圖2]接合構造體的模型圖。
[圖3]接合性的評估用試料示意圖。
[圖4]實施例1之接合構造體的接合強度試驗結果示意圖。
[圖5]實施例1之接合構造體截面圖。
[圖6]變形例1之接合構造體截面圖。
[圖7]實施例2之接合構造體截面圖。
[圖8]變形例2及變形例3之箔狀接合材截面圖。
[圖9]實施例3之半導體模組截面圖。
[圖10]實施形態之接合構造體截面圖。
以下利用圖面，說明實施形態、實施例及變形例。但，以下說明中，遇同一構成要素則標記同一符號並省略重覆說明。另，本發明並非限定於此處例舉之實施形態、實施例及變形例，在不變更要旨的範圍內可適當組合或改良。
<實施形態>
圖10為實施形態之接合構造體截面圖。接合構造體 係將複數個基材接合而成之物，該些複數個基材的至少一部分(第一基材)101係為陶瓷、半導體、玻璃的任一者。基材彼此係透過接合層而接合。接合層103是由金屬104與氧化物105所構成，氧化物105中含有V(釩)、Te(碲)。對於陶瓷、半導體、玻璃之基材，接合層103內的金屬104與基材101是透過上述組成之氧化物105而接合。此外，當基材101為氮化物的情形下，若使基材101表面氧化則有時能獲得高接合強度，在此情形下，基材101中還會包含表面氧化膜。該表面氧化膜，只要是在表面從0.1至5μm之範圍的主成分為氧化物即可。做其他任何表面處理時亦同，被改質的表面層亦包含於基材中。
此外，接合層103中，金屬104與氧化物105的交界面並不十分強固，若氧化物105凝聚則該部分會變得較脆，故在接合層103內，較佳是成為氧化物105分散於金屬104中之形態。
又，當欲接合的基材101的熱膨脹係數有很大不同的情形下，可能會因熱循環而發生剝離的問題。在此情形下，藉由使空隙分散於接合層103內，可減緩熱應力並提高對於熱循環的耐性。
接合層103之形成，是在含有V、Te的玻璃組成物、金屬粒子中適當加入溶媒而膏化，然後藉由將其塗布於基材並加熱而獲得。或是，亦可藉由將埋入有玻璃粒子的金屬箔挾持於基材間並加熱而獲得。又或是，亦可藉由將由金屬與玻璃所構成之層狀體挾持於基材間並加熱 而獲得。
用來形成接合層103之玻璃組成物，若除了V、Te之外還使其含有P(磷)，那麼玻璃轉化溫度會成為230~340℃左右、軟化流動溫度會成為350~450℃左右，能獲得高耐熱性之接合。此外，若除了V、Te之外還使其含有Ag(銀)，那麼玻璃轉化溫度會成為160~270℃左右、軟化流動溫度會成為210~350℃左右，可在低溫下接合。此外，如同銲料材般，能夠讓接合層肩負熱傳導與電氣傳導的任務。
接合前的氧化物為玻璃狀態(玻璃組成物)，但接合後的氧化物未必一定要保持玻璃狀態，也可以伴隨著玻璃的自我結晶化、與基材或接合層內的金屬之間反應而變化為其他物質。此時，若結晶化或變化後的物質之熔點高，則接合耐熱性會提升。另一方面，若結晶化或變化後的物質較脆，則也可能發生使接合強度降低的情形。此時，會使上述玻璃組成物中適當含有Fe(鐵)、Sb(銻)、W(鎢)、Ba(鋇)、K(鉀)，藉此玻璃構造會更加保持穩定，而能夠防止接合強度降低。
以V、Te、P為主成分的玻璃組成物中，Te與P為用來使其玻璃化之成分，藉由含有它們，即使以電磁波照射也能容易地使其軟化流動。P對於低熱膨脹化亦有效，但以氧化物換算，若P2O5(五氧化二磷)的含有量(質量%)比TeO2(二氧化碲)還多，則玻璃轉化點(Tg)容易變高，故將P2O5的含有量訂為TeO2的含有量 以下為佳。
以V、Te、Ag為主成分的玻璃組成物中，以氧化物換算，若V2O5(五氧化釩)+TeO2+Ag2O(氧化銀(I))≧85mass%，則特別可兼顧低軟化流動溫度及穩定的玻璃構造。
Te及P為用來使其玻璃化的成分，藉由含有它們，即使以電磁波照射仍能容易地使其軟化流動。P對於低熱膨脹化亦有效，但以氧化物換算，若P2O5的含有量(質量%)比TeO2還多，則轉化點(Tg)容易變高，故將P2O5的含有量訂為TeO2的含有量以下為佳。
欲接合之基材101所使用的陶瓷的例子，可列舉氧化鋁、氮化鋁、氮化矽等，半導體的例子則可列舉矽、碳化矽等。此外，即使欲接合之基材為金屬，仍能獲得良好的接合。一般來說，陶瓷、半導體其熱膨脹係數不同，故若與金屬接合則會變得不耐熱循環，但本接合構造中，藉由形成接合層之金屬或分散於金屬內的空隙，會減緩大幅熱膨脹係數差所造成之大幅熱應力，故可認為其能耐受熱循環。
用於形成接合層之金屬104，例如可使用Ag、Cu(銅)、Al、Sn(錫)、Zn(鋅)、Au(金)、In(銦)、Bi(鉍)、Pt(鉑)、或含有它們的合金。
另，上述玻璃組成物均考量環保而做成無鉛(不含鉛，lead-free)。本發明所稱的無鉛，係指容許RoHS指令(Restriction of Hazardous Substances：2006年 7月1日施行)中的禁止物質含有指定值以下的範圍。
[實施例1] <玻璃組成物>
說明接合材所使用之玻璃組成物的製作方法。秤量起始原料(starting material)使其達規定重量比。作為起始原料，使用高純度化學研究所公司製之氧化物粉末(純度99.9%)。一部分試料中，作為Ba來源及P來源，使用RASA工業公司製之Ba(PO3)2(偏磷酸鋇)。混合起始原料，放入白金坩堝。當原料中的Ag2O比率為40mass%以上的情形下，使用氧化鋁坩堝。混合時，考量避免讓原料粉末有不必要的吸濕，而使用金屬製湯匙在坩堝內混合。將放入原料混合粉末的坩堝設置於玻璃熔爐內，將其加熱、熔解。以10℃/min的昇溫速度昇溫，將在設定溫度(700~950℃)下熔解的玻璃一面攪拌一面保持1小時。其後，將坩堝從玻璃熔融爐取出，將玻璃灌模(熔融並流入)到預先加熱至150℃的石墨鑄模中。
接著，將灌模好的玻璃移動到預先加熱至應力消除溫度的應力消除爐中，保持1小時以除去應力後，以1℃/min的速度冷卻至室溫。將冷卻至室溫的玻璃大略粉碎，製作出玻璃組成物的玻璃料(frit)。玻璃組成物的玻璃料，平均體積粒徑為20μm以下，藉由DTA(Differential Thermal Analysis)測定其玻璃轉化溫度。 DTA係為藉由一定程式使試料及基準物質的溫度一面變化，一面測定該試料與基準物質之間的溫度差以作為溫度函數的方法。
表1揭示本實施例之玻璃組成物的特性。表中揭示了玻璃轉化點，其測定方法如下所述。將作成的玻璃予以粉碎直到體積平均粒徑成為20μm以下，然後以5℃/min的昇溫速度至550℃為止進行示差熱分析(DTA)，藉此測定玻璃轉化點(Tg)。使用氧化鋁粉末作為標準試料、Al作為試料容器。圖1揭示玻璃組成物的代表性DTA曲線。如圖中所示，玻璃轉移點(Tg)訂為第一吸熱峰值的開始溫度。除此之外，可求出屈服點(Mg)作為第一吸熱峰值溫度、軟化點(Ts)作為第二吸熱峰值溫度、發熱峰值的開始溫度(Tc)作為結晶化溫度。接合溫度與玻璃的粒徑、接合時的加壓條件及保持時間等各種因素有關，故無法一概規定，但至少必須比相當於黏度=107.65poise的軟化點Ts還加熱至更高之溫度。軟化點(Ts)係依玻璃組成而定，但為比玻璃轉移溫度(Tg)還高50~100℃左右的溫度。
各玻璃組成物之組成與玻璃轉化溫度如表1所示。如表中的No.1~10般，使玻璃組成物中含有V、Te、P，且做成滿足氧化物狀態下的關係式V2O5>TeO2>P2O5(mass%)，藉此能使玻璃轉化點成為250~340℃這樣低的值。另一方面，如表中的No.11~31般，使玻璃組成物中含有Ag、Te、V，且做成氧化物狀態下Ag2O、 V2O5、TeO2的合計為85mass%以上，則能使玻璃轉化溫度成為160~270℃這樣非常低的值。
<膏>
在製作接合構造體前，說明由上述方法製作出之玻璃組成物的玻璃料(粉末玻璃)與金屬粒子與溶媒所構成之膏的製作方法。首先，將玻璃組成物的玻璃料以噴射磨機(jet mill)粉碎至平均體積粒徑為2μm以下。接著，將玻璃組成物與金屬粒子以規定的調配比混合。混合係使用瑪瑙研缽。針對表1中No.1~10的玻璃組成物，將添加有4%樹脂黏結劑之溶劑予以混合，使其膏狀化。此處，樹脂黏結劑中使用了乙基纖維素、溶劑中使用了二乙二醇丁醚醋酸酯(butyl carbitol acetate)。二乙二醇丁醚醋酸酯不太會與No.1~10的玻璃組成物反應。但，若只有溶劑則黏度低且塗布性差，故添加了樹脂黏結劑。另，乙基纖維素可藉由加熱至300℃左右而使其揮發，不需使No.1~10的玻璃組成物軟化流動即可除去。也就是說，使用了No.1~10的玻璃組成物的膏，其使用方式是塗布於接合基材後，加熱至300℃左右將溶劑及樹脂黏結劑除去。
另一方面，針對表1中No.11~31的玻璃組成物，則僅將溶劑混合而使其膏狀化。此處，溶劑係使用α-萜品醇(α-terpineol)。α-萜品醇不太會與No.11~31的玻璃組成物反應，且具有較高的黏度，故即使不添加樹脂黏結劑也具有良好的塗布性。另，對於No.1~10的玻璃組成物，α-萜品醇會起反應，故無法用作為溶劑。α-萜品醇可藉由加熱至100~150℃左右而使其揮發，不需使 No.11~31的玻璃組成物軟化流動即可除去。
<接合構造體之形態>
接合構造體的模型圖如圖2所示。圖2揭示將基材1與另一基材3透過接合材層2接合而成之構造。基材1或基材3的其中一方係訂為陶瓷、半導體、玻璃的任一者。此外，接合之形態並不限於一種類，可為下述任一構造，即，如圖2(a)般將同一形狀基板的全面予以接合的構造、如圖2(b)般在內部留下空間的方式予以接合的構造、如圖2(c)般將大小相異的基板彼此接合的構造、如圖2(d)般將至少其中一方為非板狀之基材予以接合的構造。
<試料及評估方法>
以下，在接合性的簡易試驗中，使用如圖3所示之試料。圖3(a)為評估用試料的外觀立體圖、圖3(b)為評估用試料的截面圖。基材4為板狀，訂為陶瓷、半導體、玻璃的任一者。基材5為厚度2mm、直徑5mm的圓柱狀，材質不拘。
強度試驗，是從基材5的側面抵住工具，測定試料被破壞所需之最大力。此外，將基材5與基材4的接合面積除以20mm2而得之值，定義成剪力接合強度。
接合構造之評估，是製作出如圖3(b)所示般的截面試料，然後以掃描型電子顯微鏡觀察微細組織。 試料截面，是使用耐水研磨紙予以濕式研磨後，以氧化鋁粉末施以擦光研磨(buffing)，再藉由氬離子銑(argon ion milling)處理至平滑。
<接合構造體>
本實施例之接合構造體中，係使用陶瓷的一例即氧化鋁基材4a、及金屬基材的一例即無氧銅基材5a。接合材之材料中，玻璃組成物係使用表1的No.1、金屬粒子係使用粒徑1μm的Ag粒子。以下說明本實施例之接合構造體的製作方法。
將玻璃組成物相對於金屬粒子和玻璃組成物的總體積之比例，定義為玻璃添加量xG。將xG=0、5、10、20、30、50vol%之粉末混合體以各比率混合後，適量添加二乙二醇丁醚醋酸酯及4wt%的乙基纖維素之混合體將其膏狀化。將得到的膏塗布於氧化鋁基材4a上。在熱板(hot plate)上加熱至150℃使二乙二醇丁醚醋酸酯揮發並除去後，於大氣中加熱至350℃使乙基纖維素揮發並除去。將無氧銅基材5a疊合於塗布膜上，其後於氮氣中加熱至400℃。於加熱中，在無氧銅基材5a上放上重物，以1MPa加壓。此處，加壓力之定義，係定義為將重物的重量除以接合面積即20mm2而得之值。
針對由上述製作方法獲得之接合構造體，評估剪力接合強度。圖4為實施例1之接合構造體的接合強度試驗結果示意圖。圖4中揭示膏中的玻璃組成物的添加 量xG與剪力接合強度P之關係。xG=0vol%時P~0，在強度試驗前試料即已剝離。xG=5、10vol%時能獲得超過20MPa的高剪力接合強度。另，由於評估裝置的限制，P>20MPa之試料於破壞前便中止試驗。在這樣的情形下，圖中以向上箭頭表示。xG≧20vol%時隨著xG的增加而P有減少的傾向，xG=50vol%時試料再度於強度試驗前即剝離。另，未發生接合之xG=0、50vol%時，均是在接合材層2a與氧化鋁基材4a之間發生剝離。
圖5為實施例1之接合構造體截面圖。圖5中，揭示針對xG=5vol%、30vol%、50vol%時之試料，以電子顯微鏡觀察而得之截面組織。xG=5vol%時，如圖5(a)般，接合材層2a5是藉由金屬粒子彼此強固地結合而形成緻密的金屬燒結體6，金屬燒結體6與氧化鋁基材4a之間，多數部分是透過厚度100nm以下之薄的氧化物的層71而接合。此外，成為氧化物72或空隙8分散於金屬燒結體6中之構造。此外，金屬燒結體6與氧化鋁基材4a之間，多數部分是透過厚度100nm以下之薄的氧化物的層72而接合。藉由SEM-EDX進行氧化物71、72的元素分析，則檢測出V、Te、P、Fe，該部分可認為是來自玻璃組成物。所謂SEM-EDX，係指藉由附屬於電子顯微鏡(SEM)之能量分散式X射線分析裝置(EDX)，以SEM一面進行像觀察，一面對其視野進行元素分析之裝置，由對試料照射電子線而獲得之X射線，來特定出元素的種類。但，未必一定要保持玻璃(非晶質)構造，也不 必為單一組成。實際上，氧化物71、72在不同場所其對比度不同，一部分可觀察到被認為是結晶之方型組織。xG=30vol%時，如圖5(b)所示，分散於接合材層2a30的金屬燒結體6的內部之氧化物72的尺寸變大，此外，在金屬燒結體6與氧化物72的交界面附近開始觀察到龜裂9。又，玻璃較多之xG=50vol%時，如圖5(c)所示，接合材層2a50會成為金屬粒子61分散於氧化物72的基質(matrix)的內部之形態。
能夠獲得高強度的xG之範圍，會因所使用之玻璃組成物的成分、金屬粒子的材質或粒徑、接合時的溫度條件或加壓力等許多參數而受到影響，故無法統一規定，但該些結果教示我們，當獲得高接合強度時，接合構造具有下述特徵。(1)金屬粒子彼此充分結合而成為金屬燒結體。(2)金屬燒結體係與氧化鋁基板藉由極薄的氧化物之層而接合，氧化物含有玻璃組成物的成分。(3)接合材層中的氧化物或空隙，是以分散於金屬燒結體內的狀態而存在。
接合材層中的氧化物或空隙，有時存在較好，有時則不存在較好。
<變形例1>
本變形例之接合構造體中，係使用陶瓷的一例即氮化鋁基材4b、及無氧銅基材5a。但，接合材的材料及接合構造體之製作方法與實施例1相同。此處，進行與實施例 1完全相同之探討，但玻璃組成物的添加量係參酌實施例之結果，而僅實施了xG=10vol%。
圖6為變形例1之接合構造體截面圖。強度試驗之結果，剪力接合強度成為13MPa，雖獲得較強的接合，但相較於實施例1則接合強度低。剝離發生於氮化鋁基材4b與接合材層2b10之間。鑑此，藉由大氣中1100℃ 1hr之熱處理，在氮化鋁基材4b的表面形成厚度約1μm的氧化鋁層10，而與無氧銅基材5a。其結果，剪力接合強度超過20MPa，獲得與實施例1同等的強度。此時的接合構造體的截面如圖6模型所示。
是故，在氮化物基材的情形下接合強度雖會降低，但藉由將表面做成氧化物，便能獲得與氧化物基材同等的接合強度。當藉由如同本次熱處理般的前處理，而事先在基材的表面形成有其他物質之層的情形下，則將其他物質之層亦包含在內而稱為基材。
[實施例2]
本實施例之接合構造體中，係使用鈉玻璃(soda glass)基材4c及無氧銅基材5a。玻璃組成物係使用表1的No.27、金屬粒子係使用粒徑50μm的Sn-3.5mass% Ag粒子。圖7為實施例2之接合構造體截面圖。以下說明本實施例之接合構造體的製作方法。
此處，參酌實施例1之結果，對金屬粒子添加玻璃組成物10vol%後，加入α-萜品醇將其膏狀化。將 獲得的膏，塗布於厚度1mm、邊長10mm之玻璃基板上。在熱板上加熱至150℃使二乙二醇丁醚醋酸酯揮發後，將無氧銅基材5a置放於塗布膜上，其後於大氣中加熱至300℃，藉此使其接合。實施例1中，玻璃的軟化點高，必須將接合溫度訂為400℃，故為了抑制銅的氧化而在氮氣中加熱，但本次因玻璃的軟化點低，故將接合溫度訂為300℃而在大氣中接合。此外，於加熱中放置重物，藉此進行0.1MPa的加壓。其結果，如圖7所示，得到鈉玻璃基材4c與無氧銅基材透過接合材層2c10接合而成之接合構造體。
藉由上述製作方法獲得之接合構造體的剪力接合強度為12MPa，能獲得較強固的接合。此外，接合構造體的截面組織成為圖7所示。形成了金屬粒子彼此強固地結合而成之金屬塊體6c，而成為氧化物72分散於其中之構造。相較於實施例1，空隙量較少，這是因為本次使用之Sn-3.5mass% Ag的熔點為220℃偏低，而在液相下接合之故。此外，接合材層2的內部可發現許多Sn的氧化物12，這被認為是原料的金屬粒子的表面氧化膜殘留之故。
<變形例2>
實施例2中，導致強度降低的Sn氧化物，係來自Sn-3.5mass% Ag粒子的表面氧化物，故認為只要以箔的形狀來供給接合材，則接合強度會進一步提升。鑑此，製 作出100μm的Sn-3.5mass% Ag箔後，將No.27的玻璃粉末置放於箔上並壓延來製作出接合材2d。圖8(a)為變形例2之箔狀接合材截面圖。壓延後(接合材2d)的截面組織，如圖8(a)所示，成為玻璃粒子14分散於Sn-3.5mass% Ag內部之構造。另，玻璃粒子14多數存在於金屬箔13的表面附近。
將如此製作出的Sn-3.5mass% Ag箔(接合材2d)挾持於鈉玻璃基材4c與無氧銅基材5a之間，於大氣中加熱至300℃使其接合。另，於加熱中放置重物，藉此進行0.1MPa的加壓。其結果，Sn氧化物的量大幅減低，而獲得20MPa以上的剪力接合強度。像這樣，以箔的形態來提供接合材，相較於以膏的形態來提供之情形，不僅能夠排除金屬粒子的表面氧化膜的影響，還能免除使溶媒揮發並除去之工程，從製程簡化的觀點看來亦可謂有效。
<變形例3>
變形例2之箔形狀的接合材，未必一定要在金屬中使玻璃分散成為粒子。圖8(b)為變形例3之箔狀接合材截面圖。舉例來說，如圖8(b)般，亦可為在金屬箔13的表面形成薄的玻璃層15之形態。若做成這樣的形態，例如便可僅在玻璃比金屬更容易接合之基材側供給玻璃。
這樣的形態，是藉由在板狀的金屬上置放板狀的玻璃，然後於比玻璃軟化點還稍微低溫下壓延，藉此便能製作。玻璃的黏度會隨著溫度而連續性地逐漸變化， 故調整成形狀可維持且會發生變形之溫度，藉此便可壓延加工。
<變形例4>
除此之外，本發明團隊除氧化鋁、氮化鋁等陶瓷，鈉玻璃等玻璃以外，還針對氮化矽、矽、碳化矽等半導體評估接合性，確認了良好的接合性。此外，另一方的基材不僅是無氧銅，針對鋁、及金屬和陶瓷之複合材料(Al-SiC)亦確認了良好的接合性。
又，接合材所使用之金屬，不僅是Ag、Sn-3.5% Ag，可運用Ag、Cu、Al、Sn、Zn、Au、In、Bi、Pt等。特別是，貴金屬有在大氣中接合也不易被氧化之優點，低熔點金屬則有減小接合時的加壓也能獲得良好接合之優點。
[實施例3]
上述實施例1、變形例1、實施例2、變形例2、變形例3、變形例4所記載之接合材、接合構造體，例如能夠運用於半導體模組中的各種接合處。圖9為實施例3之半導體模組截面圖。本實施例之半導體模組中，係運用在附有鰭片的金屬或Al-SiC之基底基板16與陶瓷的絕緣基板18之間的接合材17、陶瓷的絕緣基板18與金屬配線20之間的接合材19、以及金屬配線20與矽晶片22之間的接合材21等。此外，亦可運用於LED照明的晶 片與基板之接合。
以上，已依據實施形態、實施例及變形例具體地說明了本發明者所研發之發明，但本發明當然並非限定於上述實施形態、實施例及變形例，而可進行各種變更。
101‧‧‧基材
102‧‧‧第二基材
103‧‧‧接合層
104‧‧‧金屬
105‧‧‧氧化物

Claims (14)

  1. 一種接合構造體，其特徵為，具備：第一基材；第二基材；及接合材層，將前述第一基材與前述第二基材予以接合；前述第一基材係為陶瓷或半導體或玻璃任一者之基材，前述接合材層由金屬與氧化物所構成，前述氧化物含有V與Te與Ag，在前述第一基材與前述金屬之間的至少一部分，存在有前述氧化物。
  2. 如申請專利範圍第1項之接合構造體，其中，前述氧化物分散於前述金屬中。
  3. 如申請專利範圍第2項之接合構造體，其中，空隙分散於前述金屬中。
  4. 如申請專利範圍第1項之接合構造體，其中，前述氧化物含有P。
  5. 如申請專利範圍第1項之接合構造體，其中，前述氧化物含有Sb、Ba、W、Fe、鹼金屬中的至少一種類之元素。
  6. 如申請專利範圍第1項之接合構造體，其中，前述第一基材為氧化鋁、氮化鋁、氮化矽、矽、碳化矽的任一者， 前述第二基材為金屬基材或金屬和陶瓷之複合材料基材。
  7. 如申請專利範圍第6項之接合構造體，其中，前述第二基材為Cu或Al或Al-SiC的任一者。
  8. 如申請專利範圍第1項之接合構造體，其中，前述第一基材為氮化鋁、氮化矽，且於表面從0.1至5μm之範圍的主成分係為氧化物。
  9. 如申請專利範圍第1項之接合構造體，其中，前述金屬含有Ag、Cu、Al、Sn、Zn、Au、In、Bi、Pt的至少一種類。
  10. 一種接合材，係藉由加熱而將基材彼此接合之接合材，其特徵為，具有：成分中含有V、Te、Ag，且具有Pb在RoHS指令的指定值以下之玻璃、以及金屬粒子。
  11. 如申請專利範圍第10項之接合材，其中，更具有溶劑，且為膏狀，前述金屬係為金屬粒子。
  12. 如申請專利範圍第10項之接合材，其中，在前述金屬中埋入有玻璃的粒子，前述接合材的形狀為箔或板狀。
  13. 如申請專利範圍第10項之接合材，其中，具有複數個層，前述複數個層的一個為金屬層，前述複數個層的一個為玻璃之層。
  14. 如申請專利範圍第11項至第13項任一項之接合材，其中，前述玻璃含有V2O5、TeO2、Ag2O，以氧化物 換算，V2O5+TeO2+Ag2O≧85mass%。
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JPWO2013024829A1 (ja) 2011-08-12 2015-03-05 日立化成株式会社 はんだ接着体、はんだ接着体の製造方法、素子、太陽電池、素子の製造方法および太陽電池の製造方法
JP5732414B2 (ja) 2012-01-26 2015-06-10 株式会社日立製作所 接合体および半導体モジュール

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