TWI521077B - 平面面板顯示器用配線膜形成用濺鍍靶 - Google Patents
平面面板顯示器用配線膜形成用濺鍍靶 Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims description 12
- 229910045601 alloy Inorganic materials 0.000 title description 3
- 239000000956 alloy Substances 0.000 title description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 8
- 239000010408 film Substances 0.000 description 74
- 239000000758 substrate Substances 0.000 description 21
- 239000011521 glass Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000004544 sputter deposition Methods 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
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Description
此發明係關於一種可形成比電阻值分佈全面且均一的平面面板顯示器用配線膜的濺鍍靶及使用其靶成膜的平面面板顯示器用配線膜。
本申請為依據2008年8月1日在日本已提出申請之特願2008-199559號及2009年7月2日於日本已提出申請之特願2009-157493號,且主張優先權並援用其內容於此。
作為液晶顯示器、電漿顯示器、有機EL顯示器、無機EL顯示器等平面面板顯示器之配線膜,現為使用銅合金配線膜,例如已知有一種形成含有Mg:1~5原子%、殘餘部份為由Cu及不可避免之雜質所構成之銅合金配線膜的液晶顯示裝置(參照專利文獻1)。
又,已知分別單獨含有添加元素為Al:1原子%以下、Si:0.5原子%以下、Be:2原子%以下、Cr:2原子%以下、Mg:2原子%以下、Sn:0.5原子%以下、Zn:4原子%以下、Ce:2原子%以下的銅合金配線膜係具抗遷移優異,且此等銅合金配線膜係使用含有與此等銅合金配線膜相同成分的靶,藉由濺鍍而形成(參照專利文獻2)。
前述平面面板顯示器中之銅合金配線膜係於玻璃基板上經由濺鍍成膜後進行熱處理。進行此熱處理時,銅合金配線膜中含有之添加元素成為氧化物且移動至銅合金配線膜的表面及裡面,於銅合金配線膜的表面及裡面形成添加元素之氧化物層。此添加元素的氧化物層之生成係阻止玻璃基板之基本成分的Si等朝向銅合金配線膜擴散浸透,且防止銅合金配線膜的比電阻增加,同時此添加元素之氧化物層之生成係提高對玻璃基板之銅合金配線膜的密著性。
[專利文獻1]日本特開平9-43628號公報
[專利文獻2]日本特開平6-97164號公報
平面面板顯示器近年來愈益大型化,且逐漸量產50寸以上大型液晶面板。因此,於寬的玻璃基板表面使藉由濺鍍銅合金配線膜而成膜,但於寬的玻璃基板表面上藉由濺鍍形成之銅合金配線膜係因場所而比電阻值有產生偏差,且此傾向係顯著出現在使用含Mg之銅合金靶形成之銅合金配線膜。
因此,本發明人等開發一種含Mg之銅合金製靶,其經濺鍍形成之銅合金配線膜的比電阻值依場所之偏差少,且進行欲使用此於平面面板顯示器中製得銅合金配線膜的研究。其結果,與以往之使用具有:含有Mg:1~5原子%且殘餘部份為由Cu及不可避免之雜質所構成之組成的銅合金靶,經由濺鍍成膜之銅合金薄膜相比較,使用純銅(尤其純度:99.99%以上的無氧銅)中,具有:含有Mg 0.1~5原子%,進一步含有Mn及Al之中之1種或2種合計0.1~11原子%之成分組成的銅合金靶,經由濺鍍製得之銅合金薄膜係可獲得具有比電阻值之偏差少且全體均勻的比電阻值的銅合金薄膜的研究結果。
此發明係基於上述研究結果所成,為具有以下特徵。
第1實施態樣係用以形成具有:含有Mg:0.1~5原子%,進一步含有Mn及Al之中之1種或2種的合計:0.1~11原子%,殘餘部份為由Cu及不可避免之雜質所構成之組成的平面面板顯示器用配線的濺鍍靶。
其它實施態樣係使用第1實施態樣中記載之濺鍍靶,經由濺鍍成膜而製得之銅合金薄膜,為由具有:含有Mg:0.1~5原子%,進一步含有Mn及Al之中之1種或2種合計:0.1~11原子%,且殘餘部份為由Cu及不可避免之雜質所構成之組成的銅合金薄膜所構成的平面面板顯示器用配線膜。
構成前期平面面板顯示器之配線的銅合金薄膜,係使用靶經由濺鍍而製作。此靶係例如先將純度:99.99%以上的無氧銅在惰性氣體環境中,於高純度石墨坩堝內高頻率溶解,而製得之熔湯中添加Mg 0.1~5原子%,進一步添加Mn及Al之中之1種或2種合計0.1~11原子%後進行溶解,製得之熔湯於惰性氣體環境中鑄造使之凝固,之後,再進行熱壓延,最後經由實施彎曲、退火而製作。將如此進行所製得之靶接合於底板,以一般條件經由濺鍍可形成前期之平面面板顯示器用銅合金薄膜。
對此發明之濺鍍靶及使用此靶進行成膜之銅合金薄膜的成分組成範圍,限定如前述的理由進行說明。
(a)靶之成分組成:
將靶中所含有之Mg限定為0.1~5原子%,進一步限定Mn及Al之中之1種或2種合計0.1~11原子%,係於使用Mg:0.1~5原子%、與Mn及Al之中之1種或2種合計0.1~11原子%共存而含有的靶進行濺鍍時,可使成膜之銅合金薄膜之依場所之比電阻值的偏差變少。而含有Mg:低於0.1原子%、Mn及Al之中之1種或2種合計低於0.1原子%,亦無法獲得所期望的效果,因此不佳。另一方面,使用添加Mg:超過5原子%、Mn及Al之中之1種或2種合計超過1原子%之靶進行濺鍍時,不認為可更提高所期望之特性,尤其所成膜之銅合金薄膜的電阻上昇,因此不佳。
(b)銅合金薄膜之成分組成:
Mg:
Mg係將結晶粒微細化,抑制構成平面面板顯示器中之配線膜的銅合金薄膜的表面突起(hillock)及空隙等的熱缺陷產生,使抗遷移性提高,進一步Mg於熱處理之際於銅合金薄膜的表面及裡面形成Mg氧化物層,阻止玻璃基板之主成分的Si等朝向銅合金配線膜擴散浸透,防止銅合金配線膜的比電阻增加,且同時使對玻璃基板之銅合金配線膜的密著性提高。Mg含量低於0.1原子%係無法得到所期望的效果,故不佳。另一方面,Mg含量含有超過5原子%亦不認為有提高特性,進而比電阻值增加且作為配線膜係變得不能充分顯示作用,故不佳。因此,銅合金薄膜中所含有之Mg含量定於0.1~5原子%。
Mn、Al:
此等成分,係藉由與Mg共存含有,於銅合金薄膜的表面及裡面形成Mg與Mn及/或Al的複氧化物或氧化物固溶體,可使對玻璃基板表面的密著性更提高。更且,藉由含有:形成於銅合金薄膜的表面及裡面之氧化物為化學安定性高的Mg與Mn及/或Al的複氧化物或氧化物固溶體,使得銅合金配線的化學安定性提高。添加此等成分中之1種或2種合計為低於0.1原子%的情形,係無法獲得密著性提高的效果,故不佳。另一方面,即使添加Mn,Al合計超過11原子%亦不認為提高特性,且甚至配線膜的比電阻值上升,故不佳。
P:
少量的P不會使銅合金薄膜所謀求之比電阻、表面突起、空隙、密著性等的特性變差且可容易地鑄造銅合金,故可視需要添加。但,若添加之P低於0.001原子%不會有效果;另一方面,若添加超過0.1原子%並不會使鑄造性提高。因此,P含量定為0.001~0.1原子%。
使用此發明之靶進行濺鍍時,即使玻璃基板變大、依所成膜之銅合金薄膜的場所之比電阻值之偏差少,進而,可提高對玻璃基板表面的密著性且比電阻值低,故可形成高精細化且大型化之平面面板顯示器之銅合金配線膜。
實施發明之最佳形態
準備純度:99.99質量%之無氧銅,將此無氧銅在Ar氣體環境中,於高純度石墨坩堝內高頻率溶解。所製得之熔湯中添加Mg、Mn、Al,且視需要添加P,溶解後調整為使具有表1所示之成分組成的熔湯。將製得之熔湯於經冷卻之碳鑄型中進行鑄造,進一步在熱壓延後進行最終地彎曲、退火,將製得之壓延體之表面進行旋盤加工,具有外徑:200mm×厚度:10mm的尺寸,且製作具有表1所示之成分組成的圓板狀之本發明銅合金濺鍍靶(以下,稱本發明靶)1~25及比較銅合金濺鍍靶(以下,稱比較靶)1~4及習知濺鍍靶(以下,稱習知靶)1。
進一步,準備無氧銅製底板,使此無氧銅製底板上疊合前述本發明靶1~25、比較靶1~4及習知靶1,以溫度:200℃銦焊接,於無氧銅製底板上接合本發明靶1~25、比較靶1~4及習知靶1,製作附有底板的靶。
將本發明靶1~25、比較靶1~4及習知靶1,焊接於無氧銅製底板而製得附有底板的靶,使靶與玻璃基板(具有直徑:200mm、厚度:0.7mm之尺寸的Corning公司製1737的玻璃基板)之距離:成為70mm而安裝。
電源:直流方式、濺鍍功率:600W、到達真空度:4×10-5Pa、環境氣體組成:Ar:90容量%、氧:10容量%之混合氣體、氣壓:0.2Pa、玻璃基板加熱溫度:150℃、以如上述之條件,於玻璃基板的表面,形成具有半徑:100mm、厚度:300nm且具有表2~3所示之成分組成之任一的圓形之本發明銅合金配線用薄膜(以下,稱本發明配線用薄膜)1~25及比較銅合金配線用薄膜(以下,稱比較配線用薄膜)1~4及習知銅合金配線用薄膜(以下,稱習知配線用薄膜)1。將製得之本發明配線用薄膜1~25、比較配線用薄膜1~4及習知配線用薄膜1分別裝入加熱爐中,在Ar環境中施予升溫速度:5℃/min、最高溫度:350℃,保持30分鐘的熱處理。藉由四探針法測定所得之任一的圓形之本發明配線用薄膜1~25、比較配線用薄膜1~4及習知配線用薄膜1的中心之距離中心50mm之點及距離中心100mm之點的比電阻,求出其最大與最小之差。彼等之結果示於表2~3,且評估配線用薄膜之比電阻值的偏差。
進一步,依據JIS-K5400,於本發明配線用薄膜1~25、比較配線用薄膜1~4及習知配線用薄膜1上以1mm間隔棋盤格狀地刻入刻痕後,以3M公司製之思高膠帶剝下,且於玻璃基板中央部之邊長10mm格內實施測定附著在玻璃基板上之配線用薄膜的面積%的棋盤格附著試驗。其結果示於表2~3中,且評估對玻璃基板之本發明配線用薄膜1~25、比較配線用薄膜1~4及習知配線用薄膜1的密著性。
對此等經實施熱處理之本發明配線用薄膜1~25、比較配線用薄膜1~4及習知配線用薄膜1的表面,以5000倍之SEM觀察5處之膜表面,觀察有無產生表面突起及空隙。其結果示於表2~3。
從表1~表3所示之結果可知以下事項。
(i)使用單獨含有Mg之習知靶1經由進行濺鍍而成膜之習知配線用薄膜1,係中心部的比電阻與周邊部的比電阻之差大,且甚至對玻璃基板的密著性差。相對於此,含有Mg與Mn及Al之中之1種或2種的本發明配線用薄膜1~25,係中心部的比電阻與周邊部的比電阻之差小,故比電阻值之偏差少,進而對玻璃基板之密著性優異。(ii)使用脫離此發明之條件之含有少許Mg及Mn的比較靶1,經由進行濺鍍成膜之比較配線用薄膜1,以及脫離此發明之條件之含有少許Mg及Al的比較靶2,經由進行濺鍍而成膜之比較配線用薄膜2係密著性低。又,產生表面突起及空隙,故容易發生遷移,因此不佳;另一方面,含有Mg與Mn及Al之合計脫離此發明之條件許多的比較配線用薄膜3~4,係比電阻值變得過大,不適於作為配線用薄膜。
Claims (8)
- 一種平面面板顯示器用配線膜形成用的濺鍍靶,其特徵為具有:含有Mg:0.1~5原子%、進一步含有Al:0.1~11原子%、殘餘部份為Cu及不可避免之雜質所構成之組成。
- 一種平面面板顯示器用配線膜,其特徵為由具有:含有Mg:0.1~5原子%、進一步含有Al:0.1~11原子%、殘餘部份為Cu及不可避免之雜質所構成之組成的銅合金薄膜所成。
- 一種平面面板顯示器用配線膜形成用的濺鍍靶,其特徵為具有:含有Mg:0.1~5原子%、更含有Al:0.1~11原子%、進一步含有P:0.001~0.1原子%、殘餘部份為Cu及不可避免之雜質所構成之組成。
- 一種平面面板顯示器用配線膜,其特徵為由具有:含有Mg:0.1~5原子%、更含有Al:0.1~11原子%、進一步含有P:0.001~0.1原子%、殘餘部份為Cu及不可避免之雜質所構成之組成的銅合金薄膜所成。
- 如申請專利範圍第1項的濺鍍靶,其中前述組成進一步含有Mn,Mn及Al之合計量為0.1~11原子%。
- 如申請專利範圍第2項的平面面板顯示器用配線膜,其中前述組成進一步含有Mn,Mn及Al之合計量為0.1~11原子%。
- 如申請專利範圍第3項的濺鍍靶,其中前述組成進一步含有Mn,Mn及Al之合計量為0.1~11原子%。
- 如申請專利範圍第4項的的平面面板顯示器用配線膜,其中前述組成進一步含有Mn,Mn及Al之合計量為0.1~11原子%。
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