TW202105416A - Crystallized indium tin composite oxide film, transparent electric conductive film, and production method therefor - Google Patents

Crystallized indium tin composite oxide film, transparent electric conductive film, and production method therefor Download PDF

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TW202105416A
TW202105416A TW109121069A TW109121069A TW202105416A TW 202105416 A TW202105416 A TW 202105416A TW 109121069 A TW109121069 A TW 109121069A TW 109121069 A TW109121069 A TW 109121069A TW 202105416 A TW202105416 A TW 202105416A
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indium tin
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竹下翔也
安藤豪彥
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日商日東電工股份有限公司
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Abstract

This crystallized indium tin composite oxide film 1 has a thickness of 35 nm or more. This crystallized indium tin composite oxide film 1 contains crystal particles with a mean particle diameter of 110 nm or more.

Description

結晶化銦錫複合氧化物膜、透明導電性膜及其製造方法Crystallized indium tin composite oxide film, transparent conductive film and manufacturing method thereof

本發明係關於一種結晶化銦錫複合氧化物膜、透明導電性膜及其製造方法，詳細而言係關於一種結晶化銦錫複合氧化物膜、具備其之透明導電性膜及透明導電性膜之製造方法。The present invention relates to a crystalline indium tin composite oxide film, a transparent conductive film and a manufacturing method thereof, and in detail, to a crystalline indium tin composite oxide film, a transparent conductive film and a transparent conductive film provided with the same The manufacturing method.

先前已知有透明導電性膜於透明塑膠膜基材上具備以結晶質氧化銦為主成分之透明導電膜。結晶質透明導電膜通常含有複數個晶粒(微粒)。Previously, there has been known a transparent conductive film with a transparent conductive film mainly composed of crystalline indium oxide on a transparent plastic film substrate. The crystalline transparent conductive film usually contains a plurality of crystal grains (fine particles).

例如，揭示有厚度為20 nm、平均結晶粒徑(微粒之平均粒徑)為130 nm之透明導電膜(例如，參照下述專利文獻1之實施例6)。 [先前技術文獻] [專利文獻]For example, a transparent conductive film having a thickness of 20 nm and an average crystal particle diameter (average particle diameter of fine particles) of 130 nm is disclosed (for example, refer to Example 6 of Patent Document 1 below). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特開2010-28275號公報[Patent Document 1] Japanese Patent Laid-Open No. 2010-28275

[發明所欲解決之問題][The problem to be solved by the invention]

近年來，對透明導電膜要求更低之表面電阻。因此，嘗試增厚透明導電膜之方案。In recent years, lower surface resistance has been required for transparent conductive films. Therefore, an attempt was made to thicken the transparent conductive film.

但若透明導電膜變厚，則平均結晶粒徑變小。如此，存在耐化學品性降低之不良情況。However, if the transparent conductive film becomes thicker, the average crystal grain size becomes smaller. As such, there is a disadvantage that the chemical resistance is reduced.

本發明提供一種具有較低之表面電阻、並且耐化學品性優異之透明導電性膜及其製造方法。 [解決問題之技術手段]The present invention provides a transparent conductive film with low surface resistance and excellent chemical resistance and a manufacturing method thereof. [Technical means to solve the problem]

本發明(1)包含一種結晶化銦錫複合氧化物膜，其具有35 nm以上之厚度，且含有平均粒徑為110 nm以上之晶粒。The present invention (1) includes a crystalline indium tin composite oxide film having a thickness of 35 nm or more and containing crystal grains with an average particle size of 110 nm or more.

該結晶化銦錫複合氧化物膜之厚度厚至35 nm，故具有較低之表面電阻。The thickness of the crystalline indium tin composite oxide film is as thick as 35 nm, so it has a low surface resistance.

又，該結晶化銦錫複合氧化物膜含有大至110 nm以上之平均粒徑之晶粒，故耐化學品性優異。In addition, the crystallized indium tin composite oxide film contains crystal grains with an average particle size of 110 nm or more, so it is excellent in chemical resistance.

因此，該結晶化銦錫複合氧化物膜具有較低之表面電阻，並且耐化學品性優異。Therefore, the crystalline indium tin composite oxide film has low surface resistance and excellent chemical resistance.

本發明(2)包含如(1)中記載之結晶化銦錫複合氧化物膜，其包含氧化錫之比率為8質量%以上之區域。The present invention (2) includes the crystalline indium tin composite oxide film as described in (1), which contains a region where the ratio of tin oxide is 8% by mass or more.

可降低該結晶化銦錫複合氧化物膜之表面電阻。The surface resistance of the crystalline indium tin composite oxide film can be reduced.

本發明(3)包含一種透明導電性膜，其具備：透明膜基材；及配置於上述膜基材之厚度方向一面之如(1)或(2)中記載之結晶化銦錫複合氧化物膜。The present invention (3) includes a transparent conductive film comprising: a transparent film substrate; and the crystalline indium tin composite oxide described in (1) or (2) arranged on one side of the film substrate in the thickness direction membrane.

該透明導電性膜由於具備上述結晶化銦錫複合氧化物膜，故具有較低之表面電阻，並且耐化學品性優異。Since the transparent conductive film includes the above-mentioned crystallized indium tin composite oxide film, it has low surface resistance and is excellent in chemical resistance.

本發明(4)包含如(3)中記載之透明導電性膜，其中上述透明膜基材之上述厚度方向一面具有1.0 nm以下之算術平均粗糙度Ra。The present invention (4) includes the transparent conductive film as described in (3), wherein one side of the thickness direction of the transparent film substrate has an arithmetic average roughness Ra of 1.0 nm or less.

該透明導電性膜由於透明膜基材之厚度方向一面具有小至1.0 nm以下之算術平均粗糙度Ra，故可於配置於透明膜基材之厚度方向一面之非晶質銦錫複合氧化物膜中抑制結晶生長被阻礙。因此，可於結晶化銦錫複合氧化物膜中形成平均粒徑較大之晶粒。其結果，透明導電性膜之結晶化銦錫複合氧化物膜之耐化學品性優異。Since the transparent conductive film has an arithmetic mean roughness Ra as small as 1.0 nm or less in the thickness direction of the transparent film substrate, it can be used as an amorphous indium tin composite oxide film disposed on the thickness direction of the transparent film substrate. Inhibition of crystal growth is hindered. Therefore, crystal grains with a larger average particle size can be formed in the crystallized indium tin composite oxide film. As a result, the crystallized indium tin composite oxide film of the transparent conductive film has excellent chemical resistance.

本發明(5)包含一種透明導電性膜之製造方法，其係製造如(2)或(3)中記載之透明導電性膜之方法，該方法具備：第1步驟，其藉由對上述透明膜基材之上述厚度方向一面進行濺鍍，形成非晶化銦錫複合氧化物膜；及第2步驟，其對上述非晶化銦錫複合氧化物膜進行加熱，形成結晶化銦錫複合氧化物膜；於上述第1步驟中，於分壓0.4 Pa以上之惰性氣體之存在下實施濺鍍。The present invention (5) includes a method of manufacturing a transparent conductive film, which is a method of manufacturing a transparent conductive film as described in (2) or (3), the method comprising: a first step of Sputtering on one side of the film substrate in the thickness direction to form an amorphous indium tin composite oxide film; and the second step of heating the amorphous indium tin composite oxide film to form a crystalline indium tin composite oxide Substance film; in the first step above, sputtering is performed in the presence of an inert gas with a partial pressure of 0.4 Pa or more.

於該透明導電性膜之製造方法之第1步驟中，於高至0.4 Pa以上之分壓之惰性氣體之存在下進行濺鍍，故可形成平均粒徑較大之晶粒。其結果，可製造具備耐化學品性優異之結晶化銦錫複合氧化物膜之透明導電性膜。 [發明之效果]In the first step of the manufacturing method of the transparent conductive film, sputtering is performed in the presence of an inert gas with a partial pressure of 0.4 Pa or more, so that crystal grains with a larger average particle size can be formed. As a result, a transparent conductive film having a crystalline indium tin composite oxide film excellent in chemical resistance can be manufactured. [Effects of Invention]

藉由本發明之製造方法而獲得之結晶化銦錫複合氧化物膜具有較低之表面電阻，並且耐化學品性優異。The crystalline indium tin composite oxide film obtained by the manufacturing method of the present invention has low surface resistance and excellent chemical resistance.

＜一實施方式＞ [結晶化銦錫複合氧化物膜] 對本發明之結晶化銦錫複合氧化物膜之一實施方式進行說明。<One embodiment> [Crystalline indium tin composite oxide film] An embodiment of the crystallized indium tin composite oxide film of the present invention will be described.

該結晶化銦錫複合氧化物膜具有於厚度方向上對向一面及另一面。結晶化銦錫複合氧化物膜具有沿與厚度方向正交之面方向延伸之膜形狀。The crystallized indium tin composite oxide film has one surface and the other surface facing each other in the thickness direction. The crystallized indium tin composite oxide film has a film shape extending in a plane direction orthogonal to the thickness direction.

結晶化銦錫複合氧化物膜之厚度為35 nm以上。若結晶化銦錫複合氧化物膜之厚度低於上述下限，則無法降低結晶化銦錫複合氧化物膜之表面電阻。The thickness of the crystalline indium tin composite oxide film is 35 nm or more. If the thickness of the crystallized indium tin composite oxide film is lower than the above lower limit, the surface resistance of the crystallized indium tin composite oxide film cannot be reduced.

結晶化銦錫複合氧化物膜之厚度較佳為38 nm以上，更佳為40 nm以上，進而較佳為45 nm以上，尤佳為50 nm以上，最佳為55 nm以上，進而，適宜為60 nm以上、70 nm以上、80 nm以上、100 nm以上、125 nm以上、150 nm以上。若結晶化銦錫複合氧化物膜之厚度為上述下限以上，則可充分地降低結晶化銦錫複合氧化物膜之表面電阻。The thickness of the crystalline indium tin composite oxide film is preferably 38 nm or more, more preferably 40 nm or more, still more preferably 45 nm or more, particularly preferably 50 nm or more, most preferably 55 nm or more, and more preferably 60 nm or more, 70 nm or more, 80 nm or more, 100 nm or more, 125 nm or more, 150 nm or more. If the thickness of the crystallized indium tin composite oxide film is greater than the above lower limit, the surface resistance of the crystallized indium tin composite oxide film can be sufficiently reduced.

再者，就降低結晶化銦錫複合氧化物膜之表面電阻之觀點而言，結晶化銦錫複合氧化物膜之厚度之上限無特別限定。結晶化銦錫複合氧化物膜之厚度通常為1000 nm以下，又，為500 nm以下。Furthermore, from the viewpoint of reducing the surface resistance of the crystallized indium tin composite oxide film, the upper limit of the thickness of the crystallized indium tin composite oxide film is not particularly limited. The thickness of the crystalline indium tin composite oxide film is usually 1000 nm or less, and 500 nm or less.

該結晶化銦錫複合氧化物膜含有晶粒(微粒)。晶粒(參照圖3A中之符號9)係於結晶化銦錫複合氧化物膜中存在複數個。又，複數個晶粒例如存在於結晶化銦錫複合氧化物膜之整個面方向及整個厚度方向。複數個晶粒分別由晶界(參照圖3A中之符號10)劃分。This crystallized indium tin composite oxide film contains crystal grains (fine particles). There are multiple crystal grains (refer to symbol 9 in FIG. 3A) in the crystallized indium tin composite oxide film. In addition, a plurality of crystal grains exist, for example, in the entire surface direction and the entire thickness direction of the crystallized indium tin composite oxide film. A plurality of crystal grains are respectively divided by grain boundaries (refer to symbol 10 in FIG. 3A).

晶粒之平均粒徑為110 nm以上。The average grain size of the crystal grains is 110 nm or more.

再者，晶粒之平均粒徑係對結晶化銦錫複合氧化物膜之厚度方向一面進行SEM(scanning electron microscope，掃描式電子顯微鏡)觀察時之晶粒之平均粒徑，其測定方法之詳情於以下實施例中進行詳細敍述。Furthermore, the average size of the crystal grains is the average size of the crystal grains when one side of the crystallized indium tin composite oxide film is observed in the thickness direction by SEM (scanning electron microscope). Details of the measurement method It is described in detail in the following examples.

若如參照圖3B所示，晶粒9之平均粒徑低於上述下限，則結晶化銦錫複合氧化物膜1中之晶界10之每單位面積之佔有率過度增大。如此，結晶化銦錫複合氧化物膜1之厚度方向一面暴露於液狀藥品，當上述晶界10成為藥品之滲入路徑之入口時，該入口之每單位面積之佔有率亦增大，因此耐化學品顯著降低。As shown with reference to FIG. 3B, if the average particle size of the crystal grains 9 is lower than the above-mentioned lower limit, the occupancy rate per unit area of the grain boundary 10 in the crystallized indium tin composite oxide film 1 is excessively increased. In this way, one side of the crystalline indium tin composite oxide film 1 in the thickness direction is exposed to the liquid chemical, and when the above-mentioned grain boundary 10 becomes the entrance of the penetration path of the chemical, the occupancy rate per unit area of the entrance also increases, so the resistance The chemicals are significantly reduced.

晶粒之平均粒徑較佳為130 nm以上，更佳為150 nm以上，進而較佳為170 nm以上，尤佳為200 nm以上，最佳為250 nm以上，進而，適宜為300 nm以上、400 nm以上、450 nm以上。若晶粒之平均粒徑為上述下限以上，則可充分地抑制結晶化銦錫複合氧化物膜之耐化學品之降低。The average particle size of the crystal grains is preferably 130 nm or more, more preferably 150 nm or more, still more preferably 170 nm or more, particularly preferably 200 nm or more, most preferably 250 nm or more, and more preferably 300 nm or more, Above 400 nm and above 450 nm. If the average grain size of the crystal grains is more than the above lower limit, the chemical resistance of the crystallized indium tin composite oxide film can be sufficiently suppressed to decrease.

結晶化銦錫複合氧化物膜之材料為結晶質銦錫複合氧化物(ITO)。ITO係包含銦(In)及錫(Sn)作為必需成分之複合氧化物。具體而言，ITO含有氧化錫(SnO2 )及氧化銦(In2 O3 )作為主成分。The material of the crystalline indium tin composite oxide film is crystalline indium tin composite oxide (ITO). ITO is a composite oxide containing indium (In) and tin (Sn) as essential components. Specifically, ITO contains tin oxide (SnO 2 ) and indium oxide (In 2 O 3 ) as main components.

氧化錫之含有比率相對於氧化錫及氧化銦之合計量例如為0.5質量%以上，較佳為3質量%以上，更佳為5質量%以上，進而較佳為8質量%以上，尤佳為9質量%以上，且例如為20質量%以下，較佳為15質量%以下。The content ratio of tin oxide with respect to the total amount of tin oxide and indium oxide is, for example, 0.5% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, especially 9% by mass or more, and for example, 20% by mass or less, preferably 15% by mass or less.

若氧化錫之含有比率為上述下限以上，則可降低結晶化銦錫複合氧化物膜之表面電阻。若氧化錫之含有比率為上述上限以下，則結晶化銦錫複合氧化物膜之強度優異。If the content ratio of tin oxide is more than the above lower limit, the surface resistance of the crystallized indium tin composite oxide film can be reduced. If the content ratio of tin oxide is equal to or less than the above upper limit, the strength of the crystallized indium tin composite oxide film is excellent.

氧化銦之含有比率係上述合計量中之氧化錫之含有比率之剩餘部分。再者，ITO亦可包含除主成分(必需成分)以外之追加成分，具體而言為Zn、Ga、Sb、Ti、Si、Zr、Mg、Al、Au、Ag、Cu、Pd、W、Fe、Pb、Ni、Nb、Cr、Ga等追加成分。The content ratio of indium oxide is the remainder of the content ratio of tin oxide in the above-mentioned total amount. Furthermore, ITO may also contain additional components other than the main component (essential component), specifically Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe , Pb, Ni, Nb, Cr, Ga and other additional components.

又，結晶化銦錫複合氧化物膜可包含氧化錫之比率為8質量%以上之區域。於結晶化銦錫複合氧化物膜包含氧化錫之比率為8質量%以上之區域之情形情形，可降低結晶化銦錫複合氧化物膜之表面電阻。In addition, the crystalline indium tin composite oxide film may include a region where the ratio of tin oxide is 8% by mass or more. In the case of a region where the ratio of the crystalline indium tin composite oxide film containing tin oxide is 8% by mass or more, the surface resistance of the crystalline indium tin composite oxide film can be reduced.

例如，結晶化銦錫複合氧化物膜包含：作為氧化錫之比率為8質量%以上之區域之一例的第1區域(參照符號11)、及氧化錫之比率低於第1區域中之氧化錫之比率的第2區域(參照符號12)。具體而言，結晶化銦錫複合氧化物膜依次包含層狀第1區域、及配置於第1區域之厚度方向一面之層狀第2區域。再者，第1區域及第2區域之邊界無法藉由測定裝置之觀察來確認，故容許不清晰。再者，該結晶化銦錫複合氧化物膜亦可具有氧化錫濃度自厚度方向一面向另一面逐漸變高之濃度梯度。於結晶化銦錫複合氧化物膜除上述第1區域以外還包含第2區域之情形時，可藉由調整該區域之比率獲得所需之結晶化速度。For example, a crystallized indium tin composite oxide film includes: a first region (reference symbol 11) as an example of a region where the ratio of tin oxide is 8% by mass or more, and the ratio of tin oxide is lower than tin oxide in the first region The second area of the ratio (refer to symbol 12). Specifically, the crystalline indium tin composite oxide film sequentially includes a layered first region and a layered second region arranged on one surface in the thickness direction of the first region. Furthermore, the boundary between the first area and the second area cannot be confirmed by the observation of the measuring device, so unclearness is allowed. Furthermore, the crystalline indium tin composite oxide film may also have a concentration gradient in which the tin oxide concentration gradually increases from one side to the other side in the thickness direction. When the crystalline indium tin composite oxide film includes a second region in addition to the above-mentioned first region, the desired crystallization rate can be obtained by adjusting the ratio of the region.

第1區域中之氧化錫之比率較佳為9質量%以上，更佳為10質量%以上，又，為20質量%以下。The ratio of tin oxide in the first region is preferably 9% by mass or more, more preferably 10% by mass or more, and furthermore, 20% by mass or less.

結晶化銦錫複合氧化物膜之厚度中，第1區域之厚度之比率例如超過50%，較佳為70%以上，更佳為80%以上，進而較佳為90%以上。若第1區域之厚度之比率為上述下限以上，則可提高結晶化銦錫複合氧化物膜中之氧化錫之比率，因此，可充分地降低結晶化銦錫複合氧化物膜之表面電阻。結晶化銦錫複合氧化物膜之厚度中之第1區域之厚度之比率例如為99%以下，較佳為97%以下。In the thickness of the crystalline indium tin composite oxide film, the ratio of the thickness of the first region is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If the ratio of the thickness of the first region is more than the above lower limit, the ratio of tin oxide in the crystallized indium tin composite oxide film can be increased, and therefore, the surface resistance of the crystallized indium tin composite oxide film can be sufficiently reduced. The ratio of the thickness of the first region in the thickness of the crystalline indium tin composite oxide film is, for example, 99% or less, preferably 97% or less.

第2區域中之氧化錫之比率例如未達8質量%，較佳為7質量%以下，更佳為5質量%以下，進而較佳為4質量%以下，且例如為1質量%以上，較佳為2質量%以上，更佳為3質量%以上。The ratio of tin oxide in the second region is, for example, less than 8% by mass, preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and for example, 1% by mass or more. It is preferably 2% by mass or more, and more preferably 3% by mass or more.

第1區域中之氧化錫之比率相對於第2區域中之氧化錫之比率的比(第1區域中之氧化錫之比率/第2區域中之氧化錫之比率)例如為1.5以上，較佳為2以上，更佳為2.5以上，且例如為5以下，較佳為4以下。The ratio of the ratio of tin oxide in the first area to the ratio of tin oxide in the second area (the ratio of tin oxide in the first area/the ratio of tin oxide in the second area) is, for example, 1.5 or more, preferably It is 2 or more, more preferably 2.5 or more, and for example, 5 or less, preferably 4 or less.

結晶化銦錫複合氧化物膜、第1區域及第2區域之各者中之氧化錫濃度係藉由X射線光電子光譜法進行測定。或者，氧化錫之含有比率亦可根據以濺鍍方式形成非晶質銦錫複合氧化物膜時使用之靶成分(已知)來推測。The tin oxide concentration in each of the crystallized indium tin composite oxide film, the first region and the second region was measured by X-ray photoelectron spectroscopy. Alternatively, the content ratio of tin oxide can also be estimated from the target component (known) used when the amorphous indium tin composite oxide film is formed by sputtering.

結晶化銦錫複合氧化物膜之表面電阻例如為60 Ω/□以下，較佳為50 Ω/□以下，更佳為45 Ω/□以下，進而較佳為40 Ω/□以下，尤佳為30 Ω/□以下，最佳為20 Ω/□以下。若結晶化銦錫複合氧化物膜之表面電阻為上述上限以下，則於將結晶化銦錫複合氧化物膜圖案化而用作電極時，可表現出優異之電特性。The surface resistance of the crystalline indium tin composite oxide film is, for example, 60 Ω/□ or less, preferably 50 Ω/□ or less, more preferably 45 Ω/□ or less, further preferably 40 Ω/□ or less, particularly preferably Below 30 Ω/□, preferably below 20 Ω/□. If the surface resistance of the crystalline indium tin composite oxide film is below the above upper limit, the crystalline indium tin composite oxide film can exhibit excellent electrical characteristics when it is patterned and used as an electrode.

結晶化銦錫複合氧化物膜之表面電阻之下限無特別限定。例如，結晶化銦錫複合氧化物膜之表面電阻通常超過0 Ω/□，又，為1 Ω/□以上。結晶化銦錫複合氧化物層7之表面電阻藉由四端子法進行測定。The lower limit of the surface resistance of the crystalline indium tin composite oxide film is not particularly limited. For example, the surface resistance of a crystalline indium tin composite oxide film usually exceeds 0 Ω/□, and is more than 1 Ω/□. The surface resistance of the crystallized indium tin composite oxide layer 7 was measured by the four-terminal method.

再者，關於結晶化銦錫複合氧化物膜之厚度方向另一面之算術平均粗糙度Ra，由於結晶化銦錫複合氧化物膜之厚度方向另一面密接追隨下述說明之透明膜基材之厚度方向一面，故該結晶化銦錫複合氧化物膜之厚度方向另一面之算術平均粗糙度Ra例如與透明膜基材之厚度方向另一面之算術平均粗糙度Ra相同。具體而言，結晶化銦錫複合氧化物膜之厚度方向另一面之算術平均粗糙度Ra例如為2 nm以下，較佳為1 nm以下，更佳為0.75 nm以下，進而較佳為0.5 nm以下，且例如為0.001 nm以上。Furthermore, regarding the arithmetic average roughness Ra on the other side of the crystalline indium tin composite oxide film in the thickness direction, since the other side of the crystalline indium tin composite oxide film in the thickness direction closely follows the thickness of the transparent film substrate described below In one direction, the arithmetic average roughness Ra of the other side of the crystalline indium tin composite oxide film in the thickness direction is, for example, the same as the arithmetic average roughness Ra of the other side of the transparent film substrate in the thickness direction. Specifically, the arithmetic average roughness Ra of the other side in the thickness direction of the crystalline indium tin composite oxide film is, for example, 2 nm or less, preferably 1 nm or less, more preferably 0.75 nm or less, and still more preferably 0.5 nm or less , And for example, 0.001 nm or more.

[透明導電性膜] 繼而，參照圖1對具備上述結晶化銦錫複合氧化物膜之透明導電性膜進行說明。[Transparent conductive film] Next, a transparent conductive film provided with the above-mentioned crystallized indium tin composite oxide film will be described with reference to FIG. 1.

透明導電性膜3具有沿面方向延伸之膜形狀。透明導電性膜3朝厚度方向一側依次具備透明膜基材2、及結晶化銦錫複合氧化物膜1。透明導電性膜3具備透明膜基材2、及配置於透明膜基材2之厚度方向一面之結晶化銦錫複合氧化物膜1。透明導電性膜3較佳為僅具備透明膜基材2、及結晶化銦錫複合氧化物膜1。The transparent conductive film 3 has a film shape extending in the surface direction. The transparent conductive film 3 includes a transparent film base 2 and a crystallized indium tin composite oxide film 1 in this order toward one side in the thickness direction. The transparent conductive film 3 includes a transparent film base 2 and a crystallized indium tin composite oxide film 1 arranged on one surface of the transparent film base 2 in the thickness direction. The transparent conductive film 3 preferably includes only the transparent film substrate 2 and the crystallized indium tin composite oxide film 1.

透明膜基材2形成透明導電性膜3之外形形狀。透明膜基材2乃為透明。透明膜基材2例如朝厚度方向一側依次具備抗黏連層5、透明膜6、硬塗層7、及光學調整層8。透明膜基材2具備：抗黏連層5、配置於抗黏連層5之厚度方向一面之透明膜6、配置於透明膜6之厚度方向一面之硬塗層7、及配置於硬塗層7之厚度方向一面之光學調整層8。透明膜基材2較佳為僅具備抗黏連層5、透明膜6、硬塗層7、及光學調整層8。The transparent film base material 2 has an outer shape of the transparent conductive film 3. The transparent film substrate 2 is transparent. The transparent film substrate 2 includes, for example, an anti-blocking layer 5, a transparent film 6, a hard coat layer 7, and an optical adjustment layer 8 in this order toward one side in the thickness direction. The transparent film substrate 2 includes: an anti-blocking layer 5, a transparent film 6 arranged on one side of the anti-blocking layer 5 in the thickness direction, a hard coating layer 7 arranged on one side of the thickness direction of the transparent film 6, and a hard coating layer 7 is the optical adjustment layer 8 on one side in the thickness direction. The transparent film substrate 2 preferably includes only the anti-blocking layer 5, the transparent film 6, the hard coat layer 7, and the optical adjustment layer 8.

抗黏連層5於將透明導電性膜3於厚度方向上積層之情形等時，對相互接觸之複數個透明導電性膜3之各表面賦予耐黏連性。抗黏連層5之材料例如為抗黏連組合物。作為抗黏連組合物，例如可例舉日本專利特開2016-179686號公報中記載之混合物等。混合物例如含有丙烯酸樹脂等樹脂(黏合劑樹脂)、及無機及/或有機粒子(較佳為聚苯乙烯等有機粒子)。抗黏連層5之厚度例如為0.1 μm以上，且例如為10 μm以下。The anti-blocking layer 5 imparts blocking resistance to each surface of a plurality of transparent conductive films 3 that are in contact with each other when the transparent conductive film 3 is laminated in the thickness direction. The material of the anti-adhesion layer 5 is, for example, an anti-adhesion composition. As the anti-blocking composition, for example, the mixture described in JP 2016-179686 A, etc. may be mentioned. The mixture contains, for example, resin (binder resin) such as acrylic resin, and inorganic and/or organic particles (preferably organic particles such as polystyrene). The thickness of the anti-blocking layer 5 is, for example, 0.1 μm or more, and for example, 10 μm or less.

透明膜6係透明膜基材2之必需之層。透明膜6係用以確保透明導電性膜3之機械強度之透明基材。透明膜6具有膜形狀，沿面方向延伸。透明膜6與抗黏連層5之厚度方向一面接觸。作為透明膜6之材料，例如可例舉：環烯烴樹脂(COP)、聚酯樹脂(聚對苯二甲酸乙二酯(PET)等)等樹脂。較佳可例舉環烯烴樹脂。又，透明膜6具有各向同性或雙折射性。透明膜基材2較佳為具有各向同性。透明膜基材2之面內方向之雙折射率例如為100以下，較佳為50以下，且例如為0以上。透明膜6之厚度例如為10 μm以上，且例如為100 μm以下。The transparent film 6 is an essential layer of the transparent film substrate 2. The transparent film 6 is a transparent substrate for ensuring the mechanical strength of the transparent conductive film 3. The transparent film 6 has a film shape and extends in the surface direction. The transparent film 6 is in contact with the anti-adhesion layer 5 on one side in the thickness direction. Examples of the material of the transparent film 6 include resins such as cycloolefin resin (COP) and polyester resin (polyethylene terephthalate (PET), etc.). Preferably, cycloolefin resin can be exemplified. In addition, the transparent film 6 has isotropy or birefringence. The transparent film substrate 2 preferably has isotropy. The birefringence in the in-plane direction of the transparent film base material 2 is, for example, 100 or less, preferably 50 or less, and for example, 0 or more. The thickness of the transparent film 6 is, for example, 10 μm or more, and for example, 100 μm or less.

硬塗層7係用以使透明導電性膜3不易產生擦傷之擦傷保護層。硬塗層7與透明膜6之厚度方向一面接觸。硬塗層7之材料例如為硬塗組合物。作為硬塗組合物，例如可例舉日本專利特開2016-179686號公報中記載之混合物等。混合物例如含有丙烯酸樹脂、胺基甲酸酯樹脂等樹脂(黏合劑樹脂)。硬塗層3之厚度例如為0.1 μm以上，且例如為10 μm以下。The hard coat layer 7 is a scratch protection layer for preventing the transparent conductive film 3 from being scratched. The hard coat layer 7 is in contact with the transparent film 6 on one side in the thickness direction. The material of the hard coat layer 7 is, for example, a hard coat composition. As a hard coating composition, the mixture etc. which are described in Unexamined-Japanese-Patent No. 2016-179686, etc. are mentioned, for example. The mixture contains resins (binder resins) such as acrylic resins and urethane resins, for example. The thickness of the hard coat layer 3 is, for example, 0.1 μm or more, and for example, 10 μm or less.

光學調整層8係抑制由結晶化銦錫複合氧化物膜1形成之圖案之視覺辨識而調整透明導電性膜3之光學物性(具體而言為折射率)之層。光學調整層8與硬塗層7之厚度方向一面接觸。光學調整層8之材料例如為光學調整組合物。作為光學調整組合物，例如可例舉日本專利特開2016-179686號公報中記載之混合物等。混合物例如含有丙烯酸樹脂等樹脂(黏合劑樹脂)、及無機及/或有機粒子(較佳為氧化鋯等無機粒子)。光學調整層8之厚度例如為0.05 μm以上，且例如為1 μm以下。The optical adjustment layer 8 is a layer that suppresses the visual recognition of the pattern formed by the crystallized indium tin composite oxide film 1 and adjusts the optical properties (specifically, the refractive index) of the transparent conductive film 3. The optical adjustment layer 8 is in contact with the hard coat layer 7 on one side in the thickness direction. The material of the optical adjustment layer 8 is, for example, an optical adjustment composition. As an optical adjustment composition, the mixture etc. which are described in Unexamined-Japanese-Patent No. 2016-179686, etc. are mentioned, for example. The mixture contains, for example, resin (binder resin) such as acrylic resin, and inorganic and/or organic particles (preferably inorganic particles such as zirconia). The thickness of the optical adjustment layer 8 is, for example, 0.05 μm or more, and for example, 1 μm or less.

光學調整層8之厚度方向一面之算術平均粗糙度Ra例如為2 nm以下，較佳為1 nm以下，更佳為0.75 nm以下，進而較佳為0.5 nm以下，且例如為0.001 nm以上。光學調整層8之厚度方向一面之算術平均粗糙度Ra根據JIS B0681-6(2017)求出。The arithmetic average roughness Ra of one side in the thickness direction of the optical adjustment layer 8 is, for example, 2 nm or less, preferably 1 nm or less, more preferably 0.75 nm or less, still more preferably 0.5 nm or less, and for example, 0.001 nm or more. The arithmetic average roughness Ra of one side in the thickness direction of the optical adjustment layer 8 is obtained according to JIS B0681-6 (2017).

透明膜基材2之厚度例如為10 μm以上，且例如為100 μm以下。透明膜基材2之全光線透過率例如為80%以上，較佳為90%以上，且例如為99%以下。The thickness of the transparent film substrate 2 is, for example, 10 μm or more, and for example, 100 μm or less. The total light transmittance of the transparent film substrate 2 is, for example, 80% or more, preferably 90% or more, and for example, 99% or less.

透明膜基材2之厚度方向一面之算術平均粗糙度Ra與上述光學調整層8之算術平均粗糙度Ra相同。The arithmetic average roughness Ra of one side in the thickness direction of the transparent film substrate 2 is the same as the arithmetic average roughness Ra of the optical adjustment layer 8 described above.

若透明膜基材2之厚度方向一面之算術平均粗糙度Ra為上述上限以下，則於對非晶質銦錫複合氧化物膜進行加熱而形成結晶化銦錫複合氧化物膜1時，可促進晶粒自與透明膜基材2之厚度方向一面接觸之面、即非晶質銦錫複合氧化物膜之厚度方向另一面向厚度方向一側生長。因此，可增大晶粒之平均粒徑。If the arithmetic average roughness Ra of one surface in the thickness direction of the transparent film substrate 2 is less than the above upper limit, heating the amorphous indium tin composite oxide film to form the crystalline indium tin composite oxide film 1 can promote The crystal grains grow from one side in contact with the transparent film base material 2 in the thickness direction, that is, from the other side in the thickness direction of the amorphous indium tin composite oxide film. Therefore, the average grain size of the crystal grains can be increased.

結晶化銦錫複合氧化物膜1與透明膜基材2之厚度方向一面接觸。結晶化銦錫複合氧化物膜1之厚度方向一面露出至厚度方向一側。結晶化銦錫複合氧化物膜1之厚度方向另一面與透明膜基材2之厚度方向一面密接(接觸)。結晶化銦錫複合氧化物膜1之厚度方向另一面之算術平均粗糙度Ra如上所述，例如為2 nm以下，較佳為1 nm以下，更佳為0.75 nm以下，進而較佳為0.5 nm以下，且例如為0.001 nm以上。The crystallized indium tin composite oxide film 1 and the transparent film substrate 2 are in one-surface contact in the thickness direction. One side in the thickness direction of the crystallized indium tin composite oxide film 1 is exposed to one side in the thickness direction. The other surface of the crystallized indium tin composite oxide film 1 in the thickness direction is in close contact (contact) with one surface of the transparent film substrate 2 in the thickness direction. The arithmetic average roughness Ra of the other side in the thickness direction of the crystalline indium tin composite oxide film 1 is as described above, for example, 2 nm or less, preferably 1 nm or less, more preferably 0.75 nm or less, and still more preferably 0.5 nm Below, for example, it is 0.001 nm or more.

透明導電性膜3之厚度例如為15 μm以上，且例如為120 μm以下。透明導電性膜3之全光線透過率例如為80%以上，較佳為90%以上，且例如為99%以下。 [透明導電性膜之製造方法] 繼而，對透明導電性膜之製造方法進行說明。The thickness of the transparent conductive film 3 is, for example, 15 μm or more, and for example, 120 μm or less. The total light transmittance of the transparent conductive film 3 is, for example, 80% or more, preferably 90% or more, and for example, 99% or less. [Method of manufacturing transparent conductive film] Next, the manufacturing method of a transparent conductive film is demonstrated.

透明導電性膜3之製造方法具備：第1步驟，其藉由對透明膜基材2之厚度方向一面進行濺鍍，形成非晶化銦錫複合氧化物膜；及第2步驟，其對非晶化銦錫複合氧化物膜進行加熱，形成結晶化銦錫複合氧化物膜1。又，於該製造方法中，將各層例如以卷對卷方式依次配置。The manufacturing method of the transparent conductive film 3 includes: a first step of forming an amorphous indium tin composite oxide film by sputtering one surface of the transparent film substrate 2 in the thickness direction; and a second step of forming an amorphous indium tin composite oxide film; The crystallized indium tin composite oxide film is heated to form a crystallized indium tin composite oxide film 1. Moreover, in this manufacturing method, each layer is arrange|positioned in order in a roll-to-roll system, for example.

於第1步驟中，首先準備透明膜基材2。In the first step, first, a transparent film substrate 2 is prepared.

例如，準備透明膜6。繼而，對透明膜6配置硬塗層7、抗黏連層5及光學調整層8。For example, a transparent film 6 is prepared. Then, a hard coat layer 7, an anti-blocking layer 5, and an optical adjustment layer 8 are arranged on the transparent film 6.

具體而言，首先，對透明膜6之厚度方向之兩面分別塗佈硬塗組合物之稀釋液及抗黏連組合物之稀釋液，進行乾燥後，藉由紫外線照射，分別使硬塗組合物及抗黏連組合物硬化。藉此，於透明膜6之厚度方向之兩面分別形成硬塗層7及抗黏連層5。其後，將光學調整組合物之稀釋液塗佈於硬塗層7之厚度方向一面，進行乾燥後，藉由紫外線照射，使光學調整組合物硬化。藉此，形成光學調整層8。藉此，準備朝厚度方向一側依次具備抗黏連層5、透明膜6、硬塗層7及光學調整層8之積層膜、即透明膜基材2。Specifically, first, the diluent of the hard coat composition and the diluent of the anti-blocking composition are respectively applied to both sides of the transparent film 6 in the thickness direction, and after drying, the hard coat composition is irradiated with ultraviolet rays. And the anti-adhesion composition hardens. Thereby, the hard coat layer 7 and the anti-blocking layer 5 are respectively formed on both surfaces of the transparent film 6 in the thickness direction. After that, the diluent of the optical adjustment composition is applied to one surface of the hard coat layer 7 in the thickness direction, and after drying, the optical adjustment composition is cured by ultraviolet irradiation. Thereby, the optical adjustment layer 8 is formed. Thereby, the transparent film base material 2 is prepared as a laminated film which is provided with the anti-blocking layer 5, the transparent film 6, the hard coat layer 7, and the optical adjustment layer 8 in this order toward the thickness direction side.

繼而，於第1步驟中，對透明膜基材2之厚度方向一面實施濺鍍。具體而言，於濺鍍裝置中，使透明膜基材2之厚度方向一面與包含銦錫複合氧化物之靶對向，與此同時在惰性氣體之存在下進行濺鍍。此時，除上述惰性氣體以外，例如亦可存在氧氣等反應性氣體。Then, in the first step, sputtering is performed on one surface of the transparent film substrate 2 in the thickness direction. Specifically, in the sputtering device, one surface of the transparent film substrate 2 in the thickness direction is opposed to a target containing an indium tin composite oxide, and at the same time, sputtering is performed in the presence of an inert gas. At this time, in addition to the above-mentioned inert gas, for example, a reactive gas such as oxygen may be present.

作為惰性氣體，例如可例舉氬氣等稀有氣體等。濺鍍裝置內之惰性氣體之分壓例如為0.1 Pa以上，較佳為0.3 Pa以上，更佳為0.5 Pa以上，進而較佳為0.55 Pa以上，且例如為10 Pa以下。若惰性氣體之分壓為上述下限以上，則濺鍍中之惰性氣體之原子能量降低。如此，可抑制非晶質銦錫複合氧化物膜吸收惰性氣體之原子。其結果，可促進晶粒之生長。藉此，可增大晶粒之平均粒徑。The inert gas may, for example, be a rare gas such as argon. The partial pressure of the inert gas in the sputtering device is, for example, 0.1 Pa or higher, preferably 0.3 Pa or higher, more preferably 0.5 Pa or higher, still more preferably 0.55 Pa or higher, and for example, 10 Pa or lower. If the partial pressure of the inert gas is higher than the above lower limit, the atomic energy of the inert gas in sputtering decreases. In this way, it is possible to prevent the amorphous indium tin composite oxide film from absorbing the atoms of the inert gas. As a result, the growth of crystal grains can be promoted. In this way, the average grain size of the crystal grains can be increased.

濺鍍裝置內之壓力係惰性氣體之分壓、及反應性氣體之分壓之合計壓力。The pressure in the sputtering device is the total pressure of the partial pressure of the inert gas and the partial pressure of the reactive gas.

再者，亦可於濺鍍裝置中將氧化錫濃度互不相同之第1靶及第2靶沿透明膜基材2之搬送方向依次配置。第1靶之材料例如為上述第1區域中之ITO(SnO2 濃度：8質量%以上)。第2靶之材料例如為上述第2區域中之ITO(SnO2 濃度：未達8質量%)。Furthermore, the first target and the second target having different tin oxide concentrations from each other may be sequentially arranged along the transport direction of the transparent film substrate 2 in the sputtering device. The material of the first target is, for example, ITO (SnO 2 concentration: 8% by mass or more) in the above-mentioned first region. The material of the second target is, for example, ITO (SnO 2 concentration: less than 8% by mass) in the second region.

藉由上述濺鍍，非晶質銦錫複合氧化物膜形成於透明膜基材2之厚度方向一面。Through the above-mentioned sputtering, an amorphous indium tin composite oxide film is formed on one side of the transparent film substrate 2 in the thickness direction.

再者，於非晶質銦錫複合氧化物膜藉由使用上述第1靶及第2靶之濺鍍而形成之情形時，非晶質銦錫複合氧化物膜朝厚度方向一側依次具備氧化錫濃度互不相同之第1非晶質層及第2非晶質層。第1非晶質層及第2非晶質層之各材料與第1靶及第2靶之材料相同。具體而言，第1非晶質層之ITO中之SnO2 濃度例如為8質量%以上。第2非晶質層之ITO中之SnO2 濃度例如未達8質量%。Furthermore, when the amorphous indium tin composite oxide film is formed by sputtering using the above-mentioned first target and the second target, the amorphous indium tin composite oxide film is sequentially provided with oxidation toward the thickness direction side. The first amorphous layer and the second amorphous layer with different tin concentrations. The materials of the first amorphous layer and the second amorphous layer are the same as the materials of the first target and the second target. Specifically, the SnO 2 concentration in the ITO of the first amorphous layer is, for example, 8% by mass or more. The SnO 2 concentration in the ITO of the second amorphous layer is less than 8% by mass, for example.

非晶質銦錫複合氧化物膜之厚度中之第1非晶質層之厚度之比率例如超過50%，較佳為70%以上，更佳為80%以上，進而較佳為90%以上。結晶化銦錫複合氧化物膜之厚度中之第1非晶質層之厚度之比率例如為99%以下，較佳為97%以下。The ratio of the thickness of the first amorphous layer in the thickness of the amorphous indium tin composite oxide film is, for example, more than 50%, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The ratio of the thickness of the first amorphous layer in the thickness of the crystalline indium tin composite oxide film is, for example, 99% or less, preferably 97% or less.

該非晶質銦錫複合氧化物膜尚未結晶化，即，其並非本發明之結晶化銦錫複合氧化物膜。非晶質銦錫複合氧化物膜係用以獲得結晶化銦錫複合氧化物膜之前驅物膜(中間材)。The amorphous indium tin composite oxide film has not yet been crystallized, that is, it is not the crystallized indium tin composite oxide film of the present invention. The amorphous indium tin composite oxide film is used to obtain a crystalline indium tin composite oxide film precursor film (intermediate material).

藉此，獲得包含透明膜基材2及非晶質銦錫複合氧化物膜之非晶質積層膜。Thereby, an amorphous laminated film including the transparent film base material 2 and the amorphous indium tin composite oxide film is obtained.

其後，於第2步驟中，對非晶質積層膜進行加熱。例如，藉由紅外線加熱器、烘箱等加熱裝置對非晶質銦錫複合氧化物膜進行加熱。Thereafter, in the second step, the amorphous laminated film is heated. For example, the amorphous indium tin composite oxide film is heated by a heating device such as an infrared heater and an oven.

加熱條件無特別限定。加熱溫度例如為90℃以上，較佳為110℃以上，且例如為160℃以下，較佳為140℃以下。加熱時間例如為30分鐘以上，更佳為60分鐘以上，且例如為5小時以下，較佳為3小時以下。The heating conditions are not particularly limited. The heating temperature is, for example, 90°C or higher, preferably 110°C or higher, and, for example, 160°C or lower, preferably 140°C or lower. The heating time is, for example, 30 minutes or more, more preferably 60 minutes or more, and for example, 5 hours or less, preferably 3 hours or less.

藉此，如圖1所示，非晶質銦錫複合氧化物層結晶化，形成包含複數個晶粒之結晶化銦錫複合氧化物膜1。As a result, as shown in FIG. 1, the amorphous indium tin composite oxide layer is crystallized to form a crystallized indium tin composite oxide film 1 including a plurality of crystal grains.

再者，於非晶質銦錫複合氧化物膜包含第1非晶質層及第2非晶質層之情形時，結晶化銦錫複合氧化物膜1包含與第1非晶質層及第2非晶質層分別對應之第1層11及第2區域12。Furthermore, when the amorphous indium tin composite oxide film includes the first amorphous layer and the second amorphous layer, the crystallized indium tin composite oxide film 1 includes the first amorphous layer and the second amorphous layer. The 2 amorphous layers correspond to the first layer 11 and the second region 12 respectively.

該結晶化銦錫複合氧化物膜1如上所述具有35 nm以上之厚度，又，含有平均粒徑為110 nm以上之晶粒。The crystallized indium tin composite oxide film 1 has a thickness of 35 nm or more as described above, and contains crystal grains with an average particle size of 110 nm or more.

藉此，製造具備透明膜基材2及結晶化銦錫複合氧化物膜1之透明導電性膜3。Thereby, the transparent conductive film 3 provided with the transparent film base material 2 and the crystallized indium tin composite oxide film 1 is manufactured.

其後，該透明導電性膜3例如藉由蝕刻等將結晶化銦錫複合氧化物膜1圖案化。經圖案化之結晶化銦錫複合氧化物膜1可用於觸控面板(觸控感測器)等之電極。After that, the transparent conductive film 3 is patterned, for example, by etching the crystallized indium tin composite oxide film 1. The patterned crystalline indium tin composite oxide film 1 can be used for electrodes of touch panels (touch sensors) and the like.

並且，該結晶化銦錫複合氧化物膜1之厚度厚至35 nm，故具有較低之表面電阻。In addition, the thickness of the crystalline indium tin composite oxide film 1 is as thick as 35 nm, so it has a low surface resistance.

又，該結晶化銦錫複合氧化物膜含有大至110 nm以上之平均粒徑之晶粒，故耐化學品性優異。In addition, the crystallized indium tin composite oxide film contains crystal grains with an average particle size of 110 nm or more, so it is excellent in chemical resistance.

因此，該透明導電性膜3之結晶化銦錫複合氧化物膜1之耐化學品性優異。Therefore, the crystallized indium tin composite oxide film 1 of the transparent conductive film 3 is excellent in chemical resistance.

又，結晶化銦錫複合氧化物膜1由於包含氧化錫之比率為8質量%以上之第1區域11，故可降低結晶化銦錫複合氧化物膜1之表面電阻。In addition, since the crystallized indium tin composite oxide film 1 contains the first region 11 whose tin oxide ratio is 8% by mass or more, the surface resistance of the crystallized indium tin composite oxide film 1 can be reduced.

又，該透明導電性膜3由於具備上述結晶化銦錫複合氧化物膜1，故具有較低之表面電阻，並且耐化學品性優異。In addition, since the transparent conductive film 3 includes the above-mentioned crystallized indium tin composite oxide film 1, it has a low surface resistance and is excellent in chemical resistance.

又，於該透明導電性膜3中，若透明膜基材2之厚度方向一面具有小至1.0 nm以下之算術平均粗糙度Ra，則可抑制配置於透明膜基材2之厚度方向一面之非晶質銦錫複合氧化物膜之結晶生長被阻礙，於結晶化銦錫複合氧化物膜1中形成平均粒徑較大之晶粒。其結果，透明導電性膜之耐化學品性優異。In addition, in the transparent conductive film 3, if one surface of the transparent film substrate 2 in the thickness direction has an arithmetic mean roughness Ra as small as 1.0 nm or less, it is possible to suppress non-uniformity on one surface of the transparent film substrate 2 in the thickness direction. The crystal growth of the crystalline indium tin composite oxide film is hindered, and crystal grains with a larger average particle size are formed in the crystallized indium tin composite oxide film 1. As a result, the transparent conductive film has excellent chemical resistance.

於該透明導電性膜3之製造方法之第1步驟中，若於高至0.4 Pa以上之分壓之惰性氣體之存在下進行濺鍍，則可於結晶化銦錫複合氧化物膜1中形成平均粒徑較大之晶粒。其結果，可製造具備耐化學品性優異之結晶化銦錫複合氧化物膜1之透明導電性膜3。In the first step of the manufacturing method of the transparent conductive film 3, if sputtering is performed in the presence of an inert gas with a partial pressure of 0.4 Pa or more, it can be formed in the crystallized indium tin composite oxide film 1. Crystal grains with larger average particle size. As a result, the transparent conductive film 3 provided with the crystalline indium tin composite oxide film 1 excellent in chemical resistance can be manufactured.

變化例 於變化例中，針對與一實施方式相同之構件及步驟，標附相同之參照符號，省略其詳細之說明。又，除特別記載以外，變化例可發揮與一實施方式相同之作用效果。進而，可適當組合一實施方式及其變化例。Variations In the modified example, the same reference symbols are attached to the same components and steps as in the first embodiment, and detailed descriptions thereof are omitted. In addition, except for special descriptions, the modified example can exhibit the same effects as in the first embodiment. Furthermore, an embodiment and its modification examples can be combined as appropriate.

結晶化銦錫複合氧化物膜亦可不包含氧化錫之比率未達8質量%之第2區域，而僅包含氧化錫之比率為8質量%以上之第1區域。The crystallized indium tin composite oxide film may not include the second area where the ratio of tin oxide is less than 8% by mass, and only include the first area where the ratio of tin oxide is 8% by mass or more.

透明膜基材2只要具備透明膜6，則無特別限定。本發明包含如下態樣：例如，透明膜基材2僅具備透明膜6之第1態樣；例如，透明膜基材2具備透明膜6、及選自由抗黏連層5、硬塗層7及光學調整層8所組成之群中之1層之第2態樣(共2層構成)；例如，透明膜基材2具備透明膜6、及選自由抗黏連層5、硬塗層7及光學調整層8所組成之群中之2層之第3態樣(共3層構成)。The transparent film base material 2 is not particularly limited as long as it includes the transparent film 6. The present invention includes the following aspects: for example, the transparent film substrate 2 only has the first aspect of the transparent film 6; for example, the transparent film substrate 2 has the transparent film 6, and is selected from the group consisting of an anti-blocking layer 5 and a hard coat layer 7. And the second aspect of 1 layer in the group consisting of the optical adjustment layer 8 (total of 2 layers); for example, the transparent film substrate 2 has a transparent film 6 and is selected from the group consisting of an anti-blocking layer 5 and a hard coat layer 7 And the third aspect of 2 layers in the group consisting of the optical adjustment layer 8 (a total of 3 layers).

作為第3態樣(共3層構成)之一例，如圖2所示，透明膜基材2不具備硬塗層7(參照圖1)，而僅具備抗黏連層5、透明膜6及光學調整層8。 [實施例]As an example of the third aspect (a total of 3 layers), as shown in FIG. 2, the transparent film substrate 2 does not have the hard coat layer 7 (refer to FIG. 1), but only has the anti-blocking layer 5, the transparent film 6, and Optical adjustment layer 8. [Example]

以下示出實施例及比較例，更具體地對本發明進行說明。再者，本發明並不受實施例及比較例任何限定。又，以下記載中使用之調配比率(含有比率)、物性值、參數等具體數值可替代為上述「實施方式」中記載之與該等對應之調配比率(含有比率)、物性值、參數等相應記載之上限(定義為「以下」、「未達」之數值)或下限(定義為「以上」、「超過」之數值)。Examples and comparative examples are shown below to describe the present invention more specifically. Furthermore, the present invention is not limited in any way by the examples and comparative examples. In addition, the specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following description can be replaced with the corresponding blending ratios (content ratio), physical property values, parameters, etc., described in the above-mentioned "embodiment". The upper limit (defined as the value "below" or "not reached") or lower limit (defined as the value "above" or "exceeding") of the record.

實施例1 首先，準備包含環烯烴樹脂之透明膜6(COP膜，厚度40 μm，日本瑞翁公司製造，「ZEONOR」(註冊商標)，面內之雙折射率0.0001)。Example 1 First, a transparent film 6 containing cycloolefin resin (COP film, thickness 40 μm, manufactured by Zeon Corporation, "ZEONOR" (registered trademark), in-plane birefringence 0.0001) is prepared.

繼而，於透明膜6之厚度方向一面塗佈包含黏合劑樹脂(胺基甲酸酯多官能聚丙烯酸酯，商品名「UNIDIC」，DIC公司製造)之硬塗組合物之稀釋液，並且於透明膜6之厚度方向另一面塗佈含有黏合劑樹脂(胺基甲酸酯多官能聚丙烯酸酯，商品名「UNIDIC」，DIC公司製造)及粒子(交聯丙烯酸樹脂-苯乙烯樹脂粒子，商品名「SSX105」，直徑3 μm，積水樹脂公司製造)之抗黏連組合物之稀釋液，繼而，對該等進行乾燥後，對透明膜6之厚度方向之兩面分別照射紫外線，使硬塗組合物及抗黏連組合物硬化。藉此，於透明膜6之一面形成厚度1 μm之硬塗層7，於透明膜6之厚度方向另一面形成厚度1 μm之抗黏連層5。Then, on one side in the thickness direction of the transparent film 6, a diluent of a hard coating composition containing a binder resin (urethane polyfunctional polyacrylate, trade name "UNIDIC", manufactured by DIC) was applied, and the transparent film The other side of the film 6 in the thickness direction is coated with a binder resin (urethane polyfunctional polyacrylate, trade name "UNIDIC", manufactured by DIC) and particles (crosslinked acrylic resin-styrene resin particles, trade name) "SSX105", a diameter of 3 μm, manufactured by Sekisui Jushi Co., Ltd.) is a diluent of the anti-blocking composition. After drying these, the transparent film 6 is irradiated with ultraviolet rays on both sides in the thickness direction to make the hard coating And the anti-adhesion composition hardens. Thereby, a hard coat layer 7 with a thickness of 1 μm is formed on one surface of the transparent film 6 and an anti-adhesion layer 5 with a thickness of 1 μm is formed on the other surface of the transparent film 6 in the thickness direction.

繼而，於硬塗層之厚度方向一面塗佈含有氧化鋯粒子及紫外線硬化性樹脂(丙烯酸樹脂)之光學調整組合物之稀釋液(「Opstar Z7412」，JSR公司製造，折射率1.62)，於80℃下進行3分鐘乾燥後，照射紫外線。藉此，於硬塗層7之厚度方向一面形成厚度0.1 μm之光學調整層8。藉此，獲得包含抗黏連層5、透明膜6、硬塗層7及光學調整層8之積層膜作為透明膜基材2。Then, a diluent ("Opstar Z7412", manufactured by JSR Corporation, refractive index 1.62) of an optical adjustment composition containing zirconia particles and ultraviolet curable resin (acrylic resin) was applied to one side in the thickness direction of the hard coat layer. After drying for 3 minutes at °C, ultraviolet rays were irradiated. Thereby, an optical adjustment layer 8 with a thickness of 0.1 μm is formed on one side of the hard coat layer 7 in the thickness direction. Thereby, a laminated film including the anti-blocking layer 5, the transparent film 6, the hard coat layer 7 and the optical adjustment layer 8 as the transparent film base material 2 is obtained.

其後，藉由濺鍍於光學調整層8之厚度方向一面形成厚度39.7 nm之非晶質銦錫複合氧化物層1。Thereafter, an amorphous indium tin composite oxide layer 1 with a thickness of 39.7 nm was formed on one side of the optical adjustment layer 8 in the thickness direction by sputtering.

詳細而言，首先，於濺鍍裝置，自透明膜基材2之搬送方向上游側向下游側依次配置包含氧化錫濃度為10重量%之ITO之第1靶、及包含氧化錫濃度為3.3重量%之ITO之第2靶。繼而，以非晶質銦錫複合氧化物膜中之第1非晶質層之厚度之比率、及第2非晶質層之厚度之比率分別成為95%及5%之方式進行濺鍍。再者，非晶質銦錫複合氧化物膜朝厚度方向一側依次包含第1非晶質層(氧化錫濃度10質量%)及第2非晶質層(氧化錫濃度3.3質量%)。In detail, first, in the sputtering device, a first target containing ITO with a tin oxide concentration of 10% by weight and a tin oxide concentration of 3.3% by weight are sequentially arranged from the upstream side to the downstream side in the transport direction of the transparent film substrate 2 % Of the second target of ITO. Then, sputtering is performed so that the ratio of the thickness of the first amorphous layer and the ratio of the thickness of the second amorphous layer in the amorphous indium tin composite oxide film become 95% and 5%, respectively. Furthermore, the amorphous indium tin composite oxide film includes a first amorphous layer (a tin oxide concentration of 10% by mass) and a second amorphous layer (a tin oxide concentration of 3.3% by mass) in this order toward one side in the thickness direction.

藉由調整濺鍍時之氬氣流量，將濺鍍裝置內之氬氣分壓調整為0.35 Pa。再者，濺鍍裝置內之壓力為0.42 Pa。By adjusting the flow of argon during sputtering, the partial pressure of argon in the sputtering device is adjusted to 0.35 Pa. Furthermore, the pressure inside the sputtering device is 0.42 Pa.

藉此，製造依次具備抗黏連層5、透明膜6、硬塗層7、光學調整層8及非晶質銦錫複合氧化物層之非晶質積層膜。Thereby, an amorphous laminated film including the anti-blocking layer 5, the transparent film 6, the hard coat layer 7, the optical adjustment layer 8 and the amorphous indium tin composite oxide layer in this order is manufactured.

其後，於130℃下對非晶質積層膜加熱90分鐘，使非晶質銦錫複合氧化物層結晶化，製備結晶化銦錫複合氧化物膜1。Thereafter, the amorphous laminated film was heated at 130° C. for 90 minutes to crystallize the amorphous indium tin composite oxide layer, and the crystallized indium tin composite oxide film 1 was prepared.

藉此，如圖1所示，製造具備抗黏連層5、透明膜6、硬塗層7、光學調整層8及結晶化銦錫複合氧化物膜1之透明導電性膜3。Thereby, as shown in FIG. 1, a transparent conductive film 3 including an anti-blocking layer 5, a transparent film 6, a hard coat layer 7, an optical adjustment layer 8 and a crystalline indium tin composite oxide film 1 is manufactured.

又，結晶化銦錫複合氧化物膜1包含由第1非晶質層及第2非晶質層之各者形成之第1區域11及第2區域12。In addition, the crystallized indium tin composite oxide film 1 includes a first region 11 and a second region 12 formed by each of a first amorphous layer and a second amorphous layer.

比較例1～比較例2 按照表1之記載變更配方，除此以外，以與實施例1相同之方式處理。Comparative example 1 to comparative example 2 The formula was changed according to the description in Table 1, and the treatment was performed in the same manner as in Example 1 except for this.

實施例2 形成厚度0.7 μm之光學調整層8代替實施例1之硬塗層7及光學調整層8，除此以外，以與實施例1相同之方式處理。Example 2 The optical adjustment layer 8 with a thickness of 0.7 μm was formed instead of the hard coat layer 7 and the optical adjustment layer 8 of Example 1, and the treatment was performed in the same manner as in Example 1, except for this.

即，如圖2所示，該透明膜基材2依次具備抗黏連層5、透明膜6、光學調整層8，而不具備硬塗層7。That is, as shown in FIG. 2, the transparent film base material 2 includes an anti-blocking layer 5, a transparent film 6, and an optical adjustment layer 8 in this order, but does not include a hard coat layer 7.

再者，該光學調整層8將含有氧化鋯粒子、氧化矽粒子及紫外線硬化性樹脂(丙烯酸樹脂)之光學調整組合物之稀釋液(「TYZ72-A12」TOYOCHEM公司製造，折射率1.72)塗佈於透明膜6之厚度方向一面面，於80℃下乾燥3分鐘後，照射紫外線。Furthermore, the optical adjustment layer 8 is coated with a diluent ("TYZ72-A12" manufactured by TOYOCHEM Corporation, refractive index 1.72) of an optical adjustment composition containing zirconia particles, silica particles, and ultraviolet curable resin (acrylic resin) After drying at 80°C for 3 minutes on one side in the thickness direction of the transparent film 6, ultraviolet rays were irradiated.

實施例3～實施例6 按照表1之記載變更配方，除此以外，以與實施例2相同之方式處理。 實施例7 濺鍍裝置不具備第2靶，按照表1之記載變更配方，除此以外，以與實施例2相同之方式處理。 非晶質銦錫複合氧化物膜包含第1非晶質層，而不包含第2非晶質層。結晶化銦錫複合氧化物膜1包含第1區域11，而不包含第2區域12。Example 3 ~ Example 6 The formula was changed according to the description in Table 1, and the treatment was performed in the same manner as in Example 2 except for this. Example 7 The sputtering apparatus did not include the second target, and the formula was changed according to the description in Table 1, and the treatment was performed in the same manner as in Example 2 except that. The amorphous indium tin composite oxide film includes the first amorphous layer, but does not include the second amorphous layer. The crystallized indium tin composite oxide film 1 includes the first region 11 and does not include the second region 12.

＜評估＞ 對下述項目進行評估。將該等結果示於表1。＜Evaluation＞ Evaluate the following items. These results are shown in Table 1.

[晶粒之平均粒徑] 對各實施例及各比較例中之透明導電性膜3之結晶化銦錫複合氧化物膜1之厚度方向一面進行SEM觀察。[Average size of crystal grains] SEM observation was performed on one side in the thickness direction of the crystallized indium tin composite oxide film 1 of the transparent conductive film 3 in each example and each comparative example.

將SEM觀察所確認之複數個多邊形狀之粒子定義為ITO之晶粒。然後，求出複數個晶粒之各面積。算出用各晶粒之面積除以圓周率(π)所得之值，將該值之平方根之2倍值之平均值作為晶粒之平均粒徑。The plurality of polygonal particles confirmed by SEM observation are defined as ITO crystal grains. Then, the areas of the plural crystal grains are obtained. Calculate the value obtained by dividing the area of each crystal grain by the circumference ratio (π), and the average value of the square root of this value twice as the average grain size.

於SEM觀察中，獲得縱1500 nm、橫1500 nm之視野像。於該視野像中，特定出將晶粒分隔之晶界。基於該晶界，求出複數個晶粒之面積。算出用1個晶粒之面積除以圓周率(π)所得之值，將該值之平方根之2倍值近似為1個晶粒之粒徑。再者，將粒徑未達20 nm之晶粒排除在平均值之計算外。 即，僅將粒徑為20 nm以上且上述視野像中觀察之晶粒中未自視野像伸出(即，該晶粒整體(全部)落入視野像內)之複數個晶粒之面積及數量用於算出平均值，其結果，將所獲得之平均值作為「晶粒之平均粒徑」。In the SEM observation, a visual field image of 1500 nm in length and 1500 nm in width was obtained. In this visual field image, the grain boundary separating the crystal grains is identified. Based on this grain boundary, the area of a plurality of crystal grains is obtained. Calculate the value obtained by dividing the area of one crystal grain by the pi (π), and approximate the square root of this value twice as the size of one crystal grain. Furthermore, crystal grains with a particle size of less than 20 nm are excluded from the calculation of the average value. That is, only the area of a plurality of crystal grains that are not protruding from the field image (that is, the entire (all) of the crystal grain falls within the field of view image) among the crystal grains that have a grain size of 20 nm or more and are observed in the field of view image and The quantity is used to calculate the average value, and as a result, the obtained average value is regarded as the "average grain size of crystal grains".

裝置及測定條件如下所述。 SEM裝置：Hitachi High-Technologies製造，掃描電子顯微鏡SU8020 加速電壓：0.8 kV 將實施例1之SEM照片之圖像處理圖示於圖3A，將比較例2之SEM照片之圖像處理圖示於圖3B。The equipment and measurement conditions are as follows. SEM device: manufactured by Hitachi High-Technologies, scanning electron microscope SU8020 Accelerating voltage: 0.8 kV The image processing diagram of the SEM photograph of Example 1 is shown in FIG. 3A, and the image processing diagram of the SEM photograph of Comparative Example 2 is shown in FIG. 3B.

[結晶化銦錫複合氧化物膜之表面電阻] 藉由四端子法對各實施例及各比較例中之透明導電性膜3之結晶化銦錫複合氧化物膜1之表面電阻進行測定。基於下述基準，對表面電阻進行評估。 ◎：表面電阻為40 Ω/□以下。 ○：表面電阻為60 Ω/□以下且超過40 Ω/□。 ×：表面電阻超過60 Ω/□。[Surface resistance of crystallized indium tin composite oxide film] The surface resistance of the crystallized indium tin composite oxide film 1 of the transparent conductive film 3 in each example and each comparative example was measured by the four-terminal method. Based on the following criteria, the surface resistance was evaluated. ◎: The surface resistance is 40 Ω/□ or less. ○: The surface resistance is 60 Ω/□ or less and more than 40 Ω/□. ×: The surface resistance exceeds 60 Ω/□.

[結晶化銦錫複合氧化物膜之耐化學品性] 用截切刀劃傷各實施例及各比較例中之透明導電性膜3之結晶化銦錫複合氧化物膜1之厚度方向一面。[Chemical resistance of crystalline indium tin composite oxide film] The crystalline indium tin composite oxide film 1 of the transparent conductive film 3 in each example and each comparative example was scratched with a cutter blade in the thickness direction.

其後，將透明導電性膜3於16質量%過硫酸銨水溶液中在20℃下浸漬5分鐘。其後，於3質量%氫氧化鉀水溶液中，在30℃下浸漬20分鐘。After that, the transparent conductive film 3 was immersed in a 16% by mass ammonium persulfate aqueous solution at 20° C. for 5 minutes. After that, it was immersed in a 3% by mass potassium hydroxide aqueous solution at 30°C for 20 minutes.

其後，藉由光學顯微鏡觀察劃痕，基於下述基準，對耐化學品性進行評估。 ×：確認到大量自劃痕延伸之裂紋部分。 ○：確認到極少之上述裂紋部分。 ◎：未確認到上述裂紋部分。Thereafter, the scratches were observed with an optical microscope, and the chemical resistance was evaluated based on the following criteria. ×: A large number of cracked parts extending from the scratch are confirmed. ○: The above-mentioned cracked part was confirmed very rarely. ⊚: The above-mentioned cracked part is not confirmed.

[透明膜基材之算術平均粗糙度Ra] 根據JIS B0681-6(2017)，使用原子力顯微鏡(Digital Instruments公司製造，Nonoscope IV)，求出形成非晶質銦錫複合氧化物膜前之透明導電性膜3、即透明膜基材2之厚度方向一面之算術平均粗糙度Ra。藉由原子力顯微鏡對透明膜基材2之厚度方向一面中1 μm×1 μm之範圍(視野像)進行觀察。[Arithmetic average roughness Ra of transparent film substrate] According to JIS B0681-6 (2017), using an atomic force microscope (manufactured by Digital Instruments, Nonoscope IV), the thickness of the transparent conductive film 3 before the amorphous indium tin composite oxide film is formed, that is, the transparent film substrate 2 The arithmetic average roughness of one side of the direction Ra. An atomic force microscope was used to observe a range of 1 μm×1 μm (field image) on one surface of the transparent film substrate 2 in the thickness direction.

[結晶化銦錫複合氧化物膜中之氧化錫之含有比率] 首先，根據第1靶及第2靶中之氧化錫濃度、非晶化銦錫複合氧化物膜中之第1非晶質層之厚度及第2非晶質層之厚度之比率，求出非晶化銦錫複合氧化物膜中之氧化錫之含有比率。[Content ratio of tin oxide in crystallized indium tin composite oxide film] First, the ratio of the concentration of tin oxide in the first target and the second target, the thickness of the first amorphous layer and the thickness of the second amorphous layer in the amorphous indium tin composite oxide film is used to determine the The content ratio of tin oxide in the crystalline indium tin composite oxide film.

於自非晶化銦錫複合氧化物膜向結晶化銦錫複合氧化物膜之轉化中，假定氧化錫濃度無變動，則將非晶化銦錫複合氧化物膜中之氧化錫之含有比率推定為結晶化銦錫複合氧化物膜中之氧化錫之含有比率。In the conversion from an amorphous indium tin composite oxide film to a crystalline indium tin composite oxide film, assuming that the tin oxide concentration does not change, the content ratio of tin oxide in the amorphous indium tin composite oxide film is estimated It is the content ratio of tin oxide in the crystalline indium tin composite oxide film.

[表1] 表1 實施例、比較例 透明基材膜之層構成 透明基材膜(光學調整層)之厚度方向一面之算術平均粗糙度Ra 濺鍍裝置中之氬氣分壓 非晶質銦錫複合氧化物層 結晶化銦錫複合氧化物層 抗黏連層 透明膜 硬塗層 光學調整層 厚度比 氧化錫之 含有比率 厚度 晶粒之平均粒徑 耐化學品性 表面電阻 厚度(μm) (nm) (Pa) 第1非晶質層* 1 (%) 第2非晶質層* 2 (%) (%) (nm) (nm) (Ω/□) 評估 實施例1 1 40 1 0.1 1.5 0.35 95 5 9.7 39.7 160 〇 50 〇 比較例1 1 40 1 0.1 1.5 0.35 90 10 9.3 32 240 ◎ 70 × 比較例2 1 40 1 0.1 1.5 0.35 95 5 9.7 68.9 100 × 30 ◎ 實施例2 1 40 - 0.7 0.4 0.35 95 5 9.7 39.7 210 ◎ 50 〇 實施例3 1 40 - 0.7 0.4 0.35 95 5 9.7 57.9 170 〇 40 ◎ 實施例4 1 40 - 0.7 0.4 0.55 95 5 9.7 39.5 450 ◎ 50 〇 實施例5 1 40 - 0.7 0.4 0.55 95 5 9.7 150 110 〇 15 ◎ 實施例6 1 40 - 0.7 0.4 0.55 75 25 8.3 86 170 〇 30 ◎ 實施例7 1 25 - 0.7 0.4 0.35 100 0 10 38 220 ◎ 40 ◎ *1：SnO2 濃度10%之ITO *2：SnO2 濃度3.3%之ITO 再者，上述發明係作為本發明之例示之實施方式而提供，其僅為例示，不作限定性地解釋。對於該技術領域之業者而言顯而易見之本發明之變化例包含於下述發明申請專利範圍。 [產業上之可利用性] 結晶化銦錫複合氧化物膜由透明導電性膜所具備。[Table 1] Table 1 Examples, comparative examples Layer composition of transparent base film The arithmetic average roughness of one side in the thickness direction of the transparent base film (optical adjustment layer) Ra Argon partial pressure in sputtering device Amorphous indium tin composite oxide layer Crystallized indium tin composite oxide layer Anti-blocking layer Transparent film Hard coating Optical adjustment layer Thickness ratio The content of tin oxide thickness Average grain size Chemical resistance Surface resistance Thickness (μm) (nm) (Pa) The first amorphous layer * 1 (%) The second amorphous layer * 2 (%) (%) (nm) (nm) (Ω/□) Assessment Example 1 1 40 1 0.1 1.5 0.35 95 5 9.7 39.7 160 〇 50 〇 Comparative example 1 1 40 1 0.1 1.5 0.35 90 10 9.3 32 240 ◎ 70 X Comparative example 2 1 40 1 0.1 1.5 0.35 95 5 9.7 68.9 100 X 30 ◎ Example 2 1 40 - 0.7 0.4 0.35 95 5 9.7 39.7 210 ◎ 50 〇 Example 3 1 40 - 0.7 0.4 0.35 95 5 9.7 57.9 170 〇 40 ◎ Example 4 1 40 - 0.7 0.4 0.55 95 5 9.7 39.5 450 ◎ 50 〇 Example 5 1 40 - 0.7 0.4 0.55 95 5 9.7 150 110 〇 15 ◎ Example 6 1 40 - 0.7 0.4 0.55 75 25 8.3 86 170 〇 30 ◎ Example 7 1 25 - 0.7 0.4 0.35 100 0 10 38 220 ◎ 40 ◎ *1: ITO with SnO 2 concentration 10% *2: ITO with SnO 2 concentration 3.3% In addition, the above-mentioned invention is provided as an exemplary embodiment of this invention, and it is only an illustration, and is not interpreted restrictively. Variations of the present invention that are obvious to those skilled in the art are included in the scope of the following invention applications. [Industrial Applicability] The crystallized indium tin composite oxide film is provided by a transparent conductive film.

1:結晶化銦錫複合氧化物膜 2:透明膜基材 3:透明導電性膜 5:抗黏連層 6:透明膜 7:硬塗層 8:光學調整層 9:晶粒 10:晶界 11:第1區域 12:第2區域1: Crystallized indium tin composite oxide film 2: Transparent film substrate 3: Transparent conductive film 5: Anti-blocking layer 6: Transparent film 7: Hard coating 8: Optical adjustment layer 9: Die 10: Grain boundary 11: Zone 1 12: Zone 2

圖1係本發明之結晶化銦錫複合氧化物膜及透明導電性膜之一實施方式之剖視圖。 圖2係圖1所示之透明導電性膜之變化例之剖視圖。 圖3A～圖3B係實施例之評估中之SEM照片之圖像處理圖，圖3A表示實施例1，圖3B表示比較例2。FIG. 1 is a cross-sectional view of an embodiment of a crystalline indium tin composite oxide film and a transparent conductive film of the present invention. Fig. 2 is a cross-sectional view of a modified example of the transparent conductive film shown in Fig. 1. 3A to 3B are image processing diagrams of SEM photographs in the evaluation of the examples. FIG. 3A shows Example 1, and FIG. 3B shows Comparative Example 2.

9:晶粒 9: Die

10:晶界 10: Grain boundary

Claims (5)

一種結晶化銦錫複合氧化物膜，其特徵在於：其具有35 nm以上之厚度，且 含有平均粒徑為110 nm以上之晶粒。A crystalline indium tin composite oxide film, characterized in that it has a thickness of more than 35 nm, and Contains crystal grains with an average particle size of 110 nm or more. 如請求項1之結晶化銦錫複合氧化物膜，其包含氧化錫之比率為8質量%以上之區域。Such as the crystalline indium tin composite oxide film of claim 1, which contains a region where the ratio of tin oxide is 8% by mass or more. 一種透明導電性膜，其特徵在於具備： 透明膜基材；及 配置於上述膜基材之厚度方向一面之如請求項1或2之結晶化銦錫複合氧化物膜。A transparent conductive film, which is characterized by having: Transparent film substrate; and The crystallized indium tin composite oxide film of claim 1 or 2 arranged on one side of the film substrate in the thickness direction. 如請求項3之透明導電性膜，其中上述透明膜基材之上述厚度方向一面具有1.0 nm以下之算術平均粗糙度Ra。The transparent conductive film of claim 3, wherein one side of the thickness direction of the transparent film substrate has an arithmetic average roughness Ra of 1.0 nm or less. 一種透明導電性膜之製造方法，其特徵在於：其係製造如請求項3或4之透明導電性膜之方法，該方法具備： 第1步驟，其藉由對上述透明膜基材之上述厚度方向一面進行濺鍍，形成非晶化銦錫複合氧化物膜；及 第2步驟，其對上述非晶化銦錫複合氧化物膜進行加熱，形成結晶化銦錫複合氧化物膜； 於上述第1步驟中，於分壓0.4 Pa以上之惰性氣體之存在下實施濺鍍。A method for manufacturing a transparent conductive film, characterized in that it is a method for manufacturing a transparent conductive film as claimed in claim 3 or 4, and the method includes: The first step is to form an amorphous indium tin composite oxide film by sputtering one surface of the transparent film substrate in the thickness direction; and The second step is to heat the above-mentioned amorphous indium tin composite oxide film to form a crystalline indium tin composite oxide film; In the first step above, sputtering is performed in the presence of an inert gas with a partial pressure of 0.4 Pa or more.
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