TWI826566B - 燒結體 - Google Patents

燒結體 Download PDF

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TWI826566B
TWI826566B TW108139464A TW108139464A TWI826566B TW I826566 B TWI826566 B TW I826566B TW 108139464 A TW108139464 A TW 108139464A TW 108139464 A TW108139464 A TW 108139464A TW I826566 B TWI826566 B TW I826566B
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sintered body
magnesium
zinc
atomic ratio
film
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笘井重和
上岡義弘
勝又聡
佐佐木健一
大山正嗣
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日本商出光興產股份有限公司
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Abstract

本發明之燒結體包含鋅及鎂及氧作為構成元素，且鋅相對於鋅與鎂之合計之原子比[Zn/(Zn＋Mg)]為0.20～0.75，鎂相對於鋅與鎂之合計之原子比[Mg/(Zn＋Mg)]為0.25～0.80，X射線繞射測定之結果為，該燒結體包含單一之結晶結構。

Description

燒結體
本發明係關於一種燒結體、用於形成薄膜之成膜用板片及濺鍍靶。
作為具有透光性之薄膜，使用氧化物薄膜。氧化物薄膜例如用於發光二極體等半導體裝置之電極。 MgO-ZnO系氧化物有作為透光性陶瓷應用於彩色液晶投影機之實施例(例如參照專利文獻1)。又，揭示有具有如下特徵之ZnO-MgO系濺鍍靶用燒結體：以MgO換算計含有3～50 mol%之Mg，MgO相(包含富集MgO之固溶相)之最大結晶粒徑為10 μm以下，且具有均勻地分散之組織(參照專利文獻2)。本文獻中，將獲得之薄膜用作太陽電池之窗材。
且說，於煅燒含有氧化鋅及氧化鎂之成型體之情形時，因混合比不同，存在進行濺鍍或蒸鍍後之燒結體之氧化變得不均勻，產生周邊部與中央部或表面與內部形成色調差異之問題(鋅之析出或結核等色不均之產生)之情形。產生色不均之燒結體不適合作為要求材質之均勻性之濺鍍靶或板片等成膜用材料。 於產生色不均之成膜用材料中，需要藉由研磨而全部削掉燒結體表面之色不均部分之步驟。因此，削掉之材料變得無用，又，存在需要用於研磨之附加的步驟之問題。
即便削掉色不均，亦存在藉由濺鍍而使得腐蝕部與周邊部上易再次產生色不均之問題。 如此，存在因色不均之產生而使得製造步驟繁雜化及製造費用變高之問題。 [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：國際公開第2012/014688號公報
本發明之目的在於提供一種可抑制成膜時產生色不均並減少異常放電之成膜用材料。
根據本發明之一實施形態，提供以下燒結體等。 1.一種燒結體，其包含鋅及鎂及氧作為構成元素， 且上述鋅相對於上述鋅及鎂之合計之原子比[Zn/(Zn＋Mg)]為0.20～0.75， 上述鎂相對於上述鋅及鎂之合計之原子比[Mg/(Zn＋Mg)]為0.25～0.80， X射線繞射測定之結果為，該燒結體包含單一之結晶結構。 2.如1所記載之燒結體，其中上述鋅之原子比為0.20～0.49，上述鎂之原子比為0.51～0.80。 3.如1或2所記載之燒結體，其中上述單一之結晶結構為MgO之立方晶。 4.一種成膜用板片，其包含如1至3中任一項所記載之燒結體。 5.一種濺鍍靶，其包含如1至3中任一項所記載之燒結體。
根據本發明之一實施形態，可提供一種可抑制成膜時產生色不均並減少異常放電之成膜用材料。
本發明之一實施形態之燒結體包含鋅及鎂及氧作為構成元素，X射線繞射測定之結果為包含單一之結晶結構。此處，「X射線繞射測定之結果為，該燒結體包含單一之結晶結構」係指主要僅包含1種對X射線繞射測定之結果進行WPF(全圖案擬合)及里特沃爾德分析而確認存在之結晶結構之情形。 又，除主要的結晶結構以外，即便確認微量之結晶結構，於來自其他結晶結構之繞射峰中之最大峰之峰強度(I0 )相對於來自主要的結晶結構之繞射峰中之最大峰之峰強度(I1 )之強度比(I0 /I1 )為0.01以下之情形時，亦判斷結晶結構主要包含1種。較佳為未觀察到來自其他結晶結構之繞射峰。
例如，於單一之結晶結構為MgO之立方晶之情形時，於X射線繞射圖案中，於2θ＝37.0±1.0 deg、43.0±1.0 deg及62.3±1.0 deg時觀察到繞射峰。該等之中，最大峰於2θ＝43.0±1.0 deg時被觀察到。比較本峰之峰強度(I1 )及來自其他結晶結構之繞射峰中之最大峰之峰強度(I0 )。
於本實施形態中，作為單一之結晶結構，例如可列舉MgO之立方晶。MgO之立方晶例如可利用JCPDS卡片：75-0447而確認。 又，本實施形態之燒結體只要結晶結構為單一即可，可包含一部分非晶質成分。
本實施形態之燒結體包含鋅及鎂及氧作為構成元素可利用電子探針微量分析器(EPMA)而確認。又，認為鋅、鎂及氧主要是氧化鎂之鎂之一部分構成取代鋅之混晶(氧化鎂與氧化鋅之固溶體)。
於本實施形態中，較佳為氧均勻地分散。氧均勻地分散可藉由利用電子探針微量分析器(EPMA)、於觀察燒結體之表面而獲得之元素映射中確認分析氧元素之結果而判斷。本案中，於元素映射中，於3 μm×5 μm見方之區域如實施例1之元素映射(圖1)般、濃部與淡部均勻地分散之情形時，判斷氧均勻地分散。另一方面，於如比較例1及2般、濃部與淡部清晰地分離、凝聚之情形時，判斷氧不均勻地分散。
於本實施形態中，鋅相對於鋅與鎂之合計之原子比[Zn/(Zn＋Mg)]為0.20～0.75，鎂相對於鋅與鎂之合計之原子比[Mg/(Zn＋Mg)]為0.25～0.80。若為該範圍，則燒結體中之氧進一步均勻地分散、成膜後之色不均之抑制效果進一步變大。若鋅超過0.75，則易成為MgO之立方晶與ZnO之六方晶之混合物，氧有偏集存在於鎂側之傾向。因此，有成膜時產生結核等色不均之情形。又，有濺鍍時鋅易被還原、產生異常放電之虞。於鋅未達0.20之情形時，除作為MgO之立方晶被觀察到之MgZnO相以外，有易產生成膜時析出鋅金屬等色不均、或成為異常放電之原因之虞。
鋅之原子比較佳為0.20～0.49，進而更佳為0.25～0.45。鎂之原子比較佳為0.51～0.80，進而更佳為0.55～0.75。鋅及鎂之原子比可藉由製備起始原料中之原子比而控制。燒結體之原子比與原料中之原子比相比，有鋅之比率變高之傾向。鎂之原子比為0.51～0.80之更佳之原因在於，於將使用燒結體製作之膜用作透過紫外線之電極之情形時，可兼具導電性與紫外線透過性。若鎂之原子比未達0.51，則紫外線之透過率降低。又，若鎂之原子比超過0.80，則導電性降低。 又，於本案中，鋅、鎂等之原子比可藉由X射線繞射測定、螢光X射線分析或感應耦合電漿(ICP)發光分光分析而測定。
本實施形態之燒結體可進而包含正3價之金屬氧化物。正3價意指金屬氧化物中之金屬原子之原子價為＋3。藉由包含正3價之金屬氧化物，而可於形成薄膜時降低電阻。至於作為正3價較佳之金屬氧化物，例如可列舉Al2 O3 、Ga2 O3 。該等金屬氧化物作為提高ZnO之導電性之材料為人所知，但於本實施形態中同樣地作為提高導電性之添加物亦屬有效。 正3價之金屬X之氧化物之較佳之添加量以金屬原子比[X/(X＋Zn＋Mg)]計為0.001～0.1，更佳為0.01～0.07，進而較佳為0.02～0.05。
本實施形態之燒結體之構成元素本質上可包含Mg、Zn、O、及任意正3價之金屬元素(consisting essentially of)。本實施形態之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、O、及任意正3價之金屬元素。又，本實施形態之燒結體之構成元素可僅包含Mg、Zn、O、及任意正3價之金屬元素(consisting of)。於該情形時，可包含不可避雜質。
本實施形態之燒結體例如可藉由將原料粉末混合而製備混合粉末之步驟、使混合粉末成型而製成成型體之步驟、及煅燒成型體之步驟而製造。 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、及包含任意正3價金屬之化合物之粉末。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欲獲得之燒結體之原子比而製備。
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利用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制，可採用公知之方法。又，混合時可添加黏合劑。 原料之混合例如可使用球磨機、珠磨機、噴射磨機或超音波裝置等公知之裝置進行。混合時間只要適當調整即可，但較佳為6～100小時左右。
成型方法例如可對混合粉末進行加壓成型製成成型體。藉由該步驟，可成型為製品之形狀(例如適合作為濺鍍靶之形狀)。
可藉由將混合粉末填充於模具，通常藉由模具加壓或冷均壓加壓(CIP)例如以1000 kg/cm2 以上加壓而獲得成型體。 又，成型時可使用聚乙烯醇或聚乙二醇、甲基纖維素、聚蠟、油酸、硬脂酸等成型助劑。
例如可將獲得之成型體於1200～1650℃之溫度下加熱2小時以上獲得燒結體。 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。
煅燒通常於大氣氛圍、或氧氣氛圍下加熱成型體。氧氣氛圍較佳為例如氧濃度為10～50體積%之氛圍。
本實施形態之燒結體可適當地用作用於形成具有燒結體之組成之薄膜之成膜用材料，例如以真空蒸鍍法或離子鍍覆法進行成膜時使用之板片、濺鍍靶。根據本實施形態之成膜用材料獲得之薄膜可用作紫外發光二極體、紫外發光雷射二極體等之電極基板上使用之透明導電膜。
板片例如可藉由對使原料成型為所需之形狀並煅燒而獲得之燒結體進行切削或研磨加工而製作。濺鍍靶例如可藉由對燒結體進行切削或研磨加工並接合於背襯板而製作。 藉由切削加工可除去凸凹之面。而且，可製成指定之大小。對表面進行＃200粒度號數、或＃400粒度號數、進而＃800粒度號數之研磨。藉此，可抑制濺鍍中之異常放電或粒子之產生。
可藉由視需要將研磨之燒結體洗淨之後，於接合面上塗佈金屬銦焊料等接合材料，與背襯板接合，而獲得濺鍍靶。 [實施例]
實施例1～5、比較例1、2 (A)燒結體之製作 以Mg與Zn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)粉末並混合。將混合粉末放入樹脂製坩堝，進而添加水，使用硬質ZrO2 板作為粉碎媒介，利用濕式球磨機混合20小時。取出獲得之混合漿料，進行過濾、乾燥及造粒。將獲得之造粒物放入模具，以冷均壓加壓進行3 ton/cm2 加壓並成型。
其次，將獲得之成型體載置於燒結爐內。一面以每0.1 m3 爐內容積5 L/分之比率輸入氧，一面煅燒成型體。 使燒結爐內之溫度以1℃/分自室溫升溫至1000℃，並以3℃/分自1000℃升溫至1470℃，於1470℃下煅燒5小時。其後，停止氧之輸入，使爐內溫度以10℃/分自1470℃降溫至1300℃。其次，一面以每0.1 m3 爐內容積10 L/分之比率輸入Ar，一面使爐內溫度保持1300℃ 3小時。其後，藉由放冷而獲得燒結體。
(B)濺鍍靶之製作 針對獲得之燒結體，利用杯式磨石對成為濺鍍面之面進行研磨，加工為直徑100 mm、厚5 mm。使用In系合金，於研磨之燒結體上貼合背襯板，製作濺鍍靶。
針對獲得之各燒結體，將Zn與Mg之原子比及相對密度示於表1。 又，評價濺鍍靶之成膜性。具體而言，評價成膜時是否有異常放電及成膜後之濺鍍靶中是否有色不均(鋅之析出及結核)。將結果示於表1。
[表1]
   原子比(原料) 原子比(燒結體) 相對密度 (%) 色不均 鋅析出 結核 異常放電
   Mg Zn Mg Zn
實施例1 0.80 0.20 0.72 0.28 84 無 無 無 無
實施例2 0.65 0.35 0.60 0.40 86 無 無 無 無
實施例3 0.40 0.60 0.30 0.70 90 無 無 無 無
實施例4 0.53 0.47 0.48 0.52 87 無 無 無 無
實施例5 0.57 0.43 0.52 0.48 85 無 無 無 無
比較例1 0.90 0.10 0.84 0.16 82 有 有 無 有
比較例2 0.33 0.67 0.23 0.77 92 有 無 有 有
評價法如下。 (1)燒結體之Zn與Mg之原子比及結晶結構 藉由WPF(全圖案擬合)及里特沃爾德分析而評價X射線繞射(XRD)測定之結果。XRD之測定條件如下所示。 ・裝置：Rigaku(股)製造Ultima-III ・X射線：Cu-Kα射線(波長1.5406Å、利用石墨單色器單色化) ・2θ-θ反射法、連續掃描(1.0°/分) ・取樣間隔：0.02° ・狹縫DS、SS：2/3°、RS：0.6 mm
(2)相對密度 基於阿基米德法測定燒結體之相對密度。具體而言，用燒結體之空中重量除以體積(＝燒結體之水中重量/測量溫度中之水比重)，將相對於基於下述式之理論密度ρ(g/cm3 )之百分率之值作為相對密度(單位：%)。 ρ＝(C1/100/ρ1＋C2/100/ρ2・・・＋Cn/100/ρn)−1 又，式中，C1～Cn分別表示燒結體或燒結體之構成物質之含量(質量%)，ρ1～ρn表示與C1～Cn對應之各構成物質之密度(g/cm3 )。 又，關於各構成物質之密度，密度與比重幾乎相等，故使用化學便覽 基礎編I日本化學編修定2版(丸善股份有限公司)中記載之氧化物之比重之值。
(3)濺鍍靶之成膜性之評價 使用根據各例之燒結體製作之濺鍍靶，實際地形成薄膜進行評價。成膜條件如下所示。 將作為支持基板之藍寶石基板(厚0.5 mm)放入超音波洗淨器中，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。 其後，將支持基板安裝於濺鍍裝置(ULVAC製造：ACS-4000)，使用各濺鍍靶，於支持基板上形成100 nm厚之膜。 濺鍍氣體使用Ar，溫度設為25℃。 將成膜時未觀察到異常放電之情形記為「無」，將觀察到異常放電之情形記為「有」。 分別以目視評價成膜後之濺鍍靶之表面上是否有色不均(鋅之析出及結核)。將未觀察到之情形記為「無」，將觀察到之情形記為「有」。
・元素映射 利用電子探針微量分析器(EPMA)觀察成膜後之濺鍍靶之表面。圖1中表示利用實施例1、比較例1及2中製作之濺鍍靶之EPMA所得之元素映射。如可根據圖1識別般，實施例1中，確認Mg、Zn及O都均勻地分散之情況。實施例2～5亦相同。另一方面，比較例1及2中，確認O存在於Mg側，Zn有還原跡象。
又，EPMA之測定條件如下所述。 ・裝置名：日本電子股份有限公司JXA-8200 ・測定條件 加速電壓：15 kV 照射電流：50 nA 照射時間(每分)：50 mS 圖1之各元素映射表示縱3 μm、橫5 μm之區域之元素密度，濃部(黑之部位)表示密度較低之部位。
・X射線繞射圖案 將實施例1、比較例1及2中製作之燒結體之X射線繞射圖案示於圖2。 根據圖1之EPMA之圖像可知，實施例1之燒結體係包含MgO中固溶有ZnO之單一之結晶結構(MgO之立方晶)者。實施例2～5亦相同。 比較例1中，除MgO之立方晶以外，觀察到鋅金屬之六方晶。2θ＝36.3°時有鋅金屬特有之峰。鋅金屬之六方晶之最大峰之峰強度(I0 )相對於MgO之立方晶之最大峰之峰強度(I1 )之強度比(I0 /I1 )為0.029。 比較例2中，除MgO之立方晶以外，觀察到ZnO之六方晶(例如，2θ＝36.2 deg之峰)。ZnO之六方晶之最大峰之峰強度(I0 )相對於MgO之立方晶之最大峰之峰強度(I1 )之強度比(I0 /I1 )為3.232。
將實施例1、比較例1及2中製作之濺鍍靶之成膜後之表面照片示於圖3。實施例1之濺鍍靶由於氧均勻地分佈，故可穩定地濺鍍。又，根據圖3可確認，未產生表面突起(結核)。實施例2～5亦與實施例1相同。 另一方面，比較例中，濺鍍時產生異常放電。如圖3，比較例1中，觀察到鋅之析出，比較例2中，產生了結核。
上述對本發明之實施形態及/或實施例進行了一些詳細說明，但業者容易於不實質上脫離本發明之新穎之教導及效果之條件下，對作為該等例示之實施形態及/或實施例施加較多的變更。因此，該等較多的變更亦包含於本發明之範圍。
全部引用該說明書中記載之文獻、及本案之成為巴黎條約之優先權之基礎之申請之內容。
圖1係利用實施例1、比較例1及2中製作之燒結體之EPMA所得之元素映射。 圖2係實施例1、比較例1及2中製作之燒結體之X射線繞射圖案。 圖3係實施例1、比較例1及2中製作之濺鍍靶之成膜後之表面照片。

Claims (3)

  1. 一種燒結體，其包含鋅及鎂及氧作為構成元素，且上述鋅相對於上述鋅及鎂之合計之原子比[Zn/(Zn+Mg)]為0.25~0.45，上述鎂相對於上述鋅與鎂之合計之原子比[Mg/(Zn+Mg)]為0.55~0.75，X射線繞射測定之結果為，該燒結體包含單一之結晶結構，上述單一之結晶結構為MgO之立方晶。
  2. 一種成膜用板片，其包含如請求項1之燒結體。
  3. 一種濺鍍靶，其包含如請求項1之燒結體。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460425A (zh) * 2006-06-08 2009-06-17 住友金属矿山株式会社 氧化物烧结体、靶、用它制得的透明导电膜以及透明导电性基材
JP2009184898A (ja) * 2008-02-08 2009-08-20 Sumitomo Electric Ind Ltd 透光性セラミックス
JP2010024107A (ja) * 2008-07-22 2010-02-04 Sumitomo Electric Ind Ltd 透光性セラミックス
CN102031487A (zh) * 2010-10-11 2011-04-27 深圳大学 高镁含量六方相MgZnO薄膜及其制备方法
TW201309823A (zh) * 2011-08-25 2013-03-01 Solar Applied Mat Tech Corp 靶材及其使用於鈷基或鐵基磁性紀錄媒體的基底層材料、磁紀錄媒體
CN103748055A (zh) * 2012-07-09 2014-04-23 吉坤日矿日石金属株式会社 导电性氧化物烧结体及其制造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101189358B (zh) * 2005-05-30 2010-05-19 日矿金属株式会社 溅射靶及其制造方法
CN101168837A (zh) * 2006-12-29 2008-04-30 中国科学院长春光学精密机械与物理研究所 一种高镁浓度MgZnO薄膜的制备方法
JP5260881B2 (ja) * 2007-03-20 2013-08-14 三菱瓦斯化学株式会社 Ｍｇ含有ＺｎＯ系混晶単結晶、その積層体およびそれらの製造方法
JPWO2010032422A1 (ja) * 2008-09-19 2012-02-02 出光興産株式会社 酸化物焼結体及びスパッタリングターゲット
CN101818324A (zh) * 2010-04-13 2010-09-01 浙江大学 柔性衬底生长n型ZnMgO:Ga透明导电薄膜的方法
CN102312193B (zh) * 2010-07-02 2016-06-01 三菱综合材料株式会社 薄膜形成用蒸镀材及具备该薄膜的薄膜片以及层叠片
WO2012014688A1 (ja) * 2010-07-30 2012-02-02 Jx日鉱日石金属株式会社 ＺｎＯ－ＭｇＯ系スパッタリングターゲット用焼結体
US20130108890A1 (en) * 2011-10-28 2013-05-02 Solar Applied Materials Technology Corp Target, An Underlayer Material For Co-Based Or Fe-Based Magnetic Recording Media, And Magnetic Recording Media
WO2014069367A1 (ja) * 2012-10-30 2014-05-08 Jx日鉱日石金属株式会社 導電性酸化物焼結体及び該導電性酸化物を用いた低屈折率膜
EP2767610B1 (en) * 2013-02-18 2015-12-30 Heraeus Deutschland GmbH & Co. KG ZnO-Al2O3-MgO sputtering target and method for the production thereof
CN103205706B (zh) * 2013-03-08 2015-11-18 深圳大学 一种立方结构MgZnO薄膜的制备方法
JP6396837B2 (ja) * 2015-03-31 2018-09-26 Ｊｘ金属株式会社 ＺｎＯ−ＭｇＯ系スパッタリングターゲット用焼結体及びその製造方法
CN108249911A (zh) 2016-12-29 2018-07-06 宁波江丰电子材料股份有限公司 氧化镁氧化锌靶坯的制造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101460425A (zh) * 2006-06-08 2009-06-17 住友金属矿山株式会社 氧化物烧结体、靶、用它制得的透明导电膜以及透明导电性基材
JP2009184898A (ja) * 2008-02-08 2009-08-20 Sumitomo Electric Ind Ltd 透光性セラミックス
JP2010024107A (ja) * 2008-07-22 2010-02-04 Sumitomo Electric Ind Ltd 透光性セラミックス
CN102031487A (zh) * 2010-10-11 2011-04-27 深圳大学 高镁含量六方相MgZnO薄膜及其制备方法
TW201309823A (zh) * 2011-08-25 2013-03-01 Solar Applied Mat Tech Corp 靶材及其使用於鈷基或鐵基磁性紀錄媒體的基底層材料、磁紀錄媒體
CN103748055A (zh) * 2012-07-09 2014-04-23 吉坤日矿日石金属株式会社 导电性氧化物烧结体及其制造方法

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