TW201346937A - Method for manufacturing substrate having transparent electrode - Google Patents

Method for manufacturing substrate having transparent electrode Download PDF

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Publication number
TW201346937A
TW201346937A TW102103434A TW102103434A TW201346937A TW 201346937 A TW201346937 A TW 201346937A TW 102103434 A TW102103434 A TW 102103434A TW 102103434 A TW102103434 A TW 102103434A TW 201346937 A TW201346937 A TW 201346937A
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film
transparent
transparent electrode
substrate
heating
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TW102103434A
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Chinese (zh)
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Takahisa Fujimoto
Hiroaki Ueda
Yuji Takahashi
Takashi Kuchiyama
Kenji Yamamoto
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Kaneka Corp
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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
    • C23C14/02—Pretreatment of the material to be coated
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • 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
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • C23C14/58—After-treatment
    • C23C14/584—Non-reactive treatment
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
    • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
    • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Abstract

The present invention pertains to a method for manufacturing a substrate having a transparent electrode layer comprising a metal oxide thin film provided on a transparent film. This manufacturing method has: a base material preparation step for introducing a roll-shaped wound body made from a transparent film into the base material preparation chamber of a winding-type sputtering film-forming device; a heating step in which the transparent film is subjected to a heating treatment in the base material preparation chamber, by heat from a heating unit, while being unrolled and transported from the roll-shaped wound body; and a transparent electrode layer film-forming step in which a transparent electrode layer made from an amorphous metal oxide thin film is formed on the heat-treated transparent film while an inert gas is introduced into the film-forming chamber of the winding-type sputtering film-forming device. The heating step and the transparent electrode layer film-forming step are performed continuously without the transparent film being removed from the sputtering film-forming device. In the heating step, heating is preferably performed without the transparent film and the heating unit coming into contact with each other. The pressure in the base material preparation chamber during the heating step is preferably no greater than 1.0 Pa.

Description

附有透明電極之基板的製造方法 Method for manufacturing substrate with transparent electrode

本發明係關於一種在透明薄膜上具備透明電極層之附有透明電極之基板的製造方法。 The present invention relates to a method of manufacturing a substrate having a transparent electrode provided with a transparent electrode layer on a transparent film.

在薄膜或玻璃等之透明基板上來形成透明電極層之附有透明電極之基板係使用作為觸控面板等之顯示器之透明電極。作為此種之附有透明電極之基板的製造方法係知道在透明基材上藉由濺鍍法等而形成非結晶質之金屬氧化物薄膜之後，藉由加熱而對於金屬氧化物來進行結晶化之方法(例如專利文獻1)。 A substrate having a transparent electrode on which a transparent electrode layer is formed on a transparent substrate such as a film or glass is used as a transparent electrode of a display such as a touch panel. As a method for producing a substrate having such a transparent electrode, it is known that a non-crystalline metal oxide thin film is formed on a transparent substrate by a sputtering method or the like, and then crystallization is performed on the metal oxide by heating. Method (for example, Patent Document 1).

在附有透明電極之基板來使用於靜電電容方式觸控面板之位置檢測之狀態下，於透明電極層，施行微細之圖案化。作為圖案化方法係使用例如在透明基材上之概略全面來形成透明電極層之後，於面內之一部分，藉由蝕刻等而除去透明電極層之方法。藉此而得到在基材上具有圖案化成為電極形成部(也稱為「非蝕刻部」)和電極非形成部(也稱為「蝕刻部」)之透明電極層之附有透明電極之基板。在使用於靜電電容方式觸控面板之位置檢測之透明電極，要求低電阻且透明性變高而膜質呈良好。 In the state in which the substrate with the transparent electrode is used for the position detection of the capacitive touch panel, fine patterning is performed on the transparent electrode layer. As the patterning method, for example, a method of removing a transparent electrode layer by etching or the like in one of the in-plane portions after forming a transparent electrode layer on a transparent substrate is used. Thereby, a substrate with a transparent electrode having a transparent electrode layer patterned into an electrode forming portion (also referred to as "non-etching portion") and an electrode non-forming portion (also referred to as "etching portion") on the substrate is obtained. . The transparent electrode used for detecting the position of the capacitive touch panel requires low resistance and high transparency, and the film quality is good.

作為在薄膜上形成良質之透明電極層之方法係知 道在藉由濺鍍法而造成之透明電極層之製膜前，於事前，加熱基材薄膜之方法。例如在專利文獻2，揭示：藉由在事前，加熱基材薄膜，進行熱收縮，在熱收縮率成為0.5%以下之薄膜上，製膜透明電極層，而得到抑制電阻值變動或膜剝離發生之附有透明電極之基板。此外，在專利文獻3，揭示：在捲繞式濺鍍製膜裝置內，進行基材薄膜之捲回，在製膜壓輥，加熱基材薄膜。藉由在透明電極層之製膜前，除去薄膜中之水分，而減低製膜環境之水分壓，得到低電阻之透明電極層。 As a method for forming a favorable transparent electrode layer on a film, A method of heating a substrate film before the film formation of the transparent electrode layer by sputtering. For example, Patent Document 2 discloses that by heating a base film beforehand and performing heat shrinkage, a transparent electrode layer is formed on a film having a heat shrinkage ratio of 0.5% or less, thereby suppressing variation in resistance value or film peeling. A substrate with a transparent electrode attached thereto. Further, Patent Document 3 discloses that in a wound sputter film forming apparatus, a base film is wound up, and a base film is heated by a film forming press roll. The moisture in the film is removed by removing the moisture in the film before the film formation of the transparent electrode layer, thereby obtaining a low-resistance transparent electrode layer.

在透明電極層呈圖案化之附有透明電極之基板，除了前述透明電極層之膜質改善以外，還要求不容易辨識透明電極層之圖案。在專利文獻3及專利文獻4，提議：為了抑制透明電極層圖案之辨識，因此，使用具有不同折射率之複數個介電質層之透明薄膜，在介電質層上，形成透明電極層，減低電極形成部和電極非形成部之間之反射光以及透過光之色差之方法。 In the substrate with the transparent electrode patterned in the transparent electrode layer, in addition to the improvement in the film quality of the transparent electrode layer, it is required that the pattern of the transparent electrode layer is not easily recognized. In Patent Document 3 and Patent Document 4, it is proposed to form a transparent electrode layer on a dielectric layer by using a transparent film having a plurality of dielectric layers having different refractive indexes in order to suppress recognition of a pattern of a transparent electrode layer. A method of reducing the chromatic aberration between the reflected light and the transmitted light between the electrode forming portion and the electrode non-forming portion.

【先前技術文獻】[Previous Technical Literature] 【專利文獻】[Patent Literature]

【專利文獻1】 WO2010/035598號國際公開宣傳手冊 [Patent Document 1] WO2010/035598 International Publicity Brochure

【專利文獻2】 日本特開2007-133839號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-133839

【專利文獻3】 WO2010/140275號國際公開宣傳手冊 [Patent Document 3] WO2010/140275 International Publicity Brochure

【專利文獻4】 日本特開2010-15861號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-15861

如果根據本發明人們之檢討的話，則在藉由前述光學設計而僅減低電極形成部和電極非形成部之間之反射光及透過光之色差，無法充分地抑制圖案之辨識。認為這個係起因於沿著透明導電層之圖案境界而產生皺紋並且配合皺紋之形狀而反射光。 According to the review by the present inventors, the color difference between the reflected light and the transmitted light between the electrode forming portion and the electrode non-forming portion is reduced by the optical design, and the pattern recognition cannot be sufficiently suppressed. It is considered that this is caused by wrinkles generated along the pattern boundary of the transparent conductive layer and reflecting the shape of the wrinkles to reflect light.

作為沿著透明電極層之圖案境界之皺紋之產生原因係本發明人們首先著眼於因為基材薄膜之加熱而造成之尺寸變化。也就是說，正如前述專利文獻2所揭示的，推測在藉由加熱而使得透明電極層之金屬氧化物呈結晶化之際，基材薄膜發生熱收縮係成為皺紋之原因。但是，即使是在事前，使用降低熱收縮率之基材薄膜(低熱收縮化薄膜)來進行透明電極層之製膜，也無法改善沿著透明電極層之圖案境界之皺紋。 As a cause of wrinkles along the boundary of the pattern of the transparent electrode layer, the inventors first focused on the dimensional change due to the heating of the substrate film. In other words, as disclosed in the above-mentioned Patent Document 2, it is presumed that when the metal oxide of the transparent electrode layer is crystallized by heating, the heat shrinkage of the base film becomes a cause of wrinkles. However, even if the substrate film (low heat shrinkable film) having a reduced heat shrinkage ratio is used for film formation of the transparent electrode layer, the wrinkles along the pattern boundary of the transparent electrode layer cannot be improved.

接著，本發明人們係正如專利文獻3所揭示之嘗試藉由在捲繞式濺鍍製膜裝置內之捲回而加熱薄膜，在同時進行低熱收縮化和低水分率化之後，製膜透明電極層。但是，在為了減小基材薄膜之熱收縮率而提高在捲回時之加熱溫度至80℃程度為止之時，薄膜之搬送狀態呈不安定而產生捲繞之偏離，發生謂無法製膜透明電極層之間題。 Next, the inventors of the present invention attempted to heat a film by rewinding in a wound sputter film forming apparatus as disclosed in Patent Document 3, and after performing low heat shrinkage and low moisture content, a transparent electrode was formed. Floor. However, when the heating temperature at the time of winding back is increased to 80 ° C in order to reduce the heat shrinkage rate of the base film, the conveyance state of the film is unstable and the winding is deviated. The problem between the electrode layers.

正如以上，推測在透明電極層呈圖案化之附有透明電極之基板，沿著透明導電層之圖案境界而抑制皺紋之發生係有效於圖案辨識之抑制。但是，直到目前為止，並無進行關於沿著透明電極層之圖案境界之皺紋之發生原因或者是其抑制方法之詳細檢討，並無發現抑制圖案辨識之有效手段。有鑑於前面之敘述，本發明之目的係提供藉由抑制沿著圖案化之透 明導電層之圖案境界之皺紋發生而不容易辨識圖案之附有透明電極之基板。 As described above, it is presumed that the substrate with the transparent electrode patterned in the transparent electrode layer suppresses the occurrence of wrinkles along the pattern boundary of the transparent conductive layer, which is effective for suppressing the pattern recognition. However, up to now, no detailed review has been made on the cause of the wrinkles along the pattern boundary of the transparent electrode layer or the suppression method thereof, and no effective means for suppressing pattern recognition has been found. In view of the foregoing, it is an object of the present invention to provide for the prevention of The wrinkles of the pattern boundary of the conductive layer occur without easily recognizing the substrate with the transparent electrode attached to the pattern.

本發明人們係全心地進行檢討，結果發現：藉由在非結晶質金屬氧化物薄膜之製膜前，於製膜裝置內，加熱薄膜，而在透明電極層之製膜後，抑制結晶化以及沿著在圖案化之際之圖案境界之皺紋發生，以致於完成本發明。也就是說，本發明係關於一種在透明薄膜上具備由非結晶質金屬氧化物薄膜而組成之透明電極層之附有透明電極之基板及其製造方法。 The inventors of the present invention conducted a thorough review and found that the film is heated in the film forming apparatus before the film formation of the amorphous metal oxide film, and the crystallization is suppressed after the film formation of the transparent electrode layer. Wrinkles occur along the boundary of the pattern at the time of patterning, so that the present invention is completed. That is, the present invention relates to a substrate having a transparent electrode comprising a transparent electrode layer composed of an amorphous metal oxide film on a transparent film, and a method for producing the same.

在本發明，最好是使用捲繞式濺鍍製膜裝置，在透明薄膜上，製膜由金屬氧化物薄膜而組成之透明電極層。作為透明電極層係製膜例如以ITO等之氧化銦來作為主成分之金屬氧化物薄膜。 In the present invention, it is preferable to form a transparent electrode layer composed of a metal oxide film on a transparent film by using a wound sputter film forming apparatus. A film of a transparent electrode layer is formed, for example, a metal oxide film containing indium oxide such as ITO as a main component.

捲繞式濺鍍裝置係最好是具備基材準備室和製膜室，在基材準備室內，設置加熱部。本發明之製造方法係具有：將透明薄膜之壓輥狀捲繞體，來導入至捲繞式濺鍍製膜裝置之基材準備室內之製程(基材準備製程)；在基材準備室內，由壓輥狀捲繞體開始，來抽出透明薄膜，進行搬送，同時，藉由來自加熱部之熱能而進行加熱處理，成為規定之表面溫度之製程(加熱製程)；以及在捲繞式濺鍍製膜裝置之製膜室內，導入惰性氣體，同時，在加熱處理後之透明薄膜上，形成由非結晶質金屬氧化物薄膜而組成之透明電極層之製程(透明電極層製膜製程)。 Preferably, the wound sputtering apparatus is provided with a substrate preparation chamber and a film forming chamber, and a heating portion is provided in the substrate preparation chamber. The manufacturing method of the present invention comprises: introducing a roll-form wound body of a transparent film into a substrate preparation chamber of a wound sputter film forming apparatus (substrate preparation process); and in the substrate preparation chamber, Starting from a roll-form wound body, a transparent film is taken out and transported, and heat treatment is performed by heat from the heating unit to obtain a predetermined surface temperature (heating process); and in a roll-type sputtering process In the film forming chamber of the film forming apparatus, an inert gas is introduced, and a transparent electrode layer composed of an amorphous metal oxide film is formed on the transparent film after the heat treatment (transparent electrode layer film forming process).

導入至濺鍍製膜裝置內之透明薄膜係最好是在150℃、30分鐘之加熱時之MD方向及TD方向之至少一邊之熱收縮率為0.4%以下。此外，導入至濺鍍製膜裝置內之透明薄膜係最好是藉由熱機械分析(TMA)而測定之熱收縮起始溫度為85℃以上。 It is preferable that the transparent film introduced into the sputtering film forming apparatus has a heat shrinkage ratio of at least one of the MD direction and the TD direction at a temperature of 150 ° C for 30 minutes of 0.4% or less. Further, it is preferable that the transparent film introduced into the sputtering film forming apparatus has a heat shrinkage initiation temperature of 85 ° C or more as measured by thermomechanical analysis (TMA).

加熱製程及透明電極層製膜製程係最好是不由捲繞式濺鍍製膜裝置來取出透明薄膜而連續地進行。最好是在加熱製程，透明薄膜和加熱部係呈無接觸地進行加熱處理。此外，加熱製程之基材準備室內之壓力係最好是1.0Pa以下。 The heating process and the transparent electrode layer film forming process are preferably carried out continuously without taking out the transparent film by the roll-type sputtering film forming apparatus. Preferably, in the heating process, the transparent film and the heating portion are heat-treated in a contactless manner. Further, the pressure system in the substrate preparation chamber of the heating process is preferably 1.0 Pa or less.

最好是在加熱製程後，在加熱處理後之透明薄膜來捲繞成為壓輥狀之前，於製膜室內，接著後續進行透明電極層製膜製程。最好是在加熱製程之透明薄膜之加熱時間係0.1秒鐘~600秒鐘。最好是在加熱製程之加熱部之溫度係150℃~500℃。 Preferably, after the heating process, the transparent film after the heat treatment is wound into a roll shape, and then a transparent electrode layer film forming process is subsequently performed in the film forming chamber. Preferably, the heating time of the transparent film in the heating process is from 0.1 second to 600 seconds. Preferably, the temperature in the heating section of the heating process is 150 ° C to 500 ° C.

在某一實施形態，在捲繞式濺鍍製膜裝置之基材準備室內，沿著薄膜搬送方向而設置複數個之加熱部，藉由來自這些複數個加熱部之熱能而進行加熱處理。最好是在該形態，在複數個加熱部之間，設置搬送用壓輥。 In one embodiment, a plurality of heating portions are provided in the substrate preparation chamber of the wound sputter film forming apparatus along the film transport direction, and heat treatment is performed by thermal energy from the plurality of heating portions. In this form, it is preferable to provide a transfer roller between the plurality of heating units.

最好是在本發明之製造方法，在加熱製程和透明電極層製膜製程之間，還設置透明介電質層形成製程。在透明介電質層形成製程，在透明薄膜上，藉由濺鍍法而形成至少一層之透明介電質層。最好是在介電質層形成製程，形成由至少一層之矽氧化物層而組成之介電質層。此外，最好是形成於透明電極層之正下方之透明介電質層係藉由0.4Pa以下之製膜壓 力而進行製膜。 Preferably, in the manufacturing method of the present invention, a transparent dielectric layer forming process is further provided between the heating process and the transparent electrode layer film forming process. In the transparent dielectric layer forming process, at least one layer of the transparent dielectric layer is formed on the transparent film by sputtering. Preferably, the dielectric layer forming process forms a dielectric layer composed of at least one layer of tantalum oxide. Further, it is preferable that the transparent dielectric layer formed directly under the transparent electrode layer has a film forming pressure of 0.4 Pa or less. Film is formed by force.

在某一實施形態，在透明介電質層形成製程，在透明薄膜上，依照該順序地形成折射率1.45~1.95之第一透明介電質層、折射率2.00~2.35之第二透明介電質層以及由矽氧化物而組成之第三透明介電質層。 In one embodiment, in the transparent dielectric layer forming process, a first transparent dielectric layer having a refractive index of 1.45 to 1.95 and a second transparent dielectric having a refractive index of 2.00 to 2.35 are formed on the transparent film in this order. a metal layer and a third transparent dielectric layer composed of tantalum oxide.

最好是在本發明之製造方法，在透明電極層製膜製程之製膜室內之質量數28之氣體分壓P28相對於惰性氣體之分壓PI之比值P28/PI係5×10-4以下。 Preferably, in the manufacturing method of the present invention, the ratio of the gas partial pressure P 28 of the mass number 28 to the partial pressure P I of the inert gas in the film forming chamber of the transparent electrode layer forming process is P 28 /P I is 5 × 10 -4 or less.

藉由前述製造方法而得到之附有透明電極之基板係最好是MD方向之熱收縮率為0.4%以下。透明電極層係最好是由以非結晶質之氧化銦來作為主成分之金屬氧化物薄膜而組成。 The substrate having the transparent electrode obtained by the above production method preferably has a heat shrinkage ratio in the MD direction of 0.4% or less. The transparent electrode layer is preferably composed of a metal oxide thin film containing amorphous indium oxide as a main component.

附有透明電極之基板係最好是在150℃、進行30分鐘之加熱後之藉由氧化銦結晶之out-plane(平面外)之X射線繞射測定而得到之(222)面之面間隔dout和藉由in-plane(平面內)之X射線繞射測定而得到之(222)面之面間隔din之比值dout/din為0.998~1.003。 The substrate to which the transparent electrode is attached is preferably an interval of (222) plane obtained by X-ray diffraction measurement of out-plane (out-of-plane) of indium oxide crystals after heating at 150 ° C for 30 minutes. The ratio d out /d in of the surface spacing d in of the (222) plane obtained by d- out and in-plane (in-plane) X-ray diffraction measurement is 0.998 to 1.003.

藉由本發明而得到之附有透明電極之基板係透明電極層進行結晶化，在圖案化之際，抑制沿著透明導電層之圖案境界之皺紋發生。因此，不容易辨識圖案境界，在使用於靜電電容方式之觸控面板之際，提高圖面之辨識性。 The substrate-based transparent electrode layer having the transparent electrode obtained by the present invention is crystallized, and when patterning is performed, generation of wrinkles along the pattern boundary of the transparent conductive layer is suppressed. Therefore, it is not easy to recognize the boundary of the pattern, and the visibility of the picture is improved when used in the capacitive touch panel.

10‧‧‧透明薄膜 10‧‧‧Transparent film

11‧‧‧基底薄膜 11‧‧‧Base film

12、13‧‧‧硬塗佈層 12, 13‧‧‧ hard coating layer

20‧‧‧透明介電質層 20‧‧‧Transparent dielectric layer

21~23‧‧‧透明介電質層 21~23‧‧‧Transparent dielectric layer

30‧‧‧透明電極層 30‧‧‧Transparent electrode layer

30a‧‧‧電極形成部 30a‧‧‧Electrode forming department

30b‧‧‧電極非形成部 30b‧‧‧Electrode Non-Forming Department

50‧‧‧附有透明電極之基板 50‧‧‧Substrate with transparent electrode

200‧‧‧濺鍍製膜裝置 200‧‧‧Sputter film making device

201‧‧‧基材準備室 201‧‧‧Substrate preparation room

202、203‧‧‧製膜室 202, 203‧‧ ‧ film making room

260‧‧‧製膜壓輥 260‧‧‧film roll

261‧‧‧抽出壓輥 261‧‧‧Extracting pressure roller

262‧‧‧捲繞壓輥 262‧‧‧Winding roller

271~274‧‧‧加熱部 271~274‧‧‧heating department

圖1係關於某一實施形態之附有透明電極之基板之示意剖面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a substrate with a transparent electrode according to an embodiment.

圖2係顯示捲繞式濺鍍製膜裝置之構造例之示意剖面圖。 Fig. 2 is a schematic cross-sectional view showing a configuration example of a wound sputter film forming apparatus.

圖3係顯示透明電極層來進行圖案化之附有透明電極之基板之構造例之示意剖面圖。 3 is a schematic cross-sectional view showing a structural example of a substrate with a transparent electrode which is patterned by a transparent electrode layer.

[附有透明電極之基板之構造] [Structure of substrate with transparent electrode]

在以下，就本發明之理想實施形態而參考圖式，並且，進行說明。圖1係顯示在透明薄膜10之上具備由金屬氧化物薄膜而組成之透明電極層30之附有透明電極之基板50。最好是在透明薄膜10和透明電極層30之間，形成以氧化物來作為主成分之透明介電質層20。在透明電極層30呈直接地形成於透明介電質層20上之時，透明電極層係容易進行低電阻化。 Hereinafter, the preferred embodiments of the present invention will be described with reference to the drawings. Fig. 1 shows a substrate 50 with a transparent electrode provided with a transparent electrode layer 30 composed of a metal oxide film on a transparent film 10. It is preferable to form a transparent dielectric layer 20 having an oxide as a main component between the transparent film 10 and the transparent electrode layer 30. When the transparent electrode layer 30 is directly formed on the transparent dielectric layer 20, the transparent electrode layer is easily reduced in resistance.

構成透明薄膜10之基底薄膜11係最好是至少在可見光區域，成為無色透明。在某一實施形態，透明薄膜10係在基底薄膜11之至少一邊之面，具有硬塗佈層12、13。 The base film 11 constituting the transparent film 10 is preferably colorless and transparent at least in the visible light region. In one embodiment, the transparent film 10 is provided on at least one side of the base film 11, and has hard coating layers 12 and 13.

透明介電質層20係可以僅藉由1層而組成，並且，也可以藉由2層以上而組成。在圖1，圖示由透明薄膜10之側開始而依照該順序地形成第1透明介電質層21、第2透明介電質層22和第3透明介電質層23之例子。作為構成透明介電質層20之氧化物係最好是至少在可見光區域，成為無色透明，電阻率為10Ω．cm以上。此外，在本說明書，以某物質來稱為「作為主成分」係指該物質之含有量為51重量%以上、 最好是70重量%以上、更加理想是90重量%以上。只要是不損害本發明之機能的話，則可以在各層，包含主成分以外之成分。 The transparent dielectric layer 20 may be composed of only one layer, or may be composed of two or more layers. In FIG. 1, an example in which the first transparent dielectric layer 21, the second transparent dielectric layer 22, and the third transparent dielectric layer 23 are formed in this order from the side of the transparent film 10 is shown. The oxide constituting the transparent dielectric layer 20 is preferably at least in the visible light region and is colorless and transparent, and has a specific resistance of 10 Ω . More than cm. In the present specification, the term "main component" as a substance means that the content of the substance is 51% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more. As long as the function of the present invention is not impaired, components other than the main component may be contained in each layer.

透明電極層30係非結晶質之金屬氧化物薄膜。在本說明書，所謂「非結晶質」係可以在膜中，包含一部分(80%以下)之結晶質部分。膜中之結晶質部分之含有量係在顯微鏡觀察時，於觀察視野內，由結晶粒之所佔有之面積之比例，來求出含有量。 The transparent electrode layer 30 is an amorphous metal oxide film. In the present specification, the "amorphous" system may include a part (80% or less) of a crystalline portion in the film. The content of the crystalline portion in the film is determined by the ratio of the area occupied by the crystal grains in the observation field when observed under a microscope.

作為構成透明電極層30之材料係適合使用由銦、錫、鋅、鎵、鋁、銻、鈦而組成之群組來選出之至少一種之金屬氧化物。由同時成立透明性和低電阻之觀點來看的話，則透明電極層30係最好是以氧化銦，來作為主成分。透明電極層30係最好是含有88重量%~98重量%之氧化銦，更加理想是含有90重量%~97重量%，甚至最好是含有94重量%~96重量%。透明電極層係最好是在膜中，含有用以具有載體密度而賦予導電性之摻雜不純物。在透明電極層30以氧化銦來作為主成分之狀態下，作為摻雜不純物係最好是氧化錫或氧化鋅，特別最好是氧化錫。 As the material constituting the transparent electrode layer 30, at least one metal oxide selected from the group consisting of indium, tin, zinc, gallium, aluminum, lanthanum, and titanium is suitably used. From the viewpoint of simultaneously establishing transparency and low electrical resistance, the transparent electrode layer 30 is preferably made of indium oxide as a main component. The transparent electrode layer 30 preferably contains 88% by weight to 98% by weight of indium oxide, more desirably 90% by weight to 97% by weight, and even more preferably 94% by weight to 96% by weight. The transparent electrode layer is preferably contained in the film and contains doped impurities for imparting conductivity with a carrier density. In the state in which the transparent electrode layer 30 contains indium oxide as a main component, it is preferable that the doping impurity is tin oxide or zinc oxide, and particularly preferably tin oxide.

透明電極層30係最好是在150℃來加熱30分鐘之際，轉化成為結晶質膜。在加熱後之結晶質膜係最好是電阻率為4.5×10-4Ω．cm以下。此外，在加熱後之結晶質膜係最好是表面電阻為150Ω/□以下，更加理想是140Ω/□以下。如果透明電極層為低電阻的話，則可以有助於靜電電容方式觸控面板之應答速度之提升或者是各種光學元件之省消耗電力化等。 The transparent electrode layer 30 is preferably converted into a crystalline film when heated at 150 ° C for 30 minutes. The crystalline film film after heating preferably has a specific resistance of 4.5 × 10 -4 Ω . Below cm. Further, the crystal film after heating preferably has a surface resistance of 150 Ω/□ or less, more preferably 140 Ω/□ or less. If the transparent electrode layer is low in resistance, it can contribute to an increase in the response speed of the capacitive touch panel or a power consumption of various optical components.

由透明電極層成為低電阻且高透過率之觀點來看的話，則透明電極層30之膜厚係最好是15~40nm、更加理想是21nm~38nm、甚至最好是23nm~35nm。 When the transparent electrode layer has low resistance and high transmittance, the thickness of the transparent electrode layer 30 is preferably 15 to 40 nm, more preferably 21 nm to 38 nm, and even more preferably 23 nm to 35 nm.

此種附有透明電極之基板係在使用於靜電電容方式觸控面板之位置檢測用之狀態下，正如圖3所示，透明電極層30之面內之一部分，藉由蝕刻等而圖案化成為電極形成部30a和電極非形成部30b。在該狀態下，可以藉由調整透明介電質層20之厚度或折射率，而減低不蝕刻透明電極層之殘留之電極形成部30a和以蝕刻來除去電極層之電極非形成部30b之間之透過率差、反射率差及色差，抑制電極圖案之辨識。 In the state in which the substrate with the transparent electrode is used for detecting the position of the capacitive touch panel, as shown in FIG. 3, a portion of the surface of the transparent electrode layer 30 is patterned by etching or the like. The electrode forming portion 30a and the electrode non-forming portion 30b. In this state, by adjusting the thickness or refractive index of the transparent dielectric layer 20, the electrode forming portion 30a which does not etch the remaining of the transparent electrode layer and the electrode non-forming portion 30b which removes the electrode layer by etching can be reduced. The transmittance difference, the reflectance difference, and the chromatic aberration suppress the identification of the electrode pattern.

[附有透明電極之基板的製造方法] [Manufacturing method of substrate with transparent electrode]

在以下，就本發明之理想實施形態而按照附有透明電極之基板的製造方法，來進行說明。在本發明之製造方法，使用捲繞式濺鍍製膜裝置，在透明薄膜上，形成由金屬氧化物薄膜而組成之透明電極層。捲繞式濺鍍係可以在透明薄膜上，藉由捲裝進出(Roll to Roll)方式而呈高度生產性地製膜透明電極層。在藉由捲繞式濺鍍而造成之製膜，將透明薄膜10之捲繞體，來導入至捲繞式濺鍍製膜裝置內(基材準備製程)，在捲繞式濺鍍製膜裝置內，進行加熱(加熱製程)，然後，在透明薄膜10上，形成由非結晶質金屬氧化物薄膜而組成之透明電極層30(製膜製程)。在本發明，不由濺鍍製膜裝置來取出透明薄膜至裝置外，最好是連續地進行加熱製程及透明電極層製膜製程。 Hereinafter, a preferred embodiment of the present invention will be described in accordance with a method of manufacturing a substrate having a transparent electrode. In the production method of the present invention, a transparent electrode layer composed of a metal oxide thin film is formed on a transparent film by using a wound sputter film forming apparatus. The roll-on sputtering system can form a transparent electrode layer in a highly productive manner by a roll-to-roll method on a transparent film. The film formed by the roll-sputtering is introduced into the wound sputter film forming apparatus (substrate preparation process) by the film formation by the roll-on sputtering, and the film is formed by roll-spraying. In the apparatus, heating (heating process) is performed, and then, on the transparent film 10, a transparent electrode layer 30 composed of an amorphous metal oxide film is formed (film forming process). In the present invention, it is preferable to continuously carry out the heating process and the transparent electrode layer film forming process without taking out the transparent film from the sputtering film forming apparatus to the outside of the apparatus.

(製膜裝置之構造例) (Configuration example of film forming apparatus)

圖2係顯示使用於本發明之捲繞式濺鍍製膜裝置之一例之示意剖面圖。在濺鍍製膜裝置200之中，分隔基材準備室201和製膜室202、203，鄰接於這些各室之間隔而設置製膜壓輥260。在基材準備室201之內，設置抽出壓輥261和捲繞壓輥262。此外，在基材準備室201內之抽出壓輥261和製膜壓輥260之間以及製膜壓輥260和捲繞壓輥262之間，配置搬送壓輥263~268。此外，在基材準備室201內之抽出壓輥261和製膜壓輥260之間之薄膜搬送通路附近，設置加熱器271、272，來作為加熱部。 Fig. 2 is a schematic cross-sectional view showing an example of a wound sputter film forming apparatus used in the present invention. In the sputtering and film forming apparatus 200, the substrate preparation chamber 201 and the film forming chambers 202 and 203 are partitioned, and the film forming press roller 260 is disposed adjacent to the interval between the respective chambers. Inside the substrate preparation chamber 201, a take-up press roller 261 and a take-up press roller 262 are provided. Further, between the extraction press roller 261 and the film forming press roller 260 in the substrate preparation chamber 201, and between the film forming press roller 260 and the winding press roller 262, transfer pressure rollers 263 to 268 are disposed. Further, heaters 271 and 272 are provided as heating means in the vicinity of the film transport path between the extraction press roller 261 and the film forming press roller 260 in the substrate preparation chamber 201.

在捲繞式濺鍍裝置200內，透明薄膜10之捲繞體係安裝在抽出壓輥261。透明薄膜10係由基材準備室201開始連續地搬送至製膜室202、203，同時，在製膜壓輥260上，製膜透明電極層30。製膜後之附有透明電極之基板50係再度搬送至基材準備室201，藉由捲繞壓輥262而進行捲繞，得到附有透明電極之基板之壓輥狀捲繞體250。在製膜室202、203內之製膜壓輥260之附近，配置陰極282、283，在陰極和製膜壓輥之間，配置標靶222、223。 In the wound sputter apparatus 200, the winding system of the transparent film 10 is attached to the take-up press roller 261. The transparent film 10 is continuously conveyed to the film forming chambers 202 and 203 from the substrate preparing chamber 201, and the transparent electrode layer 30 is formed on the film forming press roll 260. The substrate 50 with the transparent electrode after the film formation is again transferred to the substrate preparation chamber 201, and is wound by winding the pressure roller 262 to obtain a press roll-shaped wound body 250 having a substrate with a transparent electrode. The cathodes 282 and 283 are disposed in the vicinity of the film forming press rolls 260 in the film forming chambers 202 and 203, and the targets 222 and 223 are disposed between the cathode and the film forming press rolls.

(基材準備製程) (substrate preparation process)

構成透明薄膜10之基底薄膜11係至少在可見光區域，成為無色透明，如果是具有後面敘述之加熱製程之加熱溫度之耐熱性的話，則其材料係並無特別限定。作為透明薄膜之材料係列舉聚乙烯對苯二甲酸酯(PET)、聚丁烯對苯二甲酸酯(PBT)、聚乙烯萘二甲酸酯(PEN)等之聚酯系樹脂、環烯烴系樹脂、聚碳酸酯樹脂、聚醯亞胺樹脂、纖維素系樹脂等。 即使是在其中，也最好是聚酯系樹脂，特別最好是使用聚乙烯對苯二甲酸酯。 The base film 11 constituting the transparent film 10 is colorless and transparent at least in the visible light region, and the material is not particularly limited as long as it has heat resistance at a heating temperature of a heating process to be described later. As a material of the transparent film, polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are used. An olefin resin, a polycarbonate resin, a polyimide resin, a cellulose resin, or the like. Even among them, a polyester resin is preferable, and polyethylene terephthalate is particularly preferably used.

基底薄膜11之厚度係並無特別限定，但是，最好是10μm~400μm，更加理想是50μm~300μm。如果是厚度為前述範圍內的話，則基底薄膜11係可以具有耐久性和適度之柔軟性，因此，可以在其上面，藉由捲裝進出(Roll to Roll)方式而呈高度生產性地製膜各透明介電質層和透明電極層。 The thickness of the base film 11 is not particularly limited, but is preferably 10 μm to 400 μm, more preferably 50 μm to 300 μm. If the thickness is within the above range, the base film 11 can have durability and moderate flexibility, and therefore, it can be highly productively formed by a roll-to-roll method thereon. Each of the transparent dielectric layer and the transparent electrode layer.

作為基底薄膜11係最好是使用藉由以二軸延伸來配向分子而提高楊氏模數等之機械特性或耐熱性者。基底薄膜11係也可以仍然直接地成為透明薄膜10而供應於製膜。由在透明薄膜10具有適度之耐久性之觀點來看的話，則透明薄膜10係適合使用在基底薄膜11之單面或兩面來形成硬塗佈層12、13者。 As the base film 11, it is preferable to use a mechanical property or a heat resistance which improves the Young's modulus or the like by aligning molecules by biaxial stretching. The base film 11 may also be directly supplied to the transparent film 10 to be supplied to the film. From the viewpoint of having a moderate durability in the transparent film 10, the transparent film 10 is suitably used to form the hard coat layers 12 and 13 on one or both sides of the base film 11.

為了在透明薄膜10，具有適度之耐久性和柔軟性，因此，硬塗佈層之厚度係最好是3~10μm、更加理想是3~8μm、甚至最好是5~8μm。硬塗佈層之材料係並無特別限制，可以適度地使用塗佈．硬化胺基甲酸乙酯系樹脂、丙烯系樹脂、矽酮系樹脂等類。 In order to have moderate durability and flexibility in the transparent film 10, the thickness of the hard coat layer is preferably from 3 to 10 μm, more preferably from 3 to 8 μm, even more preferably from 5 to 8 μm. The material of the hard coat layer is not particularly limited, and the coating can be used moderately . A hardened urethane-based resin, a propylene-based resin, an anthrone-based resin or the like.

可以在基底薄膜11上，形成硬塗佈層以外之各種之機能性層。例如可以在基底薄膜11上，直接地形成透明介電質層20，或者是在硬塗佈層12上，形成透明介電質層20而成為機能性層。作為構成透明介電質層之氧化物係適合使用由Si、Nb、Ta、Ti、Zn、Zr和Hf而組成之群組來選出之一種以上元素之氧化物。透明介電質層之製膜方法係如果是形成均 勻薄膜之方法的話，則並無特別限定。作為製膜方法係列舉濺鍍法、蒸鍍法等之PVD法、各種CVD法等之乾式塗佈法、或者是旋轉塗佈法、壓輥塗佈法、噴射塗佈或浸漬塗佈等之濕式塗佈法。即使是在前述製膜方法中，也由所謂容易形成奈米位準薄膜之觀點來看的話，則最好是乾式塗佈法。 Various functional layers other than the hard coat layer may be formed on the base film 11. For example, the transparent dielectric layer 20 may be formed directly on the base film 11, or the transparent dielectric layer 20 may be formed on the hard coat layer 12 to form a functional layer. As the oxide constituting the transparent dielectric layer, an oxide of one or more elements selected from the group consisting of Si, Nb, Ta, Ti, Zn, Zr, and Hf is suitably used. The film forming method of the transparent dielectric layer is formed if The method of uniformizing the film is not particularly limited. Examples of the film forming method include a PVD method such as a sputtering method or a vapor deposition method, a dry coating method such as various CVD methods, or a spin coating method, a roll coating method, a spray coating method, or a dip coating method. Wet coating method. Even in the above-mentioned film forming method, from the viewpoint of easily forming a nano level film, a dry coating method is preferred.

可以在藉由濺鍍法而形成透明介電質層之狀態下，在捲繞式濺鍍製膜裝置200之內來導入透明薄膜10之基材準備製程之後，在形成透明電極層30之前，形成透明介電質層20。此外，可以在形成2層以上之透明介電質層之狀態下，在濺鍍製膜裝置內來導入透明薄膜之前，形成1層以上之透明介電質層，在濺鍍製膜裝置內來導入透明薄膜之後，在形成透明電極層之前，形成1層以上之透明介電質層。例如可以在透明薄膜10之上藉由濕式塗佈法而形成第一透明介電質層21之後，將形成第一透明介電質層21後之透明薄膜10，導入至濺鍍裝置內，藉由濺鍍法而連續地形成第二透明介電質層22、第三透明介電質層23和透明電極層30。由提高透明介電質層之膜厚控制或附有透明電極之薄膜之生產性之觀點來看的話，則最好是藉由濺鍍法而形成全部之透明介電質層。此外，就在基材準備製程之後、透明電極層之形成前而在同一個之捲繞式濺鍍製膜裝置內來形成透明介電質層之實施形態(透明電極層製膜製程)而言，詳細地敘述於後面。 The substrate preparation process for introducing the transparent film 10 in the roll-type sputter film forming apparatus 200 may be performed before the transparent electrode layer 30 is formed in a state where the transparent dielectric layer is formed by sputtering. A transparent dielectric layer 20 is formed. Further, in a state in which two or more transparent dielectric layers are formed, one or more transparent dielectric layers may be formed before the transparent film is introduced into the sputtering film forming apparatus, and the sputtering film forming apparatus may be used. After the transparent film is introduced, one or more transparent dielectric layers are formed before the transparent electrode layer is formed. For example, after the first transparent dielectric layer 21 is formed on the transparent film 10 by a wet coating method, the transparent film 10 after forming the first transparent dielectric layer 21 is introduced into the sputtering apparatus. The second transparent dielectric layer 22, the third transparent dielectric layer 23, and the transparent electrode layer 30 are continuously formed by sputtering. From the viewpoint of improving the film thickness control of the transparent dielectric layer or the productivity of the film with the transparent electrode, it is preferable to form all of the transparent dielectric layers by sputtering. Further, in the embodiment in which the transparent dielectric layer is formed in the same wound sputter film forming apparatus after the substrate preparation process and before the formation of the transparent electrode layer (transparent electrode layer film forming process) , described in detail later.

導入至濺鍍製膜裝置內之透明薄膜10係最好是在150℃、30分鐘加熱時之熱收縮率為0.4%以下、更加理想是0.35%以下、甚至最好是0.3%以下。在熱收縮率由於方向而 不同之狀態(不同於MD方向和TD方向之狀態)，MD方向之熱收縮率係可以是前述範圍。特別最好是MD方向和TD方向之兩者之熱收縮率係前述範圍。在以下，在並無特別限制之狀態下，本說明書之「熱收縮率」係表示在150℃、30分鐘加熱時之收縮率。熱收縮率係由加熱前之2點間距離(L0)和加熱後之2點間距離(L)，藉著下列之公式而算出。 The transparent film 10 introduced into the sputtering film forming apparatus preferably has a heat shrinkage ratio of 0.4% or less, more preferably 0.35% or less, or even more preferably 0.3% or less at 150 ° C for 30 minutes. In a state in which the heat shrinkage rate differs depending on the direction (a state different from the MD direction and the TD direction), the heat shrinkage ratio in the MD direction may be the aforementioned range. It is particularly preferable that the heat shrinkage ratio of both the MD direction and the TD direction is the aforementioned range. In the following, the "heat shrinkage ratio" in the present specification means a shrinkage ratio at 150 ° C for 30 minutes of heating. The heat shrinkage ratio was calculated from the distance between two points (L 0 ) before heating and the distance (L) between two points after heating by the following formula.

公式：熱收縮率(%)=100×(L0-L)/L0 Formula: heat shrinkage rate (%) = 100 × (L 0 - L) / L 0

導入至濺鍍製膜裝置內之透明薄膜10係最好是藉由熱機械分析而測定之熱收縮起始溫度為85℃以上、更加理想是90℃以上、甚至最好是100℃以上。透明薄膜10係最好是在直到200℃為止之範圍，無顯示熱收縮起始溫度。熱收縮起始溫度係藉著熱機器分析(TMA)，而由以規定之荷重和升溫速度來進行升溫之際之位移量之極大值，求出熱收縮起始溫度。 The transparent film 10 introduced into the sputtering film forming apparatus preferably has a heat shrinkage initiation temperature of 85 ° C or more, more preferably 90 ° C or more, and even more preferably 100 ° C or more as measured by thermomechanical analysis. The transparent film 10 is preferably in the range up to 200 ° C and does not exhibit a heat shrinkage onset temperature. The heat shrinkage initiation temperature is determined by thermal machine analysis (TMA), and the heat shrinkage onset temperature is obtained from the maximum value of the displacement amount at the time of temperature rise at a predetermined load and temperature increase rate.

(加熱製程) (heating process)

導入至濺鍍製膜裝置200內之透明薄膜10係在形成透明電極層30之前，於基材準備室201內，進行加熱處理。最好是在進行加熱處理之前，基材準備室201內之壓力係一旦減壓至0.01Pa以下。加熱處理中之基材準備室201內之壓力係最好是1.5Pa以下、更加理想是1.0Pa以下、甚至最好是0.5Pa以下。 The transparent film 10 introduced into the sputtering film forming apparatus 200 is subjected to heat treatment in the substrate preparing chamber 201 before the transparent electrode layer 30 is formed. It is preferable that the pressure in the substrate preparation chamber 201 is reduced to 0.01 Pa or less before the heat treatment. The pressure in the substrate preparation chamber 201 in the heat treatment is preferably 1.5 Pa or less, more preferably 1.0 Pa or less, or even more preferably 0.5 Pa or less.

藉由來自基材準備室內之加熱部271、272之熱能而加熱透明薄膜10。最好是設定加熱溫度而使得透明薄膜之表面溫度成為70℃~160℃。加熱製程之薄膜表面溫度係更加理 想是80℃~160℃、甚至最好是85℃~120℃。薄膜之表面溫度係可以在薄膜之表面，貼附熱標記或熱電偶而進行測定。 The transparent film 10 is heated by thermal energy from the heating portions 271, 272 in the substrate preparation chamber. It is preferable to set the heating temperature so that the surface temperature of the transparent film becomes 70 ° C to 160 ° C. The surface temperature of the film of the heating process is more rational I think it is 80 ° C ~ 160 ° C, and even better it is 85 ° C ~ 120 ° C. The surface temperature of the film can be measured by attaching a thermal mark or a thermocouple to the surface of the film.

加熱部係最好是利用微波、遠紅外線等之加熱器或加熱管等之溫度調節機構、熱風吹出噴嘴等之無接觸到薄膜者。可以在加熱製程，在加熱部和薄膜呈無接觸之狀態下，抑制起因於薄膜之急劇之熱變形等之皺紋發生或者是薄膜之搬送呈不安定。在配置加熱部而無接觸到薄膜之狀態下，加熱部和薄膜搬送通路之間隔係最好是5mm~100mm程度，更加理想是10mm~70mm程度。 It is preferable that the heating unit is a non-contact film that uses a heater such as a microwave or a far-infrared ray or a temperature adjustment mechanism such as a heating tube, or a hot air blowing nozzle. In the heating process, in the state where the heating portion and the film are in a non-contact state, wrinkles caused by sharp thermal deformation of the film or the like, or the conveyance of the film is unstable. In the state where the heating portion is disposed without contacting the film, the interval between the heating portion and the film transport path is preferably about 5 mm to 100 mm, more preferably about 10 mm to 70 mm.

透明薄膜之加熱係可以由透明薄膜之某一邊之面開始進行，也可以由兩面開始進行。由有效地進行加熱之觀點來看的話，則正如圖2所示，最好是在透明薄膜搬送通路之兩面之附近，設置加熱器271、272，由兩面開始進行加熱。可以在捲繞式濺鍍製膜裝置200之內而搬送透明薄膜10同時進行加熱之狀態下，加熱時間係藉由加熱器之形狀(薄膜搬送方向之長度)或薄膜之搬送速度而進行調整。 The heating of the transparent film can be carried out from the side of one side of the transparent film or from both sides. From the viewpoint of effective heating, as shown in Fig. 2, it is preferable to provide heaters 271 and 272 in the vicinity of both surfaces of the transparent film transport path, and to start heating from both sides. The heating time can be adjusted by the shape of the heater (the length of the film conveying direction) or the conveying speed of the film in a state where the transparent film 10 is conveyed while being heated in the winding type sputtering film forming apparatus 200.

為了確保加熱時間，因此，可以在薄膜搬送方向之2處部位以上，設置加熱部。作為沿著薄膜搬送方向而設置複數個之加熱部之形態係列舉例如在圖2，除了加熱器271、272以外，還在基材準備室201內之搬送壓輥264和搬送壓輥265之間，配置加熱器273、274之形態。 In order to secure the heating time, the heating portion can be provided at two or more locations in the film transport direction. As a series in which a plurality of heating units are provided along the film transport direction, for example, in FIG. 2, in addition to the heaters 271 and 272, between the transfer press roller 264 and the transfer press roller 265 in the substrate preparation chamber 201, The configuration of the heaters 273 and 274 is arranged.

可以藉由沿著薄膜搬送方向，設置複數個之加熱部，而不降低薄膜之搬送速度，可以確保規定之加熱時間，使得薄膜之表面溫度，成為前述範圍而進行加熱處理。因此，可 以使得加熱處理製程呈效率化，提高附有透明電極之基板之生產性。此外，可以藉由在複數個之加熱部之間，設置搬送壓輥，而有效地利用製膜準備室201內之空間，確保加熱時間，同時，可以安定薄膜之搬送，抑制由於加熱處理來造成之皺紋或鬆弛之發生。 By providing a plurality of heating portions along the film transport direction without lowering the transport speed of the film, it is possible to ensure a predetermined heating time so that the surface temperature of the film is within the above range and heat treatment is performed. Therefore, In order to make the heat treatment process efficient, the productivity of the substrate with the transparent electrode is improved. Further, by providing the transfer pressure roller between the plurality of heating portions, the space in the film preparation preparation chamber 201 can be effectively utilized to secure the heating time, and at the same time, the film can be stably conveyed to suppress the heat treatment. Wrinkles or slacks occur.

加熱處理之加熱時間係最好是0.1秒鐘~600秒鐘、更加理想是0.5秒鐘~300秒鐘、甚至最好是1秒鐘~180秒鐘。加熱部(加熱器271、272)之溫度係可以配合加熱時間或者是加熱部和薄膜搬送通路之間隔等而適度地決定，來使得薄膜之表面溫度，成為前述範圍。加熱溫度係例如最好是150℃~500℃、更加理想是180℃~400℃、甚至最好是200℃~350℃。 The heating time of the heat treatment is preferably from 0.1 second to 600 seconds, more preferably from 0.5 second to 300 seconds, even more preferably from 1 second to 180 seconds. The temperature of the heating unit (heaters 271 and 272) can be appropriately determined in accordance with the heating time or the interval between the heating unit and the film transport path, and the surface temperature of the film is in the above range. The heating temperature is, for example, preferably from 150 ° C to 500 ° C, more preferably from 180 ° C to 400 ° C, even more preferably from 200 ° C to 350 ° C.

藉由在製膜透明電極層之前，對於透明薄膜，來進行加熱處理，而在透明電極層之製膜後來進行結晶化及圖案化之際，抑制沿著圖案境界之皺紋發生。如果根據本發明人們之檢討的話，則在藉由濺鍍而製膜非結晶質之透明電極層之後，藉由加熱來使得透明電極層呈結晶化之際而彎曲之發生量變大之附有透明電極之薄膜係在然後圖案化透明電極層之際，有容易辨識在圖案境界之皺紋之傾向發生。加熱結晶化時之彎曲發生係推測因為在加熱附有透明電極之基板之際，在透明電極層和透明薄膜之界面，產生應力之緣故。在本發明，認為藉由在透明電極層之製膜前，加熱透明薄膜，而在透明電極層之製膜界面之狀態，產生變化，這個有助於皺紋之抑制。作為製膜界面之狀態變化係推測例如藉由加熱處理而有助於吸附在透明薄膜中或薄膜表面之有機成分之揮發等。 The transparent film is subjected to heat treatment before the formation of the transparent electrode layer, and when crystallization and patterning are performed after the formation of the transparent electrode layer, wrinkles along the boundary of the pattern are suppressed. According to the review by the present invention, after the amorphous electrode layer is formed by sputtering, the transparent electrode layer is crystallized by heating, and the amount of bending is increased. When the film of the electrode is patterned and then the transparent electrode layer is formed, there is a tendency that the wrinkles at the boundary of the pattern are easily recognized. The occurrence of the bending at the time of heating and crystallization is presumed to be due to the stress at the interface between the transparent electrode layer and the transparent film when the substrate to which the transparent electrode is attached is heated. In the present invention, it is considered that the transparent film is heated before the film formation of the transparent electrode layer, and a change occurs in the state of the film formation interface of the transparent electrode layer, which contributes to suppression of wrinkles. The state change of the film formation interface is presumed to be, for example, by heat treatment, which contributes to volatilization of the organic component adsorbed in the transparent film or on the surface of the film.

(製膜製程) (film making process)

加熱後之透明薄膜10係搬送至製膜室202、203，在製膜室內，形成透明電極層30。透明電極層之形成係最好是不由濺鍍製膜裝置200來取出加熱後之透明薄膜10而連續地進行。不由製膜裝置來取出加熱後之透明薄膜，藉由製膜透明電極層而在薄膜之表面，抑制大氣中之水分或有機成分等之吸附。此外，藉由連續地進行薄膜之加熱和製膜，而提高附有透明電極之基板之生產性。 The heated transparent film 10 is transferred to the film forming chambers 202 and 203, and the transparent electrode layer 30 is formed in the film forming chamber. It is preferable that the formation of the transparent electrode layer is continuously performed without taking out the heated transparent film 10 by the sputtering film forming apparatus 200. The heated transparent film is taken out by the film forming apparatus, and the transparent electrode layer is formed to suppress the adsorption of moisture or organic components in the atmosphere on the surface of the film. Further, the productivity of the substrate with the transparent electrode is improved by continuously heating and film-forming the film.

可以在使用捲繞式濺鍍製膜裝置而進行製膜之狀態下，在加熱製程後，在一旦藉由捲繞壓輥262而捲繞透明薄膜來成為壓輥狀捲繞體之後，再度由捲繞體開始，抽出透明薄膜而搬送薄膜，同時，進行製膜。在本發明，最好是在加熱後之透明薄膜來捲繞成為壓輥狀之前，後面接著進行透明電極層製膜製程。也就是說，在本發明，由壓輥狀捲繞體210來抽出之透明薄膜10係最好是在基材準備室201內，在藉由來自加熱部271、272之熱能而加熱至規定之溫度後，在製膜室202、203內之製膜壓輥260上，製膜透明電極層30。由生產效率提升等之觀點來看的話，則由加熱製程開始至製膜製程為止之時間間隔係最好是10分鐘以內、更加理想是8分鐘以內、甚至最好是5分鐘以內。在濺鍍製膜裝置內，無進行透明薄膜之捲回，可以藉由在加熱製程後，接著進行製膜製程，而使得由加熱製程開始至製膜製程為止之時間間隔，成為前述範圍。 In the state where the film is formed by the roll-type sputtering film forming apparatus, after the heating process, the transparent film is wound by the winding roller 262 to form a roll-shaped wound body, and then At the beginning of the winding body, the transparent film is taken out to transport the film, and at the same time, film formation is performed. In the present invention, it is preferable to carry out a transparent electrode layer film forming process immediately after the heated transparent film is wound into a roll shape. That is, in the present invention, the transparent film 10 extracted by the press-rolled body 210 is preferably heated in the substrate preparation chamber 201 by the heat energy from the heating portions 271 and 272 to a predetermined level. After the temperature, the transparent electrode layer 30 is formed on the film forming press rolls 260 in the film forming chambers 202 and 203. From the viewpoint of improvement in production efficiency and the like, the time interval from the start of the heating process to the film forming process is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes. In the sputtering film forming apparatus, the rewinding of the transparent film is not performed, and the film forming process can be carried out after the heating process, so that the time interval from the start of the heating process to the film forming process becomes the above range.

透明電極層30之製膜係在製膜室202、203內，導入包含氬等之惰性氣體和氧氣之載體氣體，同時，進行製 膜。導入氣體係最好是氬和氧之混合氣體。混合氣體係最好是包含0.4體積%~2.0體積%之氧，更加理想是包含0.7體積%~1.5體積%之氧。可以藉由供應前述體積之氧而提高透明電極層之透明性及導電性。此外，在混合氣體，只要是不損害本發明之機能的話，則可以包含其他之氣體。製膜室內之壓力(全壓)係最好是1.5Pa以下、更加理想是0.05Pa~1.2Pa、甚至最好是0.1Pa~0.9Pa。 The film formation of the transparent electrode layer 30 is carried out in the film forming chambers 202 and 203, and a carrier gas containing an inert gas such as argon and oxygen is introduced, and the film is formed at the same time. membrane. The introduced gas system is preferably a mixed gas of argon and oxygen. The mixed gas system preferably contains from 0.4% by volume to 2.0% by volume of oxygen, more preferably from 0.7% by volume to 1.5% by volume of oxygen. The transparency and conductivity of the transparent electrode layer can be improved by supplying oxygen of the aforementioned volume. Further, the mixed gas may contain other gases as long as it does not impair the function of the present invention. The pressure (full pressure) in the film forming chamber is preferably 1.5 Pa or less, more preferably 0.05 Pa to 1.2 Pa, and even more preferably 0.1 Pa to 0.9 Pa.

在前述透明電極層製膜製程，製膜室內之質量數28之氣體分壓P28相對於惰性氣體之分壓PI之比值P28/PI係最好是未滿5×10-4。P28/PI係更加理想是1.0×10-5~5×10-4、甚至最好是5.0×10-5~5×10-4。為了藉由降低製膜氛圍中之質量數28之氣體分壓而改變透明電極層之形成界面狀態，因此，減少透明電極層和薄膜之界面之應力，抑制彎曲之發生或者是在圖案化透明電極層之際之皺紋發生。質量數28之氣體分壓係可以藉由聯線(on-line)四層電極質量分析計(Q-mass)而進行監視。 In the transparent electrode-layer deposition process, the mass number of the film deposition chamber 28 of the gas partial pressure P ratio of 28 with respect to the partial pressure of an inert gas of P I P 28 / P I system is preferably less than 5 × 10 -4. The P 28 /P I system is more preferably 1.0 × 10 -5 to 5 × 10 -4 , and even more preferably 5.0 × 10 -5 to 5 × 10 -4 . In order to change the interface state of the transparent electrode layer by lowering the gas partial pressure of the mass number 28 in the film forming atmosphere, the stress at the interface between the transparent electrode layer and the film is reduced, the occurrence of bending is suppressed, or the patterned transparent electrode is formed. Wrinkles occur at the layer. The gas partial pressure system of mass number 28 can be monitored by an on-line four-layer electrode mass spectrometer (Q-mass).

製膜室內之質量數28之氣體係認為主要是一氧化碳和氮。一氧化碳氣體係認為藉由在透明薄膜來濺鍍．製膜透明電極層之際之電漿損傷等而釋出至製膜氛圍中。此外，氮氣係認為由形成在基底薄膜11表面之硬塗佈層12、13等而釋出至製膜氛圍中。 The mass system of the mass number 28 in the film making chamber is considered to be mainly carbon monoxide and nitrogen. The carbon monoxide gas system is believed to be sputtered by a transparent film . The plasma damage or the like at the time of forming the transparent electrode layer is released into the film forming atmosphere. Further, nitrogen gas is considered to be released into the film forming atmosphere by the hard coating layers 12, 13 and the like formed on the surface of the base film 11.

在本發明，可以藉由在透明電極層之製膜前，設置在基材準備室201內之加熱製程，而使得製膜室202、203內之質量數28之氣體分壓，成為前述範圍。也就是說，認為 藉由以比較高之溫度、短時間，來加熱透明薄膜，而在透明電極層之製膜前，由透明薄膜之內部或透明薄膜之表面開始，揮發成為一氧化碳或氮之發生原因之有機物質，抑制由於在製膜時之電漿損傷等而造成之質量數28之氣體發生。 In the present invention, the gas partial pressure of the mass number 28 in the film forming chambers 202 and 203 can be made into the above range by the heating process provided in the substrate preparing chamber 201 before the formation of the transparent electrode layer. In other words, think The transparent film is heated at a relatively high temperature for a short period of time, and the organic material which is caused by carbon monoxide or nitrogen is volatilized from the inside of the transparent film or the surface of the transparent film before the film formation of the transparent electrode layer. The generation of gas of mass 28 due to plasma damage or the like at the time of film formation is suppressed.

向來，由於降低透明薄膜中之水分量而促進金屬氧化物之結晶化之目的，因此，在透明電極層之製膜前，進行在真空下，來加熱透明薄膜。為了像這樣而減小水分量，因此，需要低溫且長時間之加熱。在由壓輥狀捲繞體210開始抽出透明薄膜10之後，在製膜壓輥260之上，直到製膜透明電極層30為止，在基材準備室201內之搬送通路中，不容易進行低水分量化用之充分之加熱處理。另一方面，本發明之加熱製程係高溫且短時間之處理。因此，可以在由壓輥狀捲繞體210開始抽出透明薄膜10之後，在製膜壓輥260之上，直到製膜透明電極層30為止之間，在基材準備室201內，進行加熱處理。也就是說，加熱處理係短時間之製程，因此，可以在加熱製程後，透明薄膜不一旦捲繞成為壓輥狀，接續於加熱製程而進行透明電極層之製膜。此外，透明薄膜10係以無接觸到加熱部271、272，來進行加熱，因此，即使是在高溫之加熱，也不容易發生例如在製膜壓輥上而進行加熱之狀態下之薄膜搬送狀態之不安定化或捲繞體之捲繞偏離等之意外。 Conventionally, since the purpose of crystallization of the metal oxide is promoted by lowering the amount of water in the transparent film, the transparent film is heated under vacuum before the formation of the transparent electrode layer. In order to reduce the amount of moisture in this manner, it is necessary to heat at a low temperature for a long period of time. After the transparent film 10 is taken out from the press roll-shaped winding body 210, it is not easy to carry out the transfer path in the substrate preparation chamber 201 until the transparent electrode layer 30 is formed on the film forming press roll 260. Adequate heat treatment for moisture quantification. On the other hand, the heating process of the present invention is a high temperature and short time process. Therefore, after the transparent film 10 is taken out by the press roll-shaped winding body 210, heat treatment can be performed in the substrate preparing chamber 201 between the film forming press rolls 260 and the film forming transparent electrode layer 30. . That is to say, the heat treatment is a short-time process. Therefore, after the heating process, the transparent film is not wound into a roll shape, and the film formation of the transparent electrode layer is continued in the heating process. Further, since the transparent film 10 is heated without being in contact with the heating portions 271 and 272, even in the case of heating at a high temperature, the film transport state in a state where heating is performed, for example, on the film forming press roller, is unlikely to occur. Unstable or unexpected winding of the winding body.

作為透明電極層製膜時之濺鍍電源係可以使用DC、RF、MF電源等。作為使用於濺鍍製膜之標靶222、223之材料係使用銦、錫、鋅、鎵、鋁、銻、鈦等之金屬、或者是這些金屬之氧化物。作為透明電極層30係在製膜氧化銦錫 (ITO)或氧化銦鋅(IZO)等之以銦作為主成分之金屬氧化物膜之狀態下，標靶最好是含有88重量%~98重量%之氧化銦，更加理想是含有90重量%~97重量%，甚至最好是含有94重量%~96重量%。 As the sputtering power source for forming a film of the transparent electrode layer, a DC, RF, MF power source or the like can be used. As the material of the targets 222 and 223 used for the sputtering film formation, a metal such as indium, tin, zinc, gallium, aluminum, antimony or titanium or an oxide of these metals is used. As the transparent electrode layer 30, the indium tin oxide is formed in the film. In the state of a metal oxide film containing indium as a main component (ITO) or indium zinc oxide (IZO), the target preferably contains 88% by weight to 98% by weight of indium oxide, more preferably 90% by weight. ~97% by weight, even more preferably from 94% by weight to 96% by weight.

透明電極層製膜時之基板溫度係可以是透明薄膜來具有耐熱性之範圍。基板溫度係最好是-40℃~40℃，更加理想是-30℃~30℃，甚至最好是-20℃~20℃，特別最好是-10℃~10℃。藉由基板溫度成為40℃以下，來抑制由於電漿損傷等而造成之質量數28之氣體發生。此外，可以藉由基板溫度成為-40℃以上，而抑制透明電極層之透過率之降低或透明薄膜之脆化。 The substrate temperature at the time of film formation of the transparent electrode layer may be a transparent film to have a range of heat resistance. The substrate temperature is preferably -40 ° C to 40 ° C, more preferably -30 ° C to 30 ° C, even more preferably -20 ° C to 20 ° C, particularly preferably -10 ° C to 10 ° C. When the substrate temperature is 40 ° C or lower, gas generation of mass 28 due to plasma damage or the like is suppressed. Further, by lowering the substrate temperature to -40 ° C or higher, the transmittance of the transparent electrode layer can be suppressed from being lowered or the embrittlement of the transparent film can be suppressed.

(介電質層製膜製程) (Dielectric layer film making process)

在本發明之某一實施形態，最好是在基材準備室201之內藉由來自加熱部271、272之熱能而對於透明薄膜10來進行加熱處理之後，在製膜室內之製膜壓輥260之上，直到製膜透明電極層30為止之間，製膜透明介電質層20。 In one embodiment of the present invention, it is preferable that after the heat treatment of the transparent film 10 by the heat energy from the heating portions 271 and 272 in the substrate preparation chamber 201, the film forming roller in the film forming chamber is preferably formed. Above the 260, the transparent dielectric layer 20 is formed until the transparent electrode layer 30 is formed.

例如在加熱透明薄膜之後，在製膜壓輥260之上，製膜透明介電質層20，在透明介電質層20製膜後之透明薄膜10一旦捲繞於捲繞體250之後，再度由捲繞體250開始抽出薄膜而進行透明電極層30之製膜。可以在該狀態下，直到再度由捲繞體250開始抽出薄膜而進行透明電極層30之製膜為止之間，再一度進行加熱處理。 For example, after the transparent film is heated, a transparent dielectric layer 20 is formed on the film forming press roll 260, and after the film is formed on the transparent dielectric layer 20, the transparent film 10 is once again wound around the wound body 250, and then re-applied. The film is taken out from the wound body 250 to form a film of the transparent electrode layer 30. In this state, the heat treatment can be performed once until the film is formed by the winding body 250 again and the transparent electrode layer 30 is formed.

在本發明，最好是在加熱透明薄膜之後，在製膜壓輥260之上，連續地製膜透明介電質層20和透明電極層30。 例如在圖2，藉由使用由構成介電質層之材料而組成之氧化物之標靶，來作為製膜室202內之標靶222，使用由構成透明電極層之材料而組成之金屬氧化物之標靶，來作為製膜室203內之標靶223，而連續地製膜透明介電質層20和透明電極層30。在圖2，圖示在2個之製膜室202、203內之各個來具有陰極282、283之構造，但是，濺鍍製膜裝置係可以具備3個以上之製膜室。可以藉由在3個以上之製膜室內之各個，具備陰極和標靶，而連續地製膜2層以上之介電質層和透明電極層(合計3層以上)。 In the present invention, it is preferable that the transparent dielectric layer 20 and the transparent electrode layer 30 are continuously formed on the film forming press roll 260 after the transparent film is heated. For example, in Fig. 2, by using a target composed of an oxide constituting a material of a dielectric layer, as a target 222 in the film forming chamber 202, metal oxidation composed of a material constituting the transparent electrode layer is used. The target of the object is used as the target 223 in the film forming chamber 203 to continuously form the transparent dielectric layer 20 and the transparent electrode layer 30. In FIG. 2, the structure in which the cathodes 282 and 283 are provided in each of the two film forming chambers 202 and 203 is shown. However, the sputtering film forming apparatus may include three or more film forming chambers. It is possible to continuously form two or more dielectric layers and transparent electrode layers (total of three or more layers) by providing a cathode and a target in each of three or more film forming chambers.

透明介電質層20係可以在其上面形成透明電極層30之際，作用成為抑制由透明薄膜10來揮發水分或有機物質之氣體障蔽層或者是減低對於透明薄膜之電漿損傷之保護層，同時，也可以作用成為膜成長之基底層。特別是在本發明，介電質層係可以作用成為氣體障蔽層，因此，期待抑制在透明電極層製膜時之質量數28之氣體發生。由在透明介電質層20具有這些機能之觀點來看的話，則透明介電質層20之膜厚係最好是10nm~100nm，更加理想是15nm~85nm，甚至最好是20nm~80nm。 The transparent dielectric layer 20 can function as a gas barrier layer for suppressing evaporation of moisture or organic substances by the transparent film 10 or a protective layer for reducing plasma damage to the transparent film when the transparent electrode layer 30 is formed thereon. At the same time, it can also act as a base layer for film growth. In particular, in the present invention, since the dielectric layer functions as a gas barrier layer, it is expected to suppress the generation of gas of mass 28 at the time of film formation of the transparent electrode layer. The film thickness of the transparent dielectric layer 20 is preferably from 10 nm to 100 nm, more preferably from 15 nm to 85 nm, even more preferably from 20 nm to 80 nm, from the viewpoint that the transparent dielectric layer 20 has these functions.

作為構成透明介電質層20之氧化物係適合使用由Si、Nb、Ta、Ti、Zn、Zr和Hf而組成之群組來選出之一種以上元素之氧化物。即使是在其中，也最好是氧化矽(SiO2)。在本發明之製造方法，藉由在以氧化矽來作為主成分之透明介電質層上，形成透明電極層30，而在圖案化透明電極層之際，有不容易發生沿著圖案境界之皺紋之傾向產生。 As the oxide constituting the transparent dielectric layer 20, an oxide of one or more elements selected from the group consisting of Si, Nb, Ta, Ti, Zn, Zr, and Hf is suitably used. Even in it, ruthenium oxide (SiO 2 ) is preferred. In the manufacturing method of the present invention, the transparent electrode layer 30 is formed on the transparent dielectric layer containing ruthenium oxide as a main component, and when the transparent electrode layer is patterned, it is less likely to occur along the boundary of the pattern. The tendency of wrinkles is produced.

可以在透明介電質層20由2層以上而組成之狀態下，藉由調整各層之厚度或折射率，而調整附有透明電極之基板之透過率或反射率，提高顯示裝置之辨識性。此外，正如圖3所示，可以在藉由蝕刻等而圖案化透明電極層30面內之一部分之狀態下，藉由調整透明介電質層之厚度或折射率，而減低電極形成部30a和電極非形成部30b之間之透過率差、反射率差、色差，抑制電極圖案之辨識。 The transmittance or reflectance of the substrate with the transparent electrode can be adjusted by adjusting the thickness or refractive index of each layer in a state where the transparent dielectric layer 20 is composed of two or more layers, thereby improving the visibility of the display device. Further, as shown in FIG. 3, the electrode forming portion 30a and the electrode forming portion 30a can be reduced by adjusting the thickness or refractive index of the transparent dielectric layer in a state where one of the faces of the transparent electrode layer 30 is patterned by etching or the like. The difference in transmittance between the electrode non-formed portions 30b, the difference in reflectance, and the chromatic aberration suppresses the identification of the electrode pattern.

透明介電質層20表面之算術平均粗糙度Ra係最好是1nm以下，更加理想是0.8nm以下，甚至最好是0.6nm以下。算術平均粗糙度Ra係根據藉由使用掃描用探針顯微鏡之非接觸法而測定之表面形狀(粗糙度曲線)，按照JIS B0601：2001(ISO1302：2002)而算出。藉由使得形成透明電極層30之界面，成為平滑，而使得形成於其上面之透明電極層30呈低電阻化，同時，在圖案化透明電極層之際，有抑制沿著圖案境界之皺紋發生之傾向產生。 The arithmetic mean roughness Ra of the surface of the transparent dielectric layer 20 is preferably 1 nm or less, more preferably 0.8 nm or less, and even more preferably 0.6 nm or less. The arithmetic mean roughness Ra is calculated according to JIS B0601:2001 (ISO1302:2002) based on the surface shape (roughness curve) measured by the non-contact method using a scanning probe microscope. By making the interface forming the transparent electrode layer 30 smooth, the transparent electrode layer 30 formed thereon is reduced in resistance, and at the same time, when the transparent electrode layer is patterned, wrinkles occurring along the pattern boundary are suppressed. The tendency arises.

在製膜矽氧化物層來作為透明介電質層之狀態下，藉由減小製膜壓力(製膜室內之全壓)，而有減小表面之算術平均粗糙度Ra之傾向產生。介電質層之製膜壓力係最好是0.4Pa以下，更加理想是0.35Pa以下，甚至最好是0.25Pa以下。在形成複數個之透明介電質層之狀態下，為了減小透明介電質層20表面之算術平均粗糙度，因此，最好是以前述製膜壓力，來製膜接合於透明電極層30之介電質層23。藉由調整接合於透明電極層30之介電質層23之製膜條件而抑制透明電極層之圖案皺紋之理由係尚未確定，但是，作為基底層之介 電質層之結晶性或表面形狀、表面性等係認為對於透明電極層之膜成長，造成影響而成為一因。 In the state in which the tantalum oxide layer is formed as a transparent dielectric layer, the film forming pressure (full pressure in the film forming chamber) is reduced, and there is a tendency to reduce the arithmetic mean roughness Ra of the surface. The film formation pressure of the dielectric layer is preferably 0.4 Pa or less, more preferably 0.35 Pa or less, and even more preferably 0.25 Pa or less. In order to reduce the arithmetic mean roughness of the surface of the transparent dielectric layer 20 in a state in which a plurality of transparent dielectric layers are formed, it is preferable to form a film bonded to the transparent electrode layer 30 by the film forming pressure. Dielectric layer 23. The reason for suppressing the pattern wrinkles of the transparent electrode layer by adjusting the film formation conditions of the dielectric layer 23 bonded to the transparent electrode layer 30 has not been determined, but as a basis layer The crystallinity, surface shape, and surface properties of the electric layer are considered to be a cause of influence on the film growth of the transparent electrode layer.

此外，在製膜2層以上之矽氧化物層來作為透明介電質層之狀態下，由抑制在圖案化透明電極層之際之皺紋發生之觀點來看的話，則無接合於透明電極層30之介電質層係也最好是在0.4Pa以下之壓力下，進行製膜。該介電質層之製膜壓力係更加理想是0.35Pa以下，甚至最好是0.25Pa以下。藉由調整無接合於透明電極層30之介電質層之製膜條件而抑制透明電極層之圖案皺紋之理由係尚未確定，但是，該介電質層之結晶性或表面形狀、表面性等係認為對於接合在透明電極層30之介電質層23或透明電極層之膜成長，造成影響而成為一因。 Further, in the state in which two or more layers of the tantalum oxide layer are formed as the transparent dielectric layer, the transparent electrode layer is not bonded from the viewpoint of suppressing occurrence of wrinkles in the patterning of the transparent electrode layer. The dielectric layer of 30 is also preferably formed under a pressure of 0.4 Pa or less. The film formation pressure of the dielectric layer is more preferably 0.35 Pa or less, and even more preferably 0.25 Pa or less. The reason for suppressing the pattern wrinkles of the transparent electrode layer by adjusting the film formation conditions of the dielectric layer not bonded to the transparent electrode layer 30 has not been determined, but the crystallinity, surface shape, surface properties, etc. of the dielectric layer are not determined. It is considered that the film growth of the dielectric layer 23 or the transparent electrode layer bonded to the transparent electrode layer 30 has an influence.

作為用以藉由光學設計而抑制電極圖案之辨識之透明介電質層20之構造之一例係列舉由透明薄膜10之側開始，由折射率n1為1.45~1.95且膜厚為1nm~25nm之第一透明介電質層21、折射率n2為2.00~2.35且膜厚為5nm~10nm之第二透明介電質層22以及折射率n3為1.43~1.55且膜厚為35nm~80nm之第三透明介電質層23之3層而組成者。此外，第一介電質層之折射率n1、第二介電質層之折射率n2以及第三介電質層之折射率n3係最好是滿足n3<n1<n2之關係。藉由各介電質層之折射率，具有此種之大小關係，而適度地控制在介電質層界面之折射率，得到辨識性呈良好之附有透明電極之基板。此外，各介電質層及透明電極層之折射率係對於藉由分光橢圓對稱法而測定之波長550nm之光之折射率。各層之膜 厚係藉由穿透型電子顯微鏡(TEM)而求出剖面。 As an example of the structure of the transparent dielectric layer 20 for suppressing the identification of the electrode pattern by optical design, starting from the side of the transparent film 10, the refractive index n 1 is 1.45 to 1.95 and the film thickness is 1 nm to 25 nm. The first transparent dielectric layer 21, the second transparent dielectric layer 22 having a refractive index n 2 of 2.00 to 2.35 and a film thickness of 5 nm to 10 nm, and a refractive index n 3 of 1.43 to 1.55 and a film thickness of 35 nm to 80 nm The third transparent dielectric layer 23 is composed of three layers. Further, the refractive index n 1 of the first dielectric layer, the refractive index n 2 of the second dielectric layer, and the refractive index n 3 of the third dielectric layer preferably satisfy n 3 <n 1 <n 2 Relationship. By having such a magnitude relationship with the refractive index of each dielectric layer, the refractive index at the interface of the dielectric layer is moderately controlled, and a substrate having a transparent electrode with good visibility is obtained. Further, the refractive indices of the respective dielectric layers and the transparent electrode layers are refractive indices of light having a wavelength of 550 nm measured by a spectroscopic ellipsometry method. The film thickness of each layer was determined by a transmission electron microscope (TEM).

在像這樣而透明介電質層20由3層來組成之構造，作為第一透明介電質層21之材料係最好是以SiOx(1.5≦x<2)來作為主成分之矽氧化物層。第一透明介電質層21之膜厚d1係最好是1nm~25nm，更加理想是2nm~22nm，甚至最好是3~20nm，特別最好是4nm~15nm。第一介電質層之折射率係最好是1.45~1.95，更加理想是1.47~1.85，甚至最好是1.49~1.75。 In such a configuration, the transparent dielectric layer 20 is composed of three layers, and the material of the first transparent dielectric layer 21 is preferably ruthenium oxide having SiO x (1.5 ≦ x < 2) as a main component. Layer of matter. The film thickness d 1 of the first transparent dielectric layer 21 is preferably from 1 nm to 25 nm, more preferably from 2 nm to 22 nm, even more preferably from 3 to 20 nm, particularly preferably from 4 nm to 15 nm. The refractive index of the first dielectric layer is preferably 1.45 to 1.95, more preferably 1.47 to 1.85, and even more preferably 1.49 to 1.75.

作為第二透明介電質層22之材料係最好是以由Nb、Ta、Ti、Zr、Zn和Hf而組成之群組來選出之金屬氧化物或者是這些金屬之複合氧化物，來作為主成分。第二透明介電質層22之膜厚係最好是4nm~12nm，更加理想是6nm~10nm。第二介電質層之折射率係最好是2.00~235，更加理想是2.05~2.30，甚至最好是2.10~2.25。 The material of the second transparent dielectric layer 22 is preferably a metal oxide selected from the group consisting of Nb, Ta, Ti, Zr, Zn, and Hf or a composite oxide of these metals. main ingredient. The film thickness of the second transparent dielectric layer 22 is preferably 4 nm to 12 nm, more preferably 6 nm to 10 nm. The refractive index of the second dielectric layer is preferably 2.00 to 235, more preferably 2.05 to 2.30, and even more preferably 2.10 to 2.25.

第二透明介電質層22係最好是可見光之短波長區域之吸收變小。由此種觀點來看的話，則作為第二透明介電質層22之材料係最好是氧化鈮(Nb2O5)、氧化鉭(Ta2O5)、氧化鈦(TiO2)或氧化鋯(ZrO2)，即使是在其中，也適合使用氧化鈮。 Preferably, the second transparent dielectric layer 22 has a smaller absorption in the short wavelength region of visible light. From such a viewpoint, the material of the second transparent dielectric layer 22 is preferably niobium oxide (Nb 2 O 5 ), tantalum oxide (Ta 2 O 5 ), titanium oxide (TiO 2 ) or oxidation. Zirconium (ZrO 2 ), even in it, is preferably used.

作為第三透明介電質層23之材料係最好是以SiO2來作為主成分之矽氧化物層。第三透明介電質層23之膜厚係最好是30nm~80nm，更加理想是35nm~70nm，甚至最好是40~70nm。此外，由光學設計呈最適當化之觀點來看的話，則第三介電質層之膜厚係最好是30nm~55nm之範圍。另一方 面，在第三介電質層之膜厚為55nm以上之狀態下，有更加地減低皺紋之傾向發生。第三透明介電質層23之折射率n3係最好是1.43~1.58，更加理想是1.45~1.55，甚至最好是1.47~1.53。 The material of the third transparent dielectric layer 23 is preferably a tantalum oxide layer having SiO 2 as a main component. The film thickness of the third transparent dielectric layer 23 is preferably 30 nm to 80 nm, more preferably 35 nm to 70 nm, and even more preferably 40 to 70 nm. Further, the film thickness of the third dielectric layer is preferably in the range of 30 nm to 55 nm from the viewpoint of optimum optical design. On the other hand, in a state where the film thickness of the third dielectric layer is 55 nm or more, there is a tendency that wrinkles are further reduced. The refractive index n 3 of the third transparent dielectric layer 23 is preferably 1.43 to 1.58, more preferably 1.45 to 1.55, and even more preferably 1.47 to 1.53.

正如前面之敘述，成為接合於透明電極層30之介電質層之第三介電質層23係透明電極層形成側界面之算術平均粗糙度Ra最好是1nm以下，更加理想是0.8nm以下，甚至最好是0.6nm以下。此外，第三介電質層之製膜壓力係最好是0.4Pa以下，更加理想是0.35Pa以下，甚至最好是0.25Pa以下。 As described above, the third dielectric layer 23 to be bonded to the dielectric layer of the transparent electrode layer 30 has an arithmetic mean roughness Ra of the transparent electrode layer forming side interface of preferably 1 nm or less, more preferably 0.8 nm or less. It is even better to be below 0.6 nm. Further, the film forming pressure of the third dielectric layer is preferably 0.4 Pa or less, more preferably 0.35 Pa or less, and even more preferably 0.25 Pa or less.

藉由各介電質層具有前述厚度和折射率，而有不容易辨識形成於其上面之透明電極層30之電極圖案之傾向發生。為了更加有效地抑制透明電極層之圖案辨識，因此，第一透明介電質層21之光學膜厚係最好是2nm~40nm，更加理想是4nm~36nm，甚至最好是6nm~32nm。第二透明介電質層之光學膜厚係最好是4nm~20nm，更加理想是5nm~15nm，甚至最好是6nm~12nm。第三透明介電質層之光學膜厚係最好是30nm~110nm，更加理想是40nm~90nm，甚至最好是45nm~80nm。由光學設計最適當化之觀點來看的話，則第三介電質層之光學膜厚係更加理想是80nm以下，甚至最好是70nm以下。另一方面，由更加地抑制皺紋發生之觀點來看的話，則第三介電質層之光學膜厚係更加理想是55nm以上，甚至最好是60nm以上。此外，光學膜厚係藉由各層之膜厚和折射率之乘積而表示。 Since each of the dielectric layers has the aforementioned thickness and refractive index, there is a tendency that the electrode pattern of the transparent electrode layer 30 formed thereon is not easily recognized. In order to more effectively suppress pattern recognition of the transparent electrode layer, the optical thickness of the first transparent dielectric layer 21 is preferably 2 nm to 40 nm, more preferably 4 nm to 36 nm, and even more preferably 6 nm to 32 nm. The optical film thickness of the second transparent dielectric layer is preferably 4 nm to 20 nm, more preferably 5 nm to 15 nm, and even more preferably 6 nm to 12 nm. The optical film thickness of the third transparent dielectric layer is preferably from 30 nm to 110 nm, more preferably from 40 nm to 90 nm, and even more preferably from 45 nm to 80 nm. From the viewpoint of the most appropriate optical design, the optical film thickness of the third dielectric layer is more desirably 80 nm or less, and even more preferably 70 nm or less. On the other hand, from the viewpoint of suppressing the occurrence of wrinkles more, the optical film thickness of the third dielectric layer is more preferably 55 nm or more, and even more preferably 60 nm or more. Further, the optical film thickness is represented by the product of the film thickness and the refractive index of each layer.

在透明介電質層20為前述3層構造之狀態下，正 如圖3所示，可以減低在圖案化透明電極層30之際之電極形成部30a和電極非形成部30b之光之反射率差或色差，藉由光學設計而抑制圖案之辨識。此外，在本發明，即使是藉著在由矽氧化物而組成之透明介電質層23之上，形成透明電極層30，而抑制在圖案化透明電極層之際之圖案皺紋之發生，也有抑制圖案辨識之傾向發生。 In the state in which the transparent dielectric layer 20 is in the above-described three-layer structure, As shown in FIG. 3, the difference in reflectance or chromatic aberration of light between the electrode forming portion 30a and the electrode non-forming portion 30b at the time of patterning the transparent electrode layer 30 can be reduced, and the pattern recognition can be suppressed by optical design. Further, in the present invention, even if the transparent electrode layer 30 is formed on the transparent dielectric layer 23 composed of tantalum oxide, the occurrence of pattern wrinkles at the time of patterning the transparent electrode layer is suppressed. The tendency to suppress pattern recognition occurs.

在藉由濺鍍法而製膜前述各介電質層之狀態下，作為標靶係可以使用金屬、金屬氧化物、金屬碳化物等。作為電源係可以使用DC、RF、MF電源等，但是，由生產性之觀點來看的話，則最好是MF電源。製膜時之施加電力係並無特別限定，但是，最好是在透明薄膜基板，無施加過剩之熱能，並且，調整於無損害生產性之範圍。例如在透明介電質層20為前述3層構造之狀態下，在第一介電質層製膜時之功率密度係最好是0.5~10W/cm2，在第二介電質層製膜時之功率密度係最好是0.5~8W/cm2，在第三介電質層製膜時之功率密度係最好是0.2~10W/cm2。 In the state in which the respective dielectric layers are formed by sputtering, a metal, a metal oxide, a metal carbide or the like can be used as the target system. As the power source system, a DC, RF, MF power source or the like can be used. However, from the viewpoint of productivity, it is preferably an MF power source. The electric power applied during film formation is not particularly limited. However, it is preferable that the transparent film substrate is not subjected to excessive heat energy and is adjusted to a range in which productivity is not impaired. For example, in a state in which the transparent dielectric layer 20 has the above-described three-layer structure, the power density at the time of film formation in the first dielectric layer is preferably 0.5 to 10 W/cm 2 , and the film is formed on the second dielectric layer. The power density at the time is preferably 0.5 to 8 W/cm 2 , and the power density at the time of film formation in the third dielectric layer is preferably 0.2 to 10 W/cm 2 .

(其他之製程) (other processes)

在加熱透明薄膜10之後，直到製膜透明電極層30為止之間，也可以包含透明介電質層20之形成以外之製程。例如可以在加熱透明薄膜10之後，進行薄膜表面來曝露於電漿之處理(轟炸碰撞處理)。認為藉由在氬等之惰性氣體之存在下，使用SUS等之標靶，進行濺鍍，產生電漿，而對於薄膜表面，進行潔淨化，抑制在透明電極層製膜時之質量數28之氣體發生。在透明電極層30之製膜前而形成透明介電質層20 之狀態下，轟炸碰撞處理係可以進行於透明介電質層20之形成前和形成後之任何一種。 After the transparent film 10 is heated, a process other than the formation of the transparent dielectric layer 20 may be included until the transparent electrode layer 30 is formed. For example, after the transparent film 10 is heated, the surface of the film may be exposed to plasma treatment (bombing collision treatment). It is considered that sputtering is carried out by using a target such as SUS in the presence of an inert gas such as argon to generate a plasma, and the surface of the film is cleaned to suppress the mass of the transparent electrode layer. Gas occurs. The transparent dielectric layer 20 is formed before the formation of the transparent electrode layer 30. In this state, the bombing collision treatment can be performed before and after the formation of the transparent dielectric layer 20.

[附有透明電極之基板之物性] [Physical properties of the substrate with a transparent electrode]

藉由前面之敘述而得到之本發明之附有透明電極之基板50係熱收縮率最好是0.4%以下，更加理想是0.35%以下，甚至最好是0.3%以下。在由於方向而使得熱收縮率呈不同之狀態(在MD方向和TD方向呈不同之狀態)，MD方向之熱收縮率係可以是前述範圍。特別是MD方向和TD方向之兩者之熱收縮率係最好是前述範圍。 The heat-shrinkage ratio of the substrate 50 with a transparent electrode of the present invention obtained by the above description is preferably 0.4% or less, more preferably 0.35% or less, even more preferably 0.3% or less. In the state in which the heat shrinkage rate is different due to the direction (the state in which the MD direction and the TD direction are different), the heat shrinkage ratio in the MD direction may be the aforementioned range. In particular, the heat shrinkage ratio of both the MD direction and the TD direction is preferably the aforementioned range.

此外，本發明之附有透明電極之基板50之熱收縮起始溫度係最好是85℃以上，更加理想是90℃以上，甚至最好是100℃以上。附有透明電極之基板係最好是在直到200℃為止之範圍，無顯示熱收縮起始溫度。 Further, the heat shrinkage initiation temperature of the substrate 50 with a transparent electrode of the present invention is preferably 85 ° C or higher, more preferably 90 ° C or higher, and even more preferably 100 ° C or higher. The substrate to which the transparent electrode is attached is preferably in the range up to 200 ° C, and the heat shrinkage onset temperature is not shown.

在本發明，可以藉由在前述加熱製程，收縮薄膜，而使得熱收縮率及熱收縮起始溫度，成為前述範圍。此外，也可以藉由使用低熱收縮率及高熱收縮起始溫度之薄膜，來作為供應於附有透明電極之基板製造之透明薄膜10，而更加地降低附有透明電極之基板之熱收縮率，更加地提高熱收縮起始溫度。如果熱收縮率及熱收縮起始溫度為前述範圍的話，則在透明電極層之結晶化或其後面之觸控面板形成製程等，抑制在加熱附有透明電極之基板之狀態下之尺寸變化，因此，可以期待容易設計元件。 In the present invention, the heat shrinkage rate and the heat shrinkage onset temperature can be made into the above range by shrinking the film in the above heating process. Further, by using a film having a low heat shrinkage rate and a high heat shrinkage onset temperature as a transparent film 10 which is supplied to a substrate having a transparent electrode, the heat shrinkage rate of the substrate with the transparent electrode can be further reduced. The heat shrinkage onset temperature is further increased. When the heat shrinkage rate and the heat shrinkage onset temperature are in the above range, the crystallization of the transparent electrode layer or the touch panel forming process or the like behind it suppresses the dimensional change in the state in which the substrate with the transparent electrode is heated. Therefore, it is expected that the components can be easily designed.

在藉由抑制以加熱來造成之尺寸變化而圖案化透明電極層之際，有抑制沿著圖案境界之皺紋產生之傾向發生。 此外，如果根據本發明人們之檢討的話，則即使是在使用加熱尺寸變化率小之薄膜來作為透明電極層30之製膜前之透明薄膜10之狀態下，也有在透明電極層之圖案境界來產生皺紋之情況發生。因此，在圖案化透明電極層之際之皺紋發生係認為並非僅起因於透明薄膜10之尺寸變化。 When the transparent electrode layer is patterned by suppressing the dimensional change caused by heating, there is a tendency to suppress generation of wrinkles along the boundary of the pattern. Further, according to the review by the present inventors, even in the state in which the film having a small change in the dimensional change rate is used as the transparent film 10 before the film formation of the transparent electrode layer 30, there is a pattern boundary of the transparent electrode layer. Wrinkles occur. Therefore, the generation of wrinkles at the time of patterning the transparent electrode layer is considered not to be caused only by the dimensional change of the transparent film 10.

正如前面之敘述，在本發明，藉由在透明電極層之製膜前，於濺鍍製膜裝置內，對於透明薄膜，進行非接觸加熱，而抑制沿著透明電極層之圖案境界之皺紋產生。藉由透明電極層製膜前之加熱處理來改變製膜界面之狀態而在用以進行結晶化之加熱時來減小賦予至透明電極層之應力係推測為抑制皺紋發生之一因。 As described above, in the present invention, by performing non-contact heating on the transparent film in the sputtering film forming apparatus before the film formation of the transparent electrode layer, wrinkles generation along the pattern boundary of the transparent electrode layer is suppressed. . The state of the film formation interface is changed by the heat treatment before the film formation of the transparent electrode layer, and the stress applied to the transparent electrode layer is reduced when heating for crystallization is presumed to be one of the causes of suppressing wrinkles.

本發明之附有透明電極之基板50之透明電極層30係在以非結晶質之氧化銦來作為主成分之金屬氧化物薄膜之狀態下，附有透明電極之基板在150℃、進行30分鐘之加熱後之藉由氧化銦結晶之out-plane(平面外)之X射線繞射測定而得到之(222)面之面間隔dout和藉由in-plane(平面內)之X射線繞射測定而得到之(222)面之面間隔din之比值dout/din係最好是接近1。具體地說，dout/din係最好是0.998~1.003、更加理想是0.999~1.002。dout/din係表示結晶之三次元歪斜之指標，表示dout/din越加離開1而結晶構造越加歪斜。 In the state in which the transparent electrode layer 30 of the substrate 50 with the transparent electrode of the present invention is a metal oxide thin film containing amorphous indium oxide as a main component, the substrate with the transparent electrode is exposed at 150 ° C for 30 minutes. The surface spacing d out of the (222) plane and the X-ray diffraction by in-plane (in-plane) obtained by X-ray diffraction measurement of out-plane (in-plane) of indium oxide crystals after heating The ratio d out /d in of the surface spacing d in of the (222) plane obtained by the measurement is preferably close to 1. Specifically, the d out /d in system is preferably 0.998 to 1.003, more preferably 0.999 to 1.002. d out /d in is an indicator of the three-dimensional skew of crystallization, indicating that d out /d in is more than 1 and the crystal structure is more skewed.

本發明之附有透明電極之基板之透明電極層係非結晶質(可以包含一部分之結晶質成分)，但是，藉由在150℃，進行30分鐘之加熱，而對於透明電極層中之金屬氧化物，進行結晶化。認為在150℃、進行30分鐘加熱後之dout/din接近 於1係表示減小在透明電極層來進行結晶化之際而賦予至膜之應力，減小在結晶化後之透明電極層內之殘留應力。推測在結晶化後之透明電極層之殘留應力變小之狀態下，為了減小在透明電極層和透明薄膜之界面之應力，因此，抑制在圖案化透明電極層之狀態下之皺紋發生。 The transparent electrode layer of the substrate with a transparent electrode of the present invention is amorphous (may contain a part of the crystalline component), but is oxidized for the metal in the transparent electrode layer by heating at 150 ° C for 30 minutes. The substance is crystallized. It is considered that the d out /d in close to 1 after heating at 150 ° C for 30 minutes means that the stress applied to the film when the crystallization is performed on the transparent electrode layer is reduced, and the transparent electrode layer after crystallization is reduced. Residual stress inside. In the state where the residual stress of the transparent electrode layer after crystallization is reduced, in order to reduce the stress at the interface between the transparent electrode layer and the transparent film, wrinkles in the state of patterning the transparent electrode layer are suppressed.

結晶之面間隔係藉由X射線繞射法而求出。附有透明電極之基板之在150℃、進行30分鐘加熱後之(222)面之繞射角2θ係最好是32°以下、更加理想是31°以下、甚至最好是30.8°以下。為了求出結晶之面間隔，因此，使用Cu．Kα射線(波長0.15418nm)，來作為X射線源，以入射角0.1°~2.0°之條件，來進行X射線繞射。 The interplanar spacing of the crystals is determined by the X-ray diffraction method. The diffraction angle 2θ of the (222) plane after heating at 150 ° C for 30 minutes on the substrate with the transparent electrode is preferably 32 or less, more preferably 31 or less, and even more preferably 30.8 or less. In order to find the interplanar spacing of the crystals, Cu is used . Kα ray (wavelength 0.15418 nm) is used as an X-ray source to perform X-ray diffraction at an incident angle of 0.1° to 2.0°.

附有透明電極之基板之在150℃、進行30分鐘加熱後之藉由以Cu．Kα射線來作為X射線源之X射線繞射而測定之(440)面之繞射角2θ以及在前述加熱前之(440)面之繞射角2θ0之差異2θ-2θ0係最好是0.50以下、更加理想是0.45以下、甚至最好是0.32以下、特別最好是0.28以下。認為在用以進行結晶化之加熱前後，在繞射角之變化小之狀態下，使得在結晶化之際而透明電極層來承受之應力變小，在透明電極層內，無產生殘留應力。因此，認為在2θ-2θ0變小之狀態下，抑制在圖案化透明電極層之際之皺紋發生。 The substrate with the transparent electrode was heated at 150 ° C for 30 minutes by Cu . The difference between the diffraction angle 2θ of the (440) plane measured by the X-ray diffraction of the X-ray source and the diffraction angle 2θ 0 of the (440) plane before the heating is 2θ-2θ 0 is preferably It is 0.50 or less, more preferably 0.45 or less, even more preferably 0.32 or less, and particularly preferably 0.28 or less. It is considered that the stress applied to the transparent electrode layer during crystallization is reduced in the state where the change in the diffraction angle is small before and after the heating for crystallization, and no residual stress is generated in the transparent electrode layer. Therefore, it is considered that the occurrence of wrinkles at the time of patterning the transparent electrode layer is suppressed in a state where 2θ-2θ 0 becomes small.

[附有透明電極之基板之用途] [Use of substrate with transparent electrode]

本發明之附有透明電極之基板係可以使用作為顯示器或發光元件、光電轉換元件等之透明電極。適合使用作為觸控面板用之透明電極。即使是在其中，也最好是使用在靜電 電容方式觸控面板。 The substrate with a transparent electrode of the present invention can be used as a transparent electrode of a display, a light-emitting element, a photoelectric conversion element, or the like. It is suitable for use as a transparent electrode for touch panels. Even in it, it is best to use it in static electricity. Capacitive touch panel.

在對於觸控面板之應用之際，附有透明電極之基板50係最好是進行加熱處理而對於透明電極層，來進行結晶化。用以進行結晶化之加熱處理係例如在120℃~150℃之烤箱中，進行30~60分鐘。或者是可以在85℃~120℃、1日~3日間等之比較低溫，進行長時間之加熱。透明電極層之加熱處理係可以進行於透明電極層之圖案化前、圖案化後之任何一種。此外，透明電極層之加熱處理係可以兼具進行在後面接著形成配線時之加熱處理等之觸控面板形成用之加熱退火處理。 In the case of application to a touch panel, the substrate 50 with the transparent electrode is preferably subjected to heat treatment to crystallize the transparent electrode layer. The heat treatment for crystallization is carried out, for example, in an oven at 120 ° C to 150 ° C for 30 to 60 minutes. Alternatively, it is possible to carry out heating for a long period of time at a relatively low temperature such as 85 ° C to 120 ° C and 1 to 3 days. The heat treatment of the transparent electrode layer may be performed before or after patterning of the transparent electrode layer. In addition, the heat treatment of the transparent electrode layer may be performed by a heat annealing treatment for forming a touch panel which is subjected to heat treatment or the like in the subsequent formation of wiring.

附有透明電極之基板50係透明電極層30進行圖案化而成為電極形成部30a和電極非形成部30b來使用。圖案化係例如藉由在形成透明電極層之後，於面內之一部分，以蝕刻等，來除去透明電極層，而進行圖案化。 The substrate 50 with the transparent electrode is patterned by the transparent electrode layer 30, and is used as the electrode forming portion 30a and the electrode non-forming portion 30b. The patterning is performed by, for example, removing the transparent electrode layer by etching or the like in one of the in-plane portions after forming the transparent electrode layer.

作為透明電極層之蝕刻方法係可以是濕式製程和乾式製程之任何一種，但是，由所謂容易呈選擇性地僅除去透明電極層30之觀點來看的話，則適合為濕式製程。本發明之附有透明電極之基板係在圖案化透明電極層之後，不容易發生沿著圖案之皺紋。因此，不容易辨識圖案，可以提高畫面之辨識性。 The etching method as the transparent electrode layer may be either a wet process or a dry process, but it is suitable as a wet process from the viewpoint of easily removing only the transparent electrode layer 30 selectively. The substrate with the transparent electrode of the present invention does not easily cause wrinkles along the pattern after patterning the transparent electrode layer. Therefore, it is not easy to recognize the pattern, and the visibility of the picture can be improved.

在觸控面板之形成，藉由在附有透明電極之基板上，塗佈導電性油墨或糊膏，進行熱處理，而形成作為環繞電路用配線之集電極。加熱處理之方法係並無特別限定，列舉藉由烤箱或IR加熱器等而造成之加熱方法。加熱處理之溫度．時間係考慮導電性糊膏附著於透明電極之溫度．時間而適度地設 定。如果是例如藉由烤箱而造成之加熱的話，如果是在120~150℃、30~60分鐘、藉由IR加熱器而造成之加熱的話，則列舉在150℃、5分鐘等之例子。此外，環繞電路用配線之形成方法係並非限定於前面之敘述，可以藉由乾式塗佈法而形成。此外，可以藉由以光微影，來形成環繞電路用配線，而進行配線之細線化。 In the formation of the touch panel, a conductive ink or a paste is applied onto a substrate having a transparent electrode, and heat treatment is performed to form a collecting electrode as a wiring for the surrounding circuit. The method of heat treatment is not particularly limited, and a heating method by an oven or an IR heater or the like is exemplified. Heat treatment temperature . The time is based on the temperature at which the conductive paste adheres to the transparent electrode . Time is set appropriately. In the case of heating by an oven, for example, if it is heated by an IR heater at 120 to 150 ° C for 30 to 60 minutes, it is exemplified by 150 ° C, 5 minutes, and the like. Further, the method of forming the wiring for the surrounding circuit is not limited to the above description, and can be formed by a dry coating method. Further, the wiring for the surrounding circuit can be formed by photolithography, and the wiring can be thinned.

【實施例】 [Examples]

在以下，列舉實施例，更加具體地說明本發明，但是，本發明係並非限定於這些實施例。 The present invention will be more specifically described below by way of examples, but the present invention is not limited to these examples.

各介電質層及透明電極層之膜厚係藉由附有透明電極之基板剖面之穿透型電子顯微鏡(TEM)之觀察而求出。 The film thickness of each of the dielectric layer and the transparent electrode layer was determined by observation of a transmission electron microscope (TEM) of a cross section of a substrate with a transparent electrode.

熱收縮率係藉由在試料，以10mm間隔，來打開2點之孔，以三次元測長器，來測定在150℃進行30分鐘之加熱前之2點間之距離L0和在加熱後之2點間之距離L，而求出熱收縮率。 The heat shrinkage rate was measured by measuring the distance L 0 between the two points before heating at 150 ° C for 30 minutes by opening a hole of 2 points at a distance of 10 mm in the sample, and measuring the length of the material by a three-dimensional length measuring device at 150 ° C for 30 minutes. The distance R between the two points is used to determine the heat shrinkage rate.

[實施例1] [Example 1]

作為透明薄膜係使用在兩面形成由胺基甲酸乙酯系樹脂而組成之硬塗佈層(折射率1.53)之厚度125μm之PET薄膜。該PET薄膜之150℃進行30分鐘加熱時之熱收縮率係MD方向為0.73%，TD方向為0.56%。該透明薄膜係導入至圖2呈示意地顯示之捲繞式濺鍍製膜裝置內。 As the transparent film, a PET film having a thickness of 125 μm in which a hard coat layer (refractive index: 1.53) composed of a urethane resin was formed on both surfaces was used. The heat shrinkage rate of the PET film at 150 ° C for 30 minutes was 0.73% in the MD direction and 0.56% in the TD direction. This transparent film is introduced into the wound sputter film forming apparatus schematically shown in Fig. 2 .

然後，一旦在基材準備室內來減壓至5×10-4Pa為止之後，以基材準備室內之壓力0.5Pa，來搬送薄膜，同時，進行薄膜之加熱。基材準備室201內之加熱器之溫度係240℃， 藉由附加於薄膜表面之熱標記而測定之薄膜表面溫度係82℃。加熱時間(薄膜搬送於加熱器間之時間)係20秒鐘。 Then, once the pressure was reduced to 5 × 10 -4 Pa in the substrate preparation chamber, the film was conveyed at a pressure of 0.5 Pa in the substrate preparation chamber, and the film was heated. The temperature of the heater in the substrate preparation chamber 201 was 240 ° C, and the film surface temperature measured by thermal labeling attached to the surface of the film was 82 ° C. The heating time (the time the film was transported between the heaters) was 20 seconds.

加熱處理後之透明薄膜係連續地搬送至製膜室，在製膜壓輥260之上，依序地製膜作為第一透明介電質層之SiOx、作為第二透明介電質層之Nb2O5、作為第三介電質層之SiO2以及作為透明電極層之ITO。製膜時之基板溫度係-20℃。 The transparent film after the heat treatment is continuously transferred to the film forming chamber, and SiO x as the first transparent dielectric layer is sequentially formed on the film forming press roll 260 as the second transparent dielectric layer. Nb 2 O 5 , SiO 2 as a third dielectric layer, and ITO as a transparent electrode layer. The substrate temperature at the time of film formation was -20 °C.

第一介電質層係使用B-Si，來作為標靶，將氧/氬(20sccm/400sccm)混合氣體，導入至製膜室內，同時，以裝置內壓力0.2Pa、功率密度1.4W/cm2之條件，來進行製膜。第二介電質層係使用鈮(Nb)，來作為標靶，將氧/氬(160sccm/1600sccm)混合氣體，導入至製膜室內，同時，以裝置內壓力0.87Pa、基板溫度-20℃、功率密度8.1W/cm2之條件，來進行製膜。第三介電質層係使用B-Si，來作為標靶，將氧/氬(190sccm/400sccm)混合氣體，導入至裝置內，同時，以裝置內壓力0.2Pa、功率密度10.2W/cm2之條件，來進行製膜。 The first dielectric layer uses B-Si as a target, and an oxygen/argon (20 sccm/400 sccm) mixed gas is introduced into the film forming chamber, and at the same time, the device has a pressure of 0.2 Pa and a power density of 1.4 W/cm. 2 conditions, to film. The second dielectric layer is made of neodymium (Nb) as a target, and an oxygen/argon (160 sccm/1600 sccm) mixed gas is introduced into the film forming chamber, and at the same time, the internal pressure of the device is 0.87 Pa, and the substrate temperature is -20 ° C. The film was formed under the conditions of a power density of 8.1 W/cm 2 . The third dielectric layer uses B-Si as a target, and an oxygen/argon (190 sccm/400 sccm) mixed gas is introduced into the apparatus, and at the same time, the internal pressure of the apparatus is 0.2 Pa, and the power density is 10.2 W/cm 2 . The conditions are used to form a film.

透明電極層係使用氧化銦和氧化錫之燒結標靶，將氧/氬(2sccm/1000sccm)混合氣體，導入至裝置內，同時，以裝置內壓力0.4Pa、功率密度5.2W/cm2之條件來進行。製膜室內之質量數28之氣體分壓P28相對於惰性氣體(氬氣)之分壓PI之比值P28/PI係4.7×10-4。像這樣而得到在透明薄膜上具備介電質層和透明電極層之附有透明電極之基板。 The transparent electrode layer is a sintered target of indium oxide and tin oxide, and an oxygen/argon (2 sccm/1000 sccm) mixed gas is introduced into the apparatus, and the pressure inside the apparatus is 0.4 Pa and the power density is 5.2 W/cm 2 . Come on. The ratio of the gas partial pressure P 28 of the mass number 28 in the film forming chamber to the partial pressure P I of the inert gas (argon gas) P 28 /P I is 4.7 × 10 -4 . In this manner, a substrate having a transparent electrode provided with a dielectric layer and a transparent electrode layer on a transparent film was obtained.

(藉由X射線繞射而造成之結晶特性之評價) (Evaluation of crystallization characteristics caused by X-ray diffraction)

該附有透明電極之基板係在150℃之烤箱內，進行 30分鐘之加熱，進行透明電極層之結晶化。在將結晶化後之附有透明電極之薄膜之在in-plane(平面內)測定之面間隔din和在out-plane(平面外)測定之(222)面之面間隔dout之比值dout/din予以測定之時，成為1.001。此外，(440)面之繞射角之差異2θ-2θ0係0.30°。 The substrate with the transparent electrode was heated in an oven at 150 ° C for 30 minutes to crystallize the transparent electrode layer. After crystallization in the film of the transparent electrodes with the measurement of (222) (out of plane) in the out-plane of the measurement surface (a plane) in-plane spacing d in the plane and the plane spacing d OUT ratio of d When out /d in is measured, it becomes 1.001. Further, the difference of the diffraction angle of the (440) plane is 2θ-2θ 0 is 0.30°.

此外，X射線繞射係使用具備Cu．Kα射線來作為X射線源之X射線繞射測定裝置(Rigaku公司製、「SmartLab」)而進行測定。平行於膜面之方向之面間隔之測定(out-plane(平面外)測定)係以對稱軸ω來作為0.4°(原點中心)，藉由薄膜測定法(2θ測定)，以X射線強度45kV．200mA、角度區域2θ=25°~62°、掃描速度1.000°/分鐘、取樣間隔0.0400°之條件，而進行測定。直交於膜面之方向之面間隔之測定(in-plane(平面內)測定)係變更成為掃描速度0.400°/分鐘、取樣間隔0.0400°，ω之角度係設定成為相同於out-plane(平面外)測定時之相同角度而進行測定。 In addition, the X-ray diffraction system uses Cu . The Kα ray was measured by an X-ray diffraction measuring apparatus ("SmartLab" manufactured by Rigaku Co., Ltd.) as an X-ray source. The measurement of the interplanar spacing in the direction parallel to the film surface (out-plane measurement) is 0.4° (center of origin) with the axis of symmetry ω, and the X-ray intensity is determined by the thin film measurement method (2θ measurement). 45kV . The measurement was carried out under the conditions of 200 mA, an angle region 2θ=25° to 62°, a scanning speed of 1.000°/min, and a sampling interval of 0.0400°. The measurement of the interplanar spacing in the direction perpendicular to the film surface (in-plane measurement) was changed to a scanning speed of 0.400°/min and a sampling interval of 0.0400°, and the angle of ω was set to be the same as out-plane (out-of-plane). The measurement was carried out at the same angle at the time of measurement.

[實施例2] [Embodiment 2]

藉由加熱用加熱器之溫度，變更成為400℃，以加熱器來造成之加熱時間，變更成為25秒鐘，而使得加熱處理之薄膜表面溫度，成為90℃。此外，第一介電質層和第三介電質層之裝置內壓力係變更成為0.1Pa。除了這些變更以外，其餘係相同於前述實施例1而得到附有透明電極之基板。此外，在實施例2，藉由改變透明介電質層和透明電極層之製膜(堆積)速度，而進行調整，使得各層之膜厚相同於實施例1。在藉由相同於實施例1之同樣方法而使得該附有透明電極之基板 來進行結晶化之後，在測定(222)面之面間隔比dout/din之時，成為0.999。 The temperature of the heating heater was changed to 400 ° C, and the heating time by the heater was changed to 25 seconds, and the surface temperature of the film subjected to the heat treatment was 90 ° C. Further, the pressure in the apparatus of the first dielectric layer and the third dielectric layer was changed to 0.1 Pa. Except for these changes, the same substrate as in the above Example 1 was obtained to obtain a substrate with a transparent electrode. Further, in Example 2, the film formation (stacking) speed of the transparent dielectric layer and the transparent electrode layer was changed, and the film thickness of each layer was the same as in Example 1. After the substrate having the transparent electrode was crystallized by the same method as in Example 1, the surface area ratio d out /d in when the (222) plane was measured was 0.999.

[實施例3] [Example 3]

藉由減小薄膜之搬送速度而使得以加熱器來造成之加熱時間，成為4倍，隨著這樣而使得加熱處理之薄膜表面溫度，成為99℃。另外，相同於前述實施例1而得到附有透明電極之基板。此外，在實施例3，藉由改變透明介電質層和透明電極層之製膜(堆積)速度，而進行調整，使得各層之膜厚相同於實施例1。在藉由相同於實施例1之同樣方法而使得該附有透明電極之基板來進行結晶化之後，在測定(222)面之面間隔比dout/din之時，成為0.998。 By reducing the transport speed of the film, the heating time by the heater is four times, and as a result, the surface temperature of the film subjected to the heat treatment is 99 °C. Further, a substrate with a transparent electrode was obtained in the same manner as in the above Example 1. Further, in Example 3, the film formation (stacking) speed of the transparent dielectric layer and the transparent electrode layer was changed so that the film thickness of each layer was the same as in Example 1. After the substrate having the transparent electrode was crystallized by the same method as in Example 1, the surface area ratio d out /d in when the (222) plane was measured was 0.998.

[實施例4、5] [Examples 4 and 5]

在實施例4，在兩面形成由胺基甲酸乙酯系樹脂而組成之硬塗佈層(折射率1.53)來作為透明薄膜之厚度125μm之PET薄膜係在導入至製膜裝置之前，進行加熱處理，進行低熱收縮率化。在實施例5，藉由在更加高於實施例4之高溫，加熱PET薄膜，而得到更加低之熱收縮率之PET薄膜。 In Example 4, a PET film having a thickness of 125 μm as a transparent film formed of a hard coat layer (refractive index: 1.53) composed of a urethane-based resin on both surfaces was heat-treated before being introduced into a film forming apparatus. , low heat shrinkage rate. In Example 5, a PET film having a lower heat shrinkage rate was obtained by heating the PET film at a temperature higher than that of Example 4.

這些低熱收縮率化之PET薄膜係使用作為透明薄膜。另外，相同於實施例1而製膜介電質層和透明電極層。在藉由相同於實施例1之同樣方法而使得在實施例5得到之附有透明電極之基板來進行結晶化之後，在測定(222)面之面間隔比dout/din之時，成為0.999。 These low heat shrinkage PET films are used as transparent films. Further, a dielectric layer and a transparent electrode layer were formed in the same manner as in Example 1. After crystallization was performed on the substrate with the transparent electrode obtained in Example 5 by the same method as in Example 1, when the surface spacing ratio d out /d in of the (222) plane was measured, 0.999.

[實施例6] [Embodiment 6]

藉由形成硬塗佈層之透明薄膜之厚度，來變更成 為100μm，加熱器之溫度，變更成為230℃，而使得加熱處理之薄膜表面溫度，成為85℃。另外，相同於前述實施例1而得到附有透明電極之基板。在藉由相同於實施例1之同樣方法而使得該附有透明電極之基板來進行結晶化之後，在測定(222)面之面間隔dout之比值dout/din之時，成為1.000。 The thickness of the transparent film forming the hard coat layer was changed to 100 μm, and the temperature of the heater was changed to 230 ° C, and the surface temperature of the film subjected to the heat treatment was 85 ° C. Further, a substrate with a transparent electrode was obtained in the same manner as in the above Example 1. After the substrate having the transparent electrode was crystallized by the same method as in Example 1, the ratio d out /d in when the surface spacing d out of the (222) plane was measured was 1.000.

[比較例1] [Comparative Example 1]

加熱用加熱器係成為截止(off)狀態，無進行製膜前之加熱。另外，相同於前述實施例1而得到附有透明電極之基板。透明電極層之製膜室內之質量數28之氣體分壓P28相對於惰性氣體(氬氣)之分壓PI之比值P28/PI係5.7×10-3。 The heater for heating is turned off, and heating before film formation is not performed. Further, a substrate with a transparent electrode was obtained in the same manner as in the above Example 1. The ratio of the gas partial pressure P 28 of the mass number 28 of the transparent electrode layer to the partial pressure P I of the inert gas (argon gas) P 28 /P I is 5.7 × 10 -3 .

[比較例2] [Comparative Example 2]

加熱用加熱器係成為截止(off)狀態，無進行製膜前之加熱。另外，相同於前述實施例4而得到附有透明電極之基板。 The heater for heating is turned off, and heating before film formation is not performed. Further, a substrate with a transparent electrode was obtained in the same manner as in the above Example 4.

[比較例3] [Comparative Example 3]

藉由加熱用加熱器之溫度，變更成為120℃，而使得加熱處理之薄膜表面溫度，成為60℃。另外，相同於前述實施例4而得到附有透明電極之基板。 The temperature of the heater for heating was changed to 120 ° C, and the surface temperature of the film subjected to heat treatment was 60 ° C. Further, a substrate with a transparent electrode was obtained in the same manner as in the above Example 4.

[比較例4] [Comparative Example 4]

將透明薄膜導入至捲繞式濺鍍製膜裝置內，在基材準備室內來減壓至5×10-4Pa為止之後，在製膜用壓輥來調溫成為溫度70℃之狀態，以基材準備室內之壓力0.5Pa，來搬送薄膜，藉由來自製膜用壓輥之熱能而進行透明薄膜之加熱。在此時，無進行對於透明薄膜上之製膜，藉由基材準備室內之捲 繞用壓輥而一旦捲繞加熱後之薄膜。藉由製膜用壓輥而造成之加熱處理時之薄膜表面溫度係40℃。 The transparent film is introduced into a wound sputter film forming apparatus, and after being decompressed to a pressure of 5 × 10 -4 Pa in the substrate preparation chamber, the temperature is adjusted to a temperature of 70 ° C by a film forming press roll. The pressure in the substrate preparation chamber was 0.5 Pa, and the film was conveyed, and the transparent film was heated by the heat energy from the film forming press roll. At this time, the film formed on the transparent film was not subjected to the winding of the substrate by the substrate, and the heated film was wound once. The surface temperature of the film at the time of heat treatment by the press roll for film formation was 40 °C.

[比較例5] [Comparative Example 5]

在製膜用壓輥來調溫成為80℃之狀態，相同於前述比較例4而嘗試進行在製膜用壓輥上之透明薄膜之加熱，但是，搬送用張力係變得不安定，在捲繞體，發生顯著之捲繞偏離，因此，無法進行其後面之製膜。 In the state in which the temperature was adjusted to 80 ° C by the pressure roller for film formation, the heating of the transparent film on the film forming roller was attempted in the same manner as in the above-mentioned Comparative Example 4. However, the tension for conveyance was unstable, and the film was rolled. A significant winding deviation occurs in the winding body, and therefore, film formation behind it cannot be performed.

[評價] [Evaluation] (圖案皺紋之評價) (evaluation of pattern wrinkles)

由在各實施例及比較例(除了比較例5以外)來得到之附有透明電極之薄膜，切出10cm角之薄片狀之薄膜。切出之薄膜係在150℃之烤箱內，進行30分鐘之加熱，透明電極層進行結晶化。 A film having a transparent electrode obtained in each of Examples and Comparative Examples (excluding Comparative Example 5) was cut out into a sheet-like film having a corner of 10 cm. The cut film was heated in an oven at 150 ° C for 30 minutes, and the transparent electrode layer was crystallized.

然後，進行藉由光微影而造成之透明電極層之圖案化。首先，在透明電極層上藉由旋轉塗佈而以大約2μm程度之膜厚來塗佈光阻劑(製品名稱：TSMR-8900(東京應化工業公司製))之後，在90℃之烤箱，進行預烘烤。透過光罩而照射40mJ之紫外線。然後，在110℃對於光阻劑層來進行後烘烤之後，使用顯影液(製品名稱：NMD-W(東京應化工業公司製))而進行圖案化。此外，使用蝕刻液(製品名稱：ITO02(關東化學公司製))而蝕刻透明電極層。最後，使用漂洗液(製品名稱：104(東京應化工業公司製))而除去殘留之光阻劑。 Then, patterning of the transparent electrode layer by photolithography is performed. First, a photoresist (product name: TSMR-8900 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) is applied to the transparent electrode layer by spin coating at a film thickness of about 2 μm, and then in an oven at 90 ° C, Pre-bake. Ultraviolet rays of 40 mJ were irradiated through a mask. Then, after the post-baking of the photoresist layer at 110 ° C, the developer (product name: NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) was used for patterning. Further, the transparent electrode layer was etched using an etching solution (product name: ITO02 (manufactured by Kanto Chemical Co., Ltd.)). Finally, the residual photoresist was removed using a rinse liquid (product name: 104 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)).

藉由目視而評價透明電極層之有無圖案皺紋。以 進行配置而使得透明電極層之圖案形成方向和直管式螢光燈之反射光呈概略直交之狀態，觀察來自螢光燈之反射光，以呈直線狀地看見螢光燈之反射像者，來作為A(無皺紋)，以看見反射線呈顯著地歪斜者，來作為E，藉由A~E之5階段而進行評價。將使用在實施例及比較例之附有透明電極之基板製造之透明薄膜之熱收縮率、加熱製程之加熱溫度、加熱時間及薄膜表面溫度、透明介電質層中之矽氧化物製膜時之製膜壓力、以及附有透明電極之基板之熱收縮率和藉由目視而造成之皺紋之評價結果，顯示於表1。 The presence or absence of pattern wrinkles of the transparent electrode layer was evaluated by visual observation. Take The arrangement is such that the pattern forming direction of the transparent electrode layer and the reflected light of the straight tube type fluorescent lamp are in a state of being substantially orthogonal, and the reflected light from the fluorescent lamp is observed to visually observe the reflected image of the fluorescent lamp. As A (no wrinkles), to see that the reflection line is significantly skewed, as E, it is evaluated by the five stages of A~E. The heat shrinkage rate of the transparent film produced by the substrate with the transparent electrode of the examples and the comparative examples, the heating temperature of the heating process, the heating time, the film surface temperature, and the ruthenium oxide film in the transparent dielectric layer were used. The film formation pressure, the heat shrinkage ratio of the substrate with the transparent electrode, and the evaluation results of wrinkles by visual observation are shown in Table 1.

由表1之結果而得知：在透明介電質層和透明電極層之製膜前，藉由以非接觸之加熱器，來進行加熱，而抑制 在透明電極層來進行圖案化之際之皺紋之發生。由實施例1和實施例3及比較例3之對比而得知：藉由提高加熱之溫度而更加地抑制附有透明電極之基板之皺紋。此外，由實施例2和實施例3之對比而得知：除了提高薄膜之表面溫度以外，還在成為介電質層之矽氧化物層之製膜壓力變小之狀態下，更加地抑制附有透明電極之基板之皺紋。由實施例1和實施例6之對比，也看見相同之傾向。 It is known from the results of Table 1 that before the film formation of the transparent dielectric layer and the transparent electrode layer, heating is performed by a non-contact heater to suppress The occurrence of wrinkles at the time of patterning on the transparent electrode layer. From the comparison between Example 1 and Example 3 and Comparative Example 3, it was found that the wrinkles of the substrate with the transparent electrode were more suppressed by increasing the temperature of heating. Further, from the comparison between the second embodiment and the third embodiment, it is known that, in addition to the surface temperature of the film, the film formation pressure of the tantalum oxide layer which becomes the dielectric layer becomes smaller, and the adhesion is further suppressed. Wrinkles of the substrate with transparent electrodes. From the comparison of Example 1 and Example 6, the same tendency was also seen.

此外，由實施例1和實施例4及實施例5之對比而得知：也藉由使用熱收縮量變小者，來作為在導入至濺鍍製膜裝置前之透明薄膜，而更加地抑制附有透明電極之基板之皺紋。 Further, from the comparison between Example 1 and Example 4 and Example 5, it is also known that the amount of heat shrinkage is reduced as a transparent film which is introduced before the sputtering film forming apparatus, and the adhesion is further suppressed. Wrinkles of the substrate with transparent electrodes.

另一方面，在比較例2，使用相同於實施例4之同樣之低熱收縮化之透明薄膜，但是，在製膜前，並無進行加熱處理，因此，在附有透明電極之基板，看見皺紋之發生。由這些結果而得知：在僅使用低熱收縮量之基材，並無充分地抑制皺紋，在製膜前而進行加熱製程係變得重要。 On the other hand, in Comparative Example 2, the same low heat shrinkable transparent film as in Example 4 was used, but no heat treatment was performed before the film formation, and therefore wrinkles were observed on the substrate with the transparent electrode. It happened. From these results, it has been found that the use of a substrate having a low heat shrinkage amount does not sufficiently suppress wrinkles, and it is important to carry out a heating process system before film formation.

無法藉由在捲繞式濺鍍製膜裝置內，重複地捲回透明薄膜，來在製膜壓輥上而進行加熱之比較例4，抑制附有透明電極之基板之皺紋之發生。由以上之結果而得知：在本發明，藉由在高溫，進行短時間之非接觸加熱，而抑制皺紋之發生。 Comparative Example 4 in which the transparent film was repeatedly wound back in the roll-type sputtering film forming apparatus and heated on the film forming roll was not able to suppress the occurrence of wrinkles in the substrate with the transparent electrode. From the above results, it is known that in the present invention, the occurrence of wrinkles is suppressed by performing non-contact heating for a short period of time at a high temperature.

此外，得知：各實施例之透明電極層係在結晶化後之(222)面之面間隔之in-plane(平面內)測定和out-plane(平面外)測定之比值dout/din接近於1，因此，在藉由加熱 而進行結晶化後之氧化銦結晶之歪斜係變小。認為由於這些結果，因此，在本發明之附有透明電極之基板，藉由在透明電極層之製膜前，進行規定之加熱處理，而在透明電極層之結晶化之際，抑制由於賦予至透明電極層之應力來造成之歪斜之發生，為了減小在透明電極層和薄膜之間之界面之應力，因此，抑制在透明電極層來進行圖案化之際之皺紋之發生。 Further, it was found that the transparent electrode layers of the respective examples are in-plane (in-plane) measurement and out-plane (out-of-plane) measurement ratio d out /d in in the plane interval of the (222) plane after crystallization. When it is close to 1, the skew of the indium oxide crystal which is crystallized by heating becomes small. According to these results, in the substrate with the transparent electrode of the present invention, predetermined heat treatment is performed before the formation of the transparent electrode layer, and the crystallization of the transparent electrode layer is suppressed. The occurrence of skew due to the stress of the transparent electrode layer, in order to reduce the stress at the interface between the transparent electrode layer and the film, suppresses the occurrence of wrinkles when the transparent electrode layer is patterned.

10‧‧‧透明薄膜 10‧‧‧Transparent film

11‧‧‧基底薄膜 11‧‧‧Base film

12、13‧‧‧硬塗佈層 12, 13‧‧‧ hard coating layer

20‧‧‧透明介電質層 20‧‧‧Transparent dielectric layer

21~23‧‧‧透明介電質層 21~23‧‧‧Transparent dielectric layer

30‧‧‧透明電極層 30‧‧‧Transparent electrode layer

50‧‧‧附有透明電極之基板 50‧‧‧Substrate with transparent electrode

Claims (12)

一種附有透明電極之基板的製造方法，將使用捲繞式濺鍍製膜裝置而在透明薄膜上具備由金屬氧化物薄膜來組成之透明電極層之附有透明電極之基板予以製造，其特徵在於：前述捲繞式濺鍍裝置係具備基材準備室和製膜室，在前述基材準備室內，設置加熱部，具有：將透明薄膜之壓輥狀捲繞體，來導入至捲繞式濺鍍製膜裝置之基材準備室內之基材準備製程；在前述基材準備室內，由前述壓輥狀捲繞體開始，來抽出前述透明薄膜，進行搬送，同時，藉由來自前述加熱部之熱能而進行加熱處理，成為表面溫度80℃~160℃之加熱製程；以及在前述捲繞式濺鍍製膜裝置之製膜室內，導入惰性氣體，同時，在加熱處理後之前述透明薄膜上，形成由非結晶質金屬氧化物薄膜而組成之透明電極層之透明電極層製膜製程；前述加熱製程及前述透明電極層製膜製程係不由前述捲繞式濺鍍製膜裝置來取出透明薄膜而連續地進行，在前述加熱製程，前述透明薄膜和前述加熱部係呈無接觸地進行前述加熱處理，前述加熱製程之基材準備室內之壓力係1.0Pa以下。 A method for producing a substrate with a transparent electrode, which is manufactured by using a wound sputter film forming apparatus and having a transparent electrode layer composed of a metal oxide film on a transparent film, which is provided with a transparent electrode. In the above-described wound-type sputtering apparatus, a substrate preparation chamber and a film forming chamber are provided, and a heating unit is provided in the substrate preparation chamber, and a roll-shaped wound body of a transparent film is introduced into the roll-up type. a substrate preparation process in a substrate preparation chamber of a plating film forming apparatus; in the substrate preparation chamber, the transparent film is taken out by the press roll-shaped winding body, and is transported, and is carried out by the heating portion Heating treatment by thermal energy to form a heating process having a surface temperature of 80 ° C to 160 ° C; and introducing an inert gas into the film forming chamber of the wound sputter film forming apparatus, and simultaneously on the transparent film after the heat treatment a transparent electrode layer forming process for forming a transparent electrode layer composed of an amorphous metal oxide film; the heating process and the transparent electrode layer film forming process are not The winding type sputtering film forming apparatus continuously performs the removal of the transparent film, and in the heating process, the transparent film and the heating unit perform the heat treatment without contact, and the substrate of the heating process prepares the pressure in the chamber. It is 1.0 Pa or less. 如申請專利範圍第1項之附有透明電極之基板的製造方法，其中，在前述加熱製程後，在加熱處理後之前述透明 薄膜來捲繞成為壓輥狀之前，於前述製膜室內，接著後續進行前述透明電極層製膜製程。 The method for manufacturing a substrate with a transparent electrode according to the first aspect of the patent application, wherein the transparent process after the heat treatment is performed after the heating process Before the film is wound into a roll shape, the transparent electrode layer forming process is subsequently performed in the film forming chamber. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述加熱製程，前述透明薄膜之加熱時間係0.1秒鐘~600秒鐘。 The method for producing a substrate having a transparent electrode according to the first or second aspect of the invention, wherein the heating period of the transparent film is 0.1 second to 600 seconds. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述加熱製程，前述加熱部之溫度係150℃~500℃。 A method for producing a substrate having a transparent electrode according to the first or second aspect of the invention, wherein the heating portion has a temperature of 150 ° C to 500 ° C in the heating process. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述透明電極層製膜製程，前述製膜室內之質量數28之氣體分壓P28相對於惰性氣體之分壓PI之比值P28/PI係5×10-4以下。 The method for producing a substrate with a transparent electrode according to the first or second aspect of the invention, wherein the gas partial pressure P 28 of the mass number 28 in the film forming chamber is opposite to the inert gas in the transparent electrode layer forming process The ratio P 28 /P I of the partial pressure P I is 5 × 10 -4 or less. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述捲繞式濺鍍製膜裝置之前述基材準備室內，沿著薄膜搬送方向而設置複數個之加熱部，在前述加熱部之間，設置搬送用壓輥，藉由來自前述複數個加熱部之熱能而進行前述加熱處理。 The method for producing a substrate having a transparent electrode according to the first or second aspect of the invention, wherein the plurality of substrates are provided in the substrate preparation chamber of the wound sputter film forming apparatus along the film transport direction. In the portion, a transfer pressure roller is provided between the heating portions, and the heat treatment is performed by thermal energy from the plurality of heating portions. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述加熱製程和前述透明電極層製膜製程之間，還具有透明介電質層形成製程，在前述透明介電質層形成製程，在前述透明薄膜上，藉由濺鍍法而形成至少一層之透明介電質層。 The method for manufacturing a substrate with a transparent electrode according to the first or second aspect of the invention, wherein a transparent dielectric layer forming process is further provided between the heating process and the transparent electrode layer film forming process, A dielectric layer forming process is formed on the transparent film by at least one transparent dielectric layer by sputtering. 如申請專利範圍第7項之附有透明電極之基板的製造方法，其中，在前述透明介電質層形成製程，形成由至少一 層之矽氧化物層而組成之介電質層。 The method for manufacturing a substrate with a transparent electrode according to claim 7, wherein the transparent dielectric layer forming process is formed by at least one A dielectric layer composed of a layer of tantalum oxide. 如申請專利範圍第7項之附有透明電極之基板的製造方法，其中，在前述透明介電質層形成製程，在前述透明薄膜上，依照該順序地形成折射率1.45~1.95之第一透明介電質層、折射率2.00~2.35之第二透明介電質層以及由矽氧化物而組成之第三透明介電質層。 The method for manufacturing a substrate with a transparent electrode according to the seventh aspect of the invention, wherein in the transparent dielectric layer forming process, the first transparent film having a refractive index of 1.45 to 1.95 is formed in the transparent film. a dielectric layer, a second transparent dielectric layer having a refractive index of 2.00 to 2.35, and a third transparent dielectric layer composed of a cerium oxide. 如申請專利範圍第7項之附有透明電極之基板的製造方法，其中，在前述透明介電質層形成製程，形成於透明電極層之正下方之透明介電質層係藉由0.4Pa以下之製膜壓力而進行製膜。 The method for manufacturing a substrate with a transparent electrode according to the seventh aspect of the invention, wherein the transparent dielectric layer forming process is performed under the transparent electrode layer, and the transparent dielectric layer is 0.4 Pa or less. The film formation pressure is carried out to form a film. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述基材準備製程，導入至濺鍍製膜裝置內之透明薄膜係在150℃、30分鐘之加熱時之MD方向之熱收縮率為0.4%以下。 The method for producing a substrate having a transparent electrode according to the first or second aspect of the invention, wherein the transparent film introduced into the sputtering film forming apparatus is heated at 150 ° C for 30 minutes in the substrate preparation process. The heat shrinkage rate in the MD direction is 0.4% or less. 如申請專利範圍第1或2項之附有透明電極之基板的製造方法，其中，在前述基材準備製程，導入至濺鍍製膜裝置內之透明薄膜係藉由熱機械分析而測定之熱收縮起始溫度為85℃以上。 The method for producing a substrate with a transparent electrode according to the first or second aspect of the invention, wherein the transparent film introduced into the sputtering film forming apparatus is heat measured by thermomechanical analysis in the substrate preparation process. The shrinkage onset temperature is 85 ° C or higher.
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