200807449 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於一種特別適合用於平面顯示器（F P D ) 的透明電極之透明導電膜及其製造方法、以及製造該透明 ' 導電膜時所使用的濺鍍靶。 【先前技術】 φ 於平面顯示器（FPD)，作爲構成透明電極之透明導 電膜，傳統上廣泛使用IΤ Ο (摻雜錫之氧化銦）（參照專 利文獻1 )。此係因IT Ο具有高導電性及可見光透過率。 於FPD的製造步驟’存在3 5 0°C以上的溫度下進行燒成的 步驟。例如於電漿顯示器面板（P D P )的製造步驟之燒成 步驟，透明電極一邊與玻璃粉接合，一邊暴露於6 0 0。(：程 度的高溫。但是，——般ITO耐熱性差，又在與玻璃粉接合 的狀態下，在3 5 0 °C以上的溫度進行燒成時，可能有電阻 • 大幅增加的問題，也有所謂原材料（例如銦）的蘊藏量的 問題。 另一方面，氧化錫（Sn02)通常化學上耐久性強，可 期待其對玻璃粉的耐侵蝕性也高。特別使用氧化錫中賦予 銻作爲摻雜劑之透明導電膜，作爲透明電極，可做成耐侵 飩性強的透明電極，可期待作爲PDP用透明電極。於專利 文獻1，提案藉由剝離（Liftoff)法之氧化錫的圖形化法 ，組合如此的圖形化技術，可形成PDP用透明電極。 專利文獻1 :日本公開專利特開平6-280055號公報 -4- 200807449 (2) 【發明內容】 發明所欲解決之課題 但是，氧化錫中賦予銻作爲摻雜劑之氧化錫，雖沒有 ITO的程度，因受玻璃粉之侵蝕作用，透明電極在與玻璃 粉接合的狀態，在3 5 0 °c以上的溫度進行燒成時，有電阻 增加的問題。而且，因銻毒性強，期望盡量不使用。 • 本發明係以提供一種對玻璃粉的侵蝕具有強耐性，在 與玻璃粉接觸的狀態下燒成也不會增加電阻之透明導電膜 及其製造方法爲目的。而且，本發明係以提供使用如此的 透明導電膜作爲透明電極之顯示器構件爲目的。 而且，本發明提供使用濺鍍法，特別是DC濺鍍法， 適合形成上述透明導電膜之濺鍍靶爲目的。 解決課題之手段 • 爲了達成上述目的，本發明提供以氧化錫爲主要成分 之透明導電膜，該透明導電膜係含有選自鎢、鉅、鈮、鉬 以及鉍所成之群之至少一種元素作爲摻雜劑，且實質上不 含銻以及銦， 使該透明導電膜中所含作爲摻雜劑之該元素的總量爲 MA，使該透明導電膜中所含的錫元素的量爲Sn時，滿足 下述式（1 ) 、（ 2 ): 〇.8< ( Sn) / ( Sn + MA) <!.0...(!) 200807449 (3) 〇·〇1< ( Ma) / ( Sn + MA) <0·2 …（2)。 本發明的透明導電膜，在與玻璃粉接觸之狀態下，使 加熱至3 5 〇 °C以上之溫度後的透明導電膜之比電阻値爲P 1 ，加熱前的透明導電膜之比電阻値爲W時’滿足下述式（ 3 )： P 1 < P 〇 ... ( 3 )。 本發明的透明導電膜，上述比電阻値P0爲5Ε-2Ωεπι 以下較理想。 本發明的透明導電膜，上述比電阻値Pl爲4Ε-2Ω(：ηι 以下較理想。 本發明的透明導電膜，其膜厚爲1 μπι以下較理想。 而且，本發明提供具有本發明的透明導電膜之顯示器 用構件。 而且，本發明係以氧化錫爲主要成分之濺鍍靶，該濺 鍍靶係含有選自鎢、钽、鈮、鉬以及鉍所成之群之至少一 種元素作爲摻雜劑，使該濺鍍靶中所含作爲摻雜劑之該元 素的總量爲ΜΑ，使該濺鍍靶中所含的錫元素的量爲Sll時 ，滿足下述式（4 ) 、（ 5 ): 〇·8< ( Sn) / ( Sn + MA) <1.0 ... ( 4 ) 0·01< ( Ma) / ( Sn + MA) <0·2 …（5) 〇 (4) 200807449 本發明的濺鍍靶，含有鈮作爲摻雜劑較理想。 含有鈮作爲摻雜劑之本發明的濺鍍靶，相對密度爲 60%以上，其表面的膜電阻値爲9Ε + 6Ω/□以下較理想。 而且，本發明提供使用上述本發明的濺鍍靶，藉由濺 鍍法，形成上述本發明的透明導電膜之透明導電膜的製造 方法。 發明的效果 本發明的透明導電膜，對玻璃粉的耐侵蝕性高，在與 玻璃粉接合的狀態下在350°C以上的溫度燒成也不會增加 電阻。所以，適合作爲製造步驟中包含在350°C以上的溫 度進行燒成的步驟之如PDP的FPD的透明電極。 本發明的透明導電膜，因不含高價的銦，可提供低成 本的透明導電膜。而且，因不含具有毒性之銻，在環境面 • 上也佳。於PDP的製造步驟，透明電極係與稱爲玻璃粉之 介電體，在500〜600°C的溫度下進行燒成而接合。此時， 使用作爲透明電極之透明導電膜，若對玻璃粉的耐侵鈾性 低，玻璃粉中或透明導電膜中，或兩者中會產生細微的氣 泡。如此的細微的氣泡之產生成爲PDP的圖像不良有關的 重大問題。本發明的透明導電膜，對玻璃粉的耐侵鈾性比 銻佳，使用鎢、鉬、鈮、鉬以及鉍作爲摻雜劑，如此的摻 雜劑，具有關於減少上述細微的氣泡產生的效果。 本發明的濺鍍靶，適合製造本發明的透明導電膜。特 200807449 (5) 別是含有鈮作爲摻雜劑之本發明的灑鍍靶’因燒結密度高 ，可使用DC濺鍍法，對透明導電膜的生產性的提高有貢 獻0 【實施方式】 本發明的透明導電膜，其係以氧化錫爲主要成分之透 明導電膜，含有選自鎢、鉬、鈮、鉬以及鉍所成之群之至 少一種元素作爲摻雜劑，且實質上不含銻以及銦。而且， 所謂含有氧化錫爲主要成分，係指膜中氧化錫，以錫元素 換算時含有80原子％以上。 本發明的透明導電膜，使所含作爲摻雜劑之鎢等元素 的總量爲Ma，錫元素的量爲Sn時，滿足下述式（1 )、 (2 )： 〇 . 8 < ( S n ) / ( S n + M a ) <1.0 …（1) • 〇·〇1< ( Ma) / ( Sn + MA) <0·2 …（2 )。 本發明人等，發現上述組成的膜，比傳統含有使用銻 作爲摻雜劑之氧化錫膜，對玻璃粉的耐侵蝕性優異。此處 ，所謂對玻璃粉的耐侵飩性，係指在與玻璃粉接合的狀態 ，於高溫下的情況，例如加熱至3 5 0 °C以上的溫度的情況 ，作爲製品不產生問題的程度之不受玻璃粉的侵蝕。 對玻璃粉的耐侵飩性的差異，被認爲與該氧化錫膜中 的這些摻雜劑的安定性有關。銻係以5或3的價數存在於 -8- 200807449 ⑹ 氧化錫膜中。價數5的銻，位在結晶格的錫的位置’賦予 氧化錫膜導電性。在與玻璃粉接合的狀態’加熱至3 5 0 °C 以上的溫度時，銻的價數由5變成3。價數變成3的銻’ 從結晶格的錫的位置除去，格子間位置不齊，而變成與構 成玻璃粉的元素形成化合物的原因。所以’在格子間的位 " 置，價數3的銻與構成玻璃粉的元素形成化合物的結果， 被認爲使氧化錫膜的電阻增加。如此一連串的作用爲玻璃 φ 粉的侵鈾作用。此外，銦係以價數3存在於氧化錫的結晶 格的錫原子的位置上。所以，作爲吸收膜中載子（電子） 之吸收子之作用，存在該情況時，氧化錫膜的電阻値容易 連帶增加。而且，即使格子間的部位（場所）存在銦的情 況，形成帶隙中雜質態，成爲移動度降低、載子密度減少 的原因。因此，與銻不同，不管存在於該結晶中的位置， 銦變成阻礙結晶性高的氧化錫之電的特性。 另一方面，钽係以5或4的價數存在於氧化錫中。價 # 數5的鉬，位於結晶格的錫的位置，賦予氧化錫膜導電性 。在與上述相同的作用下，當鉬的價數由5變成4時，價 數變成4的鉬，從結晶格的錫的位置除去，格子間位置不 齊，而變成與構成玻璃粉的元素形成化合物的原因。價數 4的钽與構成玻璃粉的元素形成化合物的結果，被認爲使 氧化錫膜的電阻增加。 但是，鉅之上述價數的變化（5^4 )比銻（5^3 )難 發生。所以，難以受到玻璃粉的侵飩作用，難以引起氧化 錫膜的電阻的增加。 -9- 200807449 (7) 而且，藉由加熱至3 50 °C以上的溫度，使鉬的價數由 4變成5。結果，被認爲藉由新的價數變成5之鉅進入結 晶格的錫的位置，以減少氧化錫膜的電阻。 以上，雖然說明摻雜鉅之氧化錫膜，於摻雜鎢、鈮、 鉬或鉍的情況，在相同的理由下，與摻雜銻的氧化錫膜比 較，對玻璃粉的耐侵蝕性優異。 而且，本發明的透明導電膜，具有實質上不含銻以及 # 銦的特徵。因實質上不含在高溫下5價的狀態不安定的銻 ，可防止燒成後的電阻値的上升，同時考慮作爲PDP用透 明電極的用途的情況，因發揮對玻璃粉的耐侵鈾性優異的 效果，所以較理想。在與玻璃粉接合的狀態，加熱至3 5 0 t以上的溫度時，銻的價數由5變成3。變成價數3之銻 ，從結晶格的錫的位置除去，格子間位置不齊，而變成與 構成玻璃粉的元素形成化合物的原因。而且，藉由實質上 不含銻，可提供對環境友善之透明導電膜，且即使加熱至 • 3 5 0 °C以上的溫度，可發揮不增加電阻的效果，所以較理 想。 此處，所謂透明導電膜實質上不含銻以及銦’係指積 極地不使用含有銻以及銦之濺鍍靶，形成透明導電膜’除 起因於不純物之銻以及銦以外，不含銻以及銦。具體地’ 係指透明導電膜中所含的銻元素的量’對錫元素的量爲 〇 · 1原子％以下，透明導電膜中所含的銦元素的量，對錫 元素的量爲〇. 1原子％以下 於本發明的透明導電膜，在與玻璃粉接觸的狀態下’ -10- 200807449 (8) 加熱至35(TC以上之溫度後的透明導電膜之比電 ，加熱前的透明導電膜之比電阻値爲Pd時，滿足 3 )： ρι<ρ〇 ... ( 3 ) ° 亦即，本發明的透明導電膜，在與玻璃粉接 下，加熱至3 5 0 °C以上之溫度時，透明導電膜的 增加，卻電阻降低。電阻降低的理由，在於剛成 在於氧化錫的結晶格間的位置之摻雜劑（鎢、鉅 或鉍），推斷因加熱而進入結晶格的錫的位置， 上升，電子散射體減少。 因此，本發明的透明導電膜，於使用作爲如 FPD的透明電極的情況，經過FPD的製造步驟 3 5 0 °C以上的溫度的燒成步驟，透明電極之電的 〇 本發明的透明導電膜，其比電阻値Pl爲4E· 下較理想。而且，所謂「E-2」係指10的-2次方 標記，對其他比電阻値也相同。比電阻値爲ρι係 過FPD的製造步驟所進行之3 50°C以上的溫度的 後’透明導電膜的比電阻値。只要比電阻値Pl爲 以下，透明導電膜的電阻足夠低，適合如PDP之 透明電極。比電阻値ρ 1爲1 E - 2 Ω c m以下更理； 以下更加理想。 阻値爲Pi 下述式（ 觸的狀態 電阻不會 膜後，存 、鈮、鉬 載子密度 PDP之 所進行之 特性提高 •2Qcm 以 。如此的 相當於經 燒成步驟 4 E - 2 Ω c m :FPD 的 匿，0.5E- -11 - 200807449 (9) 本發明的透明導電膜，其比電阻値ρ〇爲5E-2Dcm以 下較理想。只要比電阻値P〇爲5E-2Qcm以下，經過FPD 的製造步驟所進行之3 50°C以上的溫度的燒成步驟後，透 明導電膜的比電阻値Pl容易爲4E-2Dcm以下。比電阻値 p0爲4Ε·2Ω(：ιη以下更理想，lE-2Qcm以下更加理想。 本發明的透明導電膜，其膜厚爲Ιμιη以下較理想。只 要膜厚爲Ιμπι以下，透明導電膜不會有模糊等的光學缺陷 Φ 。透明導電膜的膜厚爲0.3 μιη以下更理想，0.2 μιη以下或 0.0 2 μηι以上更加理想。而且，膜厚在燒成前後幾乎沒有 變化。 本發明的透明導電膜，透明性佳者較理想。具體地， 可見光透過率（根據ns-R3 1 06 ( 1 998年）的測定）爲 80%以上較理想，85%以上更理想。而且，塗佈玻璃粉， 燒成後的可見光透過率（根據JIS-R3 1 06 ( 1 998年）的測 定）爲80%以上較理想，85%以上更理想。 # 爲了使比電阻値Po、Pi更低，本發明的透明導電膜滿 足下述式（6) 、（7)較理想。 0.85< ( Sn) / ( Sn + MA) <1.0 ... ( 6 ) 0·01< ( Μα) / ( Sn + MA) <0.15 ... ( 7 ) 式（6 ) 、 （ 7 )中的Ma以及Sn與式（1 ) 、（ 2 )中 具有相同的意義。200807449 (1) VENTION DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a transparent conductive film particularly suitable for use in a transparent electrode of a flat panel display (FPD), a method of manufacturing the same, and a method of manufacturing the transparent 'conductive film Sputter target used. [Prior Art] φ is a flat display (FPD), and as a transparent conductive film constituting a transparent electrode, IΤ Ο (tin-doped indium oxide) has been conventionally widely used (refer to Patent Document 1). This is because IT has high conductivity and visible light transmittance. The step of firing is carried out at a temperature of 350 ° C or higher in the manufacturing step of the FPD. For example, in the firing step of the manufacturing step of the plasma display panel (P D P ), the transparent electrode is exposed to 600 while being bonded to the glass frit. (The degree of high temperature. However, the ITO heat resistance is poor, and when it is fired at a temperature of 350 ° C or higher in a state of being bonded to the glass powder, there may be a problem that the resistance is greatly increased, and there is also a problem. On the other hand, tin oxide (Sn02) is generally chemically durable, and it is expected to have high corrosion resistance to glass frit. In particular, tin oxide is used as a doping in tin oxide. The transparent conductive film of the agent can be used as a transparent electrode having a strong anti-aggressive property as a transparent electrode, and can be expected as a transparent electrode for PDP. Patent Document 1 proposes a patterning method of tin oxide by a liftoff method. In the case of such a patterning technique, a transparent electrode for a PDP can be formed. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 6-280055--4-200807449 (2) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, tin oxide In the case where tin oxide is used as a dopant, the amount of ITO is not affected by the glass powder, and the transparent electrode is bonded to the glass powder at a temperature of 350 ° C or higher. At the time of firing, there is a problem that the electric resistance is increased. Moreover, since it is highly toxic, it is desirable to use it as much as possible. • The present invention provides a strong resistance to the erosion of the glass frit, and does not burn in contact with the glass frit. A transparent conductive film which increases resistance and a method of manufacturing the same are provided. Further, the present invention has an object of providing a display member using such a transparent conductive film as a transparent electrode. Moreover, the present invention provides use of a sputtering method, particularly DC sputtering. In order to achieve the above object, the present invention provides a transparent conductive film containing tin oxide as a main component, and the transparent conductive film contains a material selected from the group consisting of tungsten, and the like. At least one element of the group of giant, lanthanum, molybdenum, and lanthanum is used as a dopant, and substantially free of lanthanum and indium, so that the total amount of the element contained as a dopant in the transparent conductive film is MA, When the amount of the tin element contained in the transparent conductive film is Sn, the following formulas (1) and (2) are satisfied: 〇.8 < ( Sn) / ( Sn + MA) <!. 0... (!) 200807449 (3) 〇1 < ( Ma) / ( Sn + MA) <0·2 (2) The transparent conductive film of the present invention is heated to a temperature of 35 ° C or higher in contact with the glass frit. The specific resistance 値 of the rear transparent conductive film is P 1 , and when the specific resistance 値 of the transparent conductive film before heating is W, 'the following formula (3) is satisfied: P 1 < P 〇 (3). The transparent conductive film preferably has a specific resistance 値P0 of 5 Ε 2 Ω ε π or less. The transparent conductive film of the present invention preferably has a specific resistance 値 P1 of 4 Ε - 2 Ω (: ηι or less). The transparent conductive film of the present invention preferably has a film thickness of 1 μm or less. Moreover, the present invention provides a member for a display having the transparent conductive film of the present invention. Further, the present invention is a sputtering target containing tin oxide as a main component, the sputtering target containing at least one element selected from the group consisting of tungsten, tantalum, niobium, molybdenum, and niobium as a dopant, and the sputtering is performed. The total amount of the element contained as a dopant in the target is ΜΑ, and when the amount of the tin element contained in the sputtering target is S11, the following formulas (4) and (5) are satisfied: 〇·8< ( Sn ) / ( Sn + MA) <1.0 ... ( 4 ) 0·01 < ( Ma ) / ( Sn + MA) <0·2 (5) 〇 (4) 200807449 Sputtering of the present invention The target, which contains ruthenium as a dopant, is preferred. The sputtering target of the present invention containing cerium as a dopant has a relative density of 60% or more and a film resistance 表面 of 9 Å + 6 Ω / □ or less on the surface. Further, the present invention provides a method for producing a transparent conductive film of the above transparent conductive film of the present invention by sputtering using the above-described sputtering target of the present invention. EFFECTS OF THE INVENTION The transparent conductive film of the present invention has high corrosion resistance to glass frit, and does not increase resistance when fired at a temperature of 350 ° C or higher in a state of being bonded to glass frit. Therefore, it is suitable as a transparent electrode of a FPD such as a PDP which is subjected to a step of firing at a temperature of 350 ° C or higher in the production step. The transparent conductive film of the present invention can provide a low-cost transparent conductive film because it does not contain expensive indium. Moreover, it is also good on the environmental side because it does not contain toxic impurities. In the production step of the PDP, a transparent electrode and a dielectric called glass frit are fired and joined at a temperature of 500 to 600 °C. At this time, a transparent conductive film as a transparent electrode is used, and if the uranium resistance to the glass frit is low, fine bubbles are generated in the glass frit or in the transparent conductive film, or both. The generation of such fine bubbles is a major problem related to image defects of the PDP. The transparent conductive film of the present invention has better uranium resistance to glass powder, and uses tungsten, molybdenum, niobium, molybdenum and niobium as dopants, and such a dopant has an effect of reducing the generation of the above fine bubbles. . The sputtering target of the present invention is suitable for producing the transparent conductive film of the present invention. In particular, the sputtering target of the present invention containing ruthenium as a dopant has a high sintered density, and can contribute to improvement in productivity of a transparent conductive film by using a DC sputtering method. [Embodiment] The transparent conductive film of the invention is a transparent conductive film containing tin oxide as a main component, and contains at least one element selected from the group consisting of tungsten, molybdenum, niobium, molybdenum and niobium as a dopant, and is substantially free of antimony. And indium. In addition, the term "tin oxide as a main component" means tin oxide in the film, and is contained in an amount of 80 atom% or more in terms of tin element. In the transparent conductive film of the present invention, when the total amount of elements such as tungsten contained as a dopant is Ma, and the amount of the tin element is Sn, the following formulas (1) and (2) are satisfied: &. 8 < S n ) / ( S n + M a ) <1.0 (1) • 〇·〇1< ( Ma) / ( Sn + MA) <0·2 (2). The present inventors have found that a film having the above composition is excellent in corrosion resistance to glass frit than a conventional tin oxide film containing ruthenium as a dopant. Here, the resistance to repellency of the glass frit refers to a state in which it is bonded to the glass frit, and in a case where it is heated at a high temperature, for example, a temperature of 350 ° C or higher is used, and the product is not problematic. It is not eroded by glass frit. The difference in the resistance to repellency of the glass frit is considered to be related to the stability of these dopants in the tin oxide film. The lanthanide is present in the -8-200807449 (6) tin oxide film at a valence of 5 or 3. The valence of 5, the position of the tin in the crystal lattice gives conductivity to the tin oxide film. When it is heated to a temperature of 350 ° C or more in the state of being joined to the glass frit, the valence of hydrazine is changed from 5 to 3. The 锑 of the valence of 3 is removed from the position of the tin of the crystal lattice, and the position between the lattices is not uniform, which causes a compound to form a compound with the element constituting the glass frit. Therefore, as a result of the position between the lattices, the valence of 3 and the formation of a compound constituting the glass frit are considered to increase the electric resistance of the tin oxide film. Such a series of actions are the uranium encroachment of glass φ powder. Further, indium is present at a position of a tin atom of a crystal lattice of tin oxide at a valence of 3. Therefore, as a function of the absorber of the carrier (electron) in the absorption film, in this case, the resistance 値 of the tin oxide film is liable to increase. Further, even if indium is present in a portion (place) between the lattices, an impurity state in the band gap is formed, which causes a decrease in mobility and a decrease in carrier density. Therefore, unlike niobium, indium does not have the property of suppressing the electric power of the tin oxide having high crystallinity regardless of the position existing in the crystal. On the other hand, the lanthanide is present in the tin oxide at a valence of 5 or 4. The molybdenum of the number #5 is located at the position of the tin of the crystal lattice, and imparts conductivity to the tin oxide film. Under the same action as above, when the valence of molybdenum changes from 5 to 4, the molybdenum having a valence of 4 is removed from the position of the tin of the crystal lattice, and the positions between the lattices are not aligned, and become formed with the elements constituting the glass frit. The reason for the compound. As a result of forming a compound of valence 4 and an element constituting the glass frit, it is considered that the electric resistance of the tin oxide film is increased. However, the change in the above valence (5^4) is harder than 锑(5^3). Therefore, it is difficult to be attacked by the glass frit, and it is difficult to cause an increase in the resistance of the tin oxide film. -9- 200807449 (7) Moreover, the valence of molybdenum is changed from 4 to 5 by heating to a temperature of 3 50 °C or higher. As a result, it is considered that the position of tin entering the crystal lattice by the new valence becomes 5 to reduce the electric resistance of the tin oxide film. As described above, in the case of doping the giant tin oxide film, in the case of doping tungsten, tantalum, molybdenum or tantalum, for the same reason, it is excellent in corrosion resistance to the glass frit compared with the antimony-doped tin oxide film. Further, the transparent conductive film of the present invention has a feature of substantially no yttrium and #indium. It is possible to prevent the increase in the resistance 値 after firing, and to prevent the increase in the resistance 値 after firing, and to consider the use as a transparent electrode for PDP, and to exhibit uranium resistance against glass frit. Excellent results, so it is ideal. In the state of being bonded to the glass frit, when heated to a temperature of 305 t or more, the valence of hydrazine is changed from 5 to 3. When the valence is 3, it is removed from the position of the tin of the crystal lattice, and the position between the lattices is not uniform, which causes a compound to form a compound with the elements constituting the glass frit. Further, since it is substantially free of ruthenium, it is possible to provide a transparent conductive film which is environmentally friendly, and it is preferable to use an effect of not increasing the electric resistance even when heated to a temperature of 305 ° C or higher. Here, the transparent conductive film is substantially free of germanium and indium. The positive conductive film is formed without using a sputtering target containing germanium and indium, and the transparent conductive film is formed to contain no germanium and indium other than impurities and indium due to impurities. . Specifically, 'the amount of the lanthanum element contained in the transparent conductive film' is 〇·1 atom% or less to the tin element, and the amount of the indium element contained in the transparent conductive film is 〇. 1 atom% or less of the transparent conductive film of the present invention, in the state of being in contact with the glass frit, -10-200807449 (8) is heated to 35 (the specific electric power of the transparent conductive film after the temperature of TC or higher, and the transparent conductive before heating) When the specific resistance 値 of the film is Pd, it satisfies 3): ρι<ρ〇... (3) ° That is, the transparent conductive film of the present invention is heated to 350 ° C or higher under the contact with the glass frit. At the time of temperature, the transparent conductive film increases, but the electric resistance decreases. The reason why the electric resistance is lowered is a dopant (tungsten, giant or yttrium) which is formed at a position between crystal lattices of tin oxide, and it is estimated that the position of tin which enters the crystal lattice by heating rises and the electron scatterer decreases. Therefore, in the case of using the transparent conductive film of the present invention as a transparent electrode such as FPD, the firing step of the FPD is carried out at a temperature of 350 ° C or higher, and the transparent electrode is electrically charged with the transparent conductive film of the present invention. It is more desirable than the resistance 値Pl of 4E·. Further, the term "E-2" means a mark of 10 to the power of -2, and is the same for other specific resistances. The specific resistance 値 is ρι is the specific resistance 后 of the rear transparent conductive film at a temperature of 3 50 ° C or higher by the FPD manufacturing step. As long as the specific resistance 値P1 is below, the resistance of the transparent conductive film is sufficiently low to be suitable for a transparent electrode such as a PDP. The specific resistance 値ρ 1 is 1 E - 2 Ω c m or less; the following is more desirable. The resistance is Pi. The following equation (the state resistance of the contact is not after the film, the characteristic of the PDP of the storage, enthalpy, and molybdenum carrier density is increased by 2 Qcm. This corresponds to the firing step 4 E - 2 Ω cm : FPD, 0.5E- -11 - 200807449 (9) The transparent conductive film of the present invention preferably has a specific resistance 値ρ〇 of 5E-2Dcm or less. As long as the specific resistance 値P〇 is 5E-2Qcm or less, the FPD is passed. After the firing step of the temperature of 50 ° C or higher, the specific resistance 値 P1 of the transparent conductive film is easily 4E-2Dcm or less. The specific resistance 値p0 is 4 Ε·2 Ω (more than 1 ηη, lE) The thickness of the transparent conductive film of the present invention is preferably Ιμηη or less. The transparent conductive film does not have optical defects such as blurring as long as the film thickness is Ιμπι or less. The film thickness of the transparent conductive film is 0.3. More preferably, it is more preferably 0.2 μm or less or 0.0 2 μηι or more. Further, the film thickness hardly changes before and after firing. The transparent conductive film of the present invention is preferably excellent in transparency. Specifically, visible light transmittance (according to ns-R3 1 06 ( 1 99 The measurement of 8 years) is preferably 80% or more, and more preferably 85% or more. Further, the glass powder is coated, and the visible light transmittance after firing (measured according to JIS-R3 1 06 (1998)) is 80. More preferably, it is more than 85%, and more preferably 85% or more. # In order to make the specific resistance 値Po, Pi lower, the transparent conductive film of the present invention satisfies the following formulas (6) and (7). 0.85 < ( Sn ) / ( Sn + MA) <1.0 ... ( 6 ) 0·01 < ( Μα) / ( Sn + MA) <0.15 ( 7 ) Ma and Sn in (6 ) and ( 7 ) The formulas (1) and (2) have the same meaning.
於本發明的透明導電膜的形成，可使用灑鍍法、CVD -12- 200807449 (10) 法、溶膠-凝膠法、PLD法、各種成膜法，從大面積的均 勻性、生產性的觀點，期望使用濺鍍法。作爲濺鍍法，即 使使用燒結密度低的濺鍍法的情況下，也不會有濺鍍靶的 破損，由於膜電阻値高的濺鍍靶也可進行放電，以RF灑 鍍較理想。 ' 於使用濺鍍法形成本發明的透明導電膜的情況，可利 用錫爲主成分的金屬系濺鍍靶以及氧化錫爲主成分之氧化 • 物系濺鍍靶（氧化物燒結體灑鍍靶）。但是，於使用金屬 系濺鍍靶之成膜，難以藉由電力的控制形成薄膜，且錫的 電阻對氧的分壓非常敏感，具有必須高精度的氧氣分壓控 制的問題。另一方面，使用氧化物系濺鍍靶時，不會產生 上述問題，可實現生產性高的成膜。 作爲氧化物系濺鍍靶，可使用以氧化錫爲主成分，含 有選自鎢、鉬、鈮、鉬以及鉍所成之群之至少一種元素作 爲摻雜劑之氧化物燒結體濺鍍靶。 ® 使用如此的氧化物燒結體濺鍍靶，實施濺鍍法的情況 下，所得的薄膜的組成與氧化物燒結體濺鍍靶的組成，實 質上相同。所以，爲了藉由濺鍍法形成本發明的透明導電 膜，作爲上述氧化物燒結體濺鍍靶，只要使用所含的作爲 摻雜劑之鎢等元素的總量爲Ma，所含的錫元素的量爲Sn 時，滿足下述式（4 ) 、（ 5 )者即可。 0.8< ( Sn ) / ( Sn + MA ) <1.0 ... ( 4 ) 0·01< ( Ma) / ( Sn + MA) <〇·2 …（5) -13- 200807449 (11) 而且，本發明的氧化物燒結體濺鍍靶，實質上不含銻 以及銦較理想。因不含銻，可發揮濺鍍靶製作的作業安全 性高的效果。因不含銦，可發揮不降低濺鍍靶的導電性的 ‘效果。而且，所謂「實質上不含銻以及銦」，係如透明導 電膜中所述。 而且，於形成滿足上述式（6) 、（7)之本發明的透 φ 明導電膜的情況，作爲氧化物燒結體灑鍍靶，只要使用滿 足下述式（8 ) 、（ 9 )者即可。 0.8 5 < ( S n ) / ( Sn + MA) <1.0 ... ( 8) 0.0 1 < ( Μα ) / ( Sn + MA) <0.15 ... ( 9 ) 此處，式（8 ) 、（ 9 )中的Ma以及Sn與式（4 )、 (5)中具有相同的意義。 Φ 上述組成的氧化物燒結體濺鍍靶，可利用製造濺鍍法 時一般的順序製作。亦即，藉由將原料調配成所期望的組 成比，加壓成形後，於大氣環境中，在高溫（例如1 1 〇〇。〇 )、大氣壓下，進行燒結即可。 本發明人等發現滿足上述式（4 )、（ 5 )之氧化物燒 結體濺鍍靶，於含有鈮爲摻雜劑的情況，濺鍍靶的燒結密 度變高，可得到可能用於DC濺鍍法之濺鍍靶。 此處，含有鈮爲摻雜劑的氧化物燒結體濺鍍靶，係使 所含作爲摻雜劑的鈮元素的量爲Nb，錫元素的量爲時 -14- 200807449 (12) ，滿足下述式（10) 、（11)。 0·8< ( Sn) / ( Sn + Nb) <1.0 …（10) 0·01< ( Nb ) / ( Sn + Nb ) <0·2 …（1 1 ) 滿足上述式（1 〇 ) 、（ 1 1 )之氧化物燒結體濺鍍靶， 因相對密度高如60%以上，濺鍍靶表面的膜電阻値爲 9Ε + 6Ω/□以下，較理想爲使用作爲DC (直流）濺鍍用的濺 鍍靶。而且，作爲濺鍍法，不使用RF濺鍍法而使用DC 濺鍍法時，因成膜速度可非常地快，係爲左右是否能事業 化的重要因素之一。此處，氧化物燒結體濺鍍靶，也可含 有鈮以外的摻雜劑（鎢、钽、鉬或鉍）。 於本說明書中，相對密度可由下述式（12)求得。 相對密度（％)二（堆積密度/真密度）xl 〇〇·.·( 12) 此處，所謂堆積密度（g/cm3 )係指由製作的濺鍍靶 的尺寸與重量所求得的實際測量密度，所謂真密度，係指 由物質特有的理論密度計算所求得之理論上的密度。 所含之作爲摻雜劑的元素爲鈮時，滿足上述式（10) 、（1 1 )之氧化物燒結體濺鍍靶的相對密度爲80%以上更 理想。 而且，使用含有鈮作爲摻雜劑的氧化物燒結體濺鍍靶 · ，爲了形成滿足上述式（6 ) 、（ 7 )之本發明的透明導電 -15- 200807449 (13) 膜，只要使用滿足下述式（1 3 ) 、（ 1 4 )者作爲氧化物燒 結體濺鍍靶即可。 0.85< ( Sn) / ( Sn + Nb) <! ·° …（13) 0·01< ( Nb ) / ( Sn + Nb ) <0·15 …（14) 此處，式（1 3 ) 、（ 14 )中的Nb以及Sn與式（10 ) 、（11)中具有相同的意義。 於本發明，顯示器用構件可使用作爲如PDP的FPD 用基板，特別是FPD的前面基板，係於玻璃基板上，形成 上述本發明的透明導電膜作爲透明電極者。 玻璃基板無特別限制，例如可使用傳統習知各種玻璃 基板（鈉鈣玻璃、無鹼玻璃等）。較理想的具體態樣之一 ，例如PDP用高變形點玻璃。而且，其大小、厚度也無特 別限制。例如其縱橫的長度，分別可使用 400〜3 000mm 程度者。而且較理想，其厚度爲0.7〜3.0mm較理想，1.5 〜3.0mm更理想。 本發明的顯示器用構件，除PDP外可使用作爲各種 FPD用的基板。作爲如此的FPD的具體例，例如液晶顯示 裝置（LCD )、含有機EL之電致發光顯示器（ELD )、 場效發光顯示器（FED)等。 實施例 以下基於實施例與比較例，加以說明。本實施例始終 -16- 200807449 (14) 爲一例，不因這些而受限制。亦即，本發明所之範圍係根 據申請專利範圍而決定，包含以下記載之實施例以外的各 種變形。 (實施例1〜4 ) ' 使用純度相當於99.99%之粒徑5μπι以下之Sn02、The formation of the transparent conductive film of the present invention can be carried out by sputtering, CVD-12-200807449 (10), sol-gel method, PLD method, various film formation methods, and uniformity from a large area and productivity. From the point of view, it is desirable to use a sputtering method. As the sputtering method, even when a sputtering method having a low sintered density is used, there is no possibility that the sputtering target is broken, and the sputtering target having a high film resistance can be discharged, and RF sputtering is preferable. When a transparent conductive film of the present invention is formed by a sputtering method, a metal-based sputtering target containing tin as a main component and an oxidation-based sputtering target containing tin oxide as a main component (oxide sintered body sputtering target) ). However, in the film formation using a metal sputtering target, it is difficult to form a thin film by electric power control, and the resistance of tin is very sensitive to the partial pressure of oxygen, and there is a problem that oxygen partial pressure control with high precision is required. On the other hand, when an oxide-based sputtering target is used, the above problem does not occur, and film formation with high productivity can be realized. As the oxide-based sputtering target, an oxide sintered body sputtering target containing tin oxide as a main component and containing at least one element selected from the group consisting of tungsten, molybdenum, niobium, molybdenum and niobium as a dopant can be used. ® When such an oxide sintered body sputtering target is used and the sputtering method is performed, the composition of the obtained film is substantially the same as the composition of the oxide sintered body sputtering target. Therefore, in order to form the transparent conductive film of the present invention by the sputtering method, as the oxide sintered body sputtering target, the total amount of elements such as tungsten contained as a dopant is Ma, and the tin element contained therein is used. When the amount is Sn, the following formulas (4) and (5) are satisfied. 0.8< ( Sn ) / ( Sn + MA ) <1.0 ... ( 4 ) 0·01 < ( Ma ) / ( Sn + MA) <〇·2 ...(5) -13- 200807449 (11) Further, the oxide sintered body sputtering target of the present invention is preferably substantially free of germanium and indium. Since it does not contain antimony, it has the effect of high safety of the work produced by the sputtering target. Since it does not contain indium, it can exert the effect of not reducing the conductivity of the sputtering target. Further, "substantially free of antimony and indium" is as described in the transparent conductive film. In the case of forming the transparent conductive film of the present invention which satisfies the above formulas (6) and (7), the oxide sintered body sputtering target is used as long as the following formulas (8) and (9) are satisfied. can. 0.8 5 < ( S n ) / ( Sn + MA) <1.0 ... ( 8) 0.0 1 < ( Μα ) / ( Sn + MA) <0.15 ( 9 ) Here, the formula ( Ma and Sn in 8) and (9) have the same meanings as in formulas (4) and (5). Φ The oxide sintered body sputtering target having the above composition can be produced by a general procedure in the case of producing a sputtering method. In other words, by blending the raw materials into a desired composition ratio, after press molding, sintering may be carried out in an air atmosphere at a high temperature (for example, 1 1 Torr) at atmospheric pressure. The present inventors have found that the oxide sintered body sputtering target of the above formulas (4) and (5) is satisfied, and when the ruthenium is used as a dopant, the sputtering density of the sputtering target becomes high, and it is possible to obtain a possibility for DC sputtering. Sputter target for plating. Here, the oxide sintered body sputtering target containing ruthenium as a dopant is such that the amount of the lanthanum element contained as a dopant is Nb, and the amount of the tin element is -14-200807449 (12), which satisfies (10) and (11). 0·8<( Sn) / ( Sn + Nb) <1.0 (10) 0·01 < ( Nb ) / ( Sn + Nb ) <0·2 (1 1 ) satisfies the above formula (1 〇) (1 1 ) The oxide sintered body sputtering target has a relative density of 60% or more, and the film resistance 表面 of the surface of the sputtering target is 9 Ε + 6 Ω / □ or less, and is preferably used as DC (DC) sputtering. Sputter target used. Further, when the DC sputtering method is used as the sputtering method without using the RF sputtering method, the film formation speed can be extremely fast, which is one of the important factors for whether or not the left and right can be commercialized. Here, the oxide sintered body sputtering target may contain a dopant other than ruthenium (tungsten, ruthenium, molybdenum or ruthenium). In the present specification, the relative density can be obtained by the following formula (12). Relative density (%) 2 (bulk density/true density) xl 〇〇···(12) Here, the bulk density (g/cm3) refers to the actual size and weight of the produced sputtering target. Measuring density, the so-called true density, refers to the theoretical density obtained from the calculation of the theoretical density specific to a substance. When the element to be used as the dopant is ruthenium, the relative density of the oxide sintered body sputtering target satisfying the above formulas (10) and (1 1) is preferably 80% or more. Further, an oxide sintered body sputtering target containing ruthenium as a dopant is used, and in order to form a transparent conductive -15-200807449 (13) film of the present invention satisfying the above formulas (6) and (7), as long as the use is satisfied The equations (1 3 ) and (14) may be used as the oxide sintered body sputtering target. 0.85<( Sn) / ( Sn + Nb) <! ·° ...(13) 0·01< ( Nb ) / ( Sn + Nb ) <0·15 (14) Here, the formula (1 3 Nb and Sn in (14) have the same meanings as in formulas (10) and (11). In the present invention, the member for a display can be used as a substrate for FPD such as a PDP, in particular, a front substrate of an FPD, which is formed on a glass substrate to form the transparent conductive film of the present invention as a transparent electrode. The glass substrate is not particularly limited, and for example, various conventional glass substrates (soda lime glass, alkali-free glass, etc.) can be used. One of the more desirable specific aspects, such as high deformation point glass for PDP. Moreover, there is no particular limitation on the size and thickness thereof. For example, the length of the vertical and horizontal directions can be 400 to 3 000 mm, respectively. Further preferably, the thickness is preferably 0.7 to 3.0 mm, and more preferably 1.5 to 3.0 mm. The member for a display of the present invention can be used as a substrate for various FPDs in addition to the PDP. Specific examples of such an FPD include, for example, a liquid crystal display device (LCD), an electroluminescent display (ELD) containing an EL, a field effect light emitting display (FED), and the like. EXAMPLES Hereinafter, the examples and comparative examples will be described. This embodiment is always -16-200807449 (14) as an example, and is not limited by these. That is, the scope of the present invention is determined based on the scope of the patent application, and includes various modifications other than the embodiments described below. (Examples 1 to 4) 'Used Sn02 having a purity equivalent to 99.99% and a particle size of 5 μm or less.
Ta2〇5、W03、Mo2〇3、Nb2〇5粉，調配各金屬元素的組成 φ 比爲表1記載之組成比之粉。將粉使用乳缽進行混合，加 壓成形後，於大氣環境中，1 5 3 0 °C、大氣壓下，進行燒結 ，將該氧化物燒結體進行機械加工，修整爲濺鍍靶形狀。 所得的氧化物燒結體濺鍍靶的相對密度、表面電阻（表面 的膜電阻値）如表1所示。而且，濺鍍靶的相對密度係使 用下述式（1 2 )算出。濺鍍靶的表面的膜電阻値係使用表 面電阻測定裝置（三菱油化製：ROLESTER )進行測定。 # 相對密度（％)=(堆積密度/真密度）xlOO··· ( 12) 此處，所謂堆積密度（g/cm3 )係指由製作的濺鍍靶 的尺寸與重量所求得的實際測量密度，所謂真密度，係指 由物質特有的理論密度計算所求得之理論上的密度。 然後，使用厚度2.8mm的高變形點玻璃（旭硝子公司 製：PD200、基板的可見光透過率爲91% )，作爲玻璃基 板。該玻璃基板洗淨後，設置於基板支架。具有表1所示 的組成之氧化物燒結體濺鍍靶，安裝於RF濺鍍裝置的陰 -17- 200807449 (15) 極。將濺鍍裝置的成膜室內排氣爲真空後，藉由RF濺鍍 法，形成厚度約150nm (0·15μιη)的以氧化錫爲主成分之 膜於該玻璃基板上。使用氬及氧的混合氣體，作爲濺鍍氣 體。基板溫度爲250°C。成膜時的壓力爲0.5Pa。藉由改 變氬氣及氧氣的流量比，可形成透明且電阻小的薄膜。表 * 2表示調整該氣體比可得電阻爲最低時之膜的組成、可見 光透過率、比電阻値。而且，膜的組成、可見光透過率、 Φ 比電阻値（Po, Pi )，係藉由下述方法測定。 (1 )組成：以玻璃基板上形成膜所使用的相同製程 條件，製作300nm的膜。以螢光X射線裝置（理學電機 工業公司製RIX3000 )測定從金屬系元素放出的螢光量， 以基本參數（Fundamental Parameter)理論計算，算出各 金屬元素的量、組成比。而且，組成在燒成後也相同。 (2 )可見光透過率：由 JIS-R3 1 06 ( 1 998年），使 用分光光度計（島津製作所製：U-4 100 )，由附有所得的 • 膜之玻璃基板的透過光譜，計算附有所得的膜之玻璃基板 的可見光透過率。 (3 )比電阻値：藉由使用霍爾效應（Hall effect )測 定器 （HL5 500PC，亞生光學技術 （Accent optical technologies)公司製）之凡袍（van der Pauw)法求得。 對於膜的比電阻値，塗佈電漿電視前面板用之以氧化矽、 氧化鉛、氧化硼爲主成分之玻璃粉（旭硝子公司製，玻璃 糊料，AP5 65 5AE ( YPT065F))，在大氣環境 600°C，燒 成1小時者進行測定。表2中，ρ 〇爲未燒成的膜之比電阻 -18- 200807449 (16) 値’ Pi爲燒成後的膜之比電阻値。 由表2顯示，實施例1〜4的膜，一 玻璃粉材料接合，一邊在所謂60(TC的高 認比電阻値不會上升，顯示高導電性。 而且’塗佈玻璃粉，燒成後的可見光 施例都在80%以上。 (實施例5) 使用純度相當於99· 99%之粒徑5μιη Nb205粉，調配表丨記載之組成比的粉， 〜4相同的順序，製作氧化物燒結體濺鍍 物燒結體濺鍍靶的相對密度、表面電阻（ 電阻値）係如表1所示。如表1所示，滿 、（1 1 )之氧化物燒結體濺鍍靶（含有鈮 具有適合作爲DC濺鍍用濺鍍靶的特性。 相對密度爲60%以上，濺鍍靶表面的膜電 以下。 使用所得的氧化物燒結體濺鍍靶，利, 相同的順序，形成薄膜，膜的組成、可見 阻値（pQ，p!)，係藉由上述方法測定。 成，不使用RF濺鍍法，係使用DC濺鍍 的氧化物燒結體濺鍍靶，安裝於DC磁控 ，將濺鍍裝置的成膜室內排氣爲真空後， ，形成厚度約1 50nm的氧化錫爲主成分之 邊與氧化力強的 溫進行燒成，確 透過率，任一實 以下之 Sn02、 利用與實施例1 靶。所得的氧化 濺鍍靶表面的膜 足上述式（1 0 ) 作爲摻雜劑）， 亦即，濺鍍靶的 阻値爲9Ε + 6Ω/口 闬與實施例1〜4 光透過率、比電 但是，薄膜的形 法。亦即，所得 濺鍍裝置的陰極 藉由DC濺鍍法 膜於玻璃基板上 -19- 200807449 (17) 此時的成膜速度，與使用RF濺鍍法的情況 爲2倍的速度，工業上生產性佳。使用氬及氧的 作爲濺鍍氣體。基板溫度爲 250 T：。成膜時I 0.5Pa。藉由改變氬氣及氧氣的流量比，可形成 阻小的薄膜。表2表示調整該氣體比可得電阻爲 膜的組成、可見光透過率、比電阻値。由表2顯 例5的膜，一邊與氧化力強的玻璃粉材料接合， 謂600°C的高溫進行燒成，確認比電阻値不會上 高導電性。 而且，膜的組成在燒成後也相同，塗佈玻璃 後的可見光透過率爲80%以上。 (比較例1 ) 使用純度相當於99.99%之粒徑5μιη以下；^ Sb205粉，調配表1記載之組成比的粉，利用與 〜4相同的順序，製作氧化物燒結體濺鍍靶。所 物燒結體濺鍍靶的相對密度、表面電阻（濺鍍靶 電阻値）係如表1所示。 使用所得的氧化物燒結體濺鍍靶，利用與實: 相同的順序，形成薄膜，膜的組成、可見光透過 阻値（p〇，Pi )，係藉由上述方法測定。表2表 及氧的氣體比可得電阻爲最低時之膜的組成、可 率、比電阻値。由表2顯示，使用摻雜銻的氧化 比較，約 混合氣體 的壓力爲 透明且電 最低時之 示，竇施 一邊在所 升，顯示 粉，燒成 :Sn02、 實施例1 得的氧化 表面的膜 瓶例ί〜4 率、比電 示調整氬 見光透過 錫燒結體 -20- 200807449 (18) 濺鍍靶所形成的膜，在塗佈玻璃粉的狀態下燒成的情況， 與未燒成的膜比較，確認比電阻値約增加爲1 . 8倍。 (比較例2) ' 使用ITO濺鍍靶（TOSOH特殊材料公司製，摻雜10 * 質量％氧化錫之氧化銦濺鍍靶），利用與實施例1〜4相同 的順序，製作氧化物燒結體濺鍍靶。對所得的ITO薄膜， φ 測定比電阻値Po時爲1.5£-40〇111。利用與實施例1〜4相 同的順序，在塗佈玻璃粉的狀態下，於大氣環境600 °C， 燒成1小時時，比電阻値ρ 1增加爲約Pd的6倍，變成9 · 5 Ε-4Ω〇ιη。實施例1〜5所得的膜，燒成後的比電阻値Pl爲 2.7E-3Qcm〜7·7Ε·3Ωεπι，在實際PDP的製造步驟環境下 ，兩者的膜之電特性非常接近，顯示本發明的透明導電膜 可成爲ΙΤΟ的代替材料。 • (比較例3 ) 利用與實施例1〜4相同的順序，製作氧化物燒結體 濺鍍靶。但是，調配表1記載之組成比的粉。所得的氧化 物燒結體濺鍍靶的相對密度、表面電阻（濺鍍靶表面的膜 電阻値）係如表1所示。 使用所得的氧化物燒結體濺鍍靶，利用與實施例1〜4 相同的順序，形成薄膜，膜的組成、可見光透過率、比電 阻値（Ρ ο，Ρ1 )，係藉由上述方法測定。表2表示調整氬 及氧的氣體比可得電阻爲最低時之膜的組成、可見光透過 -21 - 200807449 (19) 率、比電阻値。由表2顯示，使用摻雜鉅的氧化錫燒結體 灑鍍靶所形成的膜，其組成不滿足式（1 )、（ 2 )的情況 下，在塗佈玻璃粉的狀態進行燒成時，與未燒成的膜比較 ，確認比電阻値增加。Ta2〇5, W03, Mo2〇3, Nb2〇5 powder, and the composition of each metal element is adjusted. The ratio of φ is the composition ratio of the powder shown in Table 1. The powder was mixed using a mortar, and after compression molding, it was sintered in an air atmosphere at 1,530 ° C under atmospheric pressure, and the oxide sintered body was machined and trimmed into a sputtering target shape. The relative density and surface resistance (film resistance 表面 of the surface) of the obtained oxide sintered body sputtering target are shown in Table 1. Further, the relative density of the sputtering target was calculated by the following formula (1 2 ). The film resistance of the surface of the sputtering target was measured using a surface resistance measuring device (manufactured by Mitsubishi Petrochemical Co., Ltd.: ROLESTER). # Relative density (%) = (bulk density / true density) xlOO··· (12) Here, the bulk density (g/cm3) refers to the actual measurement obtained from the size and weight of the produced sputtering target. Density, the true density, refers to the theoretical density obtained from the calculation of the theoretical density specific to a substance. Then, a high-deformation point glass (PD200 manufactured by Asahi Glass Co., Ltd., and a visible light transmittance of the substrate of 91%) having a thickness of 2.8 mm was used as a glass substrate. After the glass substrate is washed, it is placed on a substrate holder. An oxide sintered body sputtering target having the composition shown in Table 1 was attached to the cathode of the RF sputtering apparatus, -17-200807449 (15). After evacuating the deposition chamber of the sputtering apparatus to a vacuum, a film containing tin oxide as a main component having a thickness of about 150 nm (0.15 μm) was formed on the glass substrate by RF sputtering. A mixed gas of argon and oxygen is used as a sputtering gas. The substrate temperature was 250 °C. The pressure at the time of film formation was 0.5 Pa. By changing the flow ratio of argon gas and oxygen gas, a transparent and low-resistance film can be formed. Table * 2 shows the composition of the film, the visible light transmittance, and the specific resistance 调整 when the gas is adjusted to have the lowest available resistance. Further, the composition of the film, the visible light transmittance, and the Φ specific resistance Po (Po, Pi ) were measured by the following methods. (1) Composition: A film of 300 nm was formed under the same process conditions used for forming a film on a glass substrate. The amount of fluorescence emitted from the metal element was measured by a fluorescent X-ray apparatus (RIX3000 manufactured by Rigaku Corporation), and the amount and composition ratio of each metal element were calculated by theoretical calculation of fundamental parameters. Moreover, the composition is also the same after firing. (2) Visible light transmittance: From JIS-R3 1 06 (1998), using a spectrophotometer (manufactured by Shimadzu Corporation: U-4 100), the transmission spectrum of the glass substrate with the obtained film is calculated. The visible light transmittance of the glass substrate of the obtained film. (3) Specific resistance 値: obtained by a van der Pauw method using a Hall effect damper (HL5 500PC, manufactured by Accent Optical Technologies). For the specific resistance of the film, a glass powder containing ruthenium oxide, lead oxide or boron oxide as a main component of the plasma TV front panel (made by Asahi Glass Co., Ltd., glass paste, AP5 65 5AE (YPT065F)) is used in the atmosphere. The environment was measured at 600 ° C and baked for 1 hour. In Table 2, ρ 〇 is the specific resistance of the unfired film -18- 200807449 (16) 値' Pi is the specific resistance 膜 of the film after firing. As shown in Table 2, the films of Examples 1 to 4 were joined by a glass frit material, and the high specific resistance TC of TC did not rise, indicating high conductivity. Moreover, 'glass powder was applied, and after firing, The visible light application method was 80% or more. (Example 5) Using a particle size of 5 μm Nb205 powder having a purity equivalent to 99. 99%, the powder of the composition ratio described in Table 调 was prepared, and the oxide was sintered in the same order as 〜4. The relative density and surface resistance (resistance 値) of the body sputtering target sputtering target are shown in Table 1. As shown in Table 1, the full (1 1 ) oxide sintered body sputtering target (containing bismuth has It is suitable as a sputtering target for DC sputtering. The relative density is 60% or more, and the surface of the sputtering target is less than or equal to the film surface. Using the obtained oxide sintered body sputtering target, the film is formed in the same order. Composition, visible resistance (pQ, p!), determined by the above method. Formation, without using RF sputtering method, using DC sputtered oxide sintered body sputtering target, mounted on DC magnetron, will be splashed After the exhaust in the film forming chamber of the plating apparatus is vacuum, an oxidation of about 150 nm is formed. The side of the main component is fired at a temperature at which the oxidizing power is strong, and the transmittance is confirmed, and any of the following Sn02 and the target of the first embodiment are used. The film of the surface of the oxidized sputtering target obtained is obtained by the above formula (10). The dopant), that is, the sputtering target has a hindrance of 9 Ε + 6 Ω / 闬 and the light transmittance of the embodiment 1 to 4, but the film is formed. That is, the cathode of the obtained sputtering device is borrowed. The film is deposited on a glass substrate by a DC sputtering method. -19- 200807449 (17) The film formation speed at this time is twice as high as that in the case of using the RF sputtering method. Industrial productivity is good. Argon and oxygen are used. Sputtering gas. The substrate temperature is 250 T: I 0.5 Pa at the time of film formation. By changing the flow ratio of argon gas and oxygen gas, a film with a small resistance can be formed. Table 2 shows that the gas is adjusted to obtain the composition of the film. The visible light transmittance and the specific resistance 値. The film of the example 5 of Table 2 was bonded to a glass frit material having a strong oxidizing power, and was fired at a high temperature of 600 ° C to confirm that the specific resistance was not highly conductive. Moreover, the composition of the film is the same after firing, and the visible light after coating the glass is transmitted. (Comparative Example 1) The powder having a composition ratio of the composition shown in Table 1 was prepared using a particle size of 5 μm or less in a purity equivalent to 99.99%, and the oxide sintered body was splashed in the same order as in 〜4. The relative density and surface resistance (sputter target resistance 値) of the sintered target sputtering target are shown in Table 1. The obtained oxide sintered body sputtering target was formed in the same order as the real: The film, the composition of the film, and the visible light transmission barrier (p〇, Pi) were measured by the above method. Table 2 shows the composition, the rate, and the specific resistance of the film when the gas ratio of the oxygen is the lowest. It is shown in Table 2 that the oxidation of the doped cesium is compared with the oxidation of the doped cerium. The pressure of the mixed gas is transparent and the lowest at the time of electricity, and the sinus is raised, the powder is displayed, and the oxidized surface of Sn02, Example 1 is obtained. Membrane bottle example ί~4 Rate, specific ratio, argon, light transmission through tin sintered body -20- 200807449 (18) The film formed by the sputtering target is fired in the state where the glass powder is coated, and is not burnt. A comparison of the formed films confirmed that the specific resistance 增加 was increased by about 1.8 times. (Comparative Example 2) An oxide sintered body was produced in the same manner as in Examples 1 to 4 by using an ITO sputtering target (manufactured by TOSOH Specialty Materials Co., Ltd., doped with an indium oxide sputtering target of 10% by mass of tin oxide). Sputter target. For the obtained ITO film, φ was 1.5 to 40 〇 111 when the specific resistance 値Po was measured. In the same procedure as in the first to fourth embodiments, when the glass frit was applied, the specific resistance 値ρ 1 was increased to about 6 times Pd in the air atmosphere at 600 ° C for 1 hour, and became 9 · 5 Ε-4Ω〇ιη. In the films obtained in Examples 1 to 5, the specific resistance 値P1 after firing was 2.7E-3Qcm to 7·7Ε·3 Ω επι, and in the actual PDP production step environment, the electrical properties of the films were very close to each other. The transparent conductive film of the invention can be a substitute for germanium. (Comparative Example 3) An oxide sintered body sputtering target was produced in the same manner as in Examples 1 to 4. However, the powder of the composition ratio shown in Table 1 was prepared. The relative density and surface resistance (film resistance 値 of the surface of the sputtering target) of the obtained oxide sintered body sputtering target are shown in Table 1. Using the obtained oxide sintered body sputtering target, a film was formed in the same manner as in Examples 1 to 4, and the film composition, visible light transmittance, and specific resistance 値 (Ρο, Ρ1) were measured by the above method. Table 2 shows the composition of the film when the gas ratio of argon and oxygen was adjusted to the lowest, and the visible light transmission -21 - 200807449 (19) rate and specific resistance 値. Table 2 shows a film formed by sputtering a target with a doped tin oxide sintered body, and when the composition does not satisfy the formulas (1) and (2), when the glass powder is baked, It was confirmed that the specific resistance 値 was increased as compared with the unfired film.
表1 :濺鍍靶的組成及密度、表面電阻 例 使用元素 (Sn)/(Sn+MA) (MA)/(Sn+MA) 濺鍍靶密度 (%) 表面電阻 (Ω/口） 實施例1 MA=Ta 0.96 0.04 62 2.2M 實施例2 Ma=W 0.92 0.08 68 1.8M 實施例3 Ma=Mo 0.95 0.05 71 1.2M 實施例4 MA=Nb 0.96 0.04 85.0 0.05M 實施例5 MA=Nb 0.94 0.04 85.0 '0.05M 比較例1 MA=Sb 0.95 0.05 83 0.03M 比較例3 MA=Ta 0.78 0.22 77 1.1M 〔表2〕 表2:膜的組成及可見光透過率、比電阻値 例 使用元素 (Sn)/(Sn+MA) (MA)(Sn+MA) p〇(Qcm) pi(Qcm) 可見光透 過率(％) 實施例1 MA=Ta 0.96 0.04 0.0072 0.0027 86 實施例2 Ma=W 0.92 0.08 0.0092 0.0041 85 實施例3 Ma=Mo 0.95 0.05 0.0192 0.0077 87 實施例4 MA=Nb 0.96 0.04 0.0152 0.0062 88 實施例5 MA=Nb 0.94 0.04 0.0092 0.0066 87.6 比較例1 MA=Sb 0.95 0.05 0.0075 0.0143 82 比較例3 MA=Ta 0.78 0.22 0.0523 0.1532 76 產業上的利用可能性 -22- 200807449 (20) 本發明的透明導電膜，透明性及導電性佳，即使在與 氧化力強的玻璃粉材料接合的狀態下燒成的情況，比電阻 値也不會上升，顯示高導電性。所以，適合作爲FPD用透 明電極。而且，將近年驚人的進步之雷射圖形化技術應用 於該膜，可容易地在玻璃塑膠基板、薄膜基板、結晶基板 上形成高精細的電極圖形。而且，以氧化錫爲主要成分、 含有選自鎢、鉬、鈮、鉬以及鉍所成之群之至少一種元素 作爲摻雜劑之透明導電膜，由於所含的作爲摻雜劑之元素 在熱、化學上安定，與氧化錫爲主要成分、含有銻作爲摻 雜劑之透明導電膜比較，在塗佈玻璃粉的狀態下燒成時， 也有抑制微泡產生等的光學缺陷的效果。 此外，此處引用2006年6月6日申請之日本專利申 請2006- 1 5 75 1 5的說明書、申請專利範圍、圖面及摘要的 全部內容，使用作爲本發明的說明書之揭露。Table 1: Composition and Density of Sputtering Target, Surface Resistance Example Using Element (Sn) / (Sn + MA) (MA) / (Sn + MA) Sputtering Target Density (%) Surface Resistance (Ω / Port) Example 1 MA = Ta 0.96 0.04 62 2.2M Example 2 Ma = W 0.92 0.08 68 1.8 M Example 3 Ma = Mo 0.95 0.05 71 1.2 M Example 4 MA = Nb 0.96 0.04 85.0 0.05 M Example 5 MA = Nb 0.94 0.04 85.0 '0.05M Comparative Example 1 MA=Sb 0.95 0.05 83 0.03M Comparative Example 3 MA=Ta 0.78 0.22 77 1.1M [Table 2] Table 2: Composition of the film, visible light transmittance, specific resistance, use element (Sn) /(Sn+MA) (MA)(Sn+MA) p〇(Qcm) pi(Qcm) visible light transmittance (%) Example 1 MA=Ta 0.96 0.04 0.0072 0.0027 86 Example 2 Ma=W 0.92 0.08 0.0092 0.0041 85 Example 3 Ma = Mo 0.95 0.05 0.0192 0.0077 87 Example 4 MA = Nb 0.96 0.04 0.0152 0.0062 88 Example 5 MA = Nb 0.94 0.04 0.0092 0.0066 87.6 Comparative Example 1 MA = Sb 0.95 0.05 0.0075 0.0143 82 Comparative Example 3 MA= Ta 0.78 0.22 0.0523 0.1532 76 Industrial use possibility-22- 200807449 (20) The transparent conductive film of the present invention is excellent in transparency and conductivity, even in oxidation resistance. Fired glass in a state where the powder material is engaged, does not increase the specific resistance Zhi, exhibits high electrical conductivity. Therefore, it is suitable as a transparent electrode for FPD. Further, the laser patterning technique which has been astoundingly improved in recent years is applied to the film, and a high-definition electrode pattern can be easily formed on the glass plastic substrate, the film substrate, and the crystal substrate. Further, a transparent conductive film containing tin oxide as a main component and containing at least one element selected from the group consisting of tungsten, molybdenum, niobium, molybdenum, and niobium as a dopant, is contained in the element as a dopant. Chemically stable, compared with a transparent conductive film containing tin oxide as a main component and containing cerium as a dopant, it is also effective in suppressing optical defects such as generation of microbubbles when fired in a state in which glass frit is applied. In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2006- 159 151, filed on Jun.
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