TWI394852B - A sputtering target, a method for manufacturing the same, and a transparent conductive film - Google Patents

A sputtering target, a method for manufacturing the same, and a transparent conductive film Download PDF

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TWI394852B
TWI394852B TW095127511A TW95127511A TWI394852B TW I394852 B TWI394852 B TW I394852B TW 095127511 A TW095127511 A TW 095127511A TW 95127511 A TW95127511 A TW 95127511A TW I394852 B TWI394852 B TW I394852B
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sputtering target
metal
target
conductive film
transparent conductive
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TW095127511A
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TW200714724A (en
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Koki Yano
Kazuyoshi Inoue
Nobuo Tanaka
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Idemitsu Kosan Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C23C14/08—Oxides
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    • H01—ELECTRIC ELEMENTS
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Description

濺鍍靶、其製造方法及透明導電膜
本發明為有關濺鍍靶、其製造方法及透明導電膜。更詳言之，可降低或不使用稀少資源之銦的濺鍍靶之發明。
液晶顯示器(LCD)或有機電致發光元件(EL)顯示器，就顯示性能、省能量等觀點而言，已逐漸於手機或可攜式資訊處理機(PDA)、電腦或小型電腦(laptop computer)、電視等顯示器佔有主流之位置。前述裝置所使用之透明導電膜，一般多以銦．錫氧化物(以下簡稱為ITO)膜佔有主流之位置。但，ITO膜則使用大量之銦(通常為90質量%左右)。銦為稀少之資源且供應不穩定，又，多少含有毒性，故欲使使用透明電極之顯示裝置更能普及時，開發銦使用量較低之透明導電膜將為極重要之因素。
使用減量或未使用銦之透明導電膜，目前例如有提出使用氧化鋅－氧化錫為主成分之透明導電膜(例如，參考專利文獻1)。
但對於前述透明導電膜所具有之高電阻、電阻之面內分布較大等問題點，目前仍未有針對前述問題所進行之研究。
ITO之濺鍍靶中，已有揭示含氧量若於一定標準以上時將可形成低電阻化之內容(例如，參考專利文獻2)。
但，對於銦減量之濺鍍靶的含氧量，則仍未有任何研究。
又，目前另有公開由金屬氧化物部位與金屬部位所形成之濺鍍靶(例如，參考專利文獻3)。
此外，對於銦減量之標靶的影響則仍未有任何研究。又，金屬氧化物部位與金屬部位所形成之濺鍍靶，為金屬氧化物標靶與金屬標靶或金屬導線複合化所得之物，故使用於銦減量後之標靶時，將會產生標靶本身電阻較高、濺鍍時放電不穩定、濺鍍速度過遲等問題。
專利文獻1：特開平8－171824號公報專利文獻2：特開2000－256842號公報專利文獻3：特開2004－030934號公報
本發明為鑒於上述問題所提出者，為以提供一種即使於銦減量下亦可製得低電阻之透明導電膜的濺鍍靶及濺鍍靶之製造方法為目的。
本發明者們，為克服上述問題經過深入研究結果，得知於構成濺鍍靶之金屬原子及氧原子中，於氧原子之數目較金屬原子構成氧化物之際的化學量計量更少時，即使對銦減量下，亦可得到具有低電阻之透明導電膜。又，於濺鍍靶中使未氧化之金屬或合金分散時，可製得安定且具低含氧量之標靶，及可降低標靶之電阻，因而完成本發明。
依本發明之內容，本發明係提供下述濺鍍靶、其製造方法、透明導電膜及透明電極。
1.一種濺鍍靶，其為含有氧化鋅及氧化錫，或氧化鋅、氧化錫及氧化銦之濺鍍靶，其特徵為，金屬或合金係分散存在濺鍍靶全體中。
2.如第1項之濺鍍靶，其係滿足下述式(1)與(2)，0.65≦MZ n /(MZ n ＋MS n )≦0.9 (1) 0≦MI n /(MZ n ＋MS n ＋MI n )≦0.7 (2)[式中，MZ n 、MS n 及MI n 分別表示濺鍍靶中之Zn、Sn與In之原子數]。
3.如第1或2項之濺鍍靶，其尚滿足下述式(3)，Mo/(MZ n ＋MS n ×2＋MI n ×1.5)≦0.99 (3)[式中，MZ n 、MS n 、Mo 及MI n 分別表示濺鍍靶中之Zn、Sn、O與In之原子數]。
4.如第1至3項之濺鍍靶，其中前述金屬或合金係含有0.1至6質量%。
5.如第1至4項之濺鍍靶，其為含有氧化銦－氧化鋅所形成之六方晶相層狀化合物(In2 O3 (ZnO)m；m為3至20之整數)。
6.如第1至5項之濺鍍靶，其整體電阻為未達100m Ω cm。
7.如第1至6項之濺鍍靶，其密度為5.3至7.2g/cm3 。
8.一種如第1至7項中任一項之濺鍍靶之製造方法，其包含將金屬氧化物之粉末與金屬之粉末混合之步驟。
9.一種透明導電膜，其為使用如第1至7項中任一項之濺鍍靶所製得者。
10.一種透明電極，其為由第9項之透明導電膜經蝕刻製得者。
本發明之濺鍍靶可得到具有銦減量且具有低電阻之透明導電膜。
以下，將本發明之濺鍍靶作具體之說明。
本發明之濺鍍靶係具有於至少含有氧化鋅及氧化錫之氧化物中，金屬或合金係分散存在於全體中之形態。如此，可形成一即使銦減量下亦可製得低電阻之透明導電膜的標靶。又，濺鍍靶中經由分散有未氧化之金屬或合金之方式，而可降低標靶之電阻。
金屬或合金，只要未損及本發明性能之範圍時，則無特別之限制。一般以較標靶之煅燒溫度為低者為佳，通常為使用熔點為1300℃以下、較佳為1000℃以下、更佳為800℃以下、最佳為600℃以下之金屬或合金。熔點為1300℃以下時，可使煅燒時溶融之標靶的密度提昇，因而容易降低標靶之電阻。
又，金屬氧化物以具有導電性者為佳。前述物質例如Zn、Sn、In、Ga、Ge、Cd、Nd、Sm、Ce、Eu、Ag、Au、Al、及以其為主成分之合金為較適合使用者。特別是以Zn、Sn或In為更佳。又，前述金屬或合金，亦可將多數種混合使用。
金屬或合金，於標靶中以形成500μm以下之凝集體並分散於全體中者為佳。又，更佳為100μm以下，最佳為10μm以下，特佳為5μm以下。
是否存在有金屬或合金，可使用X線繞射之波峰進行判斷。又，分散狀態可使用X線微分析儀(EPMA)之面分析以判斷是否具有金屬原子之凝集部或低氧部分之方式予以確認。又，「分散於全體中」，係指任意之5000μm四方之區域中，確認具有1個以上500μm以下之金屬或合金之狀態之意。
又，分散有金屬或合金之形態，可依後述之製造方法予以實現。
濺鍍靶中所存在之金屬或合金之含量，較佳為0.1~6質量%，更佳為0.2~4質量%，特佳為0.3~3質量%。低於0.1質量%時，會有不能出現本發明之效果，或出現白點(white－spot)之疑慮，大於6質量%時，則因氧不足而使電阻反向增大，而會有使透明性降低之疑慮。
濺鍍靶中含有未氧化之金屬或合金時，可使用X線繞射(XRD)予以確認。
本發明之濺鍍靶，以滿足下述(1)及(2)者為佳，0.65≦MZ n /(MZ n ＋MS n )≦0.9 (1) 0≦MI n /(MZ n ＋MS n ＋MI n )≦0.7 (2)[式中，MZ n 、MS n 及MI n 分別表示濺鍍靶中之Zn、Sn與In之原子數]。
上述式(1)之值[MZ n /(MZ n ＋MS n )]為規定濺鍍靶中Zn與Sn之存在比例。該值小於0.65時，會使標靶中存在之Sn量增加而凝集為SnO2 ，其於成膜時常會有因通電而造成異常放電原因之疑慮。又，大於0.9之情形中，則會有使耐酸性降低之疑慮。故MZ n /(MZ n ＋MS n )較佳為0.7~0.85，更佳為0.7~0.8。
式(2)為規定濺鍍靶中In之量。於考量本發明之目的時，In之使用量以較少為佳，但添加In時，可降低標靶及成膜後之薄膜的電阻。故MI n /(MZ n ＋MS n ＋MI n )較佳為0.05~0.6，更佳為0.1~0.45，最佳為0.15~0.35，特佳為0.25~0.35。
本發明之濺鍍靶，又以滿足下述(3)者為佳，Mo/(MZ n ＋MS n ×2＋MI n ×1.5)≦0.99 (3)[式中，MZ n 、MS n 、Mo 及MI n 分別表示濺鍍靶中之Zn、Sn、O與In之原子數]。
式(3)為規定濺鍍靶中氧原子(O)之量。式(3)之分母為各金屬原子構成氧化物(ZnO，SnO2 ，In2 O3 )時之氧原子數。式(3)之值，即，濺鍍靶所含之氧原子之數，與金屬原子全部構成氧化物時之氧原子數之比為0.99以下時，於In減量或不使用下，皆為可得到具有低電阻之透明導電膜的濺鍍靶。又，式(3)之值，較佳為0.8~0.98，更佳為0.9~0.97。低於0.8時，於成膜後之導電膜會有著色之疑慮。
如前所述，於控制標靶中之氧含量時，可使濺鍍薄膜形成低電阻化，其正確之理由雖仍未明瞭，但，推測應為以往之方法中，較Sn及In更輕之Zn原子，將於逆濺鍍或未成膜下被排出，使膜中之氧形成過剩狀所形成者。
又、上述式(1)~(3)之值，為對濺鍍靶使用X線微分析儀(EPMA)作成份分析所得之各原子之存在比之值而求得者。
本發明之濺鍍靶之製造方法，例如將各金屬氧化物之混合粉體，再與金屬或合金之粉體混合後予以煅燒之方法。使用金屬粉體時，可容易控制標靶中之氧含量。又，因標靶本身之電阻降低，故可提昇濺鍍而可進行安定之濺鍍處理。此外，金屬粉體推測亦具有因膜中欠缺氧而形成安定化，或生成載體而形成低電阻化之機能。
又，為調整因濺鍍裝置之不同，或濺鍍條件所造成之差異時，煅燒時以略為缺氧之狀態下，而於濺鍍時導入少量氧化性氣體之方式予以調整亦可。
於各金屬氧化物之混合粉體中，混合金屬或合金之粉體進行煅燒之情形中，粉末之粒徑一般為500μm以下，較佳為100μm以下，更佳為10μm以下，特佳為5μm以下。大於500μm時，因與其他原料粉末並不能均勻的進行混合，故金屬或合金不容易於標靶中形成分散之形態，或會有增加標靶電阻之疑慮。
又，粒徑為使用光散射相當徑(JIS R1629)所測定之值。
本發明中，除上述各金屬氧化物之粉體及金屬粉體以外，於不損害本發明目的之範圍下，可再添加煅燒輔助劑(釔、鎂等)、分散劑(聚丙烯酸酸胺等)、膠黏劑、潤滑劑(硬脂酸懸浮液等)等亦可。
本發明之濺鍍靶，以含有氧化銦－氧化鋅所形成之六方晶相層狀化合物(In2O3(ZnO)m；m為3至20之整數)為佳。含有前述構造時，可提高煅燒密度，且容易使標靶之電阻降低。
前述構造，可依上述之製造方法予以製得。又，構造之解析可使用X線繞射(X RD)進行測定。
本發明之濺鍍靶，其整體電阻以0.2~未達100m Ω cm為佳。滿足此數值時，於濺鍍時可使放電安定化，亦可增加濺鍍速度。更佳為0.4~20m Ω cm以下，特佳為0.6~10m Ω cm以下。
又，濺鍍靶之密度以5.3~7.2g/cm3 為佳，以6.1~7.0g/cm3 為更佳，特別是以6.4~6.8g/cm3 為最佳。滿足此數值時，於濺鍍時可使放電安定化，亦可增加成膜速度。
本發明之透明導電膜，可將上述本發明之濺鍍靶依常用方法濺鍍成膜之方式予以製得。又，此透明導電膜可使用含有草酸或磷酸之混合酸等蝕刻液以蝕刻方式製得透明電極。
 [實施例]
以下，本發明將以實施例作更具體之說明。又，粒徑為使用電射繞射散射法予以測定之值。
實施例1
將氧化鋅粉末(粒徑1μm以下)、氧化錫粉末(粒徑0.4μm以下)及金屬鋅粉末(粒徑5μm以下)依表1所記載之添加比置入聚乙烯製瓶中，使用乾式球磨機混合72小時，而製得混合粉末。
將此混合粉末置入模具中，以300kg/cm2 之壓力加壓形成成形體。再將此成形體以3ton/cm2 之壓力下進行CIP(冷均壓；Cold Isostatic Press)成型以進行緻密化處理。其次，將此成形體放置於純氧環境之氣體煅燒爐中，依以下條件進行煅燒。
(煅燒條件)
煅燒溫度：1450℃，昇溫速度：25℃/Hr，煅燒時間：6小時，導入煅燒爐中之氣體：氧，導入氣體壓力：30mmH2 O(裝置(cage)壓)，導入氣體速度：2.6cm/分鐘，置入重量/氣體流量：0.4kg．min/L，導入氣體之起始溫度(昇溫時)：400℃，導入氣體之停止溫度(降溫時)：400℃。
所得之煅燒體之密度使用依阿基米德法測定結果，得知為5.5g/cm3 。
此煅燒體之組成分析為使用X線微分析儀(EPMA)進行分析。其結果得知，相對於金屬原子數之總數，氧原子數比(O/(Zn＋Sn＋In))為1.18。又，使用四端子法(4－point－probe)測定所得標靶之整體電阻為80m Ω cm。
又，使用X線繞射(XRD)對標靶進行解析結果，確認具有由Zn金屬產生之波峰。
又，經使用EPMA之面分析結果，確認5000μm四方之區域中，凝集有5~50μm之金屬原子，且低氧之部分中，分散存在有100個以上之金屬原子。
又，EPMA及XRD之測定條件係如下所示。
．EPMA使用裝置：島津製作所製、電子線微分析儀EPMA－2300加速電壓：15kV、樣品電流：0.05μm、Beam Size：1μm、Area Size：68.4×68.4μm、Step Size：0.2μm×0.2μm、測定元素：Zn，Sn，O，SBSE(反射電子像)
．XRD使用裝置：(股)利可谷製、Ultima－III X線：Cu－K α線(波長1.5406、以石墨(graphite)單色儀使其單色)，使用2 θ－θ反射法進行測定，連續掃描(1.0°/分鐘)、採樣間隔：0.02°，間隙：Ds，SS，2/3°，RS：0.6mm。
將此煅燒體使用濕式加工法，加工製厚度6mm之煅燒體，再使用銦焊料接合於無氧銅製接合板上作為標靶。
使用此標靶，於厚度0.7mm之玻璃基板(Corning公司製，#7059)上經由濺鍍形成透明導電膜。濺鍍條件係如以下所示。
(濺鍍條件)
RF電力：110W、氣壓：0.3Pa、濺鍍氣體：Ar、100%、膜厚：100nm、基板溫度：200℃。
將所得之導電膜依四端子法測定所得之比電阻率為50mΩ．cm。又，波長550nm下之光線透過率為90%。又，透過率係以空氣作為參考標準測定透過玻璃基板之透過率。
濺鍍標靶之原料組成、組成分析、濺鍍條件、透明導電膜之組成與性狀係如表1所示。
實施例2，3；比較例1~3
除將原料之組成比變更為表1所示內容以外，其他皆依實施例1相同方法製作標靶，濺鍍成膜。
其結果如表1所示。
評估例
於濺鍍靶之原料組成中，將Zn金屬粉末之量變更為0~4wt%，以調整ZnO粉末之量以外，其他皆依實施例3相同方法製作標靶，濺鍍成膜。
對所得之透明導電膜，評估Zn金屬粉末之量與標靶之整體電阻值之關係，及Zn金屬粉末之量與透明導電膜之比電阻值。其各自知結果係如圖1與圖2所示。
[產業上之可利用性]
使用本發明之濺鍍靶成膜所得之透明導電膜，極適合作為液晶顯示裝置、EL顯示裝置等、各種顯示裝置之透明電極使用。
[圖1]Zn金屬粉末量與標靶之整體電阻之關係圖。
[圖2]Zn金屬粉末之量與透明導電膜之比電阻值之關係圖。

Claims (10)

  1. 一種濺鍍靶，其為含有氧化鋅及氧化錫，或氧化鋅、氧化錫及氧化銦之濺鍍靶，其特徵為，金屬鋅係分散存在濺鍍靶全體中。
  2. 如申請專利範圍第1項之濺鍍靶，其係滿足下述式(1)與(2)，0.65≦MZn /(MZn +MSn )≦0.9 (1) 0≦MIn /(MZn +MSn +MIn )≦0.3 (2)[式中，MZn 、MSn 及MIn 分別表示濺鍍靶中之Zn、Sn與In之原子數]。
  3. 如申請專利範圍第1項之濺鍍靶，其尚滿足下述式(3)，MO /(MZn +MSn ×2+MIn ×1.5)≦0.99 (3)[式中，MZn 、MSn 、Mo 及MIn 分別表示濺鍍靶中之Zn、Sn、O與In之原子數]。
  4. 如申請專利範圍第1項之濺鍍靶，其中前述金屬鋅係含有0.1至4質量%。
  5. 如申請專利範圍第1項之濺鍍靶，其為含有氧化銦- 氧化鋅所形成之六方晶相層狀化合物(In2 O3 (ZnO)m；m為3至20之整數)。
  6. 如申請專利範圍第1項之濺鍍靶，其整體電阻為未達100m Ω cm。
  7. 如申請專利範圍第1項之濺鍍靶，其密度為5.3至7.2g/cm3 。
  8. 一種如申請專利範圍第1至7項中任一項之濺鍍靶之製造方法，其包含將金屬氧化物之粉末與金屬鋅之粉末混合之步驟。
  9. 一種透明導電膜，其為使用如申請專利範圍第1至7項中任一項之濺鍍靶所製得者。
  10. 一種透明電極，其為由申請專利範圍第9項之透明導電膜經蝕刻製得者。
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