TWI698328B - 陶瓷層與銅粉糊燒結體之積層體 - Google Patents
陶瓷層與銅粉糊燒結體之積層體 Download PDFInfo
- Publication number
- TWI698328B TWI698328B TW108120983A TW108120983A TWI698328B TW I698328 B TWI698328 B TW I698328B TW 108120983 A TW108120983 A TW 108120983A TW 108120983 A TW108120983 A TW 108120983A TW I698328 B TWI698328 B TW I698328B
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- Taiwan
- Prior art keywords
- copper powder
- powder paste
- sintered body
- ceramic
- copper
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000000919 ceramic Substances 0.000 title claims abstract description 77
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000001887 electron backscatter diffraction Methods 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 32
- 239000011521 glass Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- B22F7/04—Manufacture 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 layers with one or more layers not made from powder, e.g. made from solid metal
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- B22F7/02—Manufacture 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 layers
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Abstract
本發明提供一種積層體,其是藉由銅粉糊之燒結所製造之燒結體與陶瓷基材之積層體,且燒成體與陶瓷基材之密接性優異。
本發明之積層體在陶瓷層積層有銅粉糊燒結體,且在銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法(Area Fraction Method)獲得之銅的結晶粒徑為10 μm以下,且分析區域之平均可靠性指數(CI值)為0.5以上。
Description
本發明係關於一種陶瓷層與銅粉糊燒結體之積層體。
隨著電子設備之使用頻段轉向高頻側,對絕緣基板採用陶瓷之積層零件之需求高漲。就電容器而言為MLCC,就基板而言為LTCC。關於電極材料,前者正使用、或者正研究使用內部電極用之鎳粉、外部電極用之銅粉,後者正使用、或者正研究使用銀粉、或銅粉。銅粉由於較銀粉廉價,並且從電阻之觀點而言亦較鎳有利,故作為電極材料之銅粉正受到關注。
作為電極材料之金屬粉與溶劑、黏合劑樹脂等進行混合而被加工成糊,並將其印刷於陶瓷基板、或由陶瓷粒子構成之坯片(green sheet)上。藉由將該積層體例如於600℃以上之非氧化性環境、或還原環境下進行燒成,從而金屬粉彼此燒結而獲得電極。相對於基材之陶瓷,金屬之熱膨脹係數大,在燒成過程中膨脹、收縮產生差異,從而存在燒成電極與陶瓷基材剝離之情況。為了避免此種情況,將構成陶瓷層之陶瓷粒子、或稱為玻璃料(glass frit)之粒子添加於金屬粉糊中,以確保燒成電極與陶瓷基材之密接力。
MLCC存在零件大小之限制,但若可爭取增加積層數,即可增大每個零件之靜電電容,因此,為了將其實現,需要將電極糊薄塗。又,若是LTCC,則只要可使電路寬度變窄即可提高基板之安裝密度,因此有利的是能夠以窄間距不斷線地進行印刷。為了應對此種要求,嘗試有對金屬粉糊及金屬粉糊所使用之金屬粉進行改良(專利文獻1、專利文獻2)。
[先前技術文獻]
[專利文獻]
專利文獻1:國際公開第2013/125659號
專利文獻2:國際公開第2013/118893號
[發明所欲解決之課題]
如上所述,燒成電極(燒成體)是藉由銅粉等金屬粉之糊燒結而製造。另一方面,車載用途等在廣泛溫度範圍內使用該燒成體與陶瓷基材之複合體之情況正在增加。因此,要求燒成體與陶瓷基材之密接性強,從而即便是在該廣泛溫度範圍內,燒成體與陶瓷基材亦不會剝離。
因此,本發明之目的在於提供一種積層體,其是藉由銅粉糊之燒結所製造之燒結體與陶瓷基材之積層體,且燒成體與陶瓷基材之密接性優異。
[解決課題之技術手段]
本發明者進行了努力研究,結果發現,藉由下述之複合體可達成上述目的,從而完成本發明。
因此,本發明包括以下(1)。
(1)
一種積層體,其在非金屬層積層有銅粉糊燒結體,且
在銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法(Area Fraction Method)獲得之銅的結晶粒徑為10 μm以下,且分析區域之平均可靠性指數(CI值)為0.5以上。
[發明之效果]
根據本發明,可獲得一種積層體,其是藉由銅粉糊之燒結所製造之燒結體與陶瓷基材之積層體,且燒成體與陶瓷基材之密接性優異。
以下,列舉實施方式詳細地說明本發明。本發明並不限定於以下所列舉之具體實施方式。
[在非金屬層積層有銅粉糊燒結體之積層體]
本發明之積層體在非金屬層積層有銅粉糊燒結體,且在銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法獲得之銅的結晶粒徑成為10 μm以下,且分析區域之平均可靠性指數(CI值)成為0.5以上。
在較佳之實施方式中,在非金屬層積層有銅粉糊燒結體之積層體包括:包含此種積層體構造之積層體。例如,包括在非金屬層上積層有銅粉糊燒結體層並且進而在該銅粉糊燒結體層上積層有非金屬層之積層體,且包括反覆將其等積層所形成之積層體。層上是用來說明積層之朝向之表述,並不限定於在鉛直方向朝上。
在較佳之實施方式中,可將非金屬層設為陶瓷層。本說明書中,存在具體列舉陶瓷層作為較佳之非金屬層進行說明之情況。
[銅粉糊燒結體]
本發明之積層體可藉由在非金屬層,例如陶瓷層積層銅粉糊燒結體來製造。銅粉糊燒結體是藉由將塗布之銅粉糊進行燒結來製備。
在較佳之實施方式中,用來製備銅粉糊燒結體之燒結可藉由公知之手段來進行,例如可藉由在非氧化性環境、弱還原性環境、水蒸氣環境下,在500〜1000℃維持0.1〜10小時來進行燒結。
在燒結之前,將銅粉糊塗布在非金屬層,例如陶瓷層之表面。在較佳之實施方式中,塗布可藉由公知之手段來進行,例如可藉由網版印刷、點膠(dispense)工法來進行。
[銅粉糊]
銅粉糊可使用經表面處理之銅粉並利用公知之手段來製備。在較佳之實施方式中,例如可將經表面處理之銅粉與溶劑、黏合劑樹脂、及公知之添加劑進行混練來製備。在較佳之實施方式中,作為溶劑,可使用公知之溶劑,作為此種溶劑,例如可列舉:醇溶劑(例如選自由萜品醇、二氫萜品醇、異丙醇、丁基卡必醇、萜品氧基乙醇、二氫萜品氧基乙醇所組成之群中之1種以上)、二醇醚溶劑(例如丁基卡必醇)、乙酸酯溶劑(例如選自由丁基卡必醇乙酸酯、二氫萜品醇乙酸酯、二氫卡必醇乙酸酯、卡必醇乙酸酯、乙酸沈香酯、乙酸萜品酯所組成之群中之1種以上)、酮溶劑(例如甲基乙基酮)、烴溶劑(例如選自由甲苯、環己烷所組成之群中之1種以上)、賽珞蘇類(例如選自由乙基賽珞蘇、丁基賽珞蘇所組成之群中之1種以上)、鄰苯二甲酸二乙酯、或丙酸酯系溶劑(例如選自由丙酸二氫萜品酯、丙酸二烴基酯(dihydrocarbyl propionate)、丙酸異冰片酯所組成之群中之1種以上)。在較佳之實施方式中,作為黏合劑樹脂,可使用公知之黏合劑樹脂,作為此種黏合劑樹脂,例如可列舉:纖維素系樹脂、丙烯酸樹脂、醇酸樹脂、聚乙烯醇系樹脂、聚乙烯醇縮醛、酮樹脂、脲樹脂、三聚氰胺樹脂、聚酯、聚醯胺、聚胺酯(polyurethane)。
在較佳之實施方式中,作為銅粉糊,可使用未添加玻璃料之糊。
[經表面處理之銅粉]
經表面處理之銅粉用於製備銅粉糊。在較佳之實施方式中,作為供表面處理之銅粉,例如可使用次微米銅粉,例如可使用利用濕式法所製備之銅粉,例如可使用利用歧化法及化學還原法所製備之銅粉。在較佳之實施方式中,對銅粉之表面處理可藉由與銅粉表面處理劑溶液混合來進行,例如可將專利文獻1(國際公開第2013/125659號)及專利文獻2(國際公開第2013/118893號)中所公開之銅粉表面處理劑按上述文獻中所公開之步驟使用來進行表面處理。
在較佳之實施方式中,經表面處理之銅粉可使用比表面積例如為1 m2
g-1
以上、較佳為2 m2
g-1
以上之銅粉。
[非金屬層]
在較佳之實施方式中,作為非金屬層,可使用包含陶瓷、Si晶圓、及膜(例如樹脂膜)之至少1種之層。在較佳之實施方式中,作為非金屬層,可使用陶瓷層。
[陶瓷層]
在較佳之實施方式中,作為陶瓷層,可使用陶瓷基材。作為陶瓷基材之陶瓷,可使用公知之陶瓷,作為此種陶瓷,可列舉以氧化鋁、鈦酸鋇為主成分之陶瓷、CuNiZn之鐵氧體粒子之燒結體陶瓷、包含氮化鋁、氮化矽、CaZrO3
、CaTiO3
、HfO2
、BaTi2
O5
、(K,Na)NbO3
中之任一種或多種之陶瓷。該等陶瓷分別可利用公知之手段由公知之材料進行製備。
在較佳之實施方式中,作為陶瓷,可使用除O(氧)以外之元素中原子濃度最高之元素為Si並且次高之元素為Al之陶瓷。
[利用面積分數法獲得之銅之結晶粒徑、CI值]
在較佳之實施方式中,在積層體之銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法獲得之銅的結晶粒徑例如可設為10 μm以下、較佳為5 μm以下、更佳為3 μm以下,且例如可設為0.5 μm以上、較佳為1 μm以上。利用面積分數法獲得之銅之結晶粒徑具體而言可藉由實施例中下述之手段來求出。
利用面積分數法測定銅之結晶粒徑,並且求出表示在分析區域能夠以何種程度鑑定出結晶方位之平均可靠性指數(CI值)。平均可靠性指數(CI值)具體而言可藉由實施例中下述之手段來求出。在較佳之實施方式中,分析區域之平均可靠性指數(CI值)例如可設為0.5以上、較佳為0.55以上,例如0.55~1.0之範圍。
本發明者發現:若以銅粉糊燒結體成為此種狀態為指標,則該積層體所積層之層會表現出優異之密接性,膠帶剝離試驗之結果變得良好,並且兼具良好之比電阻,從而完成本發明。該機制並不明確,但本發明者推測:當成為此種再結晶晶粒為10 μm以下且CI值為0.5以上之狀態時,燒成體之強度高(霍爾-貝曲定律)且晶粒均勻,因此應變變得不容易局部地累積,由此實現優異之密接性。並且,本發明者認為:為了成為如此般之再結晶晶粒為10 μm以下且CI值為0.5以上之狀態,有效的是使銅粉糊中之經表面處理之銅粉在糊中充分地分散。更具體而言,本發明者認為:若糊中之銅粉之分散性差,即糊中存在凝集體,則在燒成銅之EBSD之測定面會產生凹凸,結晶方位之鑑定率(CI值)會降低。
[銅粉糊燒結體之中之陶瓷粒子]
在較佳之實施方式中,在銅粉糊燒結體中,在銅之晶界或晶粒內存在陶瓷粒子。存在之陶瓷粒子之粒徑例如可設為最大100 nm以下、較佳為最大50 nm。在較佳之實施方式中,在銅粉糊燒結體中,在銅之晶界或晶粒內可存在平均粒徑位於0.1 nm~100 nm之範圍、較佳為1 nm~50 nm之範圍之陶瓷粒子。
[比電阻]
在較佳之實施方式中,在非金屬層積層有銅粉糊燒結體之積層體之銅粉糊燒結體表現出優異之比電阻。在較佳之實施方式中,例如可設為1.7~10[μΩ·cm]之範圍、或1.8~3.4[μΩ·cm]之範圍。比電阻可利用公知之手段進行測定。
[剝離試驗]
在較佳之實施方式中,在非金屬層積層有銅粉糊燒結體之積層體在膠帶剝離試驗中呈現出優異之特性,即表現出優異之密接性。膠帶剝離試驗可按照下述之實施例之步驟進行。
[較佳之實施方式]
在較佳之實施方式中,本發明亦在於下述(1)及以下。
(1)
一種積層體,其在非金屬層積層有銅粉糊燒結體,且
在銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法獲得之銅的結晶粒徑為10 μm以下,且分析區域之平均可靠性指數(CI值)為0.5以上。
(2)
根據(1)所述之積層體,其中,在銅粉糊燒結體中,在晶界或晶粒內存在陶瓷粒子。
(3)
根據(2)所述之積層體,其中,陶瓷粒子之最大粒徑為100 nm以下。
(4)
根據(1)至(3)中任一項所述之積層體,其中,非金屬層是包含陶瓷、Si晶圓、及膜(例如樹脂膜)之至少1種之層。
(5)
根據(4)所述之積層體,其中,非金屬層為陶瓷層。
(6)
根據(1)至(5)中任一項所述之積層體,其中,根據EBSD圖像所求出之利用面積分數法獲得之銅的結晶粒徑為1 μm以上且10 μm以下。
(7)
根據(1)至(6)中任一項所述之積層體,其中,銅粉糊燒結體是不含玻璃料之銅粉糊的燒結體。
(8)
根據(1)至(7)中任一項所述之積層體,其中,銅粉糊燒結體係比表面積為1 m2
g-1
以上之銅粉之糊的燒結體。
(9)
根據(1)至(8)中任一項所述之積層體,其中,非金屬層為氧化鋁層、以鈦酸鋇為主成分之層、CuNiZn之鐵氧體粒子之燒結體層、氮化鋁層或氮化矽層。
(10)
根據(1)至(9)中任一項所述之積層體,其中,非金屬層為陶瓷層,且陶瓷層之陶瓷除O以外之元素中原子濃度最高之元素為Si,次高之元素為Al。
(11)
一種銅-陶瓷複合體,其包含(1)至(10)中任一項所述之積層體。
(12)
一種電子零件,其具有(1)至(10)中任一項所述之積層體。
因此,本發明包括上述積層體,包括包含上述積層體之銅-陶瓷複合體,包括具有其等之電子零件,包括搭載有該等電子零件之電子設備。
本發明之積層體如上所述,非金屬層與銅粉糊燒結體層之密接力優異。該銅粉糊燒結體之燒成銅之金屬組織如在實施例中下述,例如即便在500℃以上之高溫燒成,結晶粒徑亦會小於10 μm,具有該金屬組織之燒成銅之比電阻亦低,期待可應用於配線材料、電極材料。
在較佳之實施方式中,本發明之積層體可以作為電子零件之一部分來製作,例如可以作為MLCC等電容器、LTCC等基板之一部分來設置。在較佳之實施方式中,本發明之積層體包括以下形態:在陶瓷多層基板中,為了進行層間連接而在基板上開孔,向其中填充銅粉糊並進行燒成,由此進行製作。在較佳之實施方式中,本發明之積層體包括將銅粉糊燒結體用作電極之形態,例如可採用電極之厚度為0.1〜1000 μm、較佳為0.3〜100 μm、進而較佳為0.5〜50 μm之形態。在較佳之實施方式中,本發明之積層體包括將銅粉糊燒結體用作電路之配線之形態,例如可採用配線間距(電路寬度)為1〜5000 μm、較佳為5〜3000 μm之形態。
[實施例]
以下列舉實施例進而詳細地說明本發明。本發明並不限定於以下實施例。
(例1:次微米銅粉之製備)
向包含氧化亞銅1 kg、阿拉伯膠4 g、純水7 L之漿料中瞬間地添加25 vol%之稀硫酸2.5 L,並以500 rpm攪拌10分鐘。在由該操作所獲得之銅粉充分地沉澱之後去除上清液,添加純水7 L並以500 rpm攪拌10分鐘。反覆進行該操作直到上清液體中之來自Cu2+
之Cu濃度低於1 g/L。
(例2:實施例1〜3)
(銅粉之表面處理)
分別採取5、40、60 mL二胺基矽烷(A-1120(MOMENTIVE公司製造)),以合計成為500 mL之方式與純水混合,以200 rpm左右攪拌一晚。將例1中所製作之沉澱漿料之上清液去除,並將沉澱銅粉及二胺基矽烷水溶液以500 rpm攪拌1小時。攪拌後,利用台式離心分離裝置以1500 rpm、30分鐘之條件進行固液分離,並回收固形物(含水率10〜13%)。將其在氮氣環境下以100℃乾燥2小時,其後利用杵、研缽壓碎直到全量通過1 mm篩,並以0.4 MPa之粉碎壓利用台式噴射磨機進行壓碎。利用Macsorb HM model-1201對壓碎所獲得之粉之利用流動法所得之BET比表面積進行測定(流動法單點法,脫氣條件:150℃、20分鐘、大氣壓、氮氣環境)。結果為3.1〜3.2 m2
g-1
。
(糊之製備)
預先使萜品醇與乙基纖維素通入自轉公轉混合機、及三輥研磨機進行充分地混練,以所得之媒液與油酸、及銅粉之比率成為銅粉:乙基纖維素:油酸:萜品醇=80:2.3:1.6:16.1(重量比)之方式進行混合,並利用自轉公轉混合機進行預混練,其後,通入三輥研磨機(最終加工輥間隙5 μm),並使用自轉公轉混合機進行消泡。使用25 μm間隙之敷料器(applicator)將所獲得之糊於載玻片上塗膜,並以120℃乾燥10分鐘。利用觸針式粗糙度計對所獲得之塗膜之塗布方向之Rz進行測量,確認5點平均分別為2 μm以下。即,確認糊中所包含之凝集物之大小為2 μm以下。
(燒成體-陶瓷積層體之製作)
在表面粗糙度Ra為0.04 μm之氧化鋁基板(純度99.5%)上使用網版(不銹鋼絲網,線徑18 μm,紗厚38 μm,開口33 μm,開口率42%)印刷3條寬度5 mm、長度20 mm之線。於25℃在純水中通入氮氣,以2 L/分鐘供給該包含水蒸氣之氮氣並同時以0.75℃/分鐘之速度進行升溫直到850℃,並在850℃將其保持20分鐘。如此,在陶瓷基板上形成糊之燒成體,從而獲得燒成體-陶瓷積層體。
(電阻測定、剝離試驗)
對冷卻至室溫所獲得之寬度5 mm、長度20 mm之電路之表面電阻、及厚度進行測量,以3點平均求出比電阻。又,對電路與基板使用雙面碳膠帶(日新EM公司製造)並根據JIS Z 0237進行剝離試驗,確認在膠帶之接著面是否附著有電路。
(EBSD圖、面積分數法、CI值)
進而利用Ar離子(加速電壓15 kV)對所獲得之氧化鋁基板上之燒成電路表面進行3分鐘平面研磨,其後拍攝EBSD圖,並利用面積分數法求出結晶粒徑。一併求出表示在分析區域中能夠以何種程度鑑定出結晶方位之可靠性指數(表中,表示為平均CI值)。
裝置:SEM(SU-70(Hitachi High-Technologies公司製造))
分析對象:30 μm×30 μm
資料取得間隔:0.2 μm
分析軟體:TSL OIM Data Collection ver.5.31
(雙晶不作為晶粒計數)
(STEM觀察、EDS分析)
從燒成體面起對實施例3之積層體進行FIB加工,將燒成體與基板之積層體作為薄膜取出,並利用STEM觀察金屬組織。根據FIB加工之操作性,實際上可觀察到的是位於距界面1 μm以內之範圍之金屬組織,但確認到:FIB加工時,在燒成體之厚度方向,金屬組織均勻。利用EDS對燒成體之金屬組織之晶界上之異物進行成分分析,結果確認為大小20 nm左右之SiO2
。
裝置:STEM
剖面TEM圖像倍率:10〜50萬倍 *觀察倍率適當調整
特性X射線:照射電子之射束徑:1 nm
掃描距離:60 nm
圖1中表示實施例1之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
圖2中表示實施例3之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
圖3中表示實施例3之晶界附近之STEM觀察及EDS分析之結果。
(例3:實施例4)
將糊之組成設為銅粉:乙基纖維素:萜品醇=80:2.3:17.7(重量比),除此之外,進行與例2之實施例3相同之操作。
(例4:實施例5)
在表面處理步驟中,採用二胺基矽烷(A-1120(MOMENTIVE公司製造))20 mL、環氧矽烷(Z-6040(Dow Corning Toray公司製造))10 mL、純水470 mL,除此之外,進行與例2相同之操作。
(例5:實施例6)
在表面處理步驟中,將環氧矽烷變更為四乙氧基矽烷(東京化成工業製造),除此之外,進行與例4相同之操作。
(例6:實施例7)
在表面處理步驟中,將二胺基矽烷變更為鈦酸酯偶合劑(PLENACT 44(Ajinomoto Fine-Techno公司製造)),除此之外,進行與例2之實施例3相同之操作。
(例7:實施例8)
在表面處理步驟中,採用二胺基矽烷(A-1120(MOMENTIVE公司製造))30 mL、鈦酸酯偶合劑(PLENACT 44(Ajinomoto Fine-Techno公司製造))20 mL、純水450 mL,除此之外,進行與例4相同之操作。
(例8:實施例9)
在表面處理步驟中,採用鈦酸酯偶合劑(PLENACT 44(Ajinomoto Fine-Techno公司製造))30 mL、有機鋯化合物(ORGATIX ZC-300(Matsumoto Fine Chemical公司製造))40 mL、純水430 mL,除此之外,進行與例4相同之操作。
(例9:實施例10)
在表面處理步驟中,採用二胺基矽烷(A-1120(MOMENTIVE公司製造))30 mL、有機鋯化合物(ORGATIX ZC-300(Matsumoto Fine Chemical公司製造))40 mL、純水430 mL,除此之外,進行與例4相同之操作。
(例10:實施例11〜13)
使用實施例1〜3之糊並將燒成環境設為N2
,除此之外,進行與例2相同之操作。
(例11:實施例14)
使用實施例2之糊並將燒成環境設為包含2%H2
之N2
,除此之外,進行與例2相同之操作。
(例12:實施例15〜17)
(陶瓷基材之製作)
以BaTiO3
粒子(NISSHIN ENGINEERING製造,粒徑50 nm)與萜品醇及乙基纖維素之比率成為BaTiO3
粒子:乙基纖維素:萜品醇=50:10:40(重量比)之方式進行混合,並利用自轉公轉混合機進行預混練,其後,通入三輥研磨機(最終加工輥間隙5 μm),並使用自轉公轉混合機進行消泡。使用25 μm間隙之敷料器將所獲得之糊於PET膜上塗膜,並以120℃乾燥10分鐘。從乾燥塗膜剝下PET膜,在大氣環境下以1200℃將乾燥塗膜進行燒成。
(燒成體-陶瓷積層體之製作)
使用實施例3之糊在所獲得之基板上進行印刷,並將燒成環境設為N2
、水蒸氣、或包含2%H2
之N2
,除此之外,進行與例2相同之操作。
(例13:實施例18)
在例12中所製作之BaTiO3
片材(經1200℃燒成)上印刷實施例7之糊,並進行與例12(實施例17)相同之操作。當利用STEM對界面進行分析時,來自BaTiO3
之Ti、及來自鈦酸酯偶合劑之Ti是以Ba及Ti共存之區域為基材,算出來自鈦酸酯偶合劑之Ti之厚度。
(例14:實施例19〜21)
使用實施例3之糊印刷於作為基材之氮化矽基板(TOSHIBA MATERIALS製造)上,將燒成環境設為N2
、水蒸氣、或包含2%H2
之N2
,除此之外,進行與例2相同之操作。
(例15:實施例22)
(陶瓷基材之製備、燒成體-陶瓷積層體之製作、評價)
使用氧化鋯珠將氧化鋁粒子及二氧化矽粒子以重量比1:1進行壓碎,並以乙基纖維素與萜品醇之比率成為(氧化鋁+氧化鋯):乙基纖維素:萜品醇=50:10:40(重量比)之方式進行混合,並利用自轉公轉混合機進行預混練,其後,通入三輥研磨機(最終加工輥間隙5 μm),並使用自轉公轉混合機進行消泡。使用25 μm間隙之敷料器將所獲得之糊於PET膜上塗膜,以120℃乾燥10分鐘。乾燥塗膜之Ra為0.25 μm。從該乾燥塗膜將PET膜剝下,並印刷實施例3之糊。
以2 L/分鐘持續供給25℃通入過純水之氮氣,並同時以0.75℃/分鐘進行升溫直到700℃,在700℃保持20分鐘。
進行與例2相同之操作,對所獲得之積層體進行評價。
(例16:實施例23)
在例15中所製作之氧化鋁/二氧化矽之坯片上印刷實施例3之糊,以2 L/分鐘從壓縮機持續供給大氣並同時以0.75℃/分鐘進行升溫直到500℃,在500℃保持20分鐘。其後,以2 L/分鐘持續供給包含2%H2
之N2
並同時以0.75℃/分鐘進行升溫直到850℃,在850℃保持20分鐘。界面分析中,若從坯片側所產生之二氧化矽粒子上朝燒成銅進行操作,則會無法區分是來自構成坯片之粒子或是銅粉表面處理成分,因此從氧化鋁粒子上朝燒成銅進行掃描。除此之外,進行與例2相同之操作。
(例17:實施例24)
(陶瓷基材之製備、燒成體-陶瓷積層體之製作、評價)
以Fe2
O3
:NiO:CuO:ZnO=49.5:10.0:10.0:30.5(莫耳比)之NiCuZn之鐵氧體粒子(平均粒徑0.1 μm)與乙基纖維素及萜品醇之比率成為NiCuZn粒子:乙基纖維素:萜品醇=50:10:40(重量比)之方式進行混合,並利用自轉公轉混合機進行預混練,其後,通入三輥研磨機(最終加工輥間隙5 μm),並使用自轉公轉混合機進行消泡。使用25 μm間隙之敷料器將所獲得之糊於PET膜上塗膜,並以120℃乾燥10分鐘。乾燥塗膜之Ra為0.25 μm。從該乾燥塗膜剝下PET膜,並印刷實施例3之糊。
以2 L/分鐘持續供給25℃通入過純水之氮氣,並同時以0.75℃/分鐘進行升溫直到700℃,在700℃保持20分鐘。
進行與例2相同之操作,對所獲得之積層體進行評價。
(例18:實施例25)
在例17中所製作之NiZnCu坯片上印刷實施例3之糊,以2 L/分鐘從壓縮機持續供給大氣並同時以0.75℃/分鐘進行升溫直到500℃,在500℃保持20分鐘。其後,以2 L/分鐘持續供給包含2%H2
之N2
並同時以0.75℃/分鐘進行升溫直到850℃,在850℃保持20分鐘。進行與例2相同之操作,對所獲得之積層體進行評價。
(例19:比較例1〜5)
不進行偶合劑處理而將例1中所製作之銅粉進行離心分離並進行乾燥,將所獲得之銅粉按照例2之步驟加工成糊,進行與例11、12(實施例17)、14(實施例21)、16、18相同之操作,對所獲得之積層體進行評價。由於比較例1~5使用了包含未進行過特定表面處理之銅粉之糊,因此在晶界或晶粒內不存在陶瓷粒子,故而晶粒容易生長。因此,比較例1~5與實施例相比,結晶粒徑容易不均,應變容易局部地累積。其結果,認為比較例1~5中,銅與陶瓷之密接性變得不充分。
(例20:比較例6〜8)
採取二胺基矽烷(A-1120(MOMENTIVE公司製造))5 mL,以合計成為500 mL之方式與純水進行混合,並以200 rpm左右攪拌一晚。將例1中所製作之沉澱漿料之上清液去除,將沉澱銅粉與二胺基矽烷水溶液以500 rpm攪拌5小時。其後,按照例2之步驟獲得表面處理銅粉。將該銅粉以銅粉:乙基纖維素:油酸:萜品醇=80:2.3:1.6:16.1(重量比)之方式進行混合,並利用自轉公轉混合機進行混練來製作糊。使用該糊,按照例2之步驟製作積層體並進行評價。關於該等糊,在例2之網版印刷後之塗膜觀察到大量目視可觀察到之級別之顆粒。認為其原因在於:與例2相比,偶合劑之處理時間或糊製備條件等不同,因此分散性降低,產生凝集體。
圖4中表示比較例1之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
(結果)
將實施例及比較例之結果匯總示於表1。比較例中,平均CI值(可鑑定出燒成銅之結晶方位之比率)低。例如圖4之EBSD圖像之黑色部分是無法鑑定出結晶方位之部分。無法鑑定出結晶方位之比率高、即總CI值低之本案之比較例容易從各種陶瓷基材剝離。又,該等比較例之燒成體之比電阻高。另一方面,實施例中,可鑑定出結晶方位之比率高(圖1、圖2),牢固地接著在各種陶瓷上。推測因為可鑑定出之結晶之比率多,因此比電阻亦低。利用STEM、EDS對實施例3之金屬組織進行觀察,結果確認在晶界上析出了推測源自銅粉表面處理劑之陶瓷粒子。推測儘管在500℃以上之高溫進行燒成但所獲得之燒成銅之結晶粒徑仍小是由於:此種數10 nm左右之陶瓷粒子存在於燒成銅之晶界或晶粒內。具有本發明之金屬組織之銅粉糊燒成體與陶瓷層之積層體由於密接力高且比電阻亦低,因此期待適合於LTCC之配線材料或MLCC之內部電極、外部電極。
[產業上之可利用性]
本發明提供一種積層體,其在陶瓷層上積層有銅粉糊燒結體,且陶瓷層與銅粉糊燒結體之密接性優異。本發明是產業上有用之發明。
無
圖1是實施例1之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
圖2是實施例3之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
圖3是實施例3之晶界附近之STEM觀察及EDS分析之結果。
圖4是比較例1之結晶方點陣圖(IPF圖(Inverse Pole Figure map)。
Claims (10)
- 一種積層體,其在陶瓷層積層有銅粉糊燒結體,且在銅粉糊燒結體中,根據EBSD圖像所求出之利用面積分數法(Area Fraction Method)獲得之銅的結晶粒徑為10μm以下,且分析區域之平均可靠性指數(CI值)為0.5以上。
- 根據請求項1所述之積層體,其中,在銅粉糊燒結體中,在晶界或晶粒內存在陶瓷粒子。
- 根據請求項2所述之積層體,其中,陶瓷粒子之最大粒徑為100nm以下。
- 根據請求項1所述之積層體,其中,根據EBSD圖像所求出之利用面積分數法獲得之銅的結晶粒徑為1μm以上且10μm以下。
- 根據請求項1所述之積層體,其中,銅粉糊燒結體為不含玻璃料之銅粉糊的燒結體。
- 根據請求項1所述之積層體,其中,銅粉糊燒結體係比表面積為1m2g-1以上之銅粉之糊的燒結體。
- 根據請求項1所述之積層體,其中,陶瓷層為氧化鋁層、以鈦酸鋇為主成分之層、CuNiZn之鐵氧體粒子之燒結體層、氮化鋁層或氮化矽層。
- 根據請求項1所述之積層體,其中,陶瓷層之陶瓷除O以外之元素中原子濃度最高之元素為Si,次高之元素為Al。
- 一種銅-陶瓷複合體,其包含請求項1至8中任一項所述之積層體。
- 一種電子零件,其具有請求項1至8中任一項所述之積層體。
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