TW202106655A - 氧化物燒結體 - Google Patents

氧化物燒結體 Download PDF

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TW202106655A
TW202106655A TW109121621A TW109121621A TW202106655A TW 202106655 A TW202106655 A TW 202106655A TW 109121621 A TW109121621 A TW 109121621A TW 109121621 A TW109121621 A TW 109121621A TW 202106655 A TW202106655 A TW 202106655A
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Taiwan
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sintered body
oxide sintered
atomic ratio
less
film
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TW109121621A
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English (en)
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TWI855099B (zh
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笘井重和
上岡義弘
勝又聡
佐佐木健一
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日商出光興產股份有限公司
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Abstract

本發明係一種氧化物燒結體，其包含鋅、鎂、正3價或正4價之金屬元素X、及氧作為構成元素，金屬元素X相對於鋅、鎂及金屬元素X之總計之原子比[X/(Zn＋Mg＋X)]為0.0001以上0.6以下，鎂相對於鋅及鎂之總計之原子比[Mg/(Zn＋Mg)]為0.25以上0.8以下。

Description

氧化物燒結體
本發明係關於一種氧化物燒結體、及用於形成薄膜之成膜用材料。
MgO-ZnO系氧化物有應用於彩色液晶投影儀用透光性陶瓷(專利文獻1)、氧化物半導體(專利文獻2)、透明電極(專利文獻3)等之例。例如，專利文獻3中揭示有一種包含粒子(a)及粒子(b)之燒結體，其原子比為Al/(Zn＋Al＋Mg)＝0.005～0.1、Mg/(Zn＋Al＋Mg)＝0.001～0.05，上述粒子(a)含有氧化鋅且具有平均粒徑為10 μm以下之六方晶系纖鋅礦型結構，上述粒子(b)含有鋁且具有平均粒徑為5 μm以下之尖晶石結構。 上述燒結體係重視導電性之材料，但由於以ZnO作為主要成分，故於紫外線區域之透光性上存在課題。 先前技術文獻 專利文獻
專利文獻1：日本專利特開2009-184898號公報 專利文獻2：日本專利特開2012-066968號公報 專利文獻3：日本專利特開2011-063866號公報
本發明之目的之一在於提供一種能夠獲得紫外線區域之透光性較高，且導電性亦較高之膜的氧化物燒結體。
本發明人等發現：藉由使用於Mg及Zn系之氧化物中以特定濃度添加正3價或正4價之金屬元素而成之氧化物燒結體來進行成膜，可獲得紫外線區域之透光性較高且導電性亦良好之膜。
根據本發明，提供以下之氧化物燒結體等。 1.   一種氧化物燒結體，其包含鋅、鎂、正3價或正4價之金屬元素X、及氧作為構成元素，上述金屬元素X相對於上述鋅、上述鎂及上述金屬元素X之總計之原子比[X/(Zn＋Mg＋X)]為0.0001以上0.6以下，上述鎂相對於上述鋅及上述鎂之總計之原子比[Mg/(Zn＋Mg)]為0.25以上0.8以下。 2.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.625以上0.8以下。 3.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.626以上0.75以下。 4.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.628以上0.74以下。 5.   如2至4中任一項記載之氧化物燒結體，其包含固溶有Zn之立方晶體之MgO、及固溶有Zn之MgX2 O4 (X係正3價之金屬元素)。 6.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.25以上且未達0.625。 7.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.30以上0.60以下。 8.   如1記載之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.40以上0.59以下。 9.   如6至8中任一項記載之氧化物燒結體，其包含固溶有Zn之立方晶體之MgO、固溶有Mg之六方晶體之ZnO及固溶有Zn之MgX2 O4 (此處X係正3價之金屬元素)。 10.  如1至9中任一項記載之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.003以上0.6以下。 11.  如1至9中任一項記載之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.007以上0.5以下。 12.  如1至9中任一項記載之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.008以上0.5以下。 13.  如1至9中任一項記載之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.01以上0.5以下。 14.  如1至13中任一項記載之氧化物燒結體，其中上述X係Al及Ga中之至少一者。 15.  如14記載之氧化物燒結體，其中上述X係Al。 16.  如14記載之氧化物燒結體，其中上述X係Ga。 17.  一種成膜用材料，其包含如1至16中任一項記載之氧化物燒結體。 18.  如17記載之成膜用材料，其係成膜用小片。 19.  如17記載之成膜用材料，其係濺鍍靶。 20.  一種薄膜，其係使用如17至19中任一項記載之成膜用材料所獲得。
根據本發明，可提供一種能夠獲得紫外線區域之透光性較高且導電性亦較高之膜之氧化物燒結體。
本發明之一實施方式之氧化物燒結體包含鋅(Zn)、鎂(Mg)、正3價或正4價之金屬元素(X)、及氧(O)作為構成元素。並且，原子比[X/(Zn＋Mg＋X)]為0.0001以上0.6以下，原子比[Mg/(Zn＋Mg)]為0.25以上0.8以下。
於本實施方式中，作為正3價或正4價之金屬元素X，可列舉Al、Ga、In、Sc、Y。較佳為Al及/或Ga，更佳為Al。藉由包含Al，氧化物燒結體之相對密度變高。相對密度較高意味著能成為成膜時之異常放電之原因或產生結核之起點的空隙較少，因此，例如於將氧化物燒結體作為濺鍍靶之情形時，濺鍍時較少產生破裂等，能夠實現穩定之濺鍍。
原子比[X/(Zn＋Mg＋X)]為0.0001以上0.6以下。藉由滿足該範圍，而成為可形成兼具紫外線區域之透光性及導電性之膜之氧化物燒結體。 原子比[X/(Zn＋Mg＋X)]可為0.006以上，亦可超過0.007，亦可為0.008以上，亦可為0.01以上。又，原子比[X/(Zn＋Mg＋X)]可為0.5以下，亦可為0.2以下，亦可為0.1以下。
原子比[Mg/(Zn＋Mg)]為0.25以上0.8以下。藉由滿足該範圍，而成為可形成兼具紫外線區域之透光性及導電性之膜之氧化物燒結體。再者，於原子比超過0.8之情形時，即便對自氧化物燒結體所得之膜進行退火，亦無法獲得導電性較高之膜。另一方面，於未達0.25之情形時，膜之紫外線透過率降低。
於一實施方式中，原子比[Mg/(Zn＋Mg)]為0.625以上0.8以下。藉由滿足該範圍，成為可獲得主要紫外線區域之透光性優異之膜之氧化物燒結體。 原子比[Mg/(Zn＋Mg)]可為0.626以上，亦可為0.628以上。又，原子比[Mg/(Zn＋Mg)]可為0.75以下，亦可為0.70以下，亦可為0.67以下。
於一實施方式中，原子比[Mg/(Zn＋Mg)]為0.25以上且未達0.625。藉由滿足該範圍，成為可獲得主要導電性優異之膜之氧化物燒結體。 原子比[Mg/(Zn＋Mg)]可為0.30以上，亦可為0.40以上。又，原子比[Mg/(Zn＋Mg)]可為0.60以下，亦可為0.55以下。
鋅、鎂及金屬元素X之原子比可藉由調節起始原料之原子比來進行控制。氧化物燒結體之原子比有與起始原料之原子比相比，鋅之比率變高，金屬元素X之原子比變得大致相同之傾向。
氧化物燒結體中所含之各元素之原子比可藉由感應耦合電漿發光分析裝置(ICP-AES)，對含有元素進行分析而求出。具體而言，若藉由噴霧器使溶液試樣為霧狀，並將其導入至氬電漿(約5000～8000℃)，則試樣中之元素吸收熱能而得到激發，軌道電子自基態躍遷到高能階之軌道後，向更低能階之軌道躍遷。此時，將能量之差作為光來放射以進行發光。由於該光表示元素固有之波長(光譜線)，故可根據有無光譜線來確認元素之存在(定性分析)。又，由於光譜線之大小(發光強度)與試樣中之元素數成正比，故可藉由與已知濃度之標準溶液進行比較而求出試樣濃度(定量分析)。藉由定性分析特定所含有之元素後，藉由定量分析求出含量，根據該結果求出各元素之原子比。
本實施方式之氧化物燒結體之構成元素本質上亦可包含(consisting essentially of)Mg、Zn、金屬元素X及O。本實施方式之氧化物燒結體之構成元素之例如70 mol%以上、80 mol%以上、或90 mol%以上可為Mg、Zn、金屬元素X及O。又，本實施方式之氧化物燒結體之構成元素可僅由Mg、Zn、金屬元素X及O所構成(consisting of)。於該情形時，亦可包含不可避免之雜質。
於原子比[Mg/(Zn＋Mg)]為0.625以上0.8以下之情形時，氧化物燒結體包含固溶有Zn之立方晶體之MgO、及固溶有Zn之MgX2 O4 (X係正3價之金屬元素)。又，於原子比[Mg/(Zn＋Mg)]為0.25以上且未達0.625之情形時，氧化物燒結體包含固溶有Zn之立方晶體之MgO、固溶有Mg之六方晶體之ZnO及固溶有Zn之MgX2 O4 (此處，X係正3價之金屬元素)。藉此，即便為相對輕金屬之氧化物，亦能夠獲得高密度之燒結體。
氧化物燒結體包含上述各氧化物可藉由如下方式確認：將藉由X射線繞射(XRD)法所獲得之XRD圖、與ICDD(國際繞射資料中心)之資料庫(PDF：Powder Diffraction File)進行對照。又，各結晶固溶有其他金屬元素可藉由如下方式判斷：將藉由XRD所求出之晶格常數(實測值)與PDF中所記載之晶格常數(PDF值)進行比較。例如，於固溶有Zn之結晶之情形時，實測值變得大於PDF值。
本實施方式之氧化物燒結體例如可藉由如下步驟進行製造：混合原料粉末而製備混合粉末之步驟；將混合粉末成型而製成成型體之步驟；及對成型體進行煅燒之步驟。 作為起始原料，可使用包含Mg之化合物之粉末、包含Zn之化合物之粉末、及包含金屬元素X之化合物之粉末。化合物較佳為氧化物。例如可列舉MgO、ZnO、Al2 O3 、Ga2 O3 。 原料粉末之混合比例如可考慮所欲獲得之氧化物燒結體之原子比來進行調節。
原料粉末之平均粒徑較佳為0.1～1.2 μm，更佳為0.5～1.0 μm。原料粉末之平均粒徑可藉由雷射繞射式粒度分佈裝置等進行測定。
原料之混合、成型方法並無特別限定，可採用公知之方法。又，於混合時亦可添加黏合劑。 原料之混合時，例如可使用球磨機、珠磨機、噴射磨機或超音波裝置等公知之裝置來進行。混合時間只要適當調整即可，較佳為6～100小時左右。
成型方法例如可對混合粉末進行加壓成型而製成成型體。藉由該步驟，可成型為製品形狀(例如，作為濺鍍靶適宜之形狀)。
將混合粉末填充至模具中，通常藉由模具加壓或冷均壓加壓(CIP)，例如藉由以1000 kg/cm2 以上進行加壓，可獲得成型體。 再者，於成型時，亦可使用聚乙烯醇、聚乙二醇、甲基纖維素、聚蠟、油酸、硬脂酸等成型助劑。
可將所得之成型體例如於1200～1650℃之溫度下加熱2小時以上而獲得氧化物燒結體。 加熱溫度較佳為1350～1600℃，更佳為1400～1600℃，進而較佳為1450～1500℃。加熱時間較佳為2～72小時，更佳為3～48小時，進而較佳為4～24小時。
關於煅燒，通常將成型體於大氣環境、或氧氣環境下進行加熱。氧氣環境較佳為氧濃度例如為10～50體積%之環境。
本實施方式之氧化物燒結體可適宜地用作成膜用材料、例如藉由真空蒸鍍法或離子鍍覆法來成膜時所使用之小片、濺鍍靶，上述成膜用材料用以形成具有氧化物燒結體之組成之薄膜。自本實施方式之成膜用材料所得之薄膜可用作透明導電膜，該透明導電膜係用於紫外發光二極體、紫外發光雷射二極體等之電極基板。
再者，於成膜後以高溫對膜進行熱處理，藉此膜之紫外線透過率及導電性提高。剛成膜後之膜為均勻地混合有鋅氧化物與鎂氧化物等之狀態。藉由對該狀態之膜進行熱處理，而產生氧化物之凝聚、分離等，作為結果，推測鋅氧化物形成網狀結構，藉此表現出導電性，另一方面，鎂氧化物於鋅氧化物之網絡之間隙凝聚，藉此紫外線透過。 電極層之熱處理溫度較佳為750℃以上，更佳為900℃以上。
小片例如可藉由如下方式製作：將原料成型為所需形狀並進行煅燒而獲得氧化物燒結體，對該氧化物燒結體進行切削或研磨加工。濺鍍靶例如可藉由如下方式製作：將氧化物燒結體進行切削或研磨加工並接合於背襯板。 可藉由進行切削加工而除去凸凹之面。又，可成為指定之大小。亦可對表面進行＃200號、或＃400號、進而＃800號之研磨。藉此，可抑制濺鍍中之異常放電或顆粒之產生。
將經研磨之氧化物燒結體視需要洗淨後，於接合面塗佈金屬銦焊料等接合材料，與背襯板進行接合，藉此可獲得濺鍍靶。 [實施例]
實施例1 (A)氧化物燒結體之製作 以各金屬之原子比成為表1所示之值之方式秤量平均粒徑為1 μm以下之氧化鋅(ZnO)粉末、及平均粒徑為1 μm以下之氧化鎂(MgO)粉末、平均粒徑為1 μm以下之氧化鎵(Ga2 O3 粉末)並加以混合。再者，混合粉末之質量分率為如下：ZnO為43.9質量%，MgO為40.8質量%，Ga2 O3 為15.3質量%。 將混合粉末加入至樹脂製坩堝後，加入水，使用硬質ZrO2 球作為粉碎介質，利用濕式球磨機混合20小時。取出所得之混合漿料，進行過濾、乾燥及造粒。將所得之造粒物加入至模具，利用冷均壓加壓來加壓至3 ton/cm2 而成型。
將所得之成型體載置於燒結爐內，一面使氧氣以爐內容積每0.1 m3 為5 L/分鐘之比率流入，一面煅燒成型體。 將燒結爐內之溫度以1℃/分鐘自室溫升溫至1000℃，自1000℃以3℃/分鐘進行升溫直至1470℃，於1470℃下煅燒5小時。其後，停止流入氧氣，將爐內溫度自1470℃以10℃/分鐘降溫至1300℃。繼而，一面使Ar以爐內容積每0.1 m3 為10 L/分鐘之比率流入，一面將爐內溫度於1300℃下保持3小時。其後，藉由放置冷卻而獲得氧化物燒結體。
對於所得之氧化物燒結體評估組成及相對密度。將結果示於表2。
[表1]
   起始原料之原子比
   Mg Zn X Mg/(Zn＋Mg) X/(Zn＋Mg＋X)
實施例1 0.590 0.315 Ga：0.095 0.652 0.095
實施例2 0.590 0.315 Al：0.095 0.652 0.095
實施例3 0.380 0.120 Ga：0.500 0.760 0.500
實施例4 0.630 0.360 Al：0.010 0.636 0.010
實施例5 0.628 0.369 Al：0.003 0.630 0.003
實施例6 0.626 0.367 Al：0.007 0.630 0.007
比較例1 0.650 0.350 0 0.650 0
[表2]
   氧化物燒結體之原子比 相對密度
   Mg Zn X Mg/(Zn＋Mg) X/(Zn＋Mg＋X) (%)
實施例1 0.582 0.318 Ga：0.100 0.647 0.100 89
實施例2 0.582 0.318 Al：0.100 0.647 0.100 100
實施例3 0.370 0.130 Ga：0.500 0.740 0.500 80
實施例4 0.623 0.367 Al：0.010 0.629 0.010 95
實施例5 0.626 0.371 Al：0.003 0.628 0.003 89
實施例6 0.624 0.369 Al：0.007 0.628 0.007 89
比較例1 0.640 0.360 0 0.640 0 88
評估方法係如下所述。 (1)氧化物燒結體中之金屬元素之原子比 切出所得之氧化物燒結體之一部分，使之溶解於酸中後，藉由感應耦合電漿發光分析裝置來進行分析。 (2)相對密度 相對密度係藉由如下方式算出：藉由使用水之阿基米德法來測定氧化物燒結體之實際密度，並用所測得之實際密度除以自組成算出之理論密度。再者，理論密度係自無氧缺陷之MgO結晶、Zn氧化物、及X(Ga或Al)之氧化物之質量分率而算出。
(3)XRD測定 藉由下述裝置及條件進行測定。 ・裝置：RIGAKU股份有限公司製造之Ultima-III ・X射線：Cu-Kα射線(波長1.5406 Å、利用石墨單色器進行單色化) ・2θ-θ反射法、連續掃描(1.0°/分鐘) ・採樣間隔：0.02° ・狹縫DS、SS：2/3°、RS：0.6 mm
利用綜合粉末X射線分析軟體(RIGAKU股份有限公司製造、PDXL2)對XRD測定結果進行分析，藉此求出氧化物燒結體所含有之結晶結構及晶格常數。再者，結晶結構係藉由下述ICDD(PDF)卡來確認。 ZnO：01-079-0205(六方晶體) ZnO：01-077-0191(立方晶體) MgO：01-071-1176(立方晶體) MgAl2 O4 ：01-084-0377 MgGa2 O4 ：01-073-1721
於圖1中表示XRD圖之分析結果。自圖1確認到於氧化物燒結體中包含ZnO、MgO及MgGa2 O4 作為結晶結構。 根據晶格常數之實測值與PDF值，對固溶有Zn之MgO、及固溶有Zn之MgX2 O4 (X＝Ga或Al)之存在進行評估。 關於MgO之晶格常數a，實測值為4.2314，PDF值為4.217。關於ZnO之晶格常數a，實測值為3.2423，PDF值為3.242。關於MgGa2 O4 之晶格常數a，實測值為8.3116，PDF值為8.26。根據該結果確認到MgO及MgGa2 O4 之晶格常數a之差較大，而判斷於該等結晶中固溶有Zn。再者，於晶格常數變化0.01以上之情形時，判斷為固溶。 將結果示於表3。表中，將包含之情形設為○，將不含之情形設為×。
[表3]
   Zn固溶MgO Zn固溶MgX2 O4 X＝Ga或Al
實施例1 〇 〇
實施例2 〇 〇
實施例3 〇 〇
實施例4 〇 〇
實施例5 〇 〇
實施例6 〇 〇
比較例1 〇 ×
(B)濺鍍靶之製作 針對所得之氧化物燒結體，利用杯形磨石對成為濺鍍面之面進行研磨，加工成直徑100 mm、厚度5 mm。使用In系合金，將背襯板貼合於經研磨之氧化物燒結體而製作濺鍍靶。
使用由氧化物燒結體製作之濺鍍靶，實際地形成薄膜並進行評估。成膜條件係如下所述。 將藍寶石基板(厚度0.5 mm)放入至超音波洗淨器中，利用三氯乙烯洗淨5分鐘，利用丙酮洗淨5分鐘，利用甲醇洗淨5分鐘，最後利用蒸餾水洗淨5分鐘。 將該基板設置於濺鍍裝置(ULVAC製：ACS-4000)中，使用Ar作為濺鍍氣體，於25℃下進行成膜，於基板上形成厚度100 nm之膜。
(2)熱處理 將上述(1)中形成有膜之基板於氮氣環境下以950℃進行5分鐘熱處理(活化退火)。針對熱處理後之膜，使用三菱化學製造之LorestaFP來測定表面電阻。又，使用分光光度計(島津製作所製造：UV-2600)來評估紫外線透過率。 將評估結果示於表4。
[表4]
   紫外線透過率(%) 電阻(Ωcm)
實施例1 30 100
實施例2 30 100
實施例3 40 1×104
實施例4 20 1
實施例5 20 100
實施例6 20 1000
比較例1 35 1×105
實施例2～6、比較例1 以各金屬元素之原子比成為表1所示之值之方式秤量原料並加以混合，除此以外，以與實施例1相同之方式製作氧化物燒結體及濺鍍靶並進行評估。將結果示於表2～4。再者，於金屬元素X為Al之實施例中，使用平均粒徑為1 μm以下之氧化鋁(Al2 O3 粉末)。 於圖2中表示實施例2之氧化物燒結體之XRD圖之分析結果。於圖3中表示比較例1之氧化物燒結體之XRD圖之分析結果。
實施例7 (A)氧化物燒結體之製作 以各金屬之原子比成為表所示之值之方式秤量平均粒徑為1 μm以下之氧化鋅(ZnO)粉末、及平均粒徑為1 μm以下之氧化鎂(MgO)粉末、平均粒徑為1 μm以下之氧化鎵(Ga2 O3 粉末)並加以混合。再者，混合粉末之質量分率如下：ZnO為48.9質量%、MgO為36.3質量%、Ga2 O3 為14.8質量%。 將混合粉末加入至樹脂製坩堝中後，加入水，使用硬質ZrO2 球作為粉碎介質，利用濕式球磨機混合20小時。取出所得之混合漿料，進行過濾、乾燥及造粒。將所得之造粒物加入至模具中，利用冷均壓加壓來加壓至3 ton/cm2 而成型。
將所得之成型體載置於燒結爐內，一面使氧氣以爐內容積每0.1 m3 為5 L/分鐘之比率流入，一面煅燒成型體。 將燒結爐內之溫度以1℃/分鐘自室溫升溫至1000℃，自1000℃以3℃/分鐘升溫至1470℃，於1470℃下煅燒5小時。其後，停止流入氧氣，將爐內溫度以10℃/分鐘自1470℃降溫至1300℃。繼而，一面使Ar以爐內容積每0.1 m3 為10 L/分鐘之比率流入，一面將爐內溫度於1300℃下保持3小時。其後，藉由放置冷卻獲得氧化物燒結體。
針對所得之氧化物燒結體，以與實施例1相同之方式對組成及相對密度進行評估。將結果示於表6。
[表5]
   起始原料之原子比
   Mg Zn X Mg/(Zn＋Mg) X/(Zn＋Mg＋X)
實施例7 0.543 0.362 Ga：0.095 0.60 0.095
實施例8 0.543 0.362 Al：0.095 0.60 0.095
比較例2 0.60 0.40 0 0.60 0
實施例9 0.36 0.63 Al：0.01 0.36 0.01
實施例10 0.13 0.37 Ga：0.50 0.26 0.50
實施例11 0.538 0.459 Al：0.003 0.54 0.003
實施例12 0.536 0.457 Al：0.007 0.54 0.007
實施例13 0.535 0.455 Al：0.01 0.54 0.01
[表6]
   氧化物燒結體之原子比 相對密度
   Mg Zn X Mg/(Zn＋Mg) X/(Zn＋Mg＋X) (%)
實施例7 0.534 0.371 Ga：0.095 0.59 0.095 80
實施例8 0.534 0.371 Al：0.095 0.59 0.095 95
比較例2 0.59 0.41 0 0.59 0 90
實施例9 0.357 0.633 Al：0.01 0.361 0.01 90
實施例10 0.128 0.372 Ga：0.500 0.256 0.50 85
實施例11 0.534 0.463 Al：0.003 0.536 0.003 90
實施例12 0.533 0.460 Al：0.007 0.537 0.007 90
實施例13 0.532 0.458 Al：0.01 0.537 0.01 94
於圖4中表示XRD圖之分析結果。自圖4確認到於氧化物燒結體中包含ZnO(六方晶體)、MgO(立方晶體)、MgGa2 O4 及Ga2 O3 (ZnO)6 作為結晶結構。再者，關於Ga2 O3 (ZnO)6 ，由於擬合率較差，故推測存在。 根據晶格常數之實測值與PDF值，對固溶有Zn之MgO(立方晶體)、固溶有Mg之ZnO(六方晶體)及固溶有Zn之MgX2 O4 (X＝Ga或Al)之存在進行評估。 關於MgO之晶格常數a，實測值為4.2307，PDF值為4.217。關於ZnO之晶格常數a，實測值為3.2482，PDF值為3.242。關於MgGa2 O4 之晶格常數a，實測值為8.3121，PDF值為8.26。如上所述，晶格常數產生變化，據此判斷於ZnO中固溶有Mg，又，於MgO及MgGa2 O4 中固溶有Zn。 將結果示於表7。表中，將包含之情形時設為○，將不含之情形時設為×。
[表7]
   Zn固溶MgO Mg固溶ZnO (六方晶體) Zn固溶MgX2 O4 X＝Ga或Al
實施例7 〇 〇 〇
實施例8 〇 〇 〇
比較例2 〇 〇 ×
實施例9 〇 〇 〇
實施例10 〇 〇 〇
實施例11 〇 〇 〇
實施例12 〇 〇 〇
實施例13 〇 〇 〇
(B)濺鍍靶之製作 使用實施例7之氧化物燒結體，除此以外，以與實施例1相同之方式製作濺鍍靶並進行評估。將結果示於表8。
[表8]
   紫外線透過率(%) 電阻(Ωcm)
實施例7 12 0.001
實施例8 12 0.05
比較例2 15 1000
實施例9 10 0.001
實施例10 18 0.1
實施例11 18 1
實施例12 18 0.5
實施例13 18 0.05
實施例8～13、比較例2 以各金屬元素之原子比成為表5所示之值之方式秤量原料並加以混合，除此以外，以與實施例7相同之方式製作氧化物燒結體及濺鍍靶並進行評估。將結果示於表6～8。再者，於金屬元素X為Al之實施例中，使用平均粒徑為1 μm以下之氧化鋁(Al2 O3 粉末)。 於圖5中表示實施例8之氧化物燒結體之XRD圖之分析結果。於圖6中表示比較例2之氧化物燒結體之XRD圖之分析結果。
以上對若干本發明之實施方式及/或實施例詳細地進行了說明，但業者容易於不實質性地脫離本發明之新穎教導及效果之情況下，對該等作為例示之實施方式及/或實施例加以較多變更。因此，該等較多變更係包含於本發明之範圍內。 將該說明書所記載之文獻、及本申請之以巴黎條約之優先權為基礎之申請內容全部引用於此。
圖1係表示實施例1之氧化物燒結體之XRD圖之分析結果的圖。 圖2係表示實施例2之氧化物燒結體之XRD圖之分析結果的圖。 圖3係表示比較例1之氧化物燒結體之XRD圖之分析結果的圖。 圖4係表示實施例7之氧化物燒結體之XRD圖之分析結果的圖。 圖5係表示實施例8之氧化物燒結體之XRD圖之分析結果的圖。 圖6係表示比較例2之氧化物燒結體之XRD圖之分析結果的圖。

Claims (20)

  1. 一種氧化物燒結體，其包含鋅、鎂、正3價或正4價之金屬元素X、及氧作為構成元素， 上述金屬元素X相對於上述鋅、上述鎂及上述金屬元素X之總計之原子比[X/(Zn＋Mg＋X)]為0.0001以上0.6以下， 上述鎂相對於上述鋅及上述鎂之總計之原子比[Mg/(Zn＋Mg)]為0.25以上0.8以下。
  2. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.625以上0.8以下。
  3. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.626以上0.75以下。
  4. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.628以上0.74以下。
  5. 如請求項2之氧化物燒結體，其包含固溶有Zn之立方晶體之MgO、及固溶有Zn之MgX2 O4 (X係正3價之金屬元素)。
  6. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.25以上且未達0.625。
  7. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.30以上0.60以下。
  8. 如請求項1之氧化物燒結體，其中上述原子比[Mg/(Zn＋Mg)]為0.40以上0.59以下。
  9. 如請求項6之氧化物燒結體，其包含固溶有Zn之立方晶體之MgO、固溶有Mg之六方晶體之ZnO及固溶有Zn之MgX2 O4 (此處X係正3價之金屬元素)。
  10. 如請求項1至9中任一項之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.003以上0.6以下。
  11. 如請求項1至9中任一項之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.007以上0.5以下。
  12. 如請求項1至9中任一項之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.008以上0.5以下。
  13. 如請求項1至9中任一項之氧化物燒結體，其中上述原子比[X/(Zn＋Mg＋X)]為0.01以上0.5以下。
  14. 如請求項1至9中任一項之氧化物燒結體，其中上述X係Al及Ga中之至少一者。
  15. 如請求項14之氧化物燒結體，其中上述X係Al。
  16. 如請求項14之氧化物燒結體，其中上述X係Ga。
  17. 一種成膜用材料，其包含如請求項1至16中任一項之氧化物燒結體。
  18. 如請求項17之成膜用材料，其係成膜用小片。
  19. 如請求項17之成膜用材料，其係濺鍍靶。
  20. 一種薄膜，其係使用如請求項17至19中任一項之成膜用材料所獲得。
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