TW201342400A - Transparent conductive film - Google Patents
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- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
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- G—PHYSICS
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Abstract
Description
本發明係關於一種在透明薄膜基材上積層有以氧化銦為主的透明導電膜而成的透明導電性薄膜，尤其以本發明之透明導電性薄膜用於靜電容量式觸控面板時，由於透明導電性薄膜的比電阻低，在觸控面板的大型化與提高觸控靈敏度上很有效果。 The present invention relates to a transparent conductive film in which a transparent conductive film mainly composed of indium oxide is laminated on a transparent film substrate, and in particular, when the transparent conductive film of the present invention is used for an electrostatic capacitance type touch panel, The transparent conductive film has a low specific resistance and is effective in increasing the size of the touch panel and improving touch sensitivity.
於透明塑膠基材上積層透明且電阻小的薄膜而成的透明導電性薄膜，在利用到其導電性的用途，例如做為液晶顯示器或電致發光(EL)顯示器等那樣的平板顯示器、或觸控面板的透明電極，而被廣泛地使用在電機電子方面的用途。 a transparent conductive film obtained by laminating a transparent and low-resistance film on a transparent plastic substrate, for example, a flat panel display such as a liquid crystal display or an electroluminescence (EL) display, or The transparent electrode of the touch panel is widely used for motor electronics.
近年來，在行動電話、音樂攜帶型播放機等的攜帶型機器與汽車導航方面，搭載靜電容量式觸控面板已經普遍化。用於靜電容量式觸控面板的透明導電性基板主要是以添加氧化錫之氧化銦(ITO)積層於玻璃而成的透明導電性玻璃。透明導電性玻璃由於具有比透明導電性薄膜之比電阻更低等之優越性，故多被採用在靜電容量式觸控面板。 然而，透明導電性玻璃與透明導電性薄膜相較，既重且厚，並且有容易破裂的問題。 In recent years, in the case of portable devices such as mobile phones and music-carrying players and car navigation, electrostatic capacitive touch panels have been widely used. The transparent conductive substrate used for the electrostatic capacitance type touch panel is mainly a transparent conductive glass in which indium oxide (ITO) containing tin oxide is laminated on glass. Since the transparent conductive glass has an advantage of being lower than the specific resistance of the transparent conductive film, it is often used in a capacitive touch panel. However, the transparent conductive glass is heavy and thick compared with the transparent conductive film, and has a problem of being easily broken.
為了解決上述問題，比電阻低的透明導電性薄膜一直被探討著。為了代替透明導電性玻璃，透明導電性薄膜的比電阻期望為3.0×10-4 Ω.cm以下。依據專利文獻1~3，製作出比電阻為3.0×10-4 Ω.cm以下的透明導電性薄膜是可能的。然而，由於實施例中透明導電膜的膜厚較100nm厚，故會因透明導電膜的應力而使透明導電膜捲曲等在使用操作上有問題，並且由於要使透明導電膜成膜為厚度大於100nm，成本會增加致不適於產業上使用。因而，用專利文獻1~3的製造方法，將透明導電膜的膜厚做成薄達10~100nm而製作透明導電性薄膜之下，比電阻為大於3.0×10-4 Ω.cm，可知其做為代替透明導電性玻璃的透明導電性薄膜並不合乎期望。 In order to solve the above problems, a transparent conductive film having a lower specific resistance has been discussed. In place of the transparent conductive glass, the specific resistance of the transparent conductive film is desirably 3.0 × 10 -4 Ω·cm or less. According to Patent Documents 1 to 3, it is possible to produce a transparent conductive film having a specific resistance of 3.0 × 10 -4 Ω·cm or less. However, since the film thickness of the transparent conductive film is thicker than 100 nm in the embodiment, the transparent conductive film may be curled due to the stress of the transparent conductive film, and the like, and the transparent conductive film is formed to have a thickness larger than that. At 100 nm, the cost will increase and it will not be suitable for industrial use. Therefore, in the production method of Patent Documents 1 to 3, the film thickness of the transparent conductive film is made thinner by 10 to 100 nm to produce a transparent conductive film, and the specific resistance is more than 3.0 × 10 -4 Ω·cm. A transparent conductive film instead of a transparent conductive glass is not desirable.
〔專利文獻1〕日本特開平9-71857號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-71857
〔專利文獻2〕日本特開2000-144379號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-144379
〔專利文獻3〕國際公開第00/51139號 [Patent Document 3] International Publication No. 00/51139
鑑於上述之以往的問題，本發明之目的在於提供一種透明導電膜的比電阻低、且透明導電膜的膜厚薄的透明導電性薄膜。 In view of the above conventional problems, an object of the present invention is to provide a transparent conductive film having a low specific resistance and a thin film thickness of a transparent conductive film.
本發明係鑑於上述般的狀況而完成者，能夠解決上述問題之透明導電性薄膜係由下述構成所成。 The present invention has been made in view of the above-described circumstances, and a transparent conductive film capable of solving the above problems is obtained by the following constitution.
1.一種透明導電性薄膜，其特徵在於係在透明薄膜基材的至少一面上積層透明導電膜而成，在透明導電膜中除了含有氧化銦之外，還含有氧化錫8~15質量%，並且，透明導電膜的膜厚為10~100nm，透明導電膜係在基板溫度為-60~50℃以濺鍍法成膜，然後，在真空中、或惰性氣體及/或還原氣體中，在可維持透明薄膜基材形狀的溫度下進行熱處理，透明導電膜的比電阻為0.8×10-4~3.0×10-4 Ω.cm。 A transparent conductive film obtained by laminating a transparent conductive film on at least one surface of a transparent film substrate, and containing not more than indium oxide in addition to indium oxide, and containing 8 to 15% by mass of tin oxide. Further, the transparent conductive film has a film thickness of 10 to 100 nm, and the transparent conductive film is formed by sputtering at a substrate temperature of -60 to 50 ° C, and then in a vacuum or an inert gas and/or a reducing gas. The heat treatment is carried out at a temperature at which the shape of the transparent film substrate can be maintained, and the specific resistance of the transparent conductive film is 0.8 × 10 -4 to 3.0 × 10 -4 Ω·cm.
2.一種透明導電性薄膜，其特徵在於係在透明薄膜基材的至少一面上積層透明導電膜而成，在透明導電膜中除了含有氧化銦之外，還含有氧化錫8~15質量%，並且，透明導電膜的膜厚為10~100nm，透明導電膜的比電阻為0.8×10-4~3.0×10-4 Ω.Cm，且以下式(1)所定義的透明導電膜的穩定度指數為1.00~1.30； 2. A transparent conductive film obtained by laminating a transparent conductive film on at least one surface of a transparent film substrate, and containing not more than indium oxide in addition to indium oxide, and further containing 8 to 15% by mass of tin oxide. Further, the film thickness of the transparent conductive film is 10 to 100 nm, and the specific resistance of the transparent conductive film is 0.8 × 10 -4 to 3.0 × 10 -4 Ω·cm, and the stability of the transparent conductive film defined by the following formula (1) The index is 1.00~1.30;
(透明導電膜的穩定度指數)=A÷B...(1) (Stable stability index of transparent conductive film) = A÷B...(1)
A：使6.0莫耳/升的鹽酸成為25℃，將透明導電膜投入其中，浸漬30秒，然後浸漬於純水中10秒，在常溫下風乾1小時後的表面電阻。 A: The surface resistance of 6.0 mol/liter hydrochloric acid at 25 ° C, a transparent conductive film was put thereinto, immersed for 30 seconds, and then immersed in pure water for 10 seconds, and air-dried at normal temperature for 1 hour.
B：在投入25℃的6.0莫耳/升的鹽酸前的透明導電性薄膜的表面電阻。 B: Surface resistance of a transparent conductive film before 6.0 mol/liter hydrochloric acid at 25 ° C was charged.
依據本發明可提供一種透明導電膜的比電阻低、且透明導電膜的膜厚薄的透明導電性薄膜。本發明的透明導電性薄膜在靜電容量式觸控面板等用途上極有用。 According to the present invention, a transparent conductive film having a low specific resistance and a thin film thickness of a transparent conductive film can be provided. The transparent conductive film of the present invention is extremely useful for applications such as a capacitive touch panel.
本發明之透明導電性薄膜的透明導電膜中，較佳為除了氧化銦之外還含有氧化錫8~15質量%。氧化錫若低於8質量%，在對透明導電性薄膜進行熱處理時之透明導電性薄膜中的載體濃度會減低而比電阻會增高，故不佳。又，氧化錫若多於15質量%，在對透明導電性薄膜進行熱處理時之隨著透明導電膜的結晶化而生成的載體會減少，比電阻會增高，故不佳。於此，說明透明導電膜的結晶化之定義。在穿透型電子顯微鏡下觀察透明導電膜層時，具有多角形的區域為結晶，此外為非結晶。對相對於結晶質部的非結晶質部的比進行估計的方法，可由在穿透型電子顯微鏡下觀察時之結晶質部與非結晶質部的面積比算出。更佳為：在透明導電性薄膜的透明導電膜中更佳為除了氧化銦之外還含有氧化錫9~14質量%。 In the transparent conductive film of the transparent conductive film of the present invention, it is preferable to contain 8 to 15% by mass of tin oxide in addition to indium oxide. When the amount of the tin oxide is less than 8% by mass, the carrier concentration in the transparent conductive film when the transparent conductive film is heat-treated is lowered, and the specific resistance is increased, which is not preferable. In addition, when the amount of the tin oxide is more than 15% by mass, when the transparent conductive film is heat-treated, the carrier formed by the crystallization of the transparent conductive film is reduced, and the specific resistance is increased, which is not preferable. Here, the definition of crystallization of the transparent conductive film will be described. When the transparent conductive film layer is observed under a transmission electron microscope, the region having a polygonal shape is crystal, and further, it is amorphous. The method of estimating the ratio of the amorphous portion to the crystal portion can be calculated from the area ratio of the crystalline portion to the amorphous portion when observed under a transmission electron microscope. More preferably, the transparent conductive film of the transparent conductive film further contains 9 to 14% by mass of tin oxide in addition to indium oxide.
本發明之透明導電性薄膜的透明導電膜的膜厚，較佳為10~100nm。透明導電膜的膜厚若低於10nm，在對透明導電性薄膜進行熱處理時之透明導電膜的結晶化會變得困難，在對透明導電性薄膜進行熱處理時之隨著透明導電膜的結晶化而生成的載體會減少，比電阻會增高，故不佳。 透明導電膜的厚度若超過100nm，則因透明導電膜的應力，透明導電性薄膜會捲曲等在使用操作上不佳，並且由於將透明導電膜的膜厚成膜為大於100nm致成本較高故不佳，而且全光線透射率也降低故不佳。更佳為透明導電性薄膜的透明導電膜的膜厚為15~80nm。 The thickness of the transparent conductive film of the transparent conductive film of the present invention is preferably 10 to 100 nm. When the film thickness of the transparent conductive film is less than 10 nm, it is difficult to crystallize the transparent conductive film when the transparent conductive film is heat-treated, and the transparent conductive film is crystallized when the transparent conductive film is heat-treated. The generated carrier will be reduced, and the specific resistance will increase, so it is not good. When the thickness of the transparent conductive film exceeds 100 nm, the transparent conductive film may be curled due to the stress of the transparent conductive film, etc., and the operation is not preferable because the film thickness of the transparent conductive film is more than 100 nm. Poor, and the total light transmittance is also reduced, which is not good. More preferably, the transparent conductive film of the transparent conductive film has a film thickness of 15 to 80 nm.
本發明之透明導電性薄膜的透明導電膜之成膜時的基板溫度較佳為-60~50℃。本發明中所謂「基板」係指大致透明的薄膜基材，但也有於以透明導電膜進行積層前即在透明薄膜基材上塗布硬化型樹脂層、塗布光學調整膜或施行過成膜等的情況，包含其等透明薄膜基材單體及透明基材薄膜的事先做好的積層體，皆包含在內稱為「基板」。此處之「基板溫度」，係以控制基板溫度的冷卻器的調溫媒體的溫度代用。透明薄膜基材與玻璃或金屬等的無機基材的不同點在於其含有多量有機成分與水。因而，若基板溫度高於50℃，由於在進行透明導電膜之成膜時會自透明薄膜基材釋出大量的有機氣體與水，此等氣體會與透明導電膜反應而生成不均質的透明導電膜，故在對透明導電性薄膜進行熱處理時之透明導電膜的結晶化有困難，致使隨著在對透明導電性薄膜進行熱處理時之透明導電膜的結晶化而產生的載體會減少，比電阻增高，故不佳。基板溫度若為50℃以下，由於不易自透明薄膜基材釋出有機氣體與水，故可成膜形成均質的透明導電膜，由於在對透明導電性薄膜進行熱處理時之透明導電膜的結晶化變得容易，隨著在對透明導電性薄膜進行熱處理時之透明導電膜的結晶化而 產生的載體會增多，比電阻降低，故較佳。若要使基板溫度降低到低於-60℃，用一般的冷卻器會難以達成，在經濟考量上較不佳。更佳為基板溫度為-20~0℃。理由如下：若為水的熔點之0℃以下，則氣體的釋出變得非常少，故較佳。又，泛用冷卻器以最低溫度為-20℃以上者為多，故就經濟面考量較佳為-20℃以上。 The substrate temperature at the time of film formation of the transparent conductive film of the transparent conductive film of the present invention is preferably -60 to 50 °C. In the present invention, the term "substrate" means a substantially transparent film substrate. However, it is also possible to apply a curing resin layer, apply an optical adjustment film, or perform film formation to a transparent film substrate before laminating with a transparent conductive film. In the case, a laminate in which a transparent film substrate monomer and a transparent substrate film are prepared in advance is referred to as a "substrate". Here, the "substrate temperature" is a temperature substitute of a temperature control medium of a cooler that controls the temperature of the substrate. The transparent film substrate differs from an inorganic substrate such as glass or metal in that it contains a large amount of organic components and water. Therefore, if the substrate temperature is higher than 50 ° C, a large amount of organic gas and water are released from the transparent film substrate when the transparent conductive film is formed, and these gases react with the transparent conductive film to form an uneven transparency. Since the conductive film is difficult to crystallize the transparent conductive film when the transparent conductive film is heat-treated, the carrier generated by the crystallization of the transparent conductive film when the transparent conductive film is heat-treated is reduced. The resistance is increased, so it is not good. When the substrate temperature is 50° C. or less, since the organic gas and water are not easily released from the transparent film substrate, a homogeneous transparent conductive film can be formed into a film, and the transparent conductive film is crystallized during heat treatment of the transparent conductive film. It becomes easy, as the transparent conductive film is crystallized when heat-treating the transparent conductive film The number of carriers produced is increased, and the specific resistance is lowered, which is preferable. To reduce the substrate temperature to below -60 ° C, it is difficult to achieve with a general cooler, which is less economical. More preferably, the substrate temperature is -20 to 0 °C. The reason is as follows: If the melting point of water is 0 ° C or less, the release of gas is extremely small, which is preferable. Further, since the general-purpose cooler has a minimum temperature of -20 ° C or more, the economical consideration is preferably -20 ° C or more.
本發明之透明導電性薄膜的透明導電膜較佳為藉由濺鍍法成膜。由於濺鍍法容易生成均質且緻密的膜，故容易製作成比電阻低的透明導電膜。又，由於濺鍍法之膜厚分布優異，非常適合產業用，故較佳。 The transparent conductive film of the transparent conductive film of the present invention is preferably formed by sputtering. Since the sputtering method easily forms a homogeneous and dense film, it is easy to produce a transparent conductive film having a lower specific resistance. Further, since the sputtering method has excellent film thickness distribution and is very suitable for industrial use, it is preferable.
本發明之透明導電性薄膜，較佳為在真空中、或惰性氣體及/或還原氣體中，在可維持透明薄膜基材形狀的溫度下進行熱處理。在此說明本發明中之「可維持透明薄膜基材形狀的溫度」的定義。所謂「可維持透明薄膜基材形狀的溫度」，係在薄膜的動態黏彈性測定中，相對於在30℃的貯藏係數而言，貯藏彈性係數變成10%以上的溫度，且可維持透明薄膜基材形狀的溫度係設定為190℃以上的溫度。在低於190℃的熱處理，隨著透明導電膜的結晶化所產生的載體會減少，比電阻會變高，故不佳。因而，相對於在30℃的貯藏彈性係數而言，貯藏彈性係數為10%的溫度為低於190℃時，並非為適合於本發明的透明薄膜基材。若在較可維持透明薄膜基材形狀的溫度高的溫度，亦即，在薄膜的動態黏彈性測定中，相對於在30℃的貯藏彈性係數而言，貯藏彈性係數為10%以下的溫度，進行透明 薄膜之熱處理，則透明薄膜會變形，且透明薄膜會裂開，比電阻會增加，此外，會失去透明薄膜的平面性，故不佳。更佳為：可維持透明薄膜基材形狀的溫度，在薄膜的動態黏彈性測定中，相對於在30℃的貯藏彈性係數而言，貯藏彈性係數為12%以上的溫度，且可維持透明薄膜基材形狀的溫度為200℃以上。熱處理時間較佳為5~120分鐘。若熱處理低於5分鐘，隨著透明導電膜的結晶化而生成的載體會減少，比電阻會增高，故不佳。若進行120分鐘以上的熱處理，由於耗費成本，故不佳。 The transparent conductive film of the present invention is preferably subjected to heat treatment in a vacuum or an inert gas and/or a reducing gas at a temperature at which the shape of the transparent film substrate can be maintained. Here, the definition of "the temperature at which the shape of the transparent film substrate can be maintained" in the present invention will be described. The "temperature at which the shape of the transparent film substrate can be maintained" is a temperature at which the storage elastic modulus is 10% or more with respect to the storage coefficient at 30 ° C in the dynamic viscoelasticity measurement of the film, and the transparent film base can be maintained. The temperature of the material shape is set to a temperature of 190 ° C or higher. In the heat treatment of less than 190 ° C, the carrier generated by the crystallization of the transparent conductive film is reduced, and the specific resistance is increased, which is not preferable. Therefore, when the temperature at which the storage elastic modulus is 10% is less than 190 ° C with respect to the storage elastic modulus at 30 ° C, it is not suitable for the transparent film substrate of the present invention. If the temperature is higher than the temperature at which the shape of the transparent film substrate can be maintained, that is, in the dynamic viscoelasticity measurement of the film, the storage elastic modulus is 10% or less with respect to the storage elastic modulus at 30 ° C, Transparent When the film is heat-treated, the transparent film is deformed, and the transparent film is cracked, the specific resistance is increased, and the planarity of the transparent film is lost, which is not preferable. More preferably, the temperature of the shape of the transparent film substrate can be maintained. In the dynamic viscoelasticity measurement of the film, the storage elastic modulus is 12% or more with respect to the storage elastic modulus at 30 ° C, and the transparent film can be maintained. The temperature of the substrate shape is 200 ° C or higher. The heat treatment time is preferably from 5 to 120 minutes. If the heat treatment is less than 5 minutes, the carrier formed by the crystallization of the transparent conductive film is reduced, and the specific resistance is increased, which is not preferable. If the heat treatment is performed for 120 minutes or more, it is costly, which is not preferable.
將藉由前述方法成膜而成的透明導電性薄膜，在真空中、或惰性氣體及/或還原氣體中，在可維持透明薄膜基材形狀的溫度下進行熱處理，係與通常實施的在大氣中的熱處理有很大的不同。在大氣中的熱處理，會導致本發明那樣的添加氧化錫之氧化銦的透明導電膜之比電阻降低，也會導致增加。導致比電阻減低的原因在於，藉由熱處理，添加氧化錫之氧化銦會結晶化，此時錫會進入氧化銦的銦部位(site)，其結果會產生載體，因而使比電阻降低。而導致比電阻增加的原因在於，藉由熱處理，大氣中所含有的氧會填補添加氧化錫之氧化銦中的氧缺陷部位，其結果會導致載體消失而使比電阻上昇。 The transparent conductive film formed by the above method is subjected to heat treatment in a vacuum or an inert gas and/or a reducing gas at a temperature at which the shape of the transparent film substrate can be maintained, and is usually carried out in the atmosphere. The heat treatment in the process is very different. The heat treatment in the atmosphere causes a decrease in the specific resistance of the transparent conductive film in which tin oxide is added as in the present invention, and also causes an increase. The reason for the decrease in specific resistance is that indium oxide in which tin oxide is added is crystallized by heat treatment, and at this time, tin enters the indium site of indium oxide, and as a result, a carrier is generated, thereby lowering the specific resistance. The reason for the increase in the specific resistance is that the oxygen contained in the atmosphere fills the oxygen-defective portion of the indium oxide to which tin oxide is added by heat treatment, and as a result, the carrier disappears and the specific resistance increases.
在真空中或惰性氣體中的熱處理，與在大氣中的熱處理同樣地，藉由熱處理，添加氧化錫之氧化銦會結晶化，此時錫會進入氧化銦的銦部位，其結果會產生載體，因而使比電阻降低。又，在真空中、或惰性氣體中，由於不含 氧等之氧化氣體，故藉由熱處理不會填補添加氧化錫之氧化銦中的氧缺陷，其結果，載體不會消失且比電阻不會上昇。因而，在真空中、或惰性氣體中的熱處理較在氧化氣體之大氣中的熱處理，比電阻較降低，故較佳。本發明中所用的真空較佳為100Pa以下。若在大於100Pa的值之下進行熱處理，由於殘留氧多而會填補添加氧化錫之氧化銦中的氧缺陷，其結果載體會消失而使比電阻上昇，故不佳。更佳為1Pa以下。又，做為惰性氣體，較佳為氬、氮、氖、氦等，但並非限定於此等。 In the heat treatment in a vacuum or in an inert gas, in the same manner as the heat treatment in the atmosphere, indium oxide in which tin oxide is added is crystallized by heat treatment, and at this time, tin enters the indium portion of the indium oxide, and as a result, a carrier is generated. Therefore, the specific resistance is lowered. Also, in vacuum or inert gas, because it does not contain Since the oxidizing gas such as oxygen does not fill the oxygen deficiency in the indium oxide to which tin oxide is added by heat treatment, the carrier does not disappear and the specific resistance does not rise. Therefore, the heat treatment in a vacuum or an inert gas is preferable to the heat treatment in the atmosphere of the oxidizing gas, and the specific resistance is lowered. The vacuum used in the present invention is preferably 100 Pa or less. When the heat treatment is performed under a value of more than 100 Pa, oxygen deficiency in the indium oxide to which tin oxide is added is filled by the residual oxygen, and as a result, the carrier disappears and the specific resistance increases, which is not preferable. More preferably, it is 1 Pa or less. Further, as the inert gas, argon, nitrogen, helium, neon or the like is preferable, but it is not limited thereto.
在還原氣體中的熱處理，與在大氣中的熱處理同樣地，藉由熱處理，添加氧化錫之氧化銦會結晶化，此時錫會進入氧化銦的銦部位，其結果會產生載體，因而使比電阻降低。又，在還原氣體中，由於不含氧等之氧化氣體，故藉由熱處理不會填補添加氧化錫之氧化銦中的氧缺陷，其結果，載體不會消失且比電阻不會上昇。再者，在還原氣體中之熱處理，造成比電阻上昇之要因之多量存在於添加氧化錫之氧化銦的結晶粒界的過剩氧，容易自透明導電膜脫除，故比電阻會降低。因而，在還原氣體中的熱處理，比在氧化氣體之大氣中的熱處理，比電阻較降低，故較佳。做為還原氣體較佳為氫、一氧化碳、二氧化硫、硫化氫、甲醛等，但並非限定於此等。又，將本發明之透明導電性薄膜在混合還原氣體與惰性氣體中進行熱處理，可得到與在還原氣體中的熱處理同樣的效果，故也是較佳。 In the heat treatment in the reducing gas, in the same manner as the heat treatment in the atmosphere, indium oxide in which tin oxide is added is crystallized by heat treatment, and at this time, tin enters the indium portion of the indium oxide, and as a result, a carrier is generated, thereby making the ratio The resistance is reduced. Further, since the reducing gas does not contain an oxidizing gas such as oxygen, the oxygen deficiency in the indium oxide to which tin oxide is added is not filled by the heat treatment, and as a result, the carrier does not disappear and the specific resistance does not rise. Further, in the heat treatment in the reducing gas, the excess oxygen which is present in the crystal grain boundary of the indium oxide to which the tin oxide is added is caused by the heat treatment in the reducing gas, and is easily removed from the transparent conductive film, so that the specific resistance is lowered. Therefore, the heat treatment in the reducing gas is preferable to the heat treatment in the atmosphere of the oxidizing gas, and the specific resistance is lowered. The reducing gas is preferably hydrogen, carbon monoxide, sulfur dioxide, hydrogen sulfide, formaldehyde or the like, but is not limited thereto. Further, the transparent conductive film of the present invention is preferably subjected to heat treatment in a mixed reducing gas and an inert gas to obtain the same effect as the heat treatment in a reducing gas.
本發明之透明導電性薄膜，較佳為比電阻為0.8×10-4 ~3.0×10-4 Ω.cm。透明導電膜的比電阻雖是越低越佳，但在透明薄膜基材上的透明導電膜中要做到比0.8×10-4 Ω.Cm在技術上是有困難的。透明導電膜的比電阻若大於3.0×10-4 Ω．cm，要替代透明導電性玻璃並不佳。更佳為透明導電膜的比電阻為1.1×10-4~2.8×10-4 Ω.cm。 The transparent conductive film of the present invention preferably has a specific resistance of 0.8 × 10 -4 to 3.0 × 10 -4 Ω·cm. Although the specific resistance of the transparent conductive film is preferably as low as possible, it is technically difficult to achieve a ratio of 0.8 × 10 -4 Ω·cm in the transparent conductive film on the transparent film substrate. The specific resistance of the transparent conductive film is greater than 3.0 × 10 -4 Ω. Cm, it is not good to replace transparent conductive glass. More preferably, the specific resistance of the transparent conductive film is 1.1 × 10 -4 to 2.8 × 10 -4 Ω·cm.
要製作透明導電膜的比電阻低且透明導電膜的膜厚薄的透明導電性薄膜，較佳為透明導電膜在化學上非常穩定。化學上不穩定的透明導電膜主要有2種。第1種是非結晶多的透明導電膜。非結晶多的透明導電膜，由於結晶少因而載體量少，故比電阻高。第2種為化學上不穩定的結晶多的透明導電膜。化學上不穩定的結晶多的透明導電膜，由於容易氧化，致載體量少，故比電阻高。亦即，透明導電膜的比電阻低且透明導電膜的膜厚薄的透明導電性薄膜之透明導電膜，可認為是因為在化學上非常穩定的結晶之故。 In order to produce a transparent conductive film having a low specific resistance and a thin film thickness of the transparent conductive film, the transparent conductive film is preferably chemically stable. There are two main types of chemically unstable transparent conductive films. The first type is a transparent conductive film having a large amount of amorphous. Since the transparent conductive film having a large amount of crystals has a small amount of crystals and a small amount of the carrier, the specific resistance is high. The second type is a transparent conductive film having a large number of chemically unstable crystals. A chemically unstable transparent conductive film having a large number of crystals has a high specific resistance because it is easily oxidized and has a small amount of a carrier. That is, the transparent conductive film of the transparent conductive film having a low specific resistance and a thin film thickness of the transparent conductive film is considered to be a chemically very stable crystal.
為了製作在化學上非常穩定的透明導電膜，較佳為在基板溫度為-60~50℃間以濺鍍法成膜，然後，在真空中、或惰性氣體及/或還原氣體中，在可維持透明薄膜基材形狀的溫度下進行熱處理。 In order to produce a chemically very stable transparent conductive film, it is preferred to form a film by sputtering at a substrate temperature of -60 to 50 ° C, and then, in a vacuum, or an inert gas and/or a reducing gas, The heat treatment is performed at a temperature at which the shape of the transparent film substrate is maintained.
為了對化學上非常穩定的透明導電膜之事實進行評價，將透明導電膜的穩定度數值化。透明導電膜的穩定度指數的定義如下：(透明導電膜的穩定度指數)=A÷B...(1) In order to evaluate the fact that the chemically very stable transparent conductive film was evaluated, the stability of the transparent conductive film was quantified. The stability index of the transparent conductive film is defined as follows: (stability index of the transparent conductive film) = A ÷ B... (1)
A：使6.0莫耳/升的鹽酸成為25℃，將透明導電膜投入其 中，浸漬30秒，然後浸漬於純水中10秒，在常溫下風乾1小時後的表面電阻。 A: Put 6.0 mol/liter hydrochloric acid at 25 ° C, and put a transparent conductive film into it. The surface resistance after immersion for 30 seconds, and then immersed in pure water for 10 seconds, and air-dried at normal temperature for 1 hour.
B：在投入25℃的6.0莫耳/升的鹽酸前的透明導電性薄膜的表面電阻。 B: Surface resistance of a transparent conductive film before 6.0 mol/liter hydrochloric acid at 25 ° C was charged.
化學上不穩定的透明導電膜若浸漬於6莫耳/升的鹽酸，則會立刻溶解，透明導電膜的表面電阻會變大，而化學上穩定的透明導電膜即使浸漬於6莫耳/升的鹽酸，也難以溶解，故透明導電膜的表面電阻與投入6莫耳/升的鹽酸之前的表面電阻為相近的值。本發明之透明導電性薄膜，透明導電膜的安定度指數為1.00~1.30，更佳為1.00~1.20。透明導電膜的穩定度指數若低於1.00，將透明導電膜浸漬於鹽酸時表面電阻會減少，使得透明導電膜的膜厚變得無法增加。透明導電膜的穩定度指數若大於1.30，則為化學上不穩定的透明導電膜，透明導電膜的比電阻會大於3.0×10-4 Ω.cm，故不佳。 When the chemically unstable transparent conductive film is immersed in 6 mol/L hydrochloric acid, it dissolves immediately, and the surface resistance of the transparent conductive film becomes large, and the chemically stable transparent conductive film is immersed at 6 m/liter. The hydrochloric acid is also difficult to dissolve, so the surface resistance of the transparent conductive film is close to the surface resistance before the introduction of 6 mol/liter of hydrochloric acid. In the transparent conductive film of the present invention, the stability index of the transparent conductive film is from 1.00 to 1.30, more preferably from 1.00 to 1.20. When the stability index of the transparent conductive film is less than 1.00, the surface resistance is reduced when the transparent conductive film is immersed in hydrochloric acid, so that the film thickness of the transparent conductive film cannot be increased. When the stability index of the transparent conductive film is more than 1.30, it is a chemically unstable transparent conductive film, and the specific resistance of the transparent conductive film is more than 3.0 × 10 -4 Ω·cm, which is not preferable.
習知用藉由0.1莫耳/升的鹽酸處理前後的表面電阻來評價耐藥品性(參照例如日本特開平8-174747號公報、及日本特開平9-57892號公報)。然而，用此種藉由稀鹽酸之處理只不過可區別出結晶多的透明導電膜與非結晶多的透明導電膜，而無法區別化學上不穩定的結晶多的透明導電膜與化學上非常穩定的結晶多的透明導電膜。藉由使用6莫耳/升的鹽酸可適切對本發明之透明導電膜進行評價。 The chemical resistance is evaluated by the surface resistance before and after the treatment with 0.1 mol/L hydrochloric acid (see, for example, Japanese Laid-Open Patent Publication No. Hei 8-174747, and Japanese Laid-Open Patent Publication No. Hei 9-57892). However, the treatment with such a dilute hydrochloric acid can distinguish only a transparent conductive film having a large amount of crystals and a transparent conductive film having a large amount of crystals, and cannot distinguish a chemically unstable crystalline transparent conductive film from a chemically stable one. A crystallized transparent conductive film. The transparent conductive film of the present invention was evaluated by using 6 mol/liter hydrochloric acid.
本發明中使用的透明薄膜基材中，較佳為在薄膜的動 態黏彈性測定中，相對於在30℃的貯藏彈性係數而言，貯藏彈性係數為10%以上的溫度以上的透明薄膜基材。做為透明薄膜基材中使用的主成分可列舉：聚醯亞胺、聚醯胺、聚醯胺醯亞胺、聚醚碸、聚碳酸酯、聚芳酯等。但並非限定於此等。 In the transparent film substrate used in the present invention, it is preferred to move the film. In the viscoelasticity measurement, a transparent film substrate having a storage elastic modulus of 10% or more was used with respect to the storage elastic modulus at 30 °C. The main component used in the transparent film substrate may, for example, be polyimine, polyamine, polyamidoximine, polyether oxime, polycarbonate, polyarylate or the like. However, it is not limited to this.
本發明中使用的透明薄膜基材的厚度較佳為7~300μm的範圍，特佳為15~260μm。透明薄膜的厚度若低於7μm，操作時透明薄膜容易變形，故透明導電膜裂開的可能性變高，故不佳。另一方面，透明薄膜的厚度若超過300μm，由於接近於玻璃的厚度，故用來代替玻璃並不佳。 The thickness of the transparent film substrate used in the present invention is preferably in the range of 7 to 300 μm, particularly preferably 15 to 260 μm. When the thickness of the transparent film is less than 7 μm, the transparent film is easily deformed during the operation, so that the possibility of cracking of the transparent conductive film becomes high, which is not preferable. On the other hand, if the thickness of the transparent film exceeds 300 μm, it is not preferable to use it instead of glass because it is close to the thickness of the glass.
本發明中使用的透明薄膜基材，在無損於本發明之目的之範圍內，可對前述薄膜施以電暈放電處理、輝光放電處理、火焰處理、紫外線照射處理、電子線照射處理、臭氧處理等之表面活化處理、塗布硬化型樹脂層、塗布光學調整膜或成膜等。又，前述處理亦可組合多種而施行。 The transparent film substrate used in the present invention may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment to the above-mentioned film within the range not impairing the object of the present invention. The surface activation treatment, the coating-curable resin layer, the coating optical adjustment film, or the film formation. Further, the above treatment may be carried out in combination of a plurality of types.
以下藉由實施例進一步詳細說明本發明，但本發明並非限定於此等實施例。又，實施例中之各種測定評價係依下述方法進行。 Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto. Further, various measurement evaluations in the examples were carried out in the following manner.
依據JIS-K7136，用日本電色工業(股)公司製NDH-2000測定熱處理後的透明導電性薄膜之全光線透射率。又，靜電容量式觸控面板用途之透明導電性薄膜的實用全光線透射率的水平較佳為85~95%。 The total light transmittance of the heat-treated transparent conductive film was measured by NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-K7136. Moreover, the practical total light transmittance of the transparent conductive film for electrostatic capacitance type touch panel is preferably 85 to 95%.
依據JIS-K7194，以4端子法測定熱處理後的透明導電性薄膜之表面電阻。測定機係用三菱油化(股)公司製LorestaMP MCP-T350。比電阻可由表面電阻與於(3)所得的膜厚之乘積得到。 The surface resistance of the heat-treated transparent conductive film was measured by a 4-terminal method in accordance with JIS-K7194. The measuring machine was made of Loresta MP MCP-T350 manufactured by Mitsubishi Petrochemical Co., Ltd. The specific resistance can be obtained by multiplying the surface resistance by the film thickness obtained in (3).
將透明導電性薄膜積層而成的薄膜試料片裁切成1mm×10mm大小，將其包埋於電子顯微鏡用環氧樹脂中。將其固定於超顯微切片機的試料放置器中，製作成平行於包埋的試料之短邊的截面薄切片。然後，在此切片的薄膜之沒有明顯的損傷之部位，用穿透型電子顯微鏡(JEOL公司製，JEM-2010)，以加速電壓200kV，於明視場(bright field)下觀察倍率為1萬倍，進行照相，自得到的相片求出膜厚。 The film sample sheet in which the transparent conductive film was laminated was cut into a size of 1 mm × 10 mm, and embedded in an epoxy resin for electron microscopy. This was fixed in a sample placer of an ultramicrotome to prepare a thin section of a section parallel to the short side of the embedded sample. Then, at the portion where the film of the slice was not damaged, a transmission electron microscope (JE-2010, JE-2010) was used, and the acceleration voltage was 200 kV, and the observation magnification was 10,000 in the bright field. The film was taken, and the film thickness was determined from the obtained photograph.
將透明薄膜基材，於平行於薄膜寬方向自2處裁切出長40mm×寬5mm。對此以測定長25mm、位移上限設定25%、頻率數10Hz的條件，以5℃/分鐘的昇溫速度，測定自30℃起之動態黏彈性。貯藏彈性係數係用得自2個試樣之貯藏彈性係數的平均值。以相對於30℃的貯藏彈性係數而言貯藏彈性係數成為10%時的溫度做為可維持透明薄膜基材形狀的溫度之上限。動態黏彈性係用IT計測(股)公司製之動態黏彈性測定裝置測定。 The transparent film substrate was cut from two places in a direction parallel to the film width to a length of 40 mm × a width of 5 mm. On the other hand, the dynamic viscoelasticity from 30 ° C was measured at a temperature increase rate of 5 ° C / min under the conditions of a measurement length of 25 mm, an upper limit of displacement of 25%, and a frequency of 10 Hz. The storage elastic coefficient is the average of the storage elastic coefficients obtained from the two samples. The temperature at which the storage elastic modulus is 10% with respect to the storage elastic modulus at 30 ° C is taken as the upper limit of the temperature at which the shape of the transparent film substrate can be maintained. The dynamic viscoelasticity was measured by a dynamic viscoelasticity measuring device manufactured by IT Measurement Co., Ltd.
切取試料(約15cm2)放入石英製三角燒杯中，加入6莫耳/升的鹽酸20毫升，用薄膜密封使酸不會揮發。在室溫下經常搖蕩之下放置9天，使ITO層溶解。取出殘餘的薄膜，以溶解有ITO層的鹽酸做為測定液。溶解液中的Sn、In，係用ICP發光分析裝置(製造商名：Rigaku，裝置型號：CIROS-120 EOP)，藉由比對線求出。各元素的測定波長，係選擇沒有干擾、感度高的波長。又，標準溶液係將市售的Sn、In標準溶液稀釋而使用。 The sample (about 15 cm 2 ) was cut into a quartz triangle beaker, and 20 ml of 6 ml/liter hydrochloric acid was added, and the film was sealed to prevent the acid from evaporating. It was left to stand under shaking at room temperature for 9 days to dissolve the ITO layer. The residual film was taken out, and hydrochloric acid in which the ITO layer was dissolved was used as a measuring liquid. The Sn and In in the solution were determined by an ICP emission analyzer (manufacturer name: Rigaku, device model: CIROS-120 EOP) by a comparison line. The wavelength of measurement of each element is selected to have no interference and high sensitivity. Further, the standard solution was prepared by diluting a commercially available Sn and In standard solution.
將熱處理後的透明導電性薄膜層經積層而成的薄膜試料片裁切成1mm×10mm的大小，使導電性薄膜面向外而黏貼於適當的樹脂塊上面。將其裁切之後，藉由通常的超顯微切片的技術製作成大致平行於薄膜表面的超薄切片。 The film sample sheet obtained by laminating the heat-treated transparent conductive film layer was cut into a size of 1 mm × 10 mm, and the conductive film was exposed to the outside and adhered to an appropriate resin block. After cutting it, an ultrathin section substantially parallel to the surface of the film is produced by the usual technique of ultramicroscopic sectioning.
對此切片以穿透型電子顯微鏡(JEOL公司製，JEM-2010)觀察，選擇沒有明顯的損傷之導電性薄膜表面部份，以加速電壓200kV，以直接倍率40000倍照相。 The section was observed by a transmission electron microscope (JE-2010, JEOL Co., Ltd.), and the surface portion of the conductive film having no significant damage was selected to accelerate at a voltage of 200 kV and photographed at a direct magnification of 40,000 times.
在穿透型電子顯微鏡下觀察透明導電膜層時，多角形的區域為結晶，此外為非結晶。算出在電子顯微鏡下觀察時的結晶質部與非結晶質部的面積比，若相對於結晶質部之非結晶質部的比為0.00~0.16，係判定透明導電膜為結晶化狀態。 When the transparent conductive film layer was observed under a transmission electron microscope, the polygonal region was crystallized, and further, it was amorphous. The area ratio of the crystalline portion to the amorphous portion when observed under an electron microscope was calculated, and when the ratio of the amorphous portion to the crystalline portion was 0.00 to 0.16, the transparent conductive film was judged to be in a crystallized state.
透明導電膜的穩定度指數係以下式表示： (透明導電膜的穩定度指數)=A÷B The stability index of the transparent conductive film is expressed by the following formula: (Stable stability index of transparent conductive film) = A÷B
A：使6.0莫耳/升的鹽酸成為25℃，將透明導電膜投入其中，浸漬30秒，然後浸漬於純水中10秒，在常溫下風乾1小時後的表面電阻。 A: The surface resistance of 6.0 mol/liter hydrochloric acid at 25 ° C, a transparent conductive film was put thereinto, immersed for 30 seconds, and then immersed in pure water for 10 seconds, and air-dried at normal temperature for 1 hour.
B：在投入25℃的6.0莫耳/升的鹽酸前的透明導電性薄膜的表面電阻。 B: Surface resistance of a transparent conductive film before 6.0 mol/liter hydrochloric acid at 25 ° C was charged.
實施例中之透明導電膜製作條件記載於表1。又，各實施例中之共通的製作條件如下：將表1所記載的透明薄膜投入真空槽中，進行真空抽氣至2.0×10-4Pa。接著，導入氧氣使氧分壓值如表1，然後導入做為惰性氣體的氬氣，使全壓成為0.5Pa。 The conditions for producing the transparent conductive film in the examples are shown in Table 1. Further, the production conditions common to the respective examples were as follows: The transparent film described in Table 1 was placed in a vacuum chamber, and vacuum evacuation was performed to 2.0 × 10 -4 Pa. Next, oxygen gas was introduced to make the oxygen partial pressure value as shown in Table 1, and then introduced into an argon gas as an inert gas so that the total pressure became 0.5 Pa.
在實施例1~10中係對含有氧化錫之氧化銦燒結靶以1W/cm2的電力密度施加電力，藉由直流磁控管濺鍍法在透明薄膜上成膜為透明導電膜。有關透明導電膜的膜厚係改變薄膜通過靶上時的速度來控制。 In Examples 1 to 10, an indium oxide sintered target containing tin oxide was applied with electric power at a power density of 1 W/cm 2 , and a transparent conductive film was formed on a transparent film by a DC magnetron sputtering method. The film thickness of the transparent conductive film is controlled by changing the speed at which the film passes over the target.
成膜有透明導電膜的薄膜，以表1所記載的條件施行熱處理60分鐘後再施行評價項目的測定。測定結果示於表1。 The film in which the transparent conductive film was formed was subjected to heat treatment for 60 minutes under the conditions described in Table 1, and then the evaluation item was measured. The measurement results are shown in Table 1.
有關此等比較例的透明導電膜製作條件係記載於表1。上述實施例說明中的固定條件，於比較例也採用相同條件。成膜有透明導電膜的薄膜，以表1所記載的條件熱處理後，施行各評價項目的測定。測定結果示於表1。 The conditions for producing transparent conductive films of these comparative examples are shown in Table 1. The fixing conditions in the above description of the examples are the same as in the comparative examples. A film having a transparent conductive film was formed, and after heat treatment under the conditions shown in Table 1, measurement of each evaluation item was performed. The measurement results are shown in Table 1.
有關參考例的透明導電膜製作條件係記載於表1。上述實施例說明中的固定條件，於參考例也採用相同條件。對成膜有透明導電膜的薄膜以表1所記載的條件熱處理後，施行各評價項目的測定。測定結果示於表1。 The conditions for producing the transparent conductive film of the reference example are shown in Table 1. The fixing conditions in the above description of the examples are the same as in the reference examples. The film in which the transparent conductive film was formed was heat-treated under the conditions shown in Table 1, and the measurement of each evaluation item was performed. The measurement results are shown in Table 1.
如表1所記載，實施例1~12的透明導電性薄膜任一者之透明導電膜的比電阻皆為0.8×10-4~3.0×10-4 Ω.Cm，透明導電膜的厚度為10~100nm，透明導電膜的穩定度指數為1.00~1.30，全光線透射率也為實用的水準，因而適合於使用。有關表1的結果中的比較例1~8，比電阻的性能及透明導電膜的穩定度指數不能滿意，故不佳。有關參考例，於膜厚、全光線透射率的性能不能滿意，故不佳。 As shown in Table 1, the specific resistance of the transparent conductive film of any of the transparent conductive films of Examples 1 to 12 was 0.8 × 10 -4 to 3.0 × 10 -4 Ω·cm, and the thickness of the transparent conductive film was 10 ~100nm, the stability index of the transparent conductive film is 1.00~1.30, and the total light transmittance is also a practical level, so it is suitable for use. With respect to Comparative Examples 1 to 8 in the results of Table 1, the performance of the specific resistance and the stability index of the transparent conductive film were not satisfactory, which was not preferable. Regarding the reference example, the performance in film thickness and total light transmittance was not satisfactory, which was not preferable.
如上所述，依據本發明可提供透明導電膜的比電阻低、且透明導電膜的膜厚薄的透明導電性薄膜。此對於靜電容量式觸控面板的大型化與觸控靈敏度之提高，極為有效。 As described above, according to the present invention, it is possible to provide a transparent conductive film having a low specific resistance of the transparent conductive film and a thin film thickness of the transparent conductive film. This is extremely effective for increasing the size and sensitivity of the electrostatic capacitance type touch panel.
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