JP2014007100A - Transparent conductive film and method for producing the same - Google Patents
Transparent conductive film and method for producing the same Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 15
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 238000004544 sputter deposition Methods 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000010408 film Substances 0.000 description 136
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 31
- 239000001301 oxygen Substances 0.000 description 31
- 229910052760 oxygen Inorganic materials 0.000 description 31
- 230000015572 biosynthetic process Effects 0.000 description 15
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- 229910001873 dinitrogen Inorganic materials 0.000 description 12
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000007602 hot air drying Methods 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
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- 238000009833 condensation Methods 0.000 description 3
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- 230000007423 decrease Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QVGXLLKOCUKJST-BJUDXGSMSA-N oxygen-15 atom Chemical compound [15O] QVGXLLKOCUKJST-BJUDXGSMSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- QVGXLLKOCUKJST-OUBTZVSYSA-N oxygen-17 atom Chemical compound [17O] QVGXLLKOCUKJST-OUBTZVSYSA-N 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Abstract
Description
本発明は、透明基板上に設けられる発熱体用の透明導電膜及びその製造方法に関する。 The present invention relates to a transparent conductive film for a heating element provided on a transparent substrate and a method for producing the same.
寒冷地や冬場において道路表示灯，屋外表示装置，屋外照明装置，車両窓などの融雪，結露防止や曇り止めを行うために、透明導電膜を透明発熱体として用いるニーズがある。特に近年、熱を放出しにくいＬＥＤを用いた信号や電球等が多く用いられるようになったことで、信号や電球の融雪や結露防止を行う透明発熱体からなるデフロスターのニーズが高まっている。 There is a need to use a transparent conductive film as a transparent heating element in order to prevent snow melting, condensation, and anti-fogging in road indicators, outdoor display devices, outdoor lighting devices, vehicle windows and the like in cold and winter areas. Particularly in recent years, the need for defrosters made of transparent heating elements for preventing melting of snow and condensation of signals and light bulbs has increased due to the increasing use of signals and light bulbs using LEDs that do not easily release heat.
透明導電膜からなる透明発熱体には、１０００〜１００００Ω／ｓｑ程度のシート抵抗が求められ、このシート抵抗は、デジタルタッチパネル用電極として用いられる透明導電膜で１５０Ω／ｓｑ程度以下、アナログタッチパネル用電極として用いられる透明導電膜で４００〜８００Ω／ｓｑ程度の低抵抗が求められるのに対し、比較的高い値である。
そこで、透明導電膜を高抵抗側にシフトさせるために、ＩＴＯにＳｉＯ２を添加して透明導電膜を得る技術が知られている（例えば特許文献１）。
A transparent heating element made of a transparent conductive film is required to have a sheet resistance of about 1000 to 10000 Ω / sq. This sheet resistance is about 150 Ω / sq or less for a transparent conductive film used as an electrode for a digital touch panel. The transparent conductive film used as a low resistance of about 400 to 800 Ω / sq is required, whereas it is a relatively high value.
Therefore, a technique for obtaining a transparent conductive film by adding SiO 2 to ITO in order to shift the transparent conductive film to the high resistance side is known (for example, Patent Document 1).
特許文献１では、ＳｎＯ２，ＳｉＯ２，Ｉｎ２Ｏ３を含む成形体を焼成・焼結させて得たターゲットを用いて、ＤＣマグネトロンスパッタによりガラス基板上に厚さ１２００Åの透明導電膜を成膜したところ、０．７８〜２２×１０−３Ω・ｃｍの範囲の抵抗率で、透過率８８％以上の透明導電膜が得られることが開示されている。抵抗率をシート抵抗に換算すると、６５〜１８３３Ω／ｓｑの範囲となり、特に、ターゲット中のＳｉＯ２濃度が１０ｗｔ％のときに、１７５０又は１８３３Ω／ｓｑの高抵抗膜が得られることが開示されている。
In
しかし、特許文献１のように、ＩＴＯにＳｉＯ２を添加して得た透明導電膜では、高いシート抵抗は得られるものの、シート抵抗を細かく調整することが難しく、各製品に求められるシート抵抗の値に設定しにくかった。
特に、５００Ω／ｓｑより高いシート抵抗の範囲では、シート抵抗が高くなるにつれて当然膜厚を薄く設定する必要があるが、成膜中の酸素濃度の変動や装置内の残留水分の影響が相対的に大きくなり膜性能に敏感に表れる結果、成膜そのものが徐々に難しくなり、歩留まりが低下していく。特許文献１ではシート抵抗１８００Ω／ｓｑの膜が得られてはいるが、この１８００Ω／ｓｑ程度のシート抵抗では、薄膜として形成はされるものの抵抗値が不安定であり、さらに透過率をも考慮して双方を一定の値に安定させることは困難で、歩留まりが低くなることが分かっている。
However, as in
In particular, in the sheet resistance range higher than 500 Ω / sq, it is necessary to set the film thickness to be thinner as the sheet resistance increases. However, the relative influence of fluctuations in oxygen concentration during film formation and the residual moisture in the apparatus is relatively high. As a result, it becomes difficult to form the film itself and the yield decreases. Although a film having a sheet resistance of 1800 Ω / sq is obtained in
更に高い数千Ω／ｓｑ以上のシート抵抗の実現を図っても、ＩＴＯにＳｉＯ２を添加して成膜する方法では、安定的に成膜することが事実上不可能で、実用化が困難であった。
また、例えば、窓の曇り止め、寒冷地での信号のデフロスターなどの用途では、電気コネクタの取付け等のためにリフローハンダ付け等の工程が必要となることがあり、３００℃程度までの加熱に対する耐熱性が求められるものの、ＩＴＯにＳｉＯ２を添加して得た透明導電膜では、耐熱性が不十分であった。この点は、後述の本発明における対比例のデータにも示されている。
Even if a sheet resistance of several thousand Ω / sq or higher is achieved, it is virtually impossible to form a film by adding SiO 2 to ITO, and it is difficult to put it into practical use. Met.
Also, for example, in applications such as defrosting of windows and signal defrosters in cold regions, a process such as reflow soldering may be required for mounting electrical connectors, etc. Although heat resistance is required, the transparent conductive film obtained by adding SiO 2 to ITO has insufficient heat resistance. This point is also shown in comparative data in the present invention described later.
本発明は、上記の課題に鑑みてなされたものであり、本発明の目的は、透明発熱体に用いることが可能で、比較的高いシート抵抗を備え、安定的に供給可能で透過率の高い透明導電膜及びその製造方法を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention can be used for a transparent heating element, has a relatively high sheet resistance, can be stably supplied, and has high transmittance. It is in providing a transparent conductive film and its manufacturing method.
前記課題は、請求項１の透明導電膜によれば、透明基板に形成された透明導電膜であって、酸化インジウムスズ（ＩＴＯ）を主材料とし、窒素とケイ素酸化物が添加されており、透明発熱体用であることにより解決される。
このように、ＩＴＯを主材料とし、ケイ素酸化物だけでなく窒素が添加されているため、成膜時における透明導電膜のシート抵抗の制御幅が広くなり、各製品の要求に応じた所定のシート抵抗に設定することが可能となる。また、ケイ素酸化物だけでなく窒素が添加されているため、成膜後に熱が掛かったときのシート抵抗の変化が小さくなり、透明導電膜の耐熱性を向上できる。
その結果、比較的高抵抗で、かつ、各製品の要求に応じた所定のシート抵抗を備えた透明発熱体用の透明導電膜を、安定的に供給可能となる。
According to the transparent conductive film of
Thus, since ITO is the main material and not only silicon oxide but also nitrogen is added, the control range of the sheet resistance of the transparent conductive film at the time of film formation becomes wide, and a predetermined amount corresponding to the demand of each product The sheet resistance can be set. Further, since not only silicon oxide but also nitrogen is added, the change in sheet resistance when heat is applied after film formation is reduced, and the heat resistance of the transparent conductive film can be improved.
As a result, it is possible to stably supply a transparent conductive film for a transparent heating element having a relatively high resistance and a predetermined sheet resistance according to the requirements of each product.
このとき、請求項２のように、シート抵抗が、１０００〜３００００Ω／ｓｑで、波長５５０ｎｍにおける透過率が、９６％以上であると好適である。
このように、シート抵抗が、３００００Ω／ｓｑ以下であるため、透明発熱体として実用的な発熱量を確保できる。また、シート抵抗を、１０００Ω／ｓｑ以上としているため、従来の酸化インジウムスズ（ＩＴＯ）からなる透明導電膜では、所望のシート抵抗に制御することが難しかった１０００Ω／ｓｑ以上のシート抵抗の領域において、所望のシート抵抗に容易に制御することができる。
波長５５０ｎｍにおける透過率が、９６％以上であるため、透過性が要求される窓の曇り止め等の用途に、好適に用いることができる。
At this time, it is preferable that the sheet resistance is 1000 to 30000 Ω / sq and the transmittance at a wavelength of 550 nm is 96% or more.
Thus, since sheet resistance is 30000 ohms / sq or less, a practical calorific value as a transparent heating element is securable. Further, since the sheet resistance is set to 1000 Ω / sq or more, in the conventional transparent conductive film made of indium tin oxide (ITO), it is difficult to control the sheet resistance to a desired sheet resistance in a region of 1000 Ω / sq or more. The desired sheet resistance can be easily controlled.
Since the transmittance at a wavelength of 550 nm is 96% or more, it can be suitably used for applications such as window fogging that requires transparency.
このとき、請求項３のように、前記シート抵抗が、２０００Ω／ｓｑより大きく、３０００Ω／ｓｑ以下であると好適である。
このように、透明基板に形成された透明導電膜であって、ＩＴＯを主材料とし、窒素とケイ素酸化物が添加されており、透明発熱体用において、シート抵抗が、２０００Ω／ｓｑより大きく、３０００Ω／ｓｑ以下であるため、従来は安定して成膜することが難しかった２０００〜３０００Ω／ｓｑの耐熱性を備えた透明導電膜を供給することができ、発熱量と透過率のバランスの点から最も必要とされる透明発熱体を安定供給するというニーズに応えることが可能となる。
また、２０００Ω／ｓｑより大きく、３０００Ω／ｓｑ以下という高めのシート抵抗値帯において、比較的大型の基板に成膜されたものであっても、同一基板内の部分的なシート抵抗のばらつきが殆どなく、基板の面上の全域に亘って均一なシート抵抗を備えた透明導電膜とすることができる。
At this time, it is preferable that the sheet resistance is greater than 2000Ω / sq and equal to or less than 3000Ω / sq.
Thus, a transparent conductive film formed on a transparent substrate, with ITO as the main material, nitrogen and silicon oxide are added, and for a transparent heating element, the sheet resistance is greater than 2000 Ω / sq, Since it is 3000 Ω / sq or less, it is possible to supply a transparent conductive film having a heat resistance of 2000 to 3000 Ω / sq, which has conventionally been difficult to stably form a film. Therefore, it is possible to meet the needs for the stable supply of the most necessary transparent heating element.
Further, even when the film is formed on a relatively large substrate in a high sheet resistance value range of greater than 2000Ω / sq and less than 3000Ω / sq, there is almost no variation in partial sheet resistance within the same substrate. And a transparent conductive film having a uniform sheet resistance over the entire surface of the substrate.
また、シート抵抗が、２０００Ω／ｓｑより大きく、３０００Ω／ｓｑ以下であるため、プラスチックフィルム基板に適した透明導電膜を達成できる。一般的に、プラスチックフィルム基板では、ＩＴＯを主材料とする膜の成膜の再現性が悪いため、ある程度以上の厚みを有した膜を成膜することにより、実用的な再現性を確保している。しかし、膜が厚すぎると透過率が低下し、クラックやカール状の欠点も発生しやすくなるため、プラスチックフィルム基板上に透明導電膜を成膜する際の課題となっている。
これに対し、ＩＴＯにケイ素酸化物と窒素が添加された透明導電膜を、請求項３のように、２０００Ω／ｓｑより大きく、３０００Ω／ｓｑ以下のシート抵抗の範囲とした場合では、膜厚を１００〜２００Åと安定して成膜できる範囲とすることができるため、透明基板がプラスチックフィルム基板である場合も含め、透過率を高く維持しながら安定して成膜することができる。
Moreover, since the sheet resistance is greater than 2000Ω / sq and less than or equal to 3000Ω / sq, a transparent conductive film suitable for a plastic film substrate can be achieved. In general, plastic film substrates have poor reproducibility of film formation using ITO as the main material. Therefore, by forming a film with a certain thickness or more, practical reproducibility is ensured. Yes. However, if the film is too thick, the transmittance is reduced, and cracks and curled defects are likely to occur, which is a problem when a transparent conductive film is formed on a plastic film substrate.
On the other hand, when the transparent conductive film in which silicon oxide and nitrogen are added to ITO is in the sheet resistance range of more than 2000Ω / sq and less than 3000Ω / sq as in
このとき、請求項４のように、前記窒素を、２．０〜５．０ａｔ％含み、ケイ素を、３．０〜９．０ａｔ％含み、該３．０〜９．０ａｔ％のケイ素は、前記ケイ素酸化物として含まれていると好適である。
このように構成しているため、透明発熱体として用いるために十分な耐熱性を有すると共に、シート抵抗の制御幅が広く、各製品の要求に応じた所定のシート抵抗に設定可能な透明導電膜を達成できる。
窒素が２．０ａｔ％未満となると、成膜後に、実用上十分な耐熱性が得られず、また、成膜中のシート抵抗の制御が難しくなって、実用上必要な程度のシート抵抗の再現性が得られなくなる。窒素が５．０ａｔ％より多くなると、実用上十分な膜の透過性が得られなくなる。
ケイ素が３．０ａｔ％未満となると、シート抵抗が低下し、透明発熱体として用いるために十分なシート抵抗を得ることが困難になる。ケイ素が９．０ａｔ％より多くなると、実用的な透明発熱体に要求される抵抗値から大きい方に外れてしまう。
At this time, as in
With this configuration, the transparent conductive film has sufficient heat resistance to be used as a transparent heating element, has a wide sheet resistance control range, and can be set to a predetermined sheet resistance according to the requirements of each product. Can be achieved.
If the nitrogen content is less than 2.0 at%, practically sufficient heat resistance cannot be obtained after film formation, and it becomes difficult to control the sheet resistance during film formation, so that the sheet resistance can be reproduced to the extent necessary for practical use. Sex cannot be obtained. When the nitrogen content exceeds 5.0 at%, practically sufficient membrane permeability cannot be obtained.
When silicon is less than 3.0 at%, the sheet resistance decreases, and it becomes difficult to obtain sufficient sheet resistance for use as a transparent heating element. If the amount of silicon exceeds 9.0 at%, the resistance value required for a practical transparent heating element will deviate to the larger value.
このとき、請求項５のように、透明導電膜の製造方法であって、酸化インジウムスズ（ＩＴＯ）にケイ素酸化物を５〜１０％添加したターゲットを用い、アルゴンガスに、該アルゴンガスに対して４〜１８％の窒素を添加したガスをスパッタガスとして導入して、透明基板上に透明発熱体用の透明導電膜を成膜すると好適である。
このように構成しているため、透明発熱体として用いるために十分な耐熱性を有すると共に、シート抵抗の制御幅が広く、各製品の要求に応じた所定のシート抵抗に設定可能な透明導電膜を製造できる。
At this time, as in
With this configuration, the transparent conductive film has sufficient heat resistance to be used as a transparent heating element, has a wide sheet resistance control range, and can be set to a predetermined sheet resistance according to the requirements of each product. Can be manufactured.
酸化インジウムスズ（ＩＴＯ）を主材料とし、ケイ素酸化物だけでなく窒素が添加されているため、成膜時における透明導電膜のシート抵抗の制御幅が広くなり、各製品の要求に応じた所定のシート抵抗に設定することが可能となる。また、ケイ素酸化物だけでなく窒素が添加されているため、成膜後に熱が掛かったときのシート抵抗の変化が小さくなり、透明導電膜の耐熱性を向上できる。
その結果、比較的高抵抗で、かつ、各製品の要求に応じた所定のシート抵抗を備えた透明発熱体用の透明導電膜を、安定的に供給可能となる。
Since indium tin oxide (ITO) is the main material and not only silicon oxide but also nitrogen is added, the control range of the sheet resistance of the transparent conductive film at the time of film formation becomes wide, and it is determined according to the requirements of each product It is possible to set to a sheet resistance of. Further, since not only silicon oxide but also nitrogen is added, the change in sheet resistance when heat is applied after film formation is reduced, and the heat resistance of the transparent conductive film can be improved.
As a result, it is possible to stably supply a transparent conductive film for a transparent heating element having a relatively high resistance and a predetermined sheet resistance according to the requirements of each product.
（透明導電膜）
本実施の形態に係る透明導電膜は、透明基板に形成された透明発熱体用の透明導電膜であって、酸化インジウムスズ（ＩＴＯ）を主材料とし、窒素とケイ素酸化物が添加されている。
(Transparent conductive film)
The transparent conductive film according to the present embodiment is a transparent conductive film for a transparent heating element formed on a transparent substrate, which is mainly composed of indium tin oxide (ITO) and added with nitrogen and silicon oxide. .
本実施形態の透明基板は、ガラス基板又はプラスチックフィルム基板からなる。
プラスチックフィルム基板としては、例えばＰＥＴ（ポリエチレンテレフタレート）、ＰＥＳ（ポリエーテルサルフォン）、ポリカーボネート、ポリアリレートからなる基板が用いられる。
本実施形態の透明導電膜は、酸化インジウムスズ（ＩＴＯ）を主材料とし、３．０〜９．０ａｔ％のケイ素及び２．０〜５．０ａｔ％の窒素を含み、波長５５０ｎｍにおける透過率が、９６％以上、好ましくは９８％以上である。また、膜厚は１２０±１０Åの範囲にあり、シート抵抗が、１０００〜３００００Ω／ｓｑ、好ましくは２０００〜３０００Ω／ｓｑである。
The transparent substrate of this embodiment consists of a glass substrate or a plastic film substrate.
As the plastic film substrate, for example, a substrate made of PET (polyethylene terephthalate), PES (polyethersulfone), polycarbonate, or polyarylate is used.
The transparent conductive film of this embodiment is mainly composed of indium tin oxide (ITO), contains 3.0 to 9.0 at% silicon and 2.0 to 5.0 at% nitrogen, and has a transmittance at a wavelength of 550 nm. 96% or more, preferably 98% or more. The film thickness is in the range of 120 ± 10 mm, and the sheet resistance is 1000 to 30000 Ω / sq, preferably 2000 to 3000 Ω / sq.
本実施形態の透明導電膜は、透明基板上に成膜されており、例えば、透明導電膜の基板逆側の面に形成される一対の電極と、電極が形成される部分を除いた透明導電膜の基板逆側の面のほぼ全体を覆う絶縁膜と、絶縁膜の透明導電膜逆側の面に形成され、基板よりも赤外線の放射率が低く、透明導電膜において生じた熱が基板逆側に放射されることを抑制する低放射率膜と、が更に形成されることにより、透明導電膜発熱体を構成可能である。
本実施形態の透明導電膜を備えた透明導電膜発熱体は、例えば、寒冷地や冬場において道路表示灯，屋外表示装置，屋外照明装置，車両窓などの融雪，結露防止や曇り止めを行うために用いられる。
The transparent conductive film of this embodiment is formed on a transparent substrate. For example, the transparent conductive film excluding a pair of electrodes formed on the surface of the transparent conductive film on the opposite side of the substrate and a portion where the electrodes are formed. An insulating film that covers almost the entire surface of the film opposite to the substrate and a surface of the insulating film on the opposite side of the transparent conductive film, has a lower emissivity of infrared rays than the substrate, and heat generated in the transparent conductive film A transparent conductive film heating element can be configured by further forming a low-emissivity film that suppresses radiation to the side.
The transparent conductive film heating element provided with the transparent conductive film of the present embodiment performs, for example, prevention of snow melting, dew condensation and anti-fogging for road indicator lights, outdoor display devices, outdoor lighting devices, vehicle windows, etc. in cold regions and winter seasons. Used for.
（透明導電膜の製造方法）
本実施形態の透明導電膜の製造方法について説明する。
本実施形態の透明導電膜の成膜は、次のように行う。
公知のＤＣマグネトロンスパッタリング装置を用い、その非磁性体ターゲット用カソードに、酸化インジウムスズ（ＩＴＯ）及び５〜１０％のケイ素酸化物を含有するターゲットを取り付け、ターゲットと平行かつ対向してガラス基板又はプラスチックフィルム基板からなる透明基板を設置する。
アルゴンガスに、このアルゴンガスに対して約４〜１８％の窒素及び約０〜４％の酸素を添加したガスをスパッタガスとして導入して、公知のＤＣマグネトロンスパッタにより、透明基板上に透明導電膜を成膜する。
成膜時の基板温度は、ガラス基板の場合は、３００℃とする。
一方、プラスチックフィルム基板の場合の成膜時の基板温度は、１００℃とする。
(Method for producing transparent conductive film)
The manufacturing method of the transparent conductive film of this embodiment is demonstrated.
The transparent conductive film of this embodiment is formed as follows.
Using a known DC magnetron sputtering apparatus, a target containing indium tin oxide (ITO) and 5 to 10% silicon oxide is attached to the cathode for the non-magnetic target, and a glass substrate or A transparent substrate made of a plastic film substrate is installed.
A gas obtained by adding about 4 to 18% nitrogen and about 0 to 4% oxygen to the argon gas is introduced as a sputtering gas, and transparent conductive material is formed on the transparent substrate by a known DC magnetron sputtering. A film is formed.
The substrate temperature during film formation is 300 ° C. in the case of a glass substrate.
On the other hand, the substrate temperature at the time of film formation in the case of a plastic film substrate is 100 ° C.
成膜条件は、例えば、ターゲット−基板間距離：５０〜２００ｍｍ、到達真空度：３．０〜８．０×１０-４Ｐａ、スパッタ圧力：０．１〜１．０Ｐａ、投入電力：直流５０〜５００Ｗ、基板加熱温度：室温〜３００℃とする。
スパッタガスには、酸素を添加してもしなくてもよい。但し、ＩＴＯとＳｉＯ２を含むターゲットを用いて成膜する場合、シート抵抗が安定しない傾向があるが、酸素を添加すると、ＩＴＯとＳｉＯ２を含むターゲットを用いた場合であっても、シート抵抗が安定する。
また、酸素の代わりに、スパッタガスに二酸化炭素を添加してもよい。
The film forming conditions are, for example, target-substrate distance: 50 to 200 mm, ultimate vacuum: 3.0 to 8.0 × 10 −4 Pa, sputtering pressure: 0.1 to 1.0 Pa, input power: DC 50 ˜500 W, substrate heating temperature: room temperature to 300 ° C.
Oxygen may or may not be added to the sputtering gas. However, when forming a film using a target containing ITO and SiO 2 , the sheet resistance tends to be unstable. However, when oxygen is added, even if a target containing ITO and SiO 2 is used, the sheet resistance Is stable.
Further, carbon dioxide may be added to the sputtering gas instead of oxygen.
以下、本発明の透明導電膜の具体的実施例について説明するが、本発明は、これに限定されるものではない。
（実施例及び対比例に係る透明導電膜の形成）
以下の条件でＤＣマグネトロンスパッタによってガラス基板上に実施例１〜７及び対比例１〜９に係る透明導電膜を成膜した。
スパッタ装置：カルーセル型バッチ式スパッタ装置
ターゲット：角型、厚さ６ｍｍ
実施例１〜７，対比例１〜７：酸化インジウムスズ９０％，二酸化ケイ素１０％
実施例８〜１０，対比例８，９：酸化インジウムスズ９５％，二酸化ケイ素５％
スパッタ方式 ：ＤＣマグネトロンスパッタ
排気装置 ：ターボ分子ポンプ
到達真空度 ：５×１０-４Ｐａ
基板温度 ：実施例１〜９，対比例１〜８： ３００℃
実施例１０，対比例９： １００℃
スパッタ電力 ：１．５５Ｗ／ｃｍ２
使用基板 ：実施例１〜９，対比例１〜８：ガラス基板
実施例１０，対比例９：ＰＥＴフィルム基板
透明導電膜の膜厚：１２０±１０Åの範囲内
Hereinafter, although the specific Example of the transparent conductive film of this invention is described, this invention is not limited to this.
(Formation of transparent conductive film according to examples and comparison)
Transparent conductive films according to Examples 1 to 7 and Comparative Examples 1 to 9 were formed on a glass substrate by DC magnetron sputtering under the following conditions.
Sputtering equipment: Carousel type batch type sputtering equipment Target: Square type, thickness 6mm
Examples 1-7, Comparative 1-7: Indium tin oxide 90%,
Examples 8 to 10,
Sputtering method: DC magnetron sputtering Exhaust device: Turbo molecular pump Ultimate vacuum: 5 × 10 −4 Pa
Substrate temperature: Examples 1 to 9,
Example 10, Comparative 9: 100 ° C.
Sputtering power: 1.55 W / cm 2
Substrate used: Examples 1 to 9,
Example 10, Comparative 9: PET film substrate Film thickness of transparent conductive film: within the range of 120 ± 10 mm
Ａｒ流量 ：４５０ｓｃｃｍ
実施例１〜１０，対比例１〜９の窒素，酸素流量
実施例１：窒素２０ｓｃｃｍ，酸素０ｓｃｃｍ
実施例２：窒素２０ｓｃｃｍ，酸素５ｓｃｃｍ
実施例３−（１）（２）：窒素２０ｓｃｃｍ，酸素７ｓｃｃｍ
実施例４：窒素２０ｓｃｃｍ，酸素９ｓｃｃｍ
実施例５：窒素２０ｓｃｃｍ，酸素１１ｓｃｃｍ
実施例６：窒素２０ｓｃｃｍ，酸素１５ｓｃｃｍ
実施例７−（１）（２）：窒素４０ｓｃｃｍ，酸素１１ｓｃｃｍ
実施例８−（１）（２）：窒素４０ｓｃｃｍ，酸素０ｓｃｃｍ
実施例９−（１）（２）：窒素８０ｓｃｃｍ，酸素０ｓｃｃｍ
実施例１０：窒素５０ｓｃｃｍ，酸素０ｓｃｃｍ
対比例１：窒素０ｓｃｃｍ，酸素５ｓｃｃｍ
対比例２：窒素０ｓｃｃｍ，酸素７ｓｃｃｍ
対比例３：窒素０ｓｃｃｍ，酸素９ｓｃｃｍ
対比例４−（１）（２）：窒素０ｓｃｃｍ，酸素１１ｓｃｃｍ
対比例５：窒素０ｓｃｃｍ，酸素１３ｓｃｃｍ
対比例６−（１）（２）：窒素０ｓｃｃｍ，酸素１５ｓｃｃｍ
対比例７：窒素０ｓｃｃｍ，酸素１７ｓｃｃｍ
対比例８−（１）（２）：窒素０ｓｃｃｍ，酸素６ｓｃｃｍ
対比例９：窒素０ｓｃｃｍ，酸素６ｓｃｃｍ
なお、（１）（２）の表記はそれぞれ、同じ条件の成膜試験を２回行った場合における１バッチ目サンプル，２バッチ目サンプルを示す。
Ar flow rate: 450 sccm
Examples 1-10, Nitrogen, Oxygen Flow Rate of Comparative 1-9 Example 1: Nitrogen 20 sccm,
Example 2: Nitrogen 20 sccm,
Example 3- (1) (2): nitrogen 20 sccm, oxygen 7 sccm
Example 4: Nitrogen 20 sccm, oxygen 9 sccm
Example 5: Nitrogen 20 sccm, oxygen 11 sccm
Example 6: Nitrogen 20 sccm, oxygen 15 sccm
Example 7- (1) (2): nitrogen 40 sccm, oxygen 11 sccm
Example 8- (1) (2): nitrogen 40 sccm,
Example 9- (1) (2): nitrogen 80 sccm,
Example 10: nitrogen 50 sccm,
Comparison 1: Nitrogen 0sccm, Oxygen 5sccm
Comparison 2:
Comparison 3:
Comparative 4- (1) (2):
Comparison 5:
Comparative 6- (1) (2):
Comparison 7:
Comparative 8- (1) (2):
Comparison 9:
The notations (1) and (2) indicate the first batch sample and the second batch sample when the film formation test under the same conditions is performed twice.
（実施例及び対比例の膜組成）
上記方法で成膜された実施例３，５，７，８，９，１０，対比例６，８，９の膜組成をＸＰＳ分析により測定した結果を、表１に示す。
(Example and comparative film composition)
Table 1 shows the results obtained by measuring the film compositions of Examples 3, 5, 7, 8, 9, 10, and proportional 6, 8, 9 formed by the above method by XPS analysis.
（導入酸素量と透明導電膜のシート抵抗の関係）
図１は、スパッタガスに窒素を導入した実施例１，２，３−（１），４，５，６及びスパッタガスに窒素を導入しない対比例１，２，３，４−（１），５，６−（１），７における、成膜時の導入酸素量と成膜された透明導電膜のシート抵抗との関係をグラフに示したものである。
また、表２は、実施例１〜６からなる実施例群及び対比例１〜７からなる対比例群において、シート抵抗が下限の最小値であるボトム値を示した実施例５及び対比例６−（１）の膜特性を示している。
(Relationship between amount of introduced oxygen and sheet resistance of transparent conductive film)
FIG. 1 shows Examples 1, 2, 3- (1), 4, 5, 6 in which nitrogen is introduced into the sputtering gas, and
Table 2 shows Example 5 and Comparative Example 6 in which the bottom value is the minimum value of the sheet resistance in the Example group consisting of Examples 1 to 6 and the Comparative group consisting of Comparative Examples 1 to 7. -The film characteristic of (1) is shown.
図１より、対比例１〜７からなる対比例群のグラフよりも、実施例１〜６からなる実施例群のグラフの方が、導入酸素量が変化したときのシート抵抗の変化が少なかった。対比例群では、シート抵抗のグラフが平らになる領域がみられなかったのに対し、実施例群では、導入酸素量が５〜１５ｓｃｃｍの領域において、シート抵抗の変化が少なくなっていた。
以上より、窒素ガスをスパッタガスに添加することにより、シート抵抗の安定域が広くなることが分かった。窒素ガスをスパッタガスに添加しない場合、導入酸素量の変化に対応してシート抵抗値が変化するため、製品設計に合わせた所望のシート抵抗に設定するために、導入酸素量を厳密にコントロールする必要がある。それに対し、窒素ガスをスパッタガスに添加した場合は、シート抵抗調整のためのスパッタガスの厳密なコントロールが不要となり、スパッタガス混合比率や導入量の制御が容易になることが分かった。
From FIG. 1, the graph of the example group consisting of Examples 1 to 6 showed less change in sheet resistance when the amount of introduced oxygen was changed than the graph of the proportional group consisting of
From the above, it was found that the stability range of the sheet resistance is increased by adding nitrogen gas to the sputtering gas. When nitrogen gas is not added to the sputtering gas, the sheet resistance value changes in response to changes in the introduced oxygen amount, so the introduced oxygen amount is strictly controlled to set the desired sheet resistance according to the product design. There is a need. On the other hand, it was found that when nitrogen gas was added to the sputtering gas, it was not necessary to strictly control the sputtering gas for adjusting the sheet resistance, and it became easy to control the sputtering gas mixing ratio and the introduction amount.
また、表２より、図１のグラフにおいてシート抵抗がボトム値を示した実施例５，対比例６−（１）では、いずれも、シート抵抗が９０００〜１００００程度で、５５０ｎｍにおける透過率が９８〜９９％であり、高抵抗，高透過の透明導電膜が得られることが分かった。 Further, from Table 2, in Example 5, in which the sheet resistance shows the bottom value in the graph of FIG. 1, in Comparative 6- (1), the sheet resistance is about 9000 to 10000, and the transmittance at 550 nm is 98. It was found to be 99%, and a transparent conductive film having high resistance and high transmission was obtained.
（１０％のＳｉＯ２を含有するターゲットを用いた２００℃における耐熱性試験）
表３及び図２，図３は、それぞれ、実施例３−（１），７−（１）に係る透明導電膜付き基板と、対比例４−（１），６−（１）に係る透明導電膜付き基板を、２００℃の熱風乾燥オーブン内で１，２，３時間保持して加熱処理を行い、加熱処理前（０時間）及び１，２，３時間加熱後の透明導電膜のシート抵抗を測定した結果である。
(Heat resistance test at 200 ° C. using a target containing 10% SiO 2 )
Table 3 and FIGS. 2 and 3 show the transparent conductive film substrate according to Examples 3- (1) and 7- (1) and the transparent films according to the comparative 4- (1) and 6- (1), respectively. A substrate with a conductive film is heated in a hot air drying oven at 200 ° C. for 1, 2 or 3 hours, and heat-treated before (0 hours) and after heating for 1, 2, or 3 hours. It is the result of measuring resistance.
対比例４−（１）と実施例７−（１）を対比すると、スパッタガスに窒素を含まない対比例４−（１）の透明導電膜の３時間加熱後のシート抵抗の変化率が４４．３％であったのに対し、スパッタガスに４０ｓｃｃｍの窒素を含む実施例７−（１）の透明導電膜の３時間加熱後のシート抵抗の変化率が１６．５％であり、スパッタガスに窒素を導入することにより、透明導電膜の２００℃における耐熱性が向上することが分かった。 When the comparative 4- (1) and Example 7- (1) are compared, the change rate of the sheet resistance after heating for 3 hours of the transparent conductive film of the comparative 4- (1) containing no nitrogen in the sputtering gas is 44. The sheet resistance change rate after heating for 3 hours of the transparent conductive film of Example 7- (1) containing 40 sccm of nitrogen in the sputtering gas was 16.5%. It was found that the heat resistance at 200 ° C. of the transparent conductive film was improved by introducing nitrogen into the transparent conductive film.
（１０％のＳｉＯ２を含有するターゲットを用いた３００℃における耐熱性試験）
表４及び図４，図５は、それぞれ、実施例３−（２），７−（２）に係る透明導電膜付き基板と、対比例４−（２），６−（２）に係る透明導電膜付き基板を、３００℃の熱風乾燥オーブン内で１，２，３時間保持して加熱処理を行い、加熱処理前（０時間）及び１，２，３時間加熱後の透明導電膜のシート抵抗を測定した結果である。
(Heat resistance test at 300 ° C. using a target containing 10% SiO 2 )
Table 4 and FIGS. 4 and 5 show the substrates with transparent conductive films according to Examples 3- (2) and 7- (2), respectively, and the transparency according to comparative 4- (2) and 6- (2). A substrate with a conductive film is heated in a hot air drying oven at 300 ° C. for 1, 2, 3 hours, and heat-treated before and after the heat treatment (0 hours) and after heating for 1, 2, 3 hours. It is the result of measuring resistance.
対比例４−（２）と実施例７−（２）を対比すると、スパッタガスに酸素のみが導入され窒素を含まない対比例４−（２）の透明導電膜の３時間加熱後のシート抵抗の変化率が４５０２．９％であったのに対し、スパッタガスに４０ｓｃｃｍの窒素を含み、対比例４−（２）と同量の酸素が導入された実施例７−（２）の透明導電膜の３時間加熱後のシート抵抗の変化率は６０５．８％であり、スパッタガスに窒素を導入することにより、透明導電膜の３００℃における耐熱性が向上することが分かった。
２００℃における耐熱性試験結果である表３及び図２，図３と対比すると、２００℃の熱処理を経た場合よりも３００℃の熱処理を経た場合の方が、窒素ガスを導入したことによる透明導電膜の耐熱性向上効果が顕著にみられることが分かった。
When comparing 4- (2) and Example 7- (2), the sheet resistance after heating for 3 hours of the transparent conductive film according to 4- (2) in which only oxygen is introduced into the sputtering gas and no nitrogen is contained. The rate of change was 4502.9%, whereas the transparent conductivity of Example 7- (2), in which 40 sccm of nitrogen was contained in the sputtering gas and the same amount of oxygen as that in 4- (2) was introduced. The rate of change in sheet resistance after heating the film for 3 hours was 605.8%, and it was found that the heat resistance of the transparent conductive film at 300 ° C. was improved by introducing nitrogen into the sputtering gas.
Compared with Table 3 and FIG. 2 and FIG. 3, which are the results of the heat resistance test at 200 ° C., the transparent conductivity due to the introduction of nitrogen gas is greater when the heat treatment at 300 ° C. is performed than at the heat treatment at 200 ° C. It was found that the effect of improving the heat resistance of the film was noticeable.
（５％のＳｉＯ２を含有するターゲットを用いた耐熱性試験）
次いで、５％の二酸化ケイ素を含有するターゲットを用いてスパッタした実施例８−（１），実施例９−（１），対比例８−（１）に係る透明導電膜付き基板を、２００℃及び３００度の高温下に暴露した場合の耐熱性を対比した。
表５，図６は、実施例８−（１），実施例９−（１），対比例８−（１）に係る透明導電膜付き基板を、２００℃の熱風乾燥オーブン内で１，２，３時間保持して加熱処理を行い、加熱処理前（０時間）及び１，２，３時間加熱後の透明導電膜のシート抵抗を測定した結果である。
(Heat resistance test using a target containing 5% SiO 2 )
Subsequently, the substrate with a transparent conductive film according to Example 8- (1), Example 9- (1), and Comparative 8- (1) sputtered using a target containing 5% silicon dioxide was formed at 200 ° C. And the heat resistance when exposed to a high temperature of 300 degrees.
Table 5 and FIG. 6 show the transparent conductive film-coated substrates according to Example 8- (1), Example 9- (1), and Comparative 8- (1) in a hot air drying oven at 200 ° C. 3 is a result of measuring the sheet resistance of the transparent conductive film before the heat treatment (0 hour) and after the heat treatment for 1, 2, 3 hours.
また、表６，図７は、実施例８−（２），実施例９−（２），対比例８−（２）に係る透明導電膜付き基板を、３００℃の熱風乾燥オーブン内で１，２，３時間保持して加熱処理を行い、加熱処理前（０時間）及び１，２，３時間加熱後の透明導電膜のシート抵抗を測定した結果である。 Table 6 and FIG. 7 show that the substrate with a transparent conductive film according to Example 8- (2), Example 9- (2), and Comparative 8- (2) is 1 in a 300 ° C. hot air drying oven. , 2 and 3 hours, and the heat treatment was performed, and the sheet resistance of the transparent conductive film before the heat treatment (0 hour) and after the heat treatment for 1, 2 and 3 hours was measured.
表５，図６の結果より、二酸化ケイ素を５％含有するターゲットを用いてスパッタして得たシート抵抗１〜２×１０３Ω／ｓｑ台の膜において、温度２００℃に１〜３時間暴露した場合における耐熱性は、窒素ガスを含み、酸素ガスを含まないスパッタガスを導入して得た実施例８−（１），９−（１）と、窒素ガスを含まず、酸素ガスを含むスパッタガスを導入して得た対比例８−（１）との間で、差がなかった。
また、表６，図７の結果より、二酸化ケイ素を５％含有するターゲットを用いてスパッタして得た膜において、温度３００℃に１〜３時間暴露した場合における耐熱性は、窒素ガスを含み、酸素ガスを含まないスパッタガスを導入して得た実施例８−（２），９−（２）が、窒素ガスを含まず、酸素ガスを含むスパッタガスを導入して得た対比例８−（２）に対比して、高くなっていた。
従って、表５，図６及び表６，図７の結果より、５％の二酸化ケイ素を含有するターゲットを用い、スパッタガスに窒素ガスを混合して成膜した場合、２００℃に１〜３時間暴露したときの耐熱性に向上は見られなかったが、３００℃に１〜３時間暴露したときの耐熱性が大幅に向上することが分かった。
From the results shown in Table 5 and FIG. 6, a film having a sheet resistance of 1 to 2 × 10 3 Ω / sq obtained by sputtering using a target containing 5% of silicon dioxide is exposed to a temperature of 200 ° C. for 1 to 3 hours. In this case, the heat resistance is that of Examples 8- (1) and 9- (1) obtained by introducing a sputtering gas containing nitrogen gas and not containing oxygen gas, and oxygen gas not containing nitrogen gas. There was no difference from the comparative 8- (1) obtained by introducing the sputtering gas.
Further, from the results of Table 6 and FIG. 7, in the film obtained by sputtering using a target containing 5% of silicon dioxide, the heat resistance when exposed to a temperature of 300 ° C. for 1 to 3 hours includes nitrogen gas. Comparative Examples 8 (2) and 9- (2) obtained by introducing a sputtering gas not containing oxygen gas were obtained by introducing a sputtering gas not containing nitrogen gas but containing oxygen gas. -It was higher than (2).
Therefore, from the results of Table 5, FIG. 6, Table 6, and FIG. 7, when a film containing nitrogen gas mixed with sputtering gas using a target containing 5% silicon dioxide is formed at 200 ° C. for 1 to 3 hours. Although no improvement was observed in the heat resistance when exposed, it was found that the heat resistance when exposed to 300 ° C. for 1 to 3 hours was significantly improved.
（ＰＥＴフィルム基板に成膜した場合の耐熱性試験）
表７及び図８は、５％の二酸化ケイ素を含有するターゲットを用いてＰＥＴフィルム基板上に１００℃で成膜して得た実施例１０，対比例９に係る透明導電膜付き基板を、１２０℃の熱風乾燥オーブン内で１，２，３時間保持して加熱処理を行い、加熱処理前（０時間）及び１，２，３時間加熱後の透明導電膜のシート抵抗を測定した結果である。
(Heat resistance test when deposited on a PET film substrate)
Table 7 and FIG. 8 show a substrate with a transparent conductive film according to Example 10 and Comparative Example 9 obtained by forming a film on a PET film substrate at 100 ° C. using a target containing 5% silicon dioxide. It is the result of measuring the sheet resistance of the transparent conductive film before the heat treatment (0 hour) and after the heat treatment for 1, 2, 3 hours by performing the heat treatment for 1,2,3 hours in a hot air drying oven at 0 ° C. .
表７，図８の結果より、酸素ガスを含まず窒素ガスを含むスパッタガスを導入して得た実施例１０が、酸素ガスを含み窒素ガスを含まないスパッタガスを導入して得た対比例９に対比して、温度１２０℃に１〜３時間暴露した場合における耐熱性が高くなっていた。
従って、１００℃という比較的低温で成膜する場合でも、スパッタ時に窒素ガスを導入することにより、成膜後の１２０℃における耐熱性が向上することが分かった。
From the results shown in Table 7 and FIG. 8, Example 10 obtained by introducing a sputtering gas containing no nitrogen gas but not containing oxygen gas was obtained by introducing a sputtering gas containing oxygen gas and no nitrogen gas. Compared to 9, the heat resistance when exposed to a temperature of 120 ° C. for 1 to 3 hours was high.
Therefore, it was found that even when the film was formed at a relatively low temperature of 100 ° C., the heat resistance at 120 ° C. after the film formation was improved by introducing nitrogen gas during sputtering.
本発明の実施形態に係る透明導電膜に含まれるケイ素の状態を調べるため、実施例の幾つかの膜をＸＰＳ（X-ray Photoelectron Spectroscopy）の高分解能測定を行って分析した。ほぼ同様の結果が得られており、代表例として実施例３のグラフを図９に示す。強度のピークは、結合エネルギー１０３ｅＶ付近に現れている。
Ｓｉのピークは９９ｅＶ付近、ＳｉＯ２のピークは１０３ｅＶ付近、ＳｉＯｘＮｙのピークは１０２ｅＶ付近、Ｓｉ３Ｎ４のピークは１０１ｅＶ付近であることが知られていること（出展：ＳＣＡＳ Technical News ＸＰＳによるシリコンウェーハの分析）から、本発明の実施形態に係る透明導電膜に含まれるケイ素は、ほぼＳｉＯ２の状態であると判定された。
In order to investigate the state of silicon contained in the transparent conductive film according to the embodiment of the present invention, several films in the examples were analyzed by high-resolution measurement using XPS (X-ray Photoelectron Spectroscopy). Almost the same result was obtained, and a graph of Example 3 is shown in FIG. 9 as a representative example. The intensity peak appears in the vicinity of the binding energy of 103 eV.
It is known that the Si peak is around 99 eV, the SiO 2 peak is around 103 eV, the SiO x N y peak is around 102 eV, and the Si 3 N 4 peak is around 101 eV (Exhibition: SCAS Technical News XPS The silicon contained in the transparent conductive film according to the embodiment of the present invention was determined to be substantially in the SiO 2 state.
Claims (5)
酸化インジウムスズ（ＩＴＯ）を主材料とし、窒素とケイ素酸化物が添加されており、透明発熱体用であることを特徴とする透明導電膜。 A transparent conductive film formed on a transparent substrate,
A transparent conductive film characterized in that it is made of indium tin oxide (ITO) as a main material, nitrogen and silicon oxide are added, and is used for a transparent heating element.
ケイ素を、３．０〜９．０ａｔ％含み、
該３．０〜９．０ａｔ％のケイ素は、前記ケイ素酸化物として含まれていることを特徴とする請求項１乃至３いずれか記載の透明導電膜。 Containing 2.0 to 5.0 at% of the nitrogen,
Containing 3.0 to 9.0 at% of silicon,
4. The transparent conductive film according to claim 1, wherein the 3.0 to 9.0 at% silicon is contained as the silicon oxide. 5.
Using a target obtained by adding 5 to 10% silicon oxide to indium tin oxide (ITO), a gas obtained by adding 4 to 18% nitrogen to the argon gas as a sputtering gas is transparent. A method for producing a transparent conductive film, comprising forming a transparent conductive film for a transparent heating element on a substrate.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62202415A (en) * | 1984-12-06 | 1987-09-07 | 三井金属鉱業株式会社 | Indium oxide system light transmitting conductive film |
| JPH04206403A (en) * | 1990-11-30 | 1992-07-28 | Nitto Denko Corp | Transparent conductive coating, transparent conductive film and analogue touch panel |
| JPH04308612A (en) * | 1991-04-04 | 1992-10-30 | Nitto Denko Corp | Transparent conductive membrane and manufacture thereof, transparent conductive film, and analog touch-panel |
| JPH06157036A (en) * | 1992-11-13 | 1994-06-03 | Nippon Soda Co Ltd | Production of tin-doped indium oxide film having high resistivity |
| JPH06293957A (en) * | 1993-02-10 | 1994-10-21 | Nippon Soda Co Ltd | Indium oxide film enhanced in resistance |
| JPH06349338A (en) * | 1993-06-10 | 1994-12-22 | Teijin Ltd | Transparent conductive lamination |
| JP2000113732A (en) * | 1998-06-25 | 2000-04-21 | Asahi Glass Co Ltd | Transparent conductive film, its manufacture, substrate with transparent conductive film, and touch panel |
| JP2003105532A (en) * | 2001-06-26 | 2003-04-09 | Mitsui Mining & Smelting Co Ltd | Sputtering target for highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film |
| JP2003277921A (en) * | 2002-03-19 | 2003-10-02 | Nikko Materials Co Ltd | Sputtering target for high resistance transparent electroconductive film |
| JP2005135649A (en) * | 2003-10-28 | 2005-05-26 | Mitsui Mining & Smelting Co Ltd | Indium oxide based transparent conductive film and its manufacturing method |
| JP2007138266A (en) * | 2005-11-21 | 2007-06-07 | Mitsui Mining & Smelting Co Ltd | Sputtering target for highly resistant transparent conductive film, and highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film |
| JP2007200823A (en) * | 2006-01-30 | 2007-08-09 | Nitto Denko Corp | Crystalline transparent conductive thin film, manufacturing method therefor, transparent conductive film, and touch panel |
-
2012
- 2012-06-26 JP JP2012143161A patent/JP6080399B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62202415A (en) * | 1984-12-06 | 1987-09-07 | 三井金属鉱業株式会社 | Indium oxide system light transmitting conductive film |
| JPH04206403A (en) * | 1990-11-30 | 1992-07-28 | Nitto Denko Corp | Transparent conductive coating, transparent conductive film and analogue touch panel |
| JPH04308612A (en) * | 1991-04-04 | 1992-10-30 | Nitto Denko Corp | Transparent conductive membrane and manufacture thereof, transparent conductive film, and analog touch-panel |
| JPH06157036A (en) * | 1992-11-13 | 1994-06-03 | Nippon Soda Co Ltd | Production of tin-doped indium oxide film having high resistivity |
| JPH06293957A (en) * | 1993-02-10 | 1994-10-21 | Nippon Soda Co Ltd | Indium oxide film enhanced in resistance |
| JPH06349338A (en) * | 1993-06-10 | 1994-12-22 | Teijin Ltd | Transparent conductive lamination |
| JP2000113732A (en) * | 1998-06-25 | 2000-04-21 | Asahi Glass Co Ltd | Transparent conductive film, its manufacture, substrate with transparent conductive film, and touch panel |
| JP2003105532A (en) * | 2001-06-26 | 2003-04-09 | Mitsui Mining & Smelting Co Ltd | Sputtering target for highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film |
| JP2003277921A (en) * | 2002-03-19 | 2003-10-02 | Nikko Materials Co Ltd | Sputtering target for high resistance transparent electroconductive film |
| JP2005135649A (en) * | 2003-10-28 | 2005-05-26 | Mitsui Mining & Smelting Co Ltd | Indium oxide based transparent conductive film and its manufacturing method |
| JP2007138266A (en) * | 2005-11-21 | 2007-06-07 | Mitsui Mining & Smelting Co Ltd | Sputtering target for highly resistant transparent conductive film, and highly resistant transparent conductive film, and manufacturing method of highly resistant transparent conductive film |
| JP2007200823A (en) * | 2006-01-30 | 2007-08-09 | Nitto Denko Corp | Crystalline transparent conductive thin film, manufacturing method therefor, transparent conductive film, and touch panel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104992752A (en) * | 2015-07-16 | 2015-10-21 | 城步新鼎盛电子科技有限公司 | Production method of silver nanowire transparent conductive film |
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