TWI605140B - 氧化物濺鍍靶及光記錄媒體用保護膜 - Google Patents

氧化物濺鍍靶及光記錄媒體用保護膜 Download PDF

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TWI605140B
TWI605140B TW105137667A TW105137667A TWI605140B TW I605140 B TWI605140 B TW I605140B TW 105137667 A TW105137667 A TW 105137667A TW 105137667 A TW105137667 A TW 105137667A TW I605140 B TWI605140 B TW I605140B
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oxide
sputtering target
total
film
sno
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TW105137667A
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TW201716604A (zh
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齋藤淳
森理惠
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三菱綜合材料股份有限公司
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Description

氧化物濺鍍靶及光記錄媒體用保護膜
本發明係關於用以成膜光學記錄媒體例如CD、DVD、Blu-ray Disc(註冊商標：以下稱為BD)等中所用之光記錄媒體用保護膜之氧化物濺鍍靶以及使用該濺鍍靶而成膜之光記錄媒體用保護膜者。
本申請案係基於2012年2月6日於日本提出申請之特願2012-023397號、及於2013年1月23日於日本提出申請之特願2013-10035而主張優先權，其內容於本文中被援用。
近幾年來，隨著照相或動畫之高畫質化，朝光記錄媒體記錄時之數位數據亦隨之增大，而要求記錄媒體之高容量化，目前，作為高記錄容量之光記錄媒體，已銷售有利用多層記錄方式之具有50GB容量之光記錄媒體BD。該BD於日後亦期望進一步高容量化，而積極進行利用記錄層之多層化而高容量化之研究。
[先前技術文獻] [專利文獻]
[專利文獻1]特開2009-26378號公報(參見段落0058)
[專利文獻2]特開2005-228402號公報(參見段落0004)
[專利文獻3]特開2005-154820號公報
上述以往技術仍有以下課題。
於記錄層中使用有機色素之類型的記錄媒體，與以無機物作為記錄層之情況相較，由於記錄層之變形較大，故亦如上述專利文獻1所記載，與色素相鄰之保護層必須為低硬度。因此，過去係採用具有適度柔軟性(柔軟)之膜的ZnS-SiO2或ITO。
然而，就ZnS-SiO2而言，亦如上述專利文獻2所記載，含有硫(S)成分時，該硫與反射膜中之金屬反應而使反射率降低，其結果，有作為光記錄媒體之保存性變低之缺點。且，使用ITO時，濺鍍時發生之顆粒較多，而對記錄媒體之記錄膜帶來不良影響，且生產設備之清潔亦非常辛苦，有記錄媒體之生產性差之問題。再者，專利文獻3中，提案有具有氧化錫相之以氧化錫與氧化鋅 及3價以上元素之氧化物作為主成分之濺鍍靶，但組織中之氧化錫相成為結瘤之原因，此會有導致濺鍍時顆粒發生之問題。
本發明係鑒於前述課題而完成者，其目的係提供作為光記錄媒體保護膜形成用、可成膜保存性高、具有柔軟性之不易破裂之膜，而且可進行直流(DC)濺鍍，於濺鍍時發生之顆粒亦少之氧化物濺鍍靶及使用該濺鍍靶而成膜之光記錄媒體用保護膜。
本發明人等針對ZnO系之濺鍍靶進行研究後，發現作為濺鍍靶之製造原料而藉由於氧化鋅(ZnO)中添加氧化錫(SnO2)、氧化鋁(Al2O3)、氧化鎵(Ga2O3)及氧化銦(In2O3)中之一種以上，可獲得即使藉由直流(DC)濺鍍，亦可成膜的保存性高、具有柔軟性之不易破裂之膜的ZnO系之氧化物濺鍍靶。再者，亦發現除上述之製造原料以外，添加氧化鍺(GeO2)及氧化鉻(Cr2O3)之一種以上，亦可獲得可成膜的保存性高、具有柔軟性之不易破裂之膜的ZnO系之氧化物濺鍍靶。
此處，作為本發明之一例，係製作ZnO系之氧化物濺鍍靶。首先，準備氧化鋅(ZnO，D50=1μm)、氧化錫(SnO2，D50=10μm)及氧化鋁(Al2O2，D50=0.2μm)之各原料粉末。將以特定比率秤取之各原料以球磨機裝置進行濕式混合16小時所得之混合粉末予以乾燥 後，經造粒，於950℃以350kgf/cm2之壓力熱加壓(HP)3小時。所得氧化物燒結體經機械加工成特定形狀，製作氧化物濺鍍靶。
接著，針對該製作之氧化物濺鍍靶進行X射線繞射(XRD)之結果示於圖1。如由該結果所了解，本發明之氧化物濺鍍靶檢測出屬於ZnO之繞射峰及屬於SnO2與ZnO之複合氧化物的Zn2SnO4之繞射峰，確認存在有ZnO及Zn2SnO4之相。
且，本發明之氧化物濺鍍靶中，以EPMA(場發射型電子束探針)，觀察反射電子像(CP)及顯示各元素組成分佈之元素分佈像。所得反射電子像及元素分析像示於圖2。又，以該EPMA所得之元素分佈像實際上係以彩色圖像取得，但圖2所示之各圖像係轉換成黑白而記載，故觀於畫像中之白黑濃淡，於淺灰色部分(比較白的部分)表示特定元素濃度較高部分。由該等圖像，可知本發明之氧化物濺鍍靶之組織係由ZnO及Zn2SnO4之相所構成，Al係選擇性分散於ZnO相中。
又，上述氧化物濺鍍靶係以ZnO、SnO2與Al2O2為原料粉末所製造之情況，但該情況以外，可知以ZnO、SnO2與Al2O3、Ga2O3及In2O3中之一種以上為原料粉末而製造之氧化物濺鍍靶亦係由ZnO及Zn2SnO4之相所構成，Al、Ga及In中之一種以上係選擇性分散於ZnO相中。且，除了ZnO、SnO2與Al2O3、Ga2O3及In2O3中之一種以上之原料粉末以外，亦以GeO2及Cr2O3之一種 以上為原料粉末而製造時，可知該氧化物濺鍍靶亦係由ZnO及Zn2SnO4之相所構成，Al、Ga及In中之一種以上、Ge及Cr中之一種以上係選擇性分散於ZnO相中。
因此，本發明係基於上述見解所得者，為解決上述課題而採用以下構成。
(1)本發明之氧化物濺鍍靶，其特徵為：其係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成之氧化物燒結體。
(2)前述(1)之氧化物濺鍍靶之氧化物燒結體，其特徵為：其係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而，含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成之氧化物燒結體。
(3)本發明之光記錄媒體用保護膜，其係使用前述(1)之氧化物濺鍍靶濺鍍成膜者，其特徵為：其係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成之成分組成的氧化物。
(4)本發明之光記錄媒體用保護膜，其係使用前述(3)之氧化物濺鍍靶濺鍍成膜者，其特徵為：其係相對 於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而，含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成之成分組成的氧化物。
以上之本發明之氧化物濺鍍靶由於係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成之成分組成的氧化物，故濺鍍靶之比電阻低，而可安定地進行直流(DC)濺鍍，且可成膜於光記錄媒體中之反射率變化少、具有高保存性同時具有柔軟性之不易破裂之膜。
又，藉由於ZnO中固熔之Al、Ga或In引起載體發生，認為可降低濺鍍靶之比電阻，同時進而提高成膜之膜的熱擴散率並減輕熱損傷。
上述氧化物濺鍍靶中，Al、Ga及In中之一種以上之合計含量設為0.15at%以上之理由，係若未達0.15at%，則直流(DC)濺鍍變不安定，容易發生膜破裂之故。此處，Al、Ga及In中之一種以上之合計含量進而宜為0.20at%以上、6.0at%以下。且，上述Sn之含量設為7at%以上之理由，係因為該含量未達7at%時，膜硬度(後述之壓痕硬度)成為800mgf/μm2以上，而變硬之故。此處，Sn之含量宜為7at%以上、30at%以下。再者， Al、Ga、In及Sn之合計含量設為36at%以下之理由，係因為該等含量若超過36at%，則濺鍍靶組織中會殘存氧化錫相，因氧化錫相而會於濺鍍靶中形成結瘤，故濺鍍時，大多發生顆粒或異常放電之故。
又，進而，含有Ge及Cr中之一種以上之合計：1.0~20.0at%。Ge及Cr之合計含量設為20at%以下之理由，係因為若超過20at%，則靶材之比電阻變高而無法進行穩定之直流(DC)濺鍍之故。又，為使可能進行直流(DC)濺鍍，濺鍍靶之比電阻宜為1Ω‧cm以下。尤其為進行穩定之濺鍍，宜為0.1Ω‧cm以下，更宜為0.01Ω‧cm以下。
因此，製造本發明之氧化物濺鍍靶時，係準備ZnO、SnO2、Al2O3、Ga2O3、In2O3之各原料粉末，以成為欲成為目標而成膜之光記錄媒體用保護膜之成分組成之方式，秤取各原料粉末。
將該秤取之原料粉末與其三倍量(重量比)之氧化鋯球(直徑5mm)置入聚乙烯容器中，以球磨機裝置濕式混合16小時。且，此時之溶劑係使用例如醇。接著，使所得混合粉末乾燥後，進行造粒，在850~1050℃、較好900~1000℃，以150~400kgf/cm2之壓力在真空或惰性氣體環境中熱加壓(HP)2~9小時，獲得氧化物燒結體。接著，機械加工成特定形狀，作成氧化物濺鍍靶。
此處，使用所製作之氧化物濺鍍靶藉由濺鍍而成膜之光記錄媒體用保護膜具有與該氧化物濺鍍靶同樣 之成分組成，亦即，成為對於全金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成或Al、Ga及In中之一種以上之合計：0.15at%以上，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而含有Ge及Cr中之一種以上之合計：1.0~20.0at%之其餘為由Zn及可避免雜質所構成之成分組成之氧化物。
因此，該等光記錄媒體用保護膜成為反射率之變化小、保存性高，同時具有適度柔軟性之不易破裂之特性，可適用作為使用有機色素之記錄層例如多層化BD中之保護膜。
依據本發明之氧化物濺鍍靶，係由相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，或，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成之成分組成之氧化物燒結體所成，而可進行穩定之直流(DC)濺鍍，而且可成膜具有高保存性同時具有適度柔軟性之不易破裂之膜。
因此，以本發明之氧化物濺鍍靶成膜之光記錄媒體用保護膜適合作為使用有機色素之記錄層之BD用的介電體保護膜。
圖1為顯示本發明之氧化物濺鍍靶之X射線繞射(XRD)結果之圖。
圖2為本發明之氧化物濺鍍靶之剖面組織以EPMA測定之各元素之元素分佈像。
圖3為比較例之氧化物濺鍍靶之X射線繞射(XRD)結果之圖。
圖4為比較例之氧化物濺鍍靶之剖面組織以EPMA測定之各元素之元素分佈像。
以下針對本發明之氧化物濺鍍靶及光記錄媒體用保護膜之實施形態具體加以說明。
使用本實施形態之氧化物濺鍍靶藉由濺鍍而成膜之光記錄媒體用保護膜，係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成之成分組成，或，含有Al、Ga及In中之一種以上之合計：0.15at%以上， 且，Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成之成分組成之氧化物。
因此，為了製造氧化物濺鍍靶，而準備氧化鋅(化學式：ZnO，D50=1μm)、氧化錫(化學式：SnO2，D50=16μm)、氧化鋁(化學式：Al2O3，D50=0.2μm)、氧化鎵(化學式：Ga2O3，D50=1.7μm)、氧化銦(化學式：In2O3，D50=11μm)、氧化鍺(化學式：GeO2，D50=1.0μm)、氧化鉻(化學式：Cr2O3，D50=0.4μm)作為原料粉末。接著，以成為上述光記錄媒體用保護膜之成分組成之方式，選擇並秤取各原料成分。各原料粉末之原料組成(mol%)示於表1。
將該秤取之各原料粉末與其三倍量(重量比)之氧化鋯球(直徑5mm)置入聚乙烯容器中，以球磨機裝置濕式混合16小時，獲得實施例1~26之混合粉末。且，此時之溶劑係使用例如醇。接著，使所得之實施例1~26之混合粉末乾燥後，進行造粒，在950℃以350kgf/cm2之壓力在真空或惰性氣體環境中熱加壓(HP)3小時，獲得各氧化物燒結體。將該氧化物燒結體進行機械加工，製作實施例1~26之氧化物濺鍍靶。又，靶尺寸為直徑125mm×厚度5mm。
再者，製作為與本實施形態之氧化物濺鍍靶比較之氧化物濺鍍靶。
不含有Al2O3、Ga2O3及In2O3之原料粉末，僅使用ZnO及SnO2之原料粉末，製作比較例1之氧化物濺鍍靶。針對含有Al2O3、Ga2O3及In2O3之原料粉末之情況，但在本實施形態之成分組成比例之設定範圍外之情況，製作比較例2、3之氧化物濺鍍靶。且，針對含有Al2O3、Ga2O3及In2O3之原料粉末進而含有GeO2及Cr2O3中一種之情況，但在本實施形態之成分組成比例之設定範圍外之情況，製作比較例4~6之氧化物濺鍍靶。而且準備以往之ZnS-SiO2(比較例7)及ITO(比較例8)之濺鍍靶。ZnS-SiO2為三菱材料股分有限公司製之ZSSO靶(20mol% SiO2)，ITO為三菱材料股分有限公司製之ITO靶(10wt% SnO2)。以上之比較例1~6之氧化物濺鍍靶係以與實施例1~26之氧化物濺鍍靶之製造順序同樣地製作。比較例1~8之氧化物濺鍍靶之各原料粉末之原料組成(mol%)示於表1。
接著，針對所製作之上述實施例1~26及比較例1~6之氧化物濺鍍靶，實施金屬組成之分析後，獲得表2所示之結果。
接著，使用上述實施例1~26及比較例1~8之氧化物濺鍍靶，藉以下之成膜條件成膜實施例1~26及比較例1~8之光記錄媒體用保護膜。
〈成膜條件〉
‧電源：脈衝DC500W(一部，高頻(RF)濺鍍)
‧全壓：0.4Pa
‧濺鍍氣體：Ar=47.5sccm，O2：2.5sccm(僅比較例7為Ar=50sccm，O2=0sccm)
‧靶-基板(TS)距離：70mm
接著，針對使用上述實施例1~26及比較例1~8之氧化物濺鍍靶，藉上述成膜條件成膜之實施例1~26及比較例1~8之光記錄媒體用保護膜，實施金屬組成分析後，獲得表3所示之結果。依據該結果，可知實施例1~26及比較例1~8之光記錄媒體用保護膜之金屬組成對應於實施例1~26及比較例1~6之氧化物濺鍍靶之金屬組成。
針對上述實施例1~26及比較例1~8之氧化物濺鍍靶，及使用其等而成膜之實施例1~26及比較例1~8之光記錄媒體用保護膜進行評價。關於實施例1~26及比較例1~8之氧化物濺鍍靶，係求得密度比、比電阻、異常放電次數、顆粒量，關於實施例1~26及比較例1~8之光 記錄媒體用保護膜，係求得膜之壓痕硬度、膜之破裂、膜之比電阻、膜之XRD及反射率之變化。關於各別求得方法顯示於下。
〈密度比測定〉
密度比係將燒結體機械加工成特定尺寸後，測定重量求得鬆密度後，除以理論密度而算出。又，理論密度係基於原料重量如下述般求得。
ρ1：Al2O3之密度 C1：Al2O3之重量%
ρ2：Ga2O3之密度 C2：Ga2O3之重量%
ρ3：In2O3之密度 C3：In2O3之重量%
ρ4：ZnO之密度 C4：ZnO之重量%
ρ5：SnO2之密度 C5：SnO2之重量%
ρ6：GeO2之密度 C6：GeO2之重量%
ρ7：Cr2O3之密度 C7：Cr2O3之重量%
ρfn：理論密度
〈比電阻測定〉
濺鍍靶及膜之比電阻測定係使用三菱化學股份有限公 司製造之電阻測定器LORESTA GP測定。
〈異常放電與顆粒〉
量測在上述條件中進行12小時濺鍍之異常放電次數。隨後，開啟濺鍍腔室，確認腔室內之顆粒數。
〈反射率之變化〉
使用將Ag98.1Nd1.0Cu0.9合金濺鍍於聚碳酸酯上，使專利文獻1之實施例1所記載之下述色素成膜而成之基板，於其上以上述條件成膜出厚度14nm之各實施例及比較例之保護膜。隨後，在80℃、85%之恆溫恆濕器中放置100小時，測定其前後之反射率變化。又，反射率之測定係使用紫外可見光分光光度計(日本分光股份有限公司製造之V-550)。且，求得對於波長405nm之光之反射率。
〈膜之壓痕硬度〉
以上述成膜條件，使用Corning公司製造之1737玻璃為基板，使膜厚成為500nm進行成膜，利用壓痕荷重為35mgf之超微小壓痕硬度試驗機(ELIONIX股份有限公司製造之ENT-1100a)進行測定。又，基板係固定在27℃之裝置內，經過1小時以上後進行測定。又，以10點測定之平均值作為測定值。
〈膜破裂〉
以上述成膜條件，以100nm之膜厚成膜於厚度0.1mm之PET膜上，將薄膜彎折10次後，以顯微鏡以倍率1000倍觀察膜表面調查有無破裂。又，利用高頻(RF)濺鍍而成膜時，附加※標記。
〈膜之XRD〉
試料之準備：於CORNING公司製之1737玻璃基板上以膜厚300nm進行成膜，作成測定試料。
裝置：理學電器股份有限公司製造(RINT-Ultima/PC)
管球：Cu
管電壓：40kV
管電流：40mA
掃描範圍(2θ)：50°~80°
狹縫尺寸：發散(DS)2/3度，散射(SS)2/3度，受光(RS)0.8mm
測定步進寬度：以2θ計為0.02度
掃描速度：每分鐘2度
試料台旋轉速度：30rpm
於此處，未見到繞射峰時，以○標記表示，明確見到繞射峰時，以×標記表示。
〈靶之XRD〉
試料之準備：試料係以SiC-Paper(粗粒180)進行 濕式研磨，乾燥後作為測定試料。
以與上述膜之XRD相同條件，測定SnO2之27°附近之峰對於Zn2SnO4之附近34°附近之峰的比，調查有無SnO2相。
針對上述實施例1~26及比較例1~8之氧化物濺鍍靶，及使用其等而成膜之實施例1~26及比較例1~8之光記錄媒體用保護膜進行評價之結果，示於表4及表5。
由以上所示之評價結果可了解，實施例1~26之氧化物濺鍍靶之比電阻均為0.1Ω‧cm以下，異常放電次數極少同時顆粒量亦少。相對於此，比較例1、4、5、6、7之氧化物濺鍍靶之比電阻高而在可測定範圍外，無法進行直流(DC)濺鍍。因此，關於比較例1、4、5、6、7之氧化物濺鍍靶，係利用高頻(RF)濺鍍而成膜。 又，實施例1~26及比較例1~8之氧化物濺鍍靶密度比均為90%以上。
又，關於表示保護膜柔軟度(柔軟)之膜之壓痕硬度，比較例1、3之保護膜超過800mgf/μm2，該等保護膜會發生膜破裂。相對於此等，關於實施例1~26之保護膜均為800mgf/μm2以下，與比較例1、3相比，獲得具有柔軟性之膜，實施例1~26之保護膜並未發生膜破裂。又，ITO膜的比較例8之保護膜發生膜破裂。
再者，針對反射率變化，於ZnS-SiO2之比較例7有較大變化，相對地，實施例1~26之保護膜均為1.0%以下之較少變化率，獲得高的保存性。
又，上述實施例1~26之保護膜在常溫下為非晶型。
接著，關於實施例1~26之氧化物濺鍍靶之任一者，進行X射線繞射(XRD)之結果，檢測出屬於ZnO之繞射峰，及屬於SnO2與ZnO之複合氧化物的Zn2SnO4之繞射峰，確認存在ZnO及Zn2SnO4之相。
此處，作為參考，針對比較例2之氧化物濺鍍靶之X射線繞射(XRD)結果之圖表示於圖3，而且，利用EPMA(場發射型電子束探針)測定之反射電子像(CP)及顯示各元素組成分佈之元素分佈像示於圖4。又，EPMA測得之元素分佈像之見解與圖2所示之情況相同。由該等圖像，可知於圖2所示之本發明之氧化物濺鍍靶之元素分佈像係由ZnO及Zn2SnO4之相所構成，Al係選擇性分散於ZnO相中，但於比較例2之氧化物濺鍍靶 之情況，可知SnO2相係存在於以ZnO為主之相中。其狀態於圖像中係以虛線包圍SnO2之相顯示。SnO2相之存在，亦可由XRD之圖表中SnO2之峰顯示、6/100而確認。
又，本發明中，為利用作為氧化物濺鍍靶，較好面粗糙度：5.0μm以下，更好1.0μm以下，粒徑：20μm以下，更好10μm以下，金屬系雜質濃度：0.1原子%以下，更好為0.05原子%以下，繞射強度：50MPa以上，更好100MPa以上，而上述實施例1~26之氧化物濺鍍靶均為滿足任一該等條件者。
又，本發明之技術範圍並不限於上述實施形態及上述實施例，可在不脫離本發明精神之範圍內進行各種改變。
例如，上述實施形態及上述實施例係藉由熱加壓進行加壓燒結，但作為其他方法，亦可採用熱等靜壓式燒結法(HIP法)。
[產業上之可利用性]
本發明可提供可較好地使用作為使用有機色素之記錄層之BD用介電體保護膜之光記錄媒體用保護膜。

Claims (2)

  1. 一種氧化物膜，其特徵為：其係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成之氧化物燒結體，前述氧化物燒結體之組織係具有ZnO及Zn2SnO4之相，在前述氧化物燒結體之X射線繞射分析中，係使用SnO2相的峰強度比為1/100以下之氧化物濺鍍靶進行濺鍍成膜，相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，其餘為由Zn及不可避免雜質所構成成分組成之氧化物。
  2. 一種氧化物膜，其特徵為：其係相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而，含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成之氧化物燒結體，前述氧化物燒結體之組織係具有ZnO及Zn2SnO4之相，在前述氧化物燒結體之X射線繞射分析中，係使用SnO2相的峰強度比為1/100以下之氧化物濺鍍靶進行濺鍍成膜， 相對於全部金屬成分量，含有Al、Ga及In中之一種以上之合計：0.15at%以上，且Sn：7at%以上，Al、Ga、In及Sn之合計：36at%以下，進而，含有Ge及Cr中之一種以上之合計：1.0~20.0at%，其餘為由Zn及不可避免雜質所構成成分組成之氧化物。
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