TWI525208B - Sputtering target material - Google Patents
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- TWI525208B TWI525208B TW104113853A TW104113853A TWI525208B TW I525208 B TWI525208 B TW I525208B TW 104113853 A TW104113853 A TW 104113853A TW 104113853 A TW104113853 A TW 104113853A TW I525208 B TWI525208 B TW I525208B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
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Description
本發明係有關於含有銅或銅合金及氧化物之濺鍍靶材，特別是有關於適於形成採用銅網目之觸控面板用感測器薄膜的黑化層的濺鍍靶材。 The present invention relates to a sputtering target containing copper or a copper alloy and an oxide, and more particularly to a sputtering target suitable for forming a blackening layer of a sensor film for a touch panel using a copper mesh.
近年來，於液晶顯示器等的顯示裝置，已提供於市場上很多係直接接觸畫面以實施操作之所謂觸控面板方式。並且，於此種觸控面板，一般周知係採用靜電容量式的觸控面板用感測器薄膜。 In recent years, display devices such as liquid crystal displays have been provided in the market as a so-called touch panel method in which a direct contact with a screen is performed to perform an operation. Further, in such a touch panel, it is generally known to use an electrostatic capacitance type sensor panel for a touch panel.
於此種靜電容量式的觸控面板用感測器薄膜，係使用例如PET膜基材的透明電極膜(ITO膜：電阻值100Ω/□左右)。使用此種ITO膜之觸控面板用感測器薄膜，由於ITO膜的電阻值的問題，難以被製作大面積的觸控面板。因此，使用可實現低電阻值之銅網目之觸控面板用感測器薄膜的開發遂進展起來。 For the sensor film of the electrostatic capacitance type touch panel, for example, a transparent electrode film (ITO film: resistance value of about 100 Ω/□) of a PET film substrate is used. With the sensor film for a touch panel using such an ITO film, it is difficult to produce a large-area touch panel due to the problem of the resistance value of the ITO film. Therefore, the development of a sensor film for a touch panel using a copper mesh having a low resistance value has progressed.
經採用此種銅網目之觸控面板用感測器薄膜，係於PET膜基材上藉蒸鍍法形成銅膜，並將其銅膜加工成格子狀的網目者。採用此種銅網目之感測器薄膜，係其銅網目之電阻值為1Ω/口左右，故成為可充分對應於大 面積觸控面板者。若說明採用此銅網目之觸控用感測器薄膜的具體性製法，藉由蒸鍍法於PET膜基材上形成銅膜，並於其銅膜表面上，進一步形成被稱為黑化層之用以調整感測器薄膜的亮度之薄膜。 A sensor film for a touch panel using such a copper mesh is formed by forming a copper film by vapor deposition on a PET film substrate, and processing the copper film into a lattice-like mesh. The sensor film using the copper mesh is such that the resistance value of the copper mesh is about 1 Ω/□, so that it can sufficiently correspond to the large Area touch panel. If a specific method for the touch sensor film using the copper mesh is described, a copper film is formed on the PET film substrate by vapor deposition, and a black layer is further formed on the surface of the copper film. A film for adjusting the brightness of the sensor film.
就形成此黑化層之先前技術而言，一般周知：藉電鍍法或濺鍍法進行之表面處理而形成之方法，或採用銅或銅合金的濺鍍靶材，在濺鍍時供給氧氣或氮氣等而藉反應性濺鍍形成之方法(例如，參照專利文獻1至3)。 In the prior art for forming such a blackening layer, it is generally known that a surface treatment by electroplating or sputtering is used, or a sputtering target of copper or copper alloy is used to supply oxygen during sputtering or A method of forming by reactive sputtering using nitrogen gas or the like (for example, refer to Patent Documents 1 to 3).
於此等先前技術之黑化層的形成技術中，在表面處理法係被指出不適合於銅網目的細線化之點，在反應性濺鍍法，因氧氣等的供給的影響，成為成膜速率降低之傾向，被指出放電的不安定化。因此，於反應性濺鍍法中，為能僅以Ar氣形成黑化層，亦在研究增加銅等濺鍍靶材的氧氣含量，惟若增加濺鍍材的氧氣含量，則靶材本身的體積電阻會上升，直流電源的放電(濺鍍)變困難。 In the prior art blackening layer forming technique, the surface treatment method is pointed out that it is not suitable for the thinning of the copper mesh, and in the reactive sputtering method, the film formation rate is affected by the supply of oxygen or the like. The tendency to lower is indicated by the instability of the discharge. Therefore, in the reactive sputtering method, in order to form the blackening layer only with Ar gas, it is also studied to increase the oxygen content of the sputtering target such as copper, but if the oxygen content of the sputtering material is increased, the target itself The volume resistance rises and the discharge (sputtering) of the DC power supply becomes difficult.
專利文獻1：日本專利特開2013-129183號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2013-129183
專利文獻2：日本專利第3969743號說明書 Patent Document 2: Japanese Patent No. 3967743
專利文獻3：日本專利特開2008-311565號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-311565
本發明係以上述般的情況作為背景所開發 者，目的在於提供一種能以直流電源進行放電之含有銅或者銅合金及氧化物之濺鍍靶材者，並且，提供一種適於形成靜電容量方式的觸控用感測器薄膜的黑化層之濺鍍靶材。 The present invention is developed in the light of the above-mentioned circumstances. The object of the invention is to provide a sputtering target containing copper or a copper alloy and an oxide which can be discharged by a DC power supply, and to provide a blackening layer suitable for forming a capacitive sensing film of a capacitive type. Sputter target.
本發明有關一種具有銅系金屬相與氧化物相之混合組織，氧含量為5原子%至30原子%，相對密度為85%以上，體積電阻值為1.0×10-2Ω cm以上之濺鍍靶材。 The invention relates to a sputtering structure having a mixed structure of a copper-based metal phase and an oxide phase, an oxygen content of 5 atom% to 30 atom%, a relative density of 85% or more, and a volume resistivity of 1.0×10 -2 Ω cm or more. Target.
若依據本發明之濺鍍靶材，由於靶材本身的體積電阻值較低，故可以低廉的直流電源進行放電，可提升成膜速率。又，由於濺鍍靶材中含有高濃度的氧，故可降低濺鍍氣體中的氧量而進行濺鍍，並形成穩定的黑化層。於本發明之濺鍍靶材中之銅系金屬相，係指僅銅的單相或者銅合金相，就銅合金相而言，可例舉：銅-鎳合金相、銅-鈦合金相等。氧化物相係指僅具有銅之氧化物相(氧化銅相)或含有銅合金作為成分之氧化物相(銅合金氧化物相)。銅合金氧化物相時，其金屬成分可為與銅合金相同，亦可為相異。如此之氧化物相，可例舉：氧化銅相、銅-鎳合金的銅合氧化物相、銅-鈦合金的銅合金氧化物相等。並且，藉由成為此氧化物相與銅系金屬相混合而成之組織，於濺渡靶材的組織中，形成銅系金屬相所產生之網絡，且其網絡成為導電路徑，即使氧含量為5原子%至30原子%，仍能實現低的體積電阻值。 According to the sputtering target of the present invention, since the volume resistance of the target itself is low, the discharge can be performed with a low-cost DC power source, and the film formation rate can be improved. Further, since the sputtering target contains a high concentration of oxygen, the amount of oxygen in the sputtering gas can be lowered to perform sputtering, and a stable blackened layer can be formed. The copper-based metal phase in the sputtering target of the present invention means a single phase or a copper alloy phase of only copper, and the copper alloy phase may be a copper-nickel alloy phase or a copper-titanium alloy. The oxide phase means an oxide phase (copper alloy oxide phase) having only an oxide phase of copper (copper oxide phase) or a copper alloy as a component. In the case of a copper alloy oxide phase, the metal component may be the same as or different from the copper alloy. Such an oxide phase may be exemplified by a copper oxide phase, a copper-nickel alloy copper oxide phase, and a copper-titanium alloy copper alloy oxide. Further, by forming a structure in which the oxide phase and the copper-based metal are mixed, a network generated by the copper-based metal phase is formed in the structure of the splash target, and the network becomes a conductive path even if the oxygen content is From 5 atom% to 30 atom%, a low volume resistance value can still be achieved.
有關本發明之濺鍍靶材的氧含量，為5原子 %至30原子%，較佳為10原子%至25原子%，更佳為10原子%至20原子%。若氧含量成為5原子%以下，必須於濺鍍氣體中大量導入氧，若超過50原子%，則以直流電源之放電變困難。於本發明之濺鍍靶材中含有鎳時，鎳含量較佳為61.0原子%以下，更佳為57.0原子%以下。若鎳含量超過61.0原子%，則銅-鎳合金相顯示強磁性，與濺鍍時的成膜速率降低有關。又，本發明之濺鍍靶材中含有鈦時，則鈦含量較佳為7.50原子%以下，更佳為6.25原子%以下。若鈦含量超過7.50原子%，則形成氧化鈦相，在燒結時容易產生龜裂。 The oxygen content of the sputtering target of the present invention is 5 atoms. % to 30 atom%, preferably 10 atom% to 25 atom%, more preferably 10 atom% to 20 atom%. When the oxygen content is 5 atom% or less, it is necessary to introduce a large amount of oxygen into the sputtering gas, and if it exceeds 50 atom%, discharge by a DC power source becomes difficult. When nickel is contained in the sputtering target of the present invention, the nickel content is preferably 61.0 atom% or less, more preferably 57.0 atom% or less. If the nickel content exceeds 61.0 atom%, the copper-nickel alloy phase exhibits strong magnetism and is associated with a decrease in film formation rate at the time of sputtering. Further, when titanium is contained in the sputtering target of the present invention, the titanium content is preferably 7.50 atom% or less, more preferably 6.25 atom% or less. When the titanium content exceeds 7.50 atom%, a titanium oxide phase is formed, and cracks are likely to occur during sintering.
並且，有關本發明之濺鍍靶材的相對密度為85%以上者，較佳為90%，更佳為95%以上。相對密度愈接近100%愈良好。若相對密度成為85%以下，測濺鍍靶材中空隙增多，以致容易吸收大氣中的氣體。又，以其空隙作為起點之異常放電或濺鍍靶材的裂紋現象容易發生。 Further, the relative density of the sputtering target of the present invention is 85% or more, preferably 90%, more preferably 95% or more. The closer the relative density is to 100%, the better. If the relative density is 85% or less, the amount of voids in the sputtering target is increased, so that the gas in the atmosphere is easily absorbed. Further, the abnormal discharge or the crack phenomenon of the sputtering target with the void as a starting point is likely to occur.
再者，有關本發明之濺鍍靶材，為穩定地實施直流電源之放電，體積電阻值為1.0×10-2Ω cm以下。較佳為1.0×10-3Ω cm以下，更佳為5.0×10-4Ω cm以下。 Further, in the sputtering target of the present invention, the discharge of the DC power source is stably performed, and the volume resistance value is 1.0 × 10 -2 Ω cm or less. It is preferably 1.0 × 10 -3 Ω cm or less, more preferably 5.0 × 10 -4 Ω cm or less.
有關本發明之濺鍍靶材，較佳為銅系金屬相的平均粒徑在0.5μm至10.0μm，氧化物相的平均粒徑在0.05μm至7.0μm。更佳為銅系金屬相的平均粒徑在1.0μm至8.0μm，氧化物相的平均粒徑在0.5μm至6.0μm。為使銅系金屬相的平均粒徑為0.5μm以下，必須使使用來作為濺鍍靶材的原料之銅或銅合金、能與銅形成合金之金 屬原料粉設為小直徑，惟若使用過於小直徑的平均粒徑的原料粉，則因在原料粉表面所形成之氧化膜的影響，在製造濺鍍靶材時的燒結變成不完全，以致濺鍍靶材的氧含量容易變動。若銅系金屬相的平均粒徑超過10.0μm，則容易產生氧化物相的凝聚，以致以銅系金屬相的網絡難以形成導電路徑。又，若產生氧化物相的凝聚，則以其為起因而容易在濺鍍中產生異常放電。並且，為使氧化物相的平均粒徑為0.05μm以下，必須使使用來作為濺鍍靶材的原料之氧化物粉設為小直徑，惟由於過於小直徑的平均粒徑的氧化物粉容易發生凝聚，故難以進行濺鍍靶材之製造。若氧化物相的平均粒徑超過7.0μm以上，在濺鍍中容易產生異常放電。若具有此種平均粒徑的銅系金屬相與氧化物相經混合之組織，則可穩定地實現體積電阻值為1.0×10-2Ω cm以下之濺鍍靶材。又，為形成前述的銅系金屬相的網絡構造，於濺鍍靶材的剖面觀察中，於60μm×60μm的範圍之銅系金屬相的面積比較佳為0.32以上，更佳為0.44以上。若面積比為0.32以下，則難以形成銅系金屬相的網絡構造。 In the sputtering target of the present invention, it is preferred that the copper-based metal phase has an average particle diameter of from 0.5 μm to 10.0 μm and the oxide phase has an average particle diameter of from 0.05 μm to 7.0 μm. More preferably, the copper-based metal phase has an average particle diameter of from 1.0 μm to 8.0 μm, and the oxide phase has an average particle diameter of from 0.5 μm to 6.0 μm. In order to make the average particle diameter of the copper-based metal phase 0.5 μm or less, it is necessary to use copper or a copper alloy which is a raw material of the sputtering target, and a metal raw material powder which can form an alloy with copper as a small diameter, but if it is used too much The raw material powder having a small diameter and an average particle diameter is incompletely sintered during the production of the sputtering target due to the influence of the oxide film formed on the surface of the raw material powder, so that the oxygen content of the sputtering target is likely to vary. When the average particle diameter of the copper-based metal phase exceeds 10.0 μm, aggregation of the oxide phase is likely to occur, so that it is difficult to form a conductive path in a network of a copper-based metal phase. Further, when the agglomeration of the oxide phase occurs, abnormal discharge is likely to occur during sputtering. In addition, in order to make the average particle diameter of the oxide phase 0.05 μm or less, it is necessary to make the oxide powder which is used as a raw material of the sputtering target a small diameter, but it is easy to use an oxide powder having an average particle diameter which is too small in diameter. Since aggregation occurs, it is difficult to manufacture a sputtering target. When the average particle diameter of the oxide phase exceeds 7.0 μm or more, abnormal discharge is likely to occur during sputtering. When a structure in which a copper-based metal phase having such an average particle diameter is mixed with an oxide phase, a sputtering target having a volume resistance value of 1.0 × 10 -2 Ω cm or less can be stably achieved. Further, in order to form the network structure of the copper-based metal phase, the area of the copper-based metal phase in the range of 60 μm × 60 μm is preferably 0.32 or more, and more preferably 0.44 or more in the cross-sectional observation of the sputtering target. When the area ratio is 0.32 or less, it is difficult to form a network structure of a copper-based metal phase.
有關本發明之濺鍍靶材，較佳為氧化物相為氧化銅相或銅合金氧化物相。以銅系金屬相與氧化物相的混合組織，使用氧含量為5原子%至30原子%，且相對密度為85%以上，體積電阻值為1.0×10-2Ω cm以下者之濺鍍靶材，若於銅表面形成黑化層，則可使所形成之黑化層側的表面亮度L*為40以下。若表面亮度L*超過40，則構 成感測器薄膜之銅網目的表面反射會變強，顯示裝置的對比會降低。 Regarding the sputtering target of the present invention, it is preferred that the oxide phase be a copper oxide phase or a copper alloy oxide phase. A sputtering target in which a copper-based metal phase and an oxide phase are mixed, and an oxygen content is 5 atom% to 30 atom%, a relative density is 85% or more, and a volume resistivity is 1.0×10 -2 Ω cm or less. When a blackening layer is formed on the surface of the copper, the surface brightness L* of the formed blackening layer side can be 40 or less. If the surface brightness L* exceeds 40, the surface reflection of the copper mesh constituting the sensor film becomes strong, and the contrast of the display device is lowered.
有關本發明之濺鍍靶材，係可藉由將銅粉及/或銅合金粉或銅粉及用以形成銅合金之銅以外的金屬粉、與氧化物粉混合，在真空氣氛下，且在較銅或者銅合金的熔點低450℃至200℃的溫度範圍內之燒結溫度進行燒結而製造。若更低於較銅或銅合金的熔點為低450℃之燒結溫度，則燒結成為不充分，若超過較銅或銅合金的熔點為低200℃之燒結溫度，則由於接近銅或銅合金的熔點，難以形成銅系金屬相與氧化物相成的混合組織。於有關本發明之濺鍍靶材的製造方法中，可進行：僅銅粉與氧化物粉的混合，或僅銅合金粉與氧化物粉的混合，又，銅粉及與銅合金粉與氧化物粉的混合，以及銅粉及用以形成銅合金之銅以外的金屬粉與氧化物粉的混合，進行製造。然後，藉由調整銅粉及/或銅合金粉或用以形成銅合金之銅以外的金屬粉、與氧化物粉之混合量，可製造特定氧含量之濺鍍靶材。在此，就銅合金粉而言，可例舉如銅-鎳合金粉、銅-鈦合金粉等。又，就氧化物粉而言，可例舉如氧化銅粉、銅-鎳合金氧化物粉、銅-鈦合金氧化物粉等。再者，就用以形成銅合金之銅以外的金屬粉而言，可例舉如鎳粉：鈦粉等。 The sputtering target of the present invention can be mixed in a vacuum atmosphere by mixing copper powder and/or copper alloy powder or copper powder and metal powder other than copper for forming a copper alloy with oxide powder. It is produced by sintering at a sintering temperature lower than the melting point of copper or copper alloy at a temperature lower than 450 ° C to 200 ° C. If it is lower than the sintering temperature of 450 ° C lower than the melting point of copper or copper alloy, the sintering becomes insufficient, and if it exceeds the sintering temperature lower than the melting point of copper or copper alloy by 200 ° C, it is close to copper or copper alloy. At the melting point, it is difficult to form a mixed structure in which a copper-based metal phase and an oxide are formed. In the method for producing a sputtering target according to the present invention, it is possible to carry out: mixing only copper powder and oxide powder, or only mixing of copper alloy powder and oxide powder, and copper powder and copper alloy powder and oxidation. The mixing of the powder, and the mixing of the copper powder and the metal powder other than the copper used to form the copper alloy with the oxide powder are carried out. Then, by adjusting the amount of the copper powder and/or the copper alloy powder or the metal powder other than the copper used to form the copper alloy and the amount of the oxide powder, a sputtering target having a specific oxygen content can be produced. Here, as the copper alloy powder, for example, a copper-nickel alloy powder, a copper-titanium alloy powder, or the like can be exemplified. Further, the oxide powder may, for example, be copper oxide powder, copper-nickel alloy oxide powder or copper-titanium alloy oxide powder. Further, as the metal powder other than copper for forming a copper alloy, for example, nickel powder: titanium powder or the like can be exemplified.
本發明之濺鍍靶材的製造方法，可適用以銅粉及/或銅合金粉與氧化物粉作為原料之粉末冶金法。此種粉末冶金法，可適用在單軸壓塑成型後燒成成型物之方 法、熱壓法、電燒結法等，惟特佳為採用電燒結法。若採用電燒結法，則所混合之原料粉中的導電部分優先流通電流，進行燒結，亦即，成為對銅粉或銅合金粉的部分，或對其兩者的部分優先流通電流，形成銅系金屬相之銅粒子或銅合金粒子容易優先進行粒狀成長。其結果，於構成濺鍍靶材之銅系金屬相與氧化物相的混合組織中，確實形成銅系金屬相之銅粒子或銅合金粒子的連結，可確實地使濺鍍靶材本身的體積電阻值減少。 The method for producing a sputtering target of the present invention can be applied to a powder metallurgy method using copper powder and/or copper alloy powder and oxide powder as raw materials. This powder metallurgy method can be applied to the side of the molded product after uniaxial compression molding. Method, hot pressing method, electric sintering method, etc., but the best is to use electric sintering method. When the electric sintering method is employed, the conductive portion in the mixed raw material powder preferentially flows an electric current to be sintered, that is, a portion which is a copper powder or a copper alloy powder, or a portion of which is preferentially distributed to form a copper. The copper particles or the copper alloy particles of the metal phase are likely to preferentially grow in a granular form. As a result, in the mixed structure of the copper-based metal phase and the oxide phase constituting the sputtering target, the connection of the copper-based metal phase copper particles or the copper alloy particles is surely formed, and the volume of the sputtering target itself can be surely made. The resistance value is reduced.
若依據本發明，可實現能以直流電源進行放電之具有銅或銅合金與氧化物之濺鍍靶材，並能穩定地容易形成用以形成靜電容量方式的觸控面板用感測器薄膜之黑化層。 According to the present invention, a sputtering target having copper or a copper alloy and an oxide which can be discharged by a DC power source can be realized, and a sensor film for a touch panel for forming an electrostatic capacitance can be stably formed. Blackening layer.
第1圖係實施例1的剖面觀察。 Fig. 1 is a cross-sectional view of Example 1.
第2圖係實施例4的剖面觀察。 Fig. 2 is a cross-sectional view of Example 4.
以下，說明本發明之實施形態。首先，說明本實施形態的濺鍍靶材的製造。 Hereinafter, embodiments of the present invention will be described. First, the production of the sputtering target of the present embodiment will be described.
於本實施形態中，製作各氧含量的濺鍍靶材(實施例1至3)。為了比較，亦製作比較例1至3。表1中，表示各濺鍍靶材的數據。以下，說明各濺鍍靶材的製 造條件。 In the present embodiment, sputtering targets (Examples 1 to 3) each having an oxygen content were prepared. For comparison, Comparative Examples 1 to 3 were also prepared. In Table 1, the data of each sputtering target is shown. Hereinafter, the system for each sputtering target will be described. Make conditions.
實施例1：以平均粒徑D50=3.0μm的銅粉、及平均粒徑D50=3.0μm的氧化銅(I)粉作為原料。考量氧化銅(I)粉中的氧含量成為化學計量比(Cu：O=2：1)，以氧含量成為20原子%之方式予以秤量。將所秤量之原料粉與氧化鋯製粉碎介質投入於罐(pot)內，使用球磨機混合3小時。然後，將其混合粉篩分後，填充於直徑174mm的石墨塑模中。將填充有混合粉之石墨塑模安置在電燒結裝置(DR.SINTER/SPS Syntax(股)製)後，依下列條件進行燒結。 Example 1: average particle size D 50 = 3.0μm of copper powder, copper oxide and average particle diameter D 50 = 3.0μm (I) is used as a raw material powder. The oxygen content in the copper (I) powder was considered to be a stoichiometric ratio (Cu: O = 2: 1), and the oxygen content was adjusted to 20 atom%. The weighed raw material powder and the zirconia pulverization medium were placed in a pot and mixed for 3 hours using a ball mill. Then, the mixed powder was sieved and filled in a graphite mold having a diameter of 174 mm. The graphite mold filled with the mixed powder was placed in an electric sintering apparatus (manufactured by DR. SINTER/SPS Syntax Co., Ltd.), and sintered under the following conditions.
‧氣氛(atmosphere)：真空(壓力：40Pa(帕) ‧Atmosphere: Vacuum (pressure: 40Pa (Pa)
‧升溫時間：30℃/min(分鐘) ‧ Heating time: 30 ° C / min (minutes)
‧燒結溫度：580℃ ‧Sintering temperature: 580 ° C
‧燒結保持時間：30分鐘 ‧ Sintering retention time: 30 minutes
‧壓力：25MPa(兆帕) ‧ Pressure: 25MPa (MPa)
‧降溫：自然冷卻 ‧ Cooling: natural cooling
將依上述燒結條件所得之燒結體進行機械加工，製作直徑101.6mm、厚度5mm的濺鍍靶材。 The sintered body obtained under the above sintering conditions was machined to prepare a sputtering target having a diameter of 101.6 mm and a thickness of 5 mm.
實施例2：以原料粉的氧含量成為15原子%之方式予以秤量。其以外的製造條件，係與實施例1同樣方式。 Example 2: The raw material powder was weighed so as to have an oxygen content of 15 atom%. The other production conditions are the same as in the first embodiment.
實施例3：以原料粉的氧含量成為10原子%之方式予以秤量。其以外的製造條件，係與實施例1同樣方式。 Example 3: The raw material powder was weighed so as to have an oxygen content of 10 atom%. The other production conditions are the same as in the first embodiment.
實施例4：以平均粒徑D50=9.6μm的鎳粉及平均粒徑D50=2.5μm的氧化銅(II)粉作為原料。考量氧化銅(II)粉中的氧含量成為化學計量比(Cu：O=1：1)，以銅含量成為30原子%、鎳含量成為40原子%、氧含量成為30原子%之方式予以秤量。其以外的製造條件，係與實施例1同樣方式。 Example 4: Nickel powder having an average particle diameter D 50 = 9.6 μm and copper (II) oxide powder having an average particle diameter D 50 = 2.5 μm were used as a raw material. Considering that the oxygen content in the copper (II) oxide powder is stoichiometric (Cu: O = 1:1), and the copper content is 30 atom%, the nickel content is 40 atom%, and the oxygen content is 30 atom%. . The other production conditions are the same as in the first embodiment.
實施例5：將平均粒徑D50=9.6μm的鎳粉、平均粒徑D50=3.0μm的銅粉、以及平均粒徑D50=2.5μm的氧化銅(II)粉作為原料。考慮氧化銅(II)粉中的氧含量成為化學計量比(Cu：O=1：1)，以銅含量成為34原子%、鎳含量成為46原子%、氧含量成為20原子%之方式予以秤量。其以外的製造條件係與實施例1同樣方式。 Example 5: Nickel powder having an average particle diameter D 50 = 9.6 μm, copper powder having an average particle diameter D 50 = 3.0 μm, and copper (II) oxide powder having an average particle diameter D 50 = 2.5 μm were used as a raw material. Considering that the oxygen content in the copper (II) oxide powder is stoichiometric (Cu: O = 1:1), the copper content is 34 atom%, the nickel content is 46 atom%, and the oxygen content is 20 atom%. . The other production conditions are the same as in the first embodiment.
比較例1：至以球磨機之混合為止係與實施例1同樣方式實施，以單軸壓塑成型(加壓機壓力：500kgf(4克力)/cm2)製作直徑140mm的壓粉物。然後，使用燒成爐依下列條件進行燒成。 Comparative Example 1: A mixture of a ball mill was used in the same manner as in Example 1. A pulverized product having a diameter of 140 mm was produced by uniaxial compression molding (pressing machine pressure: 500 kgf (4 gram force)/cm 2 ). Then, it was baked using the baking furnace under the following conditions.
‧氣氛：大氣 ‧Atmosphere: Atmosphere
‧升溫時間：50℃/hr(約0.83℃/min) ‧ Heating time: 50 ° C / hr (about 0.83 ° C / min)
‧燒結溫度：900℃ ‧Sintering temperature: 900 ° C
‧燒結保持時間：4小時 ‧ Sintering retention time: 4 hours
‧降溫：50℃/hr(約0.83℃/min) ‧ Cooling: 50 ° C / hr (about 0.83 ° C / min)
將以上述燒結條件所得之燒結體進行機械加工，製作直徑101.6mm、厚度5mm的濺鍍靶材。 The sintered body obtained under the above sintering conditions was machined to prepare a sputtering target having a diameter of 101.6 mm and a thickness of 5 mm.
比較例2：除使燒成氣氛設為真空(壓力：40Pa)以外，其餘係與比較例1同樣方式。 Comparative Example 2: The same procedure as in Comparative Example 1 was carried out except that the firing atmosphere was set to vacuum (pressure: 40 Pa).
比較例3：僅使用氧化銅(I)粉作為原料粉。其氧含量為33.3原子%(Cu：O=2：1)。將氧化銅粉直接填充於直徑174mm的石墨塑模中。以後的條件，係與實施例1同樣方式實施。 Comparative Example 3: Only copper (I) oxide powder was used as the raw material powder. Its oxygen content was 33.3 at% (Cu: O = 2: 1). The copper oxide powder was directly filled in a graphite mold having a diameter of 174 mm. The subsequent conditions were carried out in the same manner as in Example 1.
對於所製作之各濺鍍靶材、實施氧含量、相對密度、體積電阻值、平均粒徑的評價。將其結果，表示於表1及表2中。又，各評價方法係如下。 The sputtering target was prepared and evaluated for oxygen content, relative density, volume resistance value, and average particle diameter. The results are shown in Tables 1 and 2. Moreover, each evaluation method is as follows.
氧含量：藉由機械加工切削燒結體的表面，從所得之切粉，採用氧氮分析裝置(EMGA-550/(股)堀場製作所製)，測定氧含量。 Oxygen content: The surface of the sintered body was machined by machining, and the oxygen content was measured from the obtained cut powder using an oxygen-nitrogen analyzer (EMGA-550/manufactured by Horiba, Ltd.).
相對密度：將濺鍍靶材的重量(g)除以其體積(cm3)，算出依下述理論式(數1)之理論密度ρ(g/cm3)之百分率，設為相對密度(%)。 Relative density: The weight (g) of the sputtering target is divided by the volume (cm 3 ), and the percentage of the theoretical density ρ (g/cm 3 ) according to the following theoretical formula (number 1) is calculated and set as the relative density ( %).
式中，C(Cu)、C(Cu2O)係分別表示濺鍍靶材中的銅系金屬相與氧化物相之含量(重量%)，ρ(Cu)、ρ(Cu2O)分別在表示銅或者銅合金的密度、氧化物的密度。銅系金屬相與氧化物相之含量(重量%)，係假定所實測之燒結體中的氧全部形成氧化銅(I)或銅合金氧化物而算出。 In the formula, C(Cu) and C(Cu 2 O) respectively indicate the content (% by weight) of the copper-based metal phase and the oxide phase in the sputtering target, and ρ(Cu) and ρ(Cu 2 O), respectively. It indicates the density of copper or copper alloy and the density of oxide. The content (% by weight) of the copper-based metal phase and the oxide phase is calculated assuming that all of the oxygen in the sintered body actually measured forms copper oxide (I) or a copper alloy oxide.
體積電阻值：使用低電阻率計(LorestaHP/(股)三菱化學Analytech製)及四探針法用探測器，測定加工後的濺鍍靶材的體積電阻值。 Volume resistance value: The volume resistivity of the processed sputtering target was measured using a low resistivity meter (Loresta HP/Mitsubishi Chemical Analytech) and a four-probe detector.
平均粒徑：將濺鍍靶材的表面研磨而作成平滑。對於該平滑表面，藉由搭載有能量分散型X光分析(EDS)/電子線後方散射繞射分析(EBSD)裝置(Pegasus System/Ametek(股)製)之FE槍型的掃瞄式電子顯微鏡(SUPRA55VP/Carl Zeiss公司製)而測定銅及鎳及氧的EDS光譜及EBSD圖型。測定條件係設為加速電壓20kV、觀察區域60×60μm、測定間隔0.5μm。附有指數之結晶相係銅系金屬相(銅相或銅合金相)及氧化物相，從EDS光譜區別兩者。對於所得之數據，選擇EBSD解析程式(OIMAnalysis/(股)TSLSolutions製)的分析目錄「Grain Size」，以算出銅系金屬相與氧化物相之各別附面積重量之平均結晶粒徑(μm)。此時，被檢出5°以上的方位差時，辨識為一般粒界者，對於銅，係在<111>軸周圍，在60°旋轉的方位關係之雙晶粒界係不視為一般粒界之方式實施。又，銅系金屬相的面積比，係如下方式予以算出。 Average particle diameter: The surface of the sputter target is ground to make it smooth. For this smooth surface, an FE-type scanning electron microscope equipped with an energy dispersive X-ray analysis (EDS)/electron beam backscatter diffraction analysis (EBSD) device (Pegasus System/Ametek) was used. (SUPRA55VP/Carl Zeiss) was used to measure the EDS spectrum and EBSD pattern of copper, nickel and oxygen. The measurement conditions were an acceleration voltage of 20 kV, an observation area of 60 × 60 μm, and a measurement interval of 0.5 μm. A copper phase metal phase (copper phase or copper alloy phase) and an oxide phase with an index of crystal phase are distinguished from the EDS spectrum. For the obtained data, the analysis catalog "Grain Size" of the EBSD analysis program (manufactured by OIMAnalysis/TSLSolutions) was selected to calculate the average crystal grain size (μm) of the respective surface area weights of the copper-based metal phase and the oxide phase. . In this case, when the azimuth difference of 5° or more is detected, it is recognized as a general grain boundary. For copper, the double grain boundary of the orientation relationship of 60° rotation around the <111> axis is not regarded as a general grain. The way to implement it. Moreover, the area ratio of the copper-based metal phase was calculated as follows.
銅系金屬相的面積比：採用之值係使用上述的解析程式，以「Color Coded Map Style」選擇「Phase(相)」，其他的設定則藉由設為初期設定而算出之「Total Fraction」的值。 The area ratio of the copper-based metal phase: the value used is the "Phase" selected by "Color Coded Map Style", and the other settings are "Total Fraction" calculated by the initial setting. Value.
如表1所示，於實施例1至3中，所製作之濺鍍靶材的氧含量，約略成為目的之水準。於比較例1之時，由於在大氣中實施燒成處理，故氧含量顯著增大(相對於原料中的氧含量20.0原子%，製造後係增加至46.8原子%)。在比較例2之時，雖然燒成溫度較高(900℃)、燒成時間較長(4hr)，但仍然成為相對密度低者。相對於此，可知經採用電燒結法之實施例1至3的相對密度成為85%以上，若採用電燒結法，可促進燒結。即使含有鎳之實施例4、5，所製成之濺鍍靶材的氧含量亦略成為目的的水準。但，如與實施例1至3相比較，與原料粉中的氧含量相比，稍為降低。認為此係藉由鎳粉與氧化銦(II)粉之反應所形成 之氧化鎳相具有氧缺損之故。另一方面，關於相對密度，實施例4、5均成為85%以上。 As shown in Table 1, in Examples 1 to 3, the oxygen content of the produced sputtering target was approximately the target level. At the time of Comparative Example 1, since the baking treatment was carried out in the air, the oxygen content was remarkably increased (20.0 atom% relative to the oxygen content in the raw material, and increased to 46.8 atom% after the production). In Comparative Example 2, although the firing temperature was high (900 ° C) and the firing time was long (4 hr), the relative density was low. On the other hand, it is understood that the relative densities of Examples 1 to 3 by the electric sintering method are 85% or more, and sintering can be promoted by the electric sintering method. Even in Examples 4 and 5 containing nickel, the oxygen content of the resulting sputtering target was slightly higher than the intended level. However, as compared with Examples 1 to 3, it was slightly lowered as compared with the oxygen content in the raw material powder. It is believed that this is formed by the reaction of nickel powder with indium(II) oxide powder. The nickel oxide phase has an oxygen deficiency. On the other hand, in Examples 4 and 5, the relative density was 85% or more.
其次，於實施例1至3中，可知體積電阻值在1.0×10-2Ω cm以下的範圍，可以直流電源進行放電。另一方面，比較例1、3成為絕緣物，不能實施體積電阻值的測定。對於比較例2，亦因體積電阻值非常大且測定值不穩定，故未能特定電阻值。又，對於比較例2，雖然具有一定的導電性，惟仍難以藉由直流電源而使其穩定地放電。 Next, in Examples 1 to 3, it is understood that the volume resistance value is in the range of 1.0 × 10 -2 Ω cm or less, and discharge can be performed by a DC power source. On the other hand, Comparative Examples 1 and 3 were insulators, and measurement of the volume resistance value could not be performed. In Comparative Example 2, since the volume resistance value was very large and the measured value was unstable, the specific resistance value was not obtained. Further, in Comparative Example 2, although it had a certain conductivity, it was difficult to stably discharge it by a DC power source.
第1圖中，表示以電子線後方散射繞射分析裝置(EBSD裝置)觀察實施例1的濺鍍靶材的剖面之結果。認為於第1圖中顯示黑色的部分為銅相，其以外的部分為氧化物相。若看到銅相，為連結成網絡狀之狀態，故於材料內部形成導電路徑者。因此，在實施例的情形，認為體積電阻值變低。再者，經算出第1圖的視野(60μm×60μm)中之銅相的面積比之結果，為0.48。另一方面，在比較例1的情形，由於氧含量較大，故認為靶材全體為以氧化物相所構成之絕緣物。又，在比較例2的情形，為結晶性低的狀態，銅相與氧化物相之區別為不明確的組織狀態。因此，認為體積電阻值亦成為非常高者。再者，在比較例3的情形，成為幾乎不能確認銅合金相之組織，因此，認為已成為接近絕緣物之狀態者。 Fig. 1 shows the results of observing the cross section of the sputtering target of Example 1 by an electron beam backscatter diffraction analysis device (EBSD device). It is considered that the portion showing black in Fig. 1 is a copper phase, and the other portions are oxide phases. If the copper phase is observed, it is connected to a network state, so that a conductive path is formed inside the material. Therefore, in the case of the embodiment, the volume resistance value is considered to be low. Further, as a result of calculating the area ratio of the copper phase in the field of view (60 μm × 60 μm) of Fig. 1, it was 0.48. On the other hand, in the case of Comparative Example 1, since the oxygen content was large, it was considered that the entire target was an insulator composed of an oxide phase. Further, in the case of Comparative Example 2, in the state in which the crystallinity is low, the difference between the copper phase and the oxide phase is an unclear state of the structure. Therefore, it is considered that the volume resistance value is also very high. Further, in the case of Comparative Example 3, the structure of the copper alloy phase was hardly confirmed, and therefore, it was considered that the state was close to the insulator.
又，第2圖中，表示觀察實施例4的濺鍍靶材的剖面之結果。第2圖中顯示黑色的部分係銅與鎳的合金相(銅系金屬相)，其以外的部分為氧化物相。從EDS光 譜及EBSD圖型的結果，可知亦含有氧化鎳相。經瞭解作為原料之鎳粉，係一部分形成銅系金屬相，其餘的部分形成銅合金氧化物相。並且，與第1圖的情形同樣，於實施例4中之銅系金屬相係連結成網絡狀之狀態。再者，算出第2圖的視野(60μm×60μm)中之銅系金屬相的面積比之結果，其為0.70。 Further, Fig. 2 shows the results of observing the cross section of the sputtering target of Example 4. In Fig. 2, the black portion is an alloy phase of copper and nickel (copper-based metal phase), and the other portions are oxide phases. From EDS light The results of the spectrum and the EBSD pattern are also known to contain a nickel oxide phase. It is understood that the nickel powder as a raw material partially forms a copper-based metal phase, and the remaining portion forms a copper alloy oxide phase. Further, similarly to the case of Fig. 1, the copper-based metal phase in the fourth embodiment is connected to a network state. Further, as a result of calculating the area ratio of the copper-based metal phase in the field of view (60 μm × 60 μm) in Fig. 2, it was 0.70.
實施例1的平均粒徑，係銅系金屬相(銅相)為4.8μm、氧化物相為3.9μm。由此，可知較以原料所使用之銅粉的平均粒徑(D50=3.0μm)更稍微進行粒成長。又，亦未確認出氧化物相的凝聚。在比較例2的情形，不知是否因燒結不充分，在EBSD裝置未明確地檢測到菊池圖型，而未能算出銅相的平均粒徑。 The average particle diameter of Example 1 was 4.8 μm in the copper-based metal phase (copper phase) and 3.9 μm in the oxide phase. From this, it was found that the grain growth was performed more slightly than the average particle diameter (D 50 = 3.0 μm) of the copper powder used for the raw material. Further, no aggregation of the oxide phase was confirmed. In the case of Comparative Example 2, it was not known whether or not the kiln pattern was not clearly detected in the EBSD apparatus due to insufficient sintering, and the average grain size of the copper phase could not be calculated.
接著，說明有關使用所製作之濺鍍靶材，而形成黑化層之結果。黑化層的評價，係於玻璃基板上以銅形成銅配絕層，並製作於其銅層表面形成有黑化層之評價試樣。 Next, the result of forming a blackened layer using the produced sputtering target will be described. The blackening layer was evaluated by forming a copper-based barrier layer on copper on a glass substrate, and preparing an evaluation sample in which a blackened layer was formed on the surface of the copper layer.
黑化層的膜厚雖然無特別限定，惟可設為5nm至100nm。濺鍍亦可僅以氬氣實施，惟就調整所形成之黑化層的光學特性之目的，亦可添加氧氣或氮氣、或兩者作為濺鍍氣體。在此種情形，所添加之氣體流量與氬氣流量之比(所添加之氣體流量/氬氣流量)較佳為20%以下，更佳為15%以下。若添加過多的氧或氮、或其兩者，則有引起成膜速率的降低或放電的不穩定之傾向。 The film thickness of the blackening layer is not particularly limited, but may be set to 5 nm to 100 nm. The sputtering may be performed only by argon gas, but for the purpose of adjusting the optical characteristics of the blackened layer formed, oxygen or nitrogen gas or both may be added as a sputtering gas. In this case, the ratio of the added gas flow rate to the argon gas flow rate (the added gas flow rate/argon gas flow rate) is preferably 20% or less, more preferably 15% or less. If too much oxygen or nitrogen or both are added, there is a tendency to cause a decrease in the film formation rate or instability of the discharge.
於此之評價試樣中，雖然形成使用純銅之 銅層，惟在感測器薄膜等所構成之銅配線時，對於低電阻的要求係使用純銅，考量與基材之密著性時係亦可使用銅合金。又，為確與基材之密著性之目的，亦可於銅配線的基底形成鈦或鉬等的密著層。銅配線的膜厚雖然無特別限制，惟亦可設為例如50nm至10000nm。 In this evaluation sample, although pure copper was formed. In the copper layer, in the case of a copper wiring formed of a sensor film or the like, pure copper is required for low resistance, and a copper alloy may be used in consideration of adhesion to a substrate. Further, for the purpose of ensuring adhesion to the substrate, an adhesion layer such as titanium or molybdenum may be formed on the base of the copper wiring. The film thickness of the copper wiring is not particularly limited, but may be, for example, 50 nm to 10000 nm.
評價試樣的製造條件，為如下所示者。首先，使所製作之各濺鍍靶材與銅製的支撐板相貼合而成為濺鍍靶。將此濺鍍靶及配線用純銅濺鍍靶，裝設於具備有直流電源之濺鍍裝置並進行成膜。成膜條件，為如下所示者。 The production conditions of the evaluation sample were as follows. First, each of the produced sputtering targets was bonded to a copper support plate to form a sputtering target. The sputtering target and the wiring using a pure copper sputtering target are mounted on a sputtering apparatus having a DC power supply and formed into a film. The film formation conditions are as follows.
‧積層膜構成：黑化層/銅配線膜/玻璃基板 ‧ laminated film composition: blackening layer / copper wiring film / glass substrate
‧黑化層厚度：20nm ‧ Blackening layer thickness: 20nm
‧銅配線層厚度：200nm ‧ Copper wiring layer thickness: 200nm
‧玻璃基板：40mm×40mm×0.7mmt ‧ Glass substrate: 40mm × 40mm × 0.7mmt
‧到達壓力：5×10-6Torr以下 ‧ Arrival pressure: 5 × 10 -6 Torr or less
‧氧流量：0.0至10.0sccm(間隔2.5sccm) ‧Oxygen flow rate: 0.0 to 10.0sccm (interval 2.5sccm)
‧氧氣流量/氬氣流量的比率：0.0至20.4% ‧Oxygen flow rate / argon flow rate ratio: 0.0 to 20.4%
‧施加電力：100W至300W(1.3W/cm2至3.7W/cm2) ‧Apply power: 100W to 300W (1.3W/cm 2 to 3.7W/cm 2 )
對於所製作之評價試樣，測定其表面的亮度(L*)。L*的測定係使用分光測色計(CM-2500d/Konica Minolta(股)製)，並以L*a*b*表色系，測定評價試樣的積層膜表面的L*。為了比較，亦製作使用市售的韌煉銅(tough-pitch copper)(C110、靶氧含量0.04at%以下)，並形成 黑化層者(比較例4)。於表2中，表示所得之各評價試樣的積層膜的最佳氧流量，及以其條件所成膜之積層膜的L*。在此所稱之最佳氧流量，係當在0.0至10.0sccm(間隔2.5sccm)的範圍形成積層膜時，表示最低的L*之情形的氧流量。 The brightness (L*) of the surface of the evaluation sample prepared was measured. The L* was measured by using a spectrophotometer (CM-2500d/Konica Minolta Co., Ltd.) and measuring the L* of the surface of the laminated film of the evaluation sample by the L*a*b* color system. For comparison, commercially available tough-pitch copper (C110, target oxygen content of 0.04 at% or less) was also produced and formed. Blackening layer (Comparative Example 4). In Table 2, the optimum oxygen flow rate of the laminated film of each of the obtained evaluation samples and the L* of the laminated film formed by the conditions are shown. The optimum oxygen flow rate referred to herein is the oxygen flow rate in the case where the laminated film is formed in the range of 0.0 to 10.0 sccm (interval 2.5 sccm).
於實施例1至5的黑化層中，係對抑制顯示裝置的對比降低作為目標之亮度L*的值為40以下的範圍者。又，可知若濺鍍靶材中的氧含量增加，即使少的氧氣流量，亮度L*之值亦變小。另一方面，在比較例4的情形，雖然使氧氣流量設為最大的10sccm而形成黑化層，但仍然未能使亮度L*形成40以下。 In the blackening layers of Examples 1 to 5, the contrast of the display device is lowered to reduce the value of the target luminance L* to 40 or less. Further, it is understood that if the oxygen content in the sputtering target increases, the value of the luminance L* becomes small even with a small oxygen flow rate. On the other hand, in the case of Comparative Example 4, although the blackening layer was formed by setting the oxygen flow rate to the maximum 10 sccm, the luminance L* was not formed to 40 or less.
若使用本發明，可有效率地製造一種可實現以直流電源進行放電之濺鍍處理，並不降低顯示裝置的對比，且具備黑化層之觸控面板用感測器薄膜。 According to the present invention, it is possible to efficiently manufacture a sensor film for a touch panel having a blackening layer without performing a sputtering process which can perform discharge by a DC power supply without reducing the contrast of the display device.
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