TW201605735A - 氧化物燒結體、其製造方法、濺鍍靶材及薄膜 - Google Patents

氧化物燒結體、其製造方法、濺鍍靶材及薄膜 Download PDF

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TW201605735A
TW201605735A TW104124818A TW104124818A TW201605735A TW 201605735 A TW201605735 A TW 201605735A TW 104124818 A TW104124818 A TW 104124818A TW 104124818 A TW104124818 A TW 104124818A TW 201605735 A TW201605735 A TW 201605735A
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sintered body
oxide sintered
oxide
powder
titanium
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TW104124818A
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TWI651268B (zh
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尾身健治
伊藤謙一
内海健太郎
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東曹股份有限公司
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Abstract

本發明的目的為提供一種於高功率成膜時,異常放電現象亦少且無靶材破裂的濺鍍靶材中所使用的氧化物燒結體。本發明的氧化物燒結體為具有鋅、鋁、鈦及氧作為構成元素的氧化物燒結體,且其特徵在於:於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,構成該燒結體的元素的原子比為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   且該燒結體中的將Zn2 TiO4 結晶相作為母相的晶粒的平均粒徑為5 μm以下。

Description

氧化物燒結體、其製造方法及濺鍍靶材
本發明是有關於一種將鋅、鋁、鈦及氧作為構成元素的氧化物燒結體及含有該燒結體而成的濺鍍靶材。
近年來,於可攜式顯示器或建築材料玻璃中作為折射率調整用途正逐步採用高折射率膜。高折射率靶材的代表例為氧化鈦靶材,但其電阻值極高而存在難以進行量產性高的直流(Direct Current,DC)濺鍍的問題。針對該課題,報告有藉由賦予微量的摻雜物(dopant)而降低比電阻,從而可進行DC放電的技術(例如,參照專利文獻1)。然而,氧化鈦系的氧化物材料因鈦與氧的結合強度強,故而留有濺鍍時不易原子化、成膜速度極慢的課題。
另外,作為高折射率靶材亦報告有包含鋅、鋁、鈦的複合氧化物燒結體(例如,參照專利文獻2)。含有鈦的氧化鋅系靶材被認為可獲得於實現折射率2.0以上的高折射率的同時發弧(arcing)的產生少且具有穩定的DC放電性能的複合氧化物燒結體。
然而,近年來,可投入高功率負荷的圓筒靶材的採用等正不斷發展,先前未設想過的投入高功率的成膜正成為主流。因此,對於在投入高功率時亦無發弧的產生或靶材破裂且可進行穩定的DC放電的高折射率靶材的需求性提高。 [現有技術文獻] [專利文獻]
[專利文獻1]日本專利特開2005-179129號公報 [專利文獻2]日本專利特開2009-298649號公報
[發明所欲解決之課題]
本發明的目的為提供一種於高功率成膜時,異常放電現象亦少且無靶材破裂的濺鍍靶材中所使用的氧化物燒結體。 [解決課題之手段]
本發明者等人針對於ZnO中添加TiO2 而成的高折射率複合氧化物的發弧現象及破裂產生的原因進行了努力研究。其結果查明:由ZnO與TiO2 形成的Zn2 TiO4 結晶相容易產生異常晶粒成長,若作為一定尺寸以上的結晶而存在於靶材內部,則於投入高功率時,蓄積極大的電荷,從而引起激烈的異常放電。
進而判明一定尺寸以上的Zn2 TiO4 結晶相亦對燒結體的強度造成影響。於異常晶粒成長後的Zn2 TiO4 結晶相的組織附近,部分晶界強度降低,進而使靶材整體的強度降低,從而於引起發弧的同時引起靶材破裂。
鑒於以上方面,本發明中發現了藉由抑制Zn2 TiO4 相的異常晶粒成長,而防止投入高功率時的發弧的產生及靶材破裂的氧化物燒結體。
即,本發明是有關於如下的發明。 (1)一種氧化物燒結體,其為具有鋅、鋁、鈦及氧作為構成元素的氧化物燒結體,且其特徵在於:於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,構成該燒結體的元素的原子比為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   且該氧化物燒結體中的將Zn2 TiO4 結晶相作為母相的晶粒的平均粒徑為5 μm以下。 (2)如(1)所述的氧化物燒結體,其中所述氧化物燒結體中不存在將粒徑超過20 μm的Zn2 TiO4 結晶相作為母相的晶粒。 (3)如(1)或(2)所述的氧化物燒結體,其中於所述氧化物燒結體的X射線繞射中,不存在氧化鋁相的繞射峰值。 (4)如(1)至(3)中任一項所述的氧化物燒結體,其相對密度為98%以上。 (5)如(1)至(4)中任一項所述的氧化物燒結體,其抗折強度為150 MPa以上。 (6)一種濺鍍靶材,其特徵在於:使用(1)至(5)中任一項所述的氧化物燒結體作為靶材材。 (7)一種薄膜,其特徵在於:使用如(6)所述的濺鍍靶材並利用濺鍍法進行成膜而成。 (8)一種氧化物燒結體的製造方法,其特徵在於:對如下成形體進行煅燒,所述成形體是將氧化鋅粉末、氧化鈦粉末及布厄特(Brunauer-Emmett-Teller,BET)比表面積為10 m2 /g以上的氧化鋁粉末作為原料粉末且於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,以元素的原子比成為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   的方式進行混合、成形後所得的成形體。 (9)如(8)所述的氧化物燒結體的製造方法,其中於大氣或惰性氣體環境下利用1300℃以下的溫度進行煅燒。
以下,對本發明進行詳細說明。
本發明為一種氧化物燒結體,其為具有鋅、鋁、鈦及氧作為構成元素的氧化物燒結體,且其特徵在於:於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,構成該燒結體的元素的原子比為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   且該氧化物燒結體中的將Zn2 TiO4 結晶相作為母相的晶粒的平均粒徑為5 μm以下。
本發明的氧化物燒結體的特徵在於:具有鋅、鋁及鈦作為構成元素。鋅為用於確保氧化物燒結體的導電性的元素,鈦為用於使進行濺鍍而獲得的膜獲得所需的高折射率的元素。絕緣性高的氧化鈦相與氧化鋅形成作為複合氧化物相的Zn2 TiO4 相,氧化鈦相並不含有於氧化物燒結體中。進而,藉由添加鋁而導電性提昇,從而本發明的氧化物燒結體可進行穩定的DC放電。
本發明的特徵在於:於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,構成燒結體的元素的原子比為Al/(Zn+Al+Ti)為0.035~0.050、Ti/(Zn+Al+Ti)=0.05~0.20。若為此種組成的範圍,則可抑制由氧化鈦與氧化鋅形成的Zn2 TiO4 相的異常晶粒成長。
Al/(Zn+Al+Ti)為0.035~0.050,較佳為0.037~0.046。若Al/(Zn+Al+Ti)未滿0.035,則難以抑制Zn2 TiO4 相的異常晶粒成長,若Al/(Zn+Al+Ti)超過0.050,則不能與氧化鋅相固溶置換的鋁會作為絕緣性的氧化鋁或其複合氧化物而於燒結體晶界析出,燒結體的電阻率會變高。
另外,Ti/(Zn+Al+Ti)為0.05~0.20,較佳為0.05~0.19。若Ti/(Zn+Al+Ti)未滿0.05,則進行濺鍍而獲得的膜的折射率會降低,若Ti/(Zn+Al+Ti)超過0.20,則燒結體的電阻率會急劇增大,從而不能進行穩定的DC放電。
本發明的氧化物燒結體主要由將ZnO相作為母相的晶粒與將Zn2 TiO4 相作為母相的晶粒構成,但若於氧化物燒結體中ZnO相與Zn2 TiO4 相的粒徑產生差,則晶界部分的強度變得不均衡(unbalance),從而存在成為不耐受熱衝擊的燒結體的可能性,故而,將Zn2 TiO4 相作為母相的晶粒的平均粒徑較佳為5 μm以下,更佳為3.5 μm以下。進而更佳為不存在將粒徑超過20 μm的Zn2 TiO4 結晶相作為母相的晶粒,特佳為不存在將粒徑超過10 μm的Zn2 TiO4 結晶相作為母相的晶粒。
另外,於本發明中,較佳為於所得的氧化物燒結體的X射線繞射中,不存在相當於氧化鋁相的繞射峰值。其原因為絕緣體的氧化鋁會引起濺鍍時的發弧。本發明中,藉由使用BET比表面積為10 m2 /g以上的氧化鋁粉末而可將煅燒溫度設為相對較低的溫度,從而不能與ZnO相固溶的過剩的氧化鋁的再凝聚、晶粒成長得到抑制,故而不會出現氧化鋁的X射線繞射峰值。
本發明的氧化物燒結體較佳為相對密度為98%以上。其原因為若相對密度未滿98%,則有發弧的產生頻率變高的傾向。
進而,為了進行穩定的DC放電,本發明的氧化物燒結體的體電阻較佳為10 Ωcm以下,更佳為1 Ωcm以下,進而較佳為0.1 Ωcm以下。
另外,本發明的氧化物燒結體較佳為抗折強度為150 MPa以上,更佳為180 MPa以上。若抗折強度為150 MPa以上,則於研削加工中亦不會產生破裂,良率高,故而生產性良好。進而,即便用於在濺鍍中投入有高功率的圓筒形濺鍍靶材的情況下,亦難以產生破裂的問題。
再者,靶材中的投入負荷藉由用投入電力除以靶材的侵蝕面積而得的電力密度(W/cm2 )而得以標準化。通常生產中的一般的電力密度為1 W/cm2 ~2.5 W/cm2 左右,但於本發明中,於4 W/cm2 以上的高功率條件下,亦可獲得發弧的產生極少且成為高品質的靶材材料的氧化物燒結體。
本發明的氧化物燒結體的製造方法的特徵在於:對如下成形體進行煅燒,所述成形體是將氧化鋅粉末、氧化鈦粉末及BET比表面積為10 m2 /g以上的氧化鋁粉末作為原料粉末且於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,以元素的原子比成為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   的方式進行混合、成形後所得的成形體。
以下,關於本發明的氧化物燒結體的製造方法,針對每個步驟來進行說明。
(1)原料混合步驟
若考慮到處理性,則原料粉末較佳為氧化鋅、氧化鋁、氧化鈦的各氧化物粉末。各原料粉末的純度較佳為99.9%以上,更佳為99.99%以上。若含有雜質,則會引起煅燒步驟中的異常晶粒成長,故而欠佳。
關於氧化鋁粉末,必須使用BET比表面積為10 m2 /g以上者。若為BET比表面積未滿10 m2 /g的氧化鋁粉末,則無法抑制煅燒時所形成的Zn2 TiO4 相的激烈的晶粒成長。另外,氧化鋁粉末較佳為使用D50為0.15 μm~0.35 μm、D90為0.30 μm~0.65 μm者。
於原料混合步驟中,於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,必須以元素的原子比成為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   的方式對氧化鋅粉末、氧化鋁粉末及氧化鈦粉末進行混合,較佳為以成為   Al/(Zn+Al+Ti)=0.037~0.046 Ti/(Zn+Al+Ti)=0.05~0.19   的方式對氧化鋅粉末、氧化鋁粉末及氧化鈦粉末進行混合。
另外,為了抑制Zn2 TiO4 相的晶粒成長,較佳為將原料粉末均勻地混合。為了進行均勻混合,粉碎混合後的混合粉的BET比表面積較佳為較作為主構成原料的氧化鋅粉末的BET比表面積高1 m2 /g以上,更佳為2 m2 /g以上。混合粉的BET比表面積若過高,則粉末的成形性降低,故而較佳為製備為15 m2 /g以下。
關於該些各粉末的粉碎混合處理,若為可進行均勻混合的設備,則並無特別限定,可例示使用氧化鋯(zirconia)、氧化鋁(alumina)、尼龍(nylon)樹脂等的球或珠的乾式、濕式的介質(media)攪拌型磨機或無介質(medialess)的容器旋轉式、機械攪拌式或氣流式等的粉碎混合方法。具體而言,可列舉:球磨機(ball mill)、珠磨機(beads mill)、磨碎機(attritor)、振動磨機、行星式磨機(planetary mill)、噴射磨機(jet mill)、雙軸行星攪拌式混合機等。於使用濕式法的球磨機或珠磨機、磨碎機、振動磨機、行星式磨機、噴射磨機等的情況下,必須對粉碎後的漿料(slurry)進行乾燥。該乾燥方法並無特別限定,例如可例示過濾乾燥、流動層乾燥、噴霧乾燥等。
(2)成形步驟
成形方法可適當選擇可將混合後的原料粉末成形為目標形狀的成形方法,並無特別限定。可例示壓製成形法、澆鑄成形法、射出成形法等。
若成形體不產生龜裂(crack)等且為可進行處理的成形體,則成形壓力並無特別限定,但成形密度較佳為盡可能高。因此,亦可使用冷等靜壓(Cold Isostatic Press,CIP)成形等方法。為了得到充分的壓密效果,CIP壓力較佳為1 ton/cm2 以上,更佳為2 ton/cm2 以上,特佳為2 ton/cm2 ~3 ton/cm2
(3)煅燒步驟
繼而,利用電爐煅燒爐等對所得的成形體進行煅燒。被煅燒物的昇溫速度並無特別限定,通常為20℃/小時~600℃/小時的範圍。降溫速度亦並無特別限定,可考慮燒結爐的容量、燒結體的尺寸及形狀、破裂容易度等而適當決定。較佳為於煅燒保持溫度為1100℃~1300℃的範圍內進行,保持時間較佳為0.5小時~8小時,更佳為1小時~5小時。若將煅燒保持溫度及保持時間設為該條件,則容易抑制煅燒時所生成的Zn2 TiO4 相的異常晶粒成長。煅燒時的環境並無特別限制,但為了抑制鋅的昇華,較佳為設為大氣或氧氣環境。
(4)靶材化步驟
使用平面研削盤、圓筒研削盤、旋轉盤、切斷機、綜合加工機(machining center)等機械加工機將所得的燒結體研削加工為板狀、圓狀、圓筒狀等所需的形狀。進而,視需要使用銦焊料等來接合(焊接(bonding))於包含無氧銅或鈦等的支承板(backing plate)、支承管(backing tube)上,藉此可獲得將本發明的氧化物燒結體作為靶材材的濺鍍靶材。
燒結體的尺寸並無特別限定,由本發明所得的燒結體的強度高,故而可製造大型的靶材。於為平板形濺鍍靶材的情況下,可製作縱310 mm´橫420 mm(靶材面的面積為1302 cm2 )以上的大型的燒結體,於為圓筒形濺鍍靶材的情況下,可製作外徑91 mmf´170 mm(靶材面的面積為486 cm2 )以上的大型的燒結體。再者,此處所述的靶材面的面積是指經濺鍍之側的燒結體表面的面積。於為包含多個燒結體的多分割靶材的情況下,將各個燒結體中經濺鍍之側的燒結體表面的面積為最大者設為多分割靶材中的靶材面的面積。 [發明的效果]
本發明的氧化物燒結體具有導電性,於作為濺鍍靶材而使用的情況下,可進行DC放電且於投入高功率時,異常放電(發弧)的產生或靶材的破裂亦少,所形成的薄膜為高電阻的膜。另外,燒結體的強度高,故而可容易地進行加工,且可良率良好地製造大型的靶材。
[實施例]
以下,藉由實施例來對本發明進行更具體的說明,但本發明並不限定於此。再者,如以下般進行本實施例中的各測定。
(1)粉末的BET比表面積 粉末的BET比表面積是使用比表面積測定裝置(特力斯達(TriStar)3000、島津製作所製造)並利用氣體吸附法進行測定。
(2)粉末的粒徑測定 粉末的粒徑是使用粒子徑分佈測定裝置(SALD-7100、島津製作所製造)並利用雷射繞射散射法進行測定,利用體積度數分佈求出D50(50%粒徑)與D90(90%粒徑)。
(3)燒結體的密度 燒結體的相對密度是依據日本工業標準(Japanese Industrial Standards,JIS)R 1634並利用阿基米德(Archimedes)法求出體積密度,進而除以真密度而求出相對密度。燒結體的真密度是將燒結體中的Zn、Ti、Al換算為氧化物並分別設為氧化鋅、氧化鋁、氧化鈦時,使用各自的量a(g)、b(g)、c(g)與各自的真密度5.606(g/cm3 )、3.95(g/cm3 )、4.23(g/cm3 )並藉由下述式所表示的算數平均而算出。   d=(a+b+c)/((a/5.606)+(b/3.95)+(c/4.23))
(4)X射線繞射試驗 對鏡面研磨後的燒結體試樣的2θ=20°~70°的範圍的X射線繞射圖案進行測定。 掃描方法:步進掃描法(FT法) X射線源:CuKa 功率:40 kV、40 mA 步進幅度:0.01°
(5)結晶粒徑 進行鏡面研磨並藉由利用電子探針微量分析(Electron Probe Microanalysis,EPMA)的組成分析鑑定ZnO相與Zn2 TiO4 相後,根據掃描電子顯微鏡(Scanning Electron Microscope,SEM)圖像並利用直徑法對結晶粒徑進行測定。對樣品的任意3點以上進行觀察,並分別對300個以上的粒子進行測定。 (EPMA分析條件) 裝置:波長分散型電子束微量分析儀 加速電壓:15 kV 照射電流:30 nA
(6)抗折強度 依據JIS R 1601進行測定。 (抗折強度的測定條件) 試驗方法:3點彎折試驗 支點間距離:30 mm 試樣尺寸:3 mm´4 mm´40 mm 頭速度:0.5 mm/min
(7)體電阻 將所得的燒結體加工為約10 mm´20 mm´1 mmt,於測定探針的接觸點(4點)塗佈銀膏,使用粒子徑分佈測定裝置(羅萊絲塔(LORESTA)HP MCP-T410、三菱油化公司製造)並利用4端子法進行測定。
(8)濺鍍評價 將所得的燒結體加工為101.6 mmf´6 mmt後,利用銦焊料而焊接於無氧銅製的支承板上,從而製成濺鍍靶材。使用該靶材並於以下的條件下使投入功率變化而進行濺鍍,進行發弧測量及靶材破裂的觀察。 (濺鍍條件) 氣體:氬+氧(3%) 壓力:0.6 Pa 電源:DC 投入功率:400 W(4.9 W/cm2 ) 600 W(7.4 W/cm2 ) 800 W(9.9 W/cm2 ) 放電時間:各120分鐘 發弧測量條件(臨限電壓):濺鍍電壓-50[V]
(實施例1) 對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(a)的粉末以成為Al/(Zn+Al+Ti)=0.045、Ti/(Zn+Al+Ti)=0.05的比例進行秤量。將所秤量的粉末與直徑為15 mm的鐵芯樹脂製球放入至聚乙烯製的罐(pot)中,利用乾式球磨機混合20小時。使混合後的粉末通過300 μm的篩,利用模具壓製於300 kg/cm2 的壓力下製作120 mm´120 mm´8 mmt的成形體後,於2 ton/cm2 的壓力下進行CIP處理。 繼而,將該成形體設置於氧化鋁製的托架(setter)上,於以下的條件下,利用電阻加熱式的電爐(爐內容積:250 mm´250 mm´250 mm)進行煅燒。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。 (煅燒條件) 煅燒溫度:1100℃ 保持時間:1小時 昇溫速度:100℃/小時 環境:氧流通環境(200 mL/min) 降溫速度:300℃/小時
(實施例2) 以Al/(Zn+Al+Ti)=0.040、Ti/(Zn+Al+Ti)=0.10的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(a)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1200℃且將保持時間變更為3小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(實施例3) 以Al/(Zn+Al+Ti)=0.038、Ti/(Zn+Al+Ti)=0.19的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(b)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1300℃且將保持時間變更為5小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(實施例4) 將乾式球磨機的混合時間設為10小時,除此以外,以與實施例3相同的條件製作燒結體。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(實施例5) 將混合粉末的製備方法設為使用下述條件的濕式珠磨機與噴霧乾燥機(spray dryer)且使所得的粉末通過150 μm的篩,除此以外,於與實施例2相同的條件下獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將保持時間變更為1小時,除此以外,以與實施例2相同的條件利用電阻加熱式的電爐進行煅燒。 (珠磨機條件) 珠粒徑:0.3 mmf 珠粒填充率:85% 周速:7 m/sec 通過次數:10次 漿料濃度:粉末60 wt% (噴霧乾燥機條件) 熱風溫度:入口180℃、出口120℃ 圓盤轉速:10000 rpm
將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(成膜評價) 使用實施例1~實施例5中所得的濺鍍靶材並於以下的條件下進行成膜,進行薄膜電阻的測定。為薄膜電阻均為105 Ω以上的高電阻膜。
(濺鍍條件) 氣體:氬+氧(3%) 壓力:0.6 Pa 電源:DC 投入功率:400 W(4.9 W/cm2 ) 膜厚:80 nm 基板:無鹼玻璃(康寧(corning)公司製造的益格(EAGLE)XG、厚度0.7 mm)
(電阻的測定條件) 裝置:羅萊絲塔(LORESTA)HP(三菱油化公司製造的MCP-T410) 測定方式:4端子法
(比較例1) 以Al/(Zn+Al+Ti)=0.025、Ti/(Zn+Al+Ti)=0.10的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(a)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1250℃且將保持時間變更為5小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將濺鍍靶材的濺鍍評價結果示於表3。
(比較例2) 以Al/(Zn+Al+Ti)=0.025、Ti/(Zn+Al+Ti)=0.10的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(a)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1350℃且將保持時間變更為10小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將濺鍍靶材的濺鍍評價結果示於表3。
(比較例3) 以Al/(Zn+Al+Ti)=0.040、Ti/(Zn+Al+Ti)=0.10的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(c)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1250℃且將保持時間變更為5小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(比較例4) 以Al/(Zn+Al+Ti)=0.040、Ti/(Zn+Al+Ti)=0.10的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(c)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1350℃且將保持時間變更為10小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2,將所得的濺鍍靶材的濺鍍評價結果示於表3。
(比較例5) 以Al/(Zn+Al+Ti)=0.040、Ti/(Zn+Al+Ti)=0.25的比例且於與實施例1相同的條件下對表1中所示的粉末物性的氧化鋅粉末、氧化鈦粉末、氧化鋁(a)的粉末進行處理而獲得CIP處理成形體。將該成形體設置於氧化鋁製的托架上,將煅燒溫度變更為1350℃且將保持時間變更為5小時,除此以外,以與實施例1相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體的評價結果示於表2。所得的燒結體的體電阻高,故而無法實施濺鍍評價。
(實施例6) 代替模具壓製,使用CIP成形用模具於1 ton/cm2 的壓力下製作351 mm´477 mm´8 mmt的成形體後,於2 ton/cm2 的壓力下進行CIP處理,除此以外,於與實施例2相同的條件下獲得9片CIP處理成形體。繼而,將該成形體設置於氧化鋁製的托架上,於電爐(爐內容積:1500 mm´1200 mm´600 mm)內將氧流量變更為120 L/min,除此以外,以與實施例2相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體加工為310 mm´420 mm´6 mmt,獲得無破裂的9片燒結體。繼而,將3片燒結體作為一組且利用銦焊料而焊接於無氧銅製的支承板上,從而獲得3根濺鍍靶材。將所得的燒結體的評價結果示於表2。
(實施例7) 代替模具壓製,使用CIP成形用模具於2 ton/cm2 的壓力下製作內徑86 mm´外徑116 mm´長度200 mm的成形體,除此以外,於與實施例2相同的條件下獲得9個成形體。繼而,將該成形體設置於氧化鋁製的托架上,以與實施例2相同的條件利用電阻加熱式的電爐進行煅燒。將所得的燒結體加工為內徑77 mm´外徑91 mm´長度170 mm,獲得無破裂的9個燒結體。繼而,將3個燒結體作為一組且利用銦焊料而焊接於鈦製的支承管上,從而獲得3根濺鍍靶材。將所得的燒結體的評價結果示於表2。
[表1]
[表2]
[表3]

Claims (9)

  1. 一種氧化物燒結體,其為具有鋅、鋁、鈦及氧作為構成元素的氧化物燒結體,且其特徵在於:於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,構成所述燒結體的元素的原子比為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   且所述燒結體中的將Zn2 TiO4 結晶相作為母相的晶粒的平均粒徑為5 μm以下。
  2. 如申請專利範圍第1項所述的氧化物燒結體,其中所述氧化物燒結體中不存在將粒徑超過20 μm的Zn2 TiO4 結晶相作為母相的晶粒。
  3. 如申請專利範圍第1項或第2項所述的氧化物燒結體,其中於所述氧化物燒結體的X射線繞射中,不存在氧化鋁相的繞射峰值。
  4. 如申請專利範圍第1項至第3項中任一項所述的氧化物燒結體,其相對密度為98%以上。
  5. 如申請專利範圍第1項至第4項中任一項所述的氧化物燒結體,其抗折強度為150 MPa以上。
  6. 一種濺鍍靶材,其特徵在於:使用如申請專利範圍第1項至第5項中任一項所述的氧化物燒結體作為靶材材。
  7. 一種薄膜,其特徵在於:使用如申請專利範圍第6項所述的濺鍍靶材並利用濺鍍法進行成膜而成。
  8. 一種氧化物燒結體的製造方法,其特徵在於:對如下成形體進行煅燒,所述成形體是將氧化鋅粉末、氧化鈦粉末及布厄特比表面積為10 m2 /g以上的氧化鋁粉末作為原料粉末且於將鋅、鋁、鈦的含量分別設為Zn、Al、Ti時,以元素的原子比成為   Al/(Zn+Al+Ti)=0.035~0.050 Ti/(Zn+Al+Ti)=0.05~0.20   的方式進行混合、成形後所得的成形體。
  9. 如申請專利範圍第8項所述的氧化物燒結體的製造方法,其中於大氣或惰性氣體環境下利用1300℃以下的溫度進行煅燒。
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JPS59149604A (ja) * 1983-02-16 1984-08-27 株式会社日立製作所 金属酸化物薄膜の製造方法
DE3566184D1 (en) * 1984-06-22 1988-12-15 Hitachi Ltd Oxide resistor
WO2004043871A1 (fr) * 2002-11-07 2004-05-27 Saint-Gobain Glass France Systeme de couches pour substrats transparents et substrat revêtu
JP4711619B2 (ja) 2003-12-19 2011-06-29 京セラ株式会社 導電性酸化チタン焼結体、スパッタリングターゲット、透光性部材、および画像表示装置
CN101495664B (zh) 2006-07-28 2012-04-25 株式会社爱发科 透明导电膜的成膜方法
JP5003600B2 (ja) 2008-06-13 2012-08-15 住友金属鉱山株式会社 酸化物焼結体、ターゲット、およびそれを用いて得られる透明導電膜、導電性積層体
JP5585046B2 (ja) * 2009-10-27 2014-09-10 東ソー株式会社 複合酸化物焼結体、ターゲット及び酸化物透明導電膜
CN102762518A (zh) * 2010-02-18 2012-10-31 住友化学株式会社 氧化物烧结体、氧化物混合物、它们的制造方法以及使用它们的靶
KR101859787B1 (ko) * 2010-09-29 2018-05-18 토소가부시키가이샤 복합 산화물 소결체 및 그 제조방법, 스퍼터링 타겟 및 산화물 투명 도전막 및 그 제조방법
JP2012106878A (ja) * 2010-11-16 2012-06-07 Sumitomo Chemical Co Ltd 酸化亜鉛系透明導電膜形成材料の製造方法、該透明導電膜形成材料を用いたターゲット、および酸化亜鉛系透明導電膜の形成方法
JP2012140276A (ja) * 2010-12-28 2012-07-26 Sumitomo Chemical Co Ltd 酸化亜鉛系透明導電膜形成材料、それを用いたターゲット、酸化亜鉛系透明導電膜の形成方法および透明導電性基板
JP2013177262A (ja) * 2012-02-28 2013-09-09 Sumitomo Chemical Co Ltd 酸化物焼結体およびその製造方法
JP6014454B2 (ja) * 2012-03-02 2016-10-25 住友化学株式会社 酸化亜鉛系焼結体の製造方法

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