JPH08151233A - Transparent heating body - Google Patents
Transparent heating bodyInfo
- Publication number
- JPH08151233A JPH08151233A JP6290067A JP29006794A JPH08151233A JP H08151233 A JPH08151233 A JP H08151233A JP 6290067 A JP6290067 A JP 6290067A JP 29006794 A JP29006794 A JP 29006794A JP H08151233 A JPH08151233 A JP H08151233A
- Authority
- JP
- Japan
- Prior art keywords
- film
- transparent
- glass
- heating element
- gzo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3423—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings comprising a suboxide
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、透明発熱体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent heating element.
【0002】[0002]
【従来の技術】近年、自動車用ガラス、建築用ガラスの
分野においては、デザイン意匠性、快適さ、空調負荷低
減等を目的として、熱線反射性能の付加が要求されつつ
あるが、従来のSnO2 含有In2 O3 (ITO)膜や
ZnO膜などの透明導電膜では熱線反射性能は充分では
ない。In recent years, automotive glass, in the field of architectural glass, design design property, comfort, for the purpose of air-conditioning load reduction, etc., but the addition of the heat ray reflection performance is being requested, the conventional SnO 2 A transparent conductive film such as a contained In 2 O 3 (ITO) film or a ZnO film does not have sufficient heat ray reflection performance.
【0003】また、自動車用のガラスにおいては、防曇
・融氷性能が要求される一方で、自動車用防曇・融氷機
能付きガラス(EHW)として保安部品として用いる場
合は、その性能と耐久性とが保証されなければならな
い。Further, while the glass for automobiles is required to have anti-fogging / melting ice performance, when the glass for automobiles (EHW) with anti-fog / ice-melting function is used as a security component, the performance and durability thereof are required. Sex must be guaranteed.
【0004】劣化により、膜が破断したり膜抵抗が上昇
したような導電膜では、もはや定格の発熱量を発生でき
なくなったり、甚だしい場合には膜破断部分が異常発熱
して中間膜発泡や、ガラス破壊にもつながり得る。With a conductive film in which the film is broken or the film resistance is increased due to deterioration, it is no longer possible to generate the rated amount of heat generation, or in extreme cases, the broken part of the film abnormally heats up and foams the intermediate film. It can also lead to glass breakage.
【0005】[0005]
【発明が解決しようとする課題】本発明は、従来技術が
有していた前述の欠点を解消するものであり、高い信頼
性と耐久性を有し、安価に製造され得る、熱線遮断性能
が付与された透明発熱体の提供を目的とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, has high reliability and durability, and can be manufactured at low cost. The purpose is to provide the attached transparent heating element.
【0006】[0006]
【課題を解決するための手段】本発明は、前述の課題を
解決するべくなされたものであり、透明基体上に、Zn
に対するGaの含有量が0.1〜15原子%であるZn
Oを主成分とする透明導電膜がコートされてなる透明発
熱体であって、該透明導電膜の上層には、SiとZrの
複合酸化物膜および特定のオーバーコート膜が形成さ
れ、該特定のオーバーコート膜は、Cr、Ti、Zrお
よびHfからなる群から選ばれる少なくとも1種の金属
の、窒化物膜、酸窒化物膜と、Ti、W、Mo、Nb、
TaおよびVからなる群から選ばれる少なくとも1種の
金属の低級酸化物膜の中から選択される膜であることを
特徴とする透明発熱体を提供する。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, in which Zn is formed on a transparent substrate.
Zn whose Ga content is 0.1 to 15 atomic% with respect to
A transparent heating element comprising a transparent conductive film containing O as a main component, wherein a composite oxide film of Si and Zr and a specific overcoat film are formed on the transparent conductive film. The overcoat film is a nitride film or oxynitride film of at least one metal selected from the group consisting of Cr, Ti, Zr and Hf, and Ti, W, Mo, Nb,
Provided is a transparent heating element, which is a film selected from lower oxide films of at least one metal selected from the group consisting of Ta and V.
【0007】本発明においては、信頼性と耐久性、コス
ト、および熱線反射性能の観点から、透明導電膜(以
下、GZO膜という)として、ZnOを主成分とし、添
加物としてGaをZnに対して0.1原子%以上15原
子%以下含有するものを用いることが重要である。In the present invention, from the viewpoints of reliability, durability, cost, and heat ray reflection performance, the transparent conductive film (hereinafter referred to as the GZO film) contains ZnO as a main component and Ga as an additive with respect to Zn. It is important to use those containing 0.1 atomic% or more and 15 atomic% or less.
【0008】GZO膜は、低比抵抗のものが効率よく生
産でき、また、耐久性も向上することから、Si、T
i、Zr、Hf、YおよびLaからなる群から選ばれる
少なくとも1種の金属を含有するものが好ましく、その
含有割合としては、Znに対して、0.01〜10原子
%であることが好ましい。As the GZO film, one having a low specific resistance can be efficiently produced and the durability is improved.
Those containing at least one metal selected from the group consisting of i, Zr, Hf, Y and La are preferable, and the content ratio thereof is preferably 0.01 to 10 atom% with respect to Zn. .
【0009】また、GZO膜は、耐久性の観点から、X
線回折パターンにおいて(002)面による回折ピーク
を有し、かつ、(002)面による回折線の半値幅が
0.6°以下であることが好ましい。From the viewpoint of durability, the GZO film has an X content.
It is preferable that the line diffraction pattern has a diffraction peak due to the (002) plane, and the half width of the diffraction line due to the (002) plane is 0.6 ° or less.
【0010】GZO膜の膜厚は、100〜10000Å
であることが好ましい。100Å未満であると通電に対
する長期信頼性が不足し、また、10000Å超えると
成膜時間が長くなり、生産性と材料費が上昇するため好
ましくない。The thickness of the GZO film is 100 to 10000Å
It is preferred that If it is less than 100 Å, long-term reliability against energization is insufficient, and if it exceeds 10,000 Å, the film formation time becomes long, and productivity and material cost increase, which is not preferable.
【0011】GZO膜は、成膜後、次工程までの保管
中、あるいは実使用中に、雰囲気との間で水分を可逆的
にやり取りして、水を吸着・脱離することにより、抵抗
変化を起こし易いことが、検討の結果、明らかになっ
た。After the GZO film is formed, the resistance changes by reversibly exchanging water with the atmosphere during storage until the next step or during actual use to adsorb and desorb water. As a result of the examination, it became clear that the above-mentioned tendency to occur.
【0012】さらに検討を進めたところ、GZO膜の上
層に、SiとZrの複合酸化物膜(以下、SZO膜とい
う)および特定のオーバーコート膜を形成することによ
り、環境中から前記透明導電膜中へ到達する水分量を効
果的に抑制し、その結果、前記透明導電膜の抵抗を著し
く安定化させて、信頼性、耐久性を向上せしめる効果が
発揮されることが新規に見いだされた。As a result of further study, the transparent conductive film was formed from the environment by forming a composite oxide film of Si and Zr (hereinafter referred to as SZO film) and a specific overcoat film on the GZO film. It has been newly found that the effect of effectively suppressing the amount of water reaching the inside and, as a result, significantly stabilizing the resistance of the transparent conductive film and improving the reliability and durability is exhibited.
【0013】本発明において用いるSZO膜の、Siと
Zrの割合は、酸化物換算で、SiO2 /ZrO2 のモ
ル比が、10/90〜98/2、特に、20/80〜9
0/10であることが、水分拡散を有効に抑えられるこ
とから好ましい。The SZO film used in the present invention has a ratio of Si to Zr in terms of oxide of SiO 2 / ZrO 2 molar ratio of 10/90 to 98/2, particularly 20/80 to 9.
It is preferably 0/10 because water diffusion can be effectively suppressed.
【0014】SZO膜の膜厚は、50Å〜3000Åで
あることが好ましい。50Å未満であると、GZO膜の
信頼性や耐久性の確保が困難であり、また3000Åを
超えると生産性が悪くなったり、材料費が高くなってし
まうため好ましくない。The thickness of the SZO film is preferably 50Å to 3000Å. When it is less than 50Å, it is difficult to secure the reliability and durability of the GZO film, and when it exceeds 3000Å, productivity is deteriorated and the material cost is increased, which is not preferable.
【0015】該特定のオーバーコート膜は、Cr、T
i、ZrおよびHfからなる群から選ばれる少なくとも
1種の金属の、窒化物膜、酸窒化物膜と、Ti、W、M
o、Nb、TaおよびVからなる群から選ばれる少なく
とも1種の金属の低級酸化物膜の中から選択される膜で
ある。The specific overcoat film is composed of Cr, T
A nitride film, an oxynitride film of at least one metal selected from the group consisting of i, Zr and Hf, and Ti, W and M
It is a film selected from lower oxide films of at least one metal selected from the group consisting of o, Nb, Ta and V.
【0016】前記の特定のオーバーコート膜の膜厚は、
10Å〜500Åであることが好ましい。10Å未満で
あると日射透過率の低減効果がなくなってしまい、ま
た、500Åを超えると可視光線透過率が著しく低くな
ってしまうため好ましくない。The thickness of the above specific overcoat film is
It is preferably 10Å to 500Å. When it is less than 10 Å, the effect of reducing the solar radiation transmittance is lost, and when it exceeds 500 Å, the visible light transmittance is significantly lowered, which is not preferable.
【0017】本発明の透明発熱体の構成として、透明基
体、GZO膜、特定のオーバーコート膜、SZO膜の順
で積層したものが挙げられる。前記構成で積層すると、
GZO膜が意図しない酸化を受け、導電に寄与する酸素
欠陥を消滅させてしまう等の問題が発生しにくいため好
ましい。実施にあたってはもちろん、この積層順に限定
されるものではない。Examples of the constitution of the transparent heating element of the present invention include a transparent substrate, a GZO film, a specific overcoat film, and an SZO film, which are laminated in this order. When laminated with the above configuration,
This is preferable because the GZO film is less likely to undergo unintended oxidation and to eliminate problems such as eliminating oxygen defects that contribute to conductivity. Of course, the implementation is not limited to this stacking order.
【0018】成膜条件や使用条件によっては成膜前に基
体表面に吸着していた水が、前記透明導電膜中に浸透し
ていくことにより、抵抗値の変化を引き起こすこともあ
り、その場合には、前記特定のオーバーコート膜を、G
ZO膜と基板との間に用いることも有効である。Depending on the film forming conditions and use conditions, the water adsorbed on the surface of the substrate before film forming may penetrate into the transparent conductive film, causing a change in resistance value. In that case The above-mentioned specific overcoat film is
It is also effective to use it between the ZO film and the substrate.
【0019】前記特定のオーバーコート膜を用いると、
抵抗を安定化させて、信頼性、耐久性を向上せしめる効
果と合わせて、太陽光の中の熱線成分を選択的に遮断す
る効果をも同時に付与することができる。すなわち、前
記特定のオーバーコート膜は、波長400〜700nm
の可視域では吸収が少なく、700〜2100nmに渡
る近赤外・赤外域で吸収が大きい特徴を有する。したが
って、可視域に対して太陽の熱線成分の透過を選択的に
低減させる効果をもたせることができる。When the above specific overcoat film is used,
In addition to the effect of stabilizing the resistance and improving the reliability and durability, it is possible to simultaneously provide the effect of selectively blocking the heat ray component in sunlight. That is, the specific overcoat film has a wavelength of 400 to 700 nm.
Has a feature that absorption is small in the visible region and absorption is large in the near infrared / infrared region over 700 to 2100 nm. Therefore, the effect of selectively reducing the transmission of the heat ray component of the sun with respect to the visible range can be provided.
【0020】特に、Ti、ZrおよびCrからなる群か
ら選ばれる少なくとも1種の金属の、窒化物膜や酸窒化
物膜が、太陽光の中の熱線成分を選択的に遮断する性能
に優れていることから好ましく、Ti、ZrおよびCr
からなる群から選ばれる少なくとも1種の金属の窒化物
膜が特に好ましい。In particular, a nitride film or an oxynitride film of at least one metal selected from the group consisting of Ti, Zr and Cr is excellent in the ability to selectively block the heat ray component in sunlight. It is preferable that Ti, Zr and Cr
A nitride film of at least one metal selected from the group consisting of is particularly preferable.
【0021】なお、近年要求される熱線反射性能は、太
陽光線透過率として表わすと、2mm厚のクリアーガラ
ス2枚を0.76mm厚のポリビニールブチラールを介
して接着した合わせガラスの場合、65%以下である。The heat ray reflection performance required in recent years is 65% in the case of a laminated glass obtained by adhering two 2 mm-thick clear glasses through 0.76 mm-thick polyvinyl butyral, in terms of sunlight transmittance. It is the following.
【0022】また、酸化物膜を積層する際に、下にGZ
O膜や窒化物膜などが存在すると、GZO膜や窒化物膜
などは酸化を受けて、比抵抗が増加したり、可視域と赤
外域の選択的透過性能が悪くなってしまうことがある。
こうした性能の劣化を防ぐ目的で、酸化物膜の直下に、
酸化物膜を構成する金属成分やTi等の金属膜層を極く
薄く挿入することも可能であり、意図した性能を発揮さ
せるのに有効な手段となる。When stacking the oxide films, the GZ
When an O film or a nitride film is present, the GZO film or the nitride film may be oxidized to increase the specific resistance or deteriorate the selective transmission performance in the visible region and the infrared region.
In order to prevent such deterioration of performance, directly below the oxide film,
It is also possible to insert a metal film constituting the oxide film or a metal film layer such as Ti very thinly, which is an effective means for exhibiting the intended performance.
【0023】前記極薄の金属膜層の膜厚は、材料によっ
て異なるが、おおむね10〜50Åであり、通常、酸化
膜の成膜中に、酸化され、透明化し得る厚さを上限とし
て決められる。The thickness of the ultra-thin metal film layer varies depending on the material, but is generally 10 to 50 Å, and is usually determined with the upper limit being the thickness that can be oxidized and made transparent during the formation of the oxide film. .
【0024】本発明の透明発熱体においては、発熱電力
調整、透過・反射色調調整、熱線反射性能調整、耐久性
・信頼性向上、高温を要する工程中の特性変化の抑制、
傷付き防止等の目的に応じて、GZO膜、SZO膜およ
び特定のオーバーコート膜のそれぞれについて膜厚調整
が必要になるが、現実的な膜厚範囲としてはおよそ、G
ZO膜は、100〜5000Å、SZO膜は、10〜3
000Å、特定のオーバーコート膜は、50〜700Å
である。In the transparent heating element of the present invention, heat generation power adjustment, transmission / reflection color tone adjustment, heat ray reflection performance adjustment, durability / reliability improvement, suppression of characteristic changes during processes requiring high temperature,
It is necessary to adjust the film thickness of each of the GZO film, the SZO film, and the specific overcoat film depending on the purpose of preventing scratches, etc.
The ZO film is 100 to 5000 Å, and the SZO film is 10 to 3
000Å, specific overcoat film is 50-700Å
Is.
【0025】本発明において用いる透明基体としては、
ガラス、プラスチックス等が挙げられる。As the transparent substrate used in the present invention,
Examples thereof include glass and plastics.
【0026】透明基体がソーダライムガラスのように、
その成分としてアルカリ金属を含む場合には、成膜時あ
るいは熱処理時における基体から導電膜へのアルカリ金
属の拡散を防止するために、基体表面にSi、Al、Z
r等の金属の酸化物、窒化物を主成分とする下地層を形
成することが好ましい。The transparent substrate is like soda lime glass,
When an alkali metal is contained as the component, in order to prevent the diffusion of the alkali metal from the substrate to the conductive film during film formation or heat treatment, Si, Al, Z is formed on the substrate surface.
It is preferable to form an underlayer whose main component is an oxide or nitride of a metal such as r.
【0027】本発明の透明発熱体においては、外観を調
整する目的で、GZO膜と透明基体の間や、GZO膜の
上に、透過・反射色調や可視光線反射率の調整するため
の膜を設けることも可能である。In the transparent heating element of the present invention, for the purpose of adjusting the appearance, a film for adjusting the transmission / reflection color tone and the visible light reflectance is provided between the GZO film and the transparent substrate or on the GZO film. It is also possible to provide.
【0028】また他の基体とともに合わせ構造、あるい
は複層構造にしたりする際、また、電極リードの取り出
し部を取り付けたりする際の接着性を調整する目的で、
最表層に接着力調整層を別に設けてもよい。For the purpose of adjusting the adhesiveness when forming a laminated structure or a multi-layer structure together with another substrate, or when attaching the lead-out portion of the electrode lead,
An adhesive force adjusting layer may be separately provided on the outermost layer.
【0029】本発明のGZO膜の形成法に関しては特に
限定されず、スパッタリング法、真空蒸着法等の物理蒸
着法や、CVD法などの化学蒸着法が用いられるが、よ
り低温度で良好な導電膜特性が得られることから、物理
蒸着法が望ましい。The method of forming the GZO film of the present invention is not particularly limited, and a physical vapor deposition method such as a sputtering method or a vacuum vapor deposition method or a chemical vapor deposition method such as a CVD method may be used. The physical vapor deposition method is preferable because the film characteristics can be obtained.
【0030】特に、結晶性を促進させるために有効な高
密度プラズマを活性化手段として用いたマグネトロンス
パッタリング法、高磁場を用いた低電圧スパッタリング
法、プラズマ活性化蒸着法が、低抵抗で耐熱性に優れる
膜が得られることから好ましく用いられる。In particular, the magnetron sputtering method using a high-density plasma effective for promoting crystallinity as an activation means, the low-voltage sputtering method using a high magnetic field, and the plasma-activated deposition method have low resistance and heat resistance. It is preferably used because a film having excellent properties can be obtained.
【0031】本発明の透明発熱体においては、最低2箇
所以上の、通電のための電極を設け、該電極に直流およ
び/または交流の電圧を印加し、ジュール熱により加熱
することができる。The transparent heating element of the present invention can be heated by Joule heat by providing at least two electrodes for energization, applying a DC and / or AC voltage to the electrodes.
【0032】また、本発明の透明発熱体においては、必
要に応じて、通電加熱時の温度制御、異常発熱、透明発
熱体の割れなどの異常検出を目的とした、検出手段を設
けることができる。Further, in the transparent heating element of the present invention, if necessary, detection means can be provided for the purpose of temperature control during electric heating, abnormal heat generation, and abnormality detection such as cracking of the transparent heating element. .
【0033】[0033]
[実施例1]透明基体として、充分に洗浄したクリアー
ガラス(10cm×10cm×2mm厚)を準備し、該
基体上にスクリーン印刷・焼成により向かい合った2辺
に電極を形成した(工程1)。[Example 1] As a transparent substrate, a sufficiently washed clear glass (10 cm x 10 cm x 2 mm thick) was prepared, and electrodes were formed on the opposite sides by screen printing and firing on the substrate (step 1).
【0034】次に、この基体上に、直流スパッタ法によ
り、膜厚1500ÅのGZO膜を形成した。このとき用
いたターゲットは、Znに対する添加量が、Gaが5.
0原子%、Siが0.05原子%となるように、ZnO
中に、Ga2 O3 とSiO2とをそれぞれ添加し、10
00℃以上の温度で60分間以上保持したGa2 O3を
ZnO中に充分固溶させたターゲットであり、スパッタ
時の圧力は、1mTorr、スパッタガスは、Arガス
とした。得られたGZO膜の組成は用いたターゲットと
ほぼ同様の組成であった(工程2)。Next, a 1500 Å-thick GZO film was formed on this substrate by the DC sputtering method. The target used at this time had a Ga addition amount of 5.
ZnO so that 0 atomic% and Si are 0.05 atomic%.
Ga 2 O 3 and SiO 2 are added to each of the
This is a target in which Ga 2 O 3 held at a temperature of 00 ° C. or more for 60 minutes or more is sufficiently dissolved in ZnO, the pressure during sputtering is 1 mTorr, and the sputtering gas is Ar gas. The composition of the obtained GZO film was almost the same as that of the target used (step 2).
【0035】次に、GZO膜上に、Ar/N2 混合ガス
中で膜厚50ÅのTiN膜、さらに、O2 ガス中で膜厚
200ÅのSZO(SiO2 :66.7mol%)膜を
順次形成した(工程3)。なお、いずれの成膜中におい
ても基板加熱は行わなかった。Next, a TiN film having a film thickness of 50Å in an Ar / N 2 mixed gas and an SZO (SiO 2 : 66.7 mol%) film having a film thickness of 200Å in an O 2 gas are sequentially formed on the GZO film. Formed (step 3). The substrate was not heated during any film formation.
【0036】本実施例ではスパッタリング法として直流
法を示しているが、これを高周波法で行ってもよいこと
はいうまでもない。In this embodiment, the direct current method is shown as the sputtering method, but it goes without saying that this may be performed by the high frequency method.
【0037】最後に、0.76mm厚のポリビニルブチ
ラール(PVB)膜を用いて、電極部分相当を切り欠い
たブロンズガラス(10cm×8.5cm×2mm厚)
と合わせ処理を行い、ガラス/PVB/SZO/TiN
/GZO/ガラスなる構成の合わせガラスの透明発熱体
を形成した(工程4)。Finally, a 0.76 mm-thick polyvinyl butyral (PVB) film was used to cut out a portion of the electrode corresponding to the bronze glass (10 cm × 8.5 cm × 2 mm thick).
Combined with glass, PVB / SZO / TiN
A transparent heating element of laminated glass having a structure of / GZO / glass was formed (step 4).
【0038】この透明発熱体について電極間の抵抗を測
定したところ、102.4Ω(初期値)であった。電極
間に電圧33.3Vを印加して単位面積当たりの発熱
量:1500W/m2 で通電試験を行ったところ、6週
間経過後も、抵抗値、外観とも変化を示さず一定であっ
た。When the resistance between the electrodes of this transparent heating element was measured, it was 102.4 Ω (initial value). When a voltage of 33.3 V was applied between the electrodes and an energization test was carried out at a heat generation amount per unit area of 1500 W / m 2 , the resistance value and the appearance did not change and were constant even after 6 weeks.
【0039】また、工程3までで得られた、SZO/T
iN/GZO/ガラスなる構成のガラスについての光学
性能を表1に示す。表1の通り、太陽光線透過率低減幅
が12%になっており、充分な熱線反射性能を有するこ
とが確認された。Further, SZO / T obtained in the steps up to step 3
Table 1 shows the optical performance of the glass having a structure of iN / GZO / glass. As shown in Table 1, the solar radiation transmittance reduction width was 12%, and it was confirmed that the solar cell had sufficient heat ray reflection performance.
【0040】(比較例1)実施例1の工程2および3に
おいて、GZO膜、TiN膜、SZO膜を成膜した替わ
りに、ZnおよびAgのターゲットを備えたインライン
式スパッタ装置を用いて、ZnO/Ag/ZnOの3層
からなる高透過率の導電膜を成膜した他は実施例1と同
様にして、ガラス/PVB/ZnO/Ag/ZnO/ガ
ラスなる構成の合わせガラスの透明発熱体を形成した。(Comparative Example 1) In steps 2 and 3 of Example 1, instead of forming the GZO film, the TiN film and the SZO film, an in-line type sputtering apparatus equipped with Zn and Ag targets was used. A transparent laminated glass heating element having a structure of glass / PVB / ZnO / Ag / ZnO / glass was prepared in the same manner as in Example 1 except that a conductive film having a high transmittance composed of three layers of / Ag / ZnO was formed. Formed.
【0041】この場合、ZnO層はZnをターゲットと
して、ArとO2 の混合ガス雰囲気中で、反応性スパッ
タにより成膜した。Ag層はAgをターゲットとして、
純Ar雰囲気中で成膜した。各層の膜厚は、基板側から
順に450Å、100Å、450Åとした。In this case, the ZnO layer was formed by reactive sputtering in a mixed gas atmosphere of Ar and O 2 with Zn as a target. The Ag layer targets Ag,
The film was formed in a pure Ar atmosphere. The film thickness of each layer was 450Å, 100Å, and 450Å in order from the substrate side.
【0042】実施例1と同様に、端子間抵抗を測定した
ところ初期値は7.1Ωであった。また、電極間に電圧
8.8Vを印加して単位面積当たりの発熱量:1,50
0W/m2 で通電試験を行ったところ、外観は変化なか
ったが、3週間経過後に端子間抵抗が12.9Ωまで増
加した。引き続き通電試験を行ったところ、6週間目に
100Ωを超えてしまった。When the resistance between terminals was measured in the same manner as in Example 1, the initial value was 7.1Ω. In addition, a voltage of 8.8 V is applied between the electrodes, and the heat generation amount per unit area: 1,50
When an energization test was performed at 0 W / m 2 , the appearance did not change, but the resistance between terminals increased to 12.9Ω after 3 weeks. When the current-carrying test was conducted subsequently, it exceeded 100 Ω in 6 weeks.
【0043】(比較例2)実施例1の工程2および3に
おいて、GZO膜、TiN膜、SZO膜を成膜した替わ
りに、ITOターゲットを備えたインライン式スパッタ
装置を用いて、膜厚2400ÅのITO膜を成膜し、I
TO膜付きガラスを得た。(Comparative Example 2) In steps 2 and 3 of Example 1, instead of forming the GZO film, the TiN film and the SZO film, an in-line type sputtering apparatus equipped with an ITO target was used to obtain a film thickness of 2400Å. Ito film is formed and I
A glass with a TO film was obtained.
【0044】この場合、スパッタリングガスとしてはA
rと、Arに対して2体積%のO2を加えた混合ガスを
用いて、マスフローメーターでスパッタ中の成膜室圧力
が2mTorrになるように導入した。成膜中に基板加
熱は行わなかった。In this case, the sputtering gas is A
Using a mixed gas of r and 2% by volume of O 2 with respect to Ar, the mixture was introduced by a mass flow meter so that the pressure in the film forming chamber during sputtering was 2 mTorr. The substrate was not heated during the film formation.
【0045】30cm角の基板面内でのシート抵抗分布
を測定したところ、±30%のバラツキがあった。電極
間に22Vの電圧を印加したところ、高抵抗部分ではほ
とんど発熱せず、電熱ガラスとして機能に問題があるこ
とが確認された。When the sheet resistance distribution in a 30 cm square substrate surface was measured, there was a variation of ± 30%. When a voltage of 22 V was applied between the electrodes, almost no heat was generated in the high resistance portion, and it was confirmed that there was a problem in the function as electrothermal glass.
【0046】[実施例2]実施例1の工程1〜4と同様
にして、ガラス/PVB/SZO/TiN/GZO/ガ
ラスなる構成の合わせガラスの透明発熱体を作製した。
本実施例においては、GZO膜は600Åとし、TiN
膜を0〜200Åで変化させ、SZO膜を0〜500Å
で変化させた。作製されたそれぞれの透明発熱体につい
て、100℃、2ヶ月間の高温耐久性試験を行い、抵抗
上昇率を測定した。図1に、抵抗上昇率の経時変化を示
す。Example 2 In the same manner as in steps 1 to 4 of Example 1, a laminated glass transparent heating element having a structure of glass / PVB / SZO / TiN / GZO / glass was prepared.
In this embodiment, the GZO film has a thickness of 600 Å, and TiN is
Change the film from 0 to 200Å and change the SZO film from 0 to 500Å
Changed. Each of the produced transparent heating elements was subjected to a high temperature durability test at 100 ° C. for 2 months, and the resistance increase rate was measured. FIG. 1 shows the change in resistance increase rate over time.
【0047】図1より明らかなように、TiN膜および
SZO膜が存在することによって耐久性が格段に向上す
る。As is clear from FIG. 1, the presence of the TiN film and the SZO film significantly improves the durability.
【0048】[実施例3]実施例1の工程1〜4と同様
にして、ガラス/PVB/SZO/TiN/GZO/ガ
ラスなる構成の合わせガラスの透明発熱体を作製した。
本実施例においては、GZO膜は600Åとし、TiN
膜を0〜100Åで変化させ、SZO膜を0〜200Å
で変化させた。作製されたそれぞれの透明基体につい
て、600℃、5分間の加熱処理試験を行い、抵抗上昇
率を測定した。図2に、抵抗上昇率の経時変化を示す。[Example 3] In the same manner as in steps 1 to 4 of Example 1, a laminated glass transparent heating element having a structure of glass / PVB / SZO / TiN / GZO / glass was prepared.
In this embodiment, the GZO film has a thickness of 600 Å, and TiN is
Change the film from 0 to 100Å and change the SZO film from 0 to 200Å
Changed. A heat treatment test was performed at 600 ° C. for 5 minutes on each of the produced transparent substrates, and the resistance increase rate was measured. FIG. 2 shows the change in resistance increase rate with time.
【0049】図2より明らかなように、TiN膜および
SZO膜が存在することによって耐久性が格段に向上す
る。As is clear from FIG. 2, the presence of the TiN film and the SZO film significantly improves the durability.
【0050】[実施例4]実施例1の工程1〜4におい
て、GZO膜(600Å)、TiN膜(50Å)、SZ
O膜(200Å)を成膜し、GZO膜のスパッタ時の圧
力を変化させた他は同様にして、ガラス/PVB/SZ
O/TiN/GZO/ガラスなる構成の合わせガラスの
透明発熱体を作製した。[Example 4] In steps 1 to 4 of Example 1, a GZO film (600Å), a TiN film (50Å), an SZ film
Glass / PVB / SZ was formed in the same manner except that an O film (200 Å) was formed and the pressure during sputtering of the GZO film was changed.
A transparent heating element of laminated glass having a structure of O / TiN / GZO / glass was prepared.
【0051】また、SiO2 無添加のターゲットを用い
た以外は上記と同様にして、GZO膜のスパッタ時の圧
力を変化させて同じ構成の透明発熱体を作製した。Further, a transparent heating element having the same structure was prepared by changing the pressure during sputtering of the GZO film in the same manner as described above except that a target containing no SiO 2 was used.
【0052】このとき、GZO膜のスパッタ時の圧力と
成膜したGZO膜の比抵抗との関係を調べた。結果を図
3に示す。At this time, the relationship between the pressure during sputtering of the GZO film and the specific resistance of the formed GZO film was investigated. The results are shown in Fig. 3.
【0053】図3より明らかなように、SiO2 を極微
量添加することによって、スパッタ時の圧力が多少悪条
件側に寄っても、低比抵抗の膜を得ることができる。As is apparent from FIG. 3, by adding a very small amount of SiO 2 , it is possible to obtain a film having a low specific resistance even if the pressure during sputtering is closer to the bad condition side.
【0054】次に、GZO膜のスパッタ時の圧力が5.
0×10-5Torrの場合の合わせガラスの透明発熱体
について、100℃、2ヶ月間の高温耐久性試験を行
い、抵抗上昇率を測定した。図4に、抵抗上昇率の経時
変化を示す。Next, the pressure during sputtering of the GZO film was 5.
A transparent heating element of laminated glass in the case of 0 × 10 −5 Torr was subjected to a high temperature durability test at 100 ° C. for 2 months, and the resistance increase rate was measured. FIG. 4 shows the change in resistance increase rate with time.
【0055】図4より明らかなように、SiO2 を添加
することによって耐久性が格段に向上する。As is apparent from FIG. 4, the durability is remarkably improved by adding SiO 2 .
【0056】[実施例5]実施例1の工程1〜4におい
て、TiN膜をCrN膜に替えた以外は同様にして、ガ
ラス/PVB/SZO/CrN/GZO/ガラスなる構
成の合わせガラスの透明発熱体を作製した。[Embodiment 5] In steps 1 to 4 of Embodiment 1, the laminated glass having the structure of glass / PVB / SZO / CrN / GZO / glass is transparent in the same manner except that the TiN film is replaced with a CrN film. A heating element was produced.
【0057】本実施例においては、GZO膜は600Å
とし、CrN膜を0〜200Åで変化させ、SZO膜を
0〜200Åで変化させた。作製されたそれぞれの透明
発熱体について、100℃、2ヶ月間の高温耐久性試験
を行い、抵抗上昇率を測定した。図5に、抵抗上昇率の
経時変化を示す。In this embodiment, the GZO film is 600 Å
The CrN film was changed from 0 to 200Å and the SZO film was changed from 0 to 200Å. Each of the produced transparent heating elements was subjected to a high temperature durability test at 100 ° C. for 2 months, and the resistance increase rate was measured. FIG. 5 shows the change over time in the rate of increase in resistance.
【0058】図5より明らかなように、SZO膜および
CrN膜が存在することによって耐久性が格段に向上す
る。As is clear from FIG. 5, the presence of the SZO film and the CrN film significantly improves the durability.
【0059】実施例5において、CrN膜を、ZrN
膜、あるいはCrON膜に替えて同様に行ったところ、
同様の結果が得られた。In Example 5, the CrN film was replaced with ZrN.
When the same procedure was performed by replacing the film or CrON film,
Similar results were obtained.
【0060】[実施例6]実施例1の工程1〜4におい
て、TiN膜を酸窒化クロム膜(CrON膜)に替え、
SZO膜との成膜順序を逆にした以外は同様にして、ガ
ラス/PVB/CrON/SZO/GZO/ガラスなる
構成の合わせガラスの透明発熱体を作製した。[Example 6] In steps 1 to 4 of Example 1, the TiN film was replaced with a chromium oxynitride film (CrON film),
A transparent heating element of laminated glass having a structure of glass / PVB / CrON / SZO / GZO / glass was prepared in the same manner except that the order of film formation with the SZO film was reversed.
【0061】本実施例においては、GZO膜は600Å
とし、SZO膜を200Åとし、CrON膜を0〜20
0Åで変化させた。作製されたそれぞれの透明発熱体に
ついて、100℃、2ヶ月間の高温耐久性試験を行い、
抵抗上昇率を測定した。図6に、抵抗上昇率の経時変化
を示す。In this embodiment, the GZO film is 600 Å
, SZO film is 200Å, CrON film is 0-20
Change with 0Å. Each of the produced transparent heating elements was subjected to a high temperature durability test of 100 ° C. for 2 months,
The rate of resistance increase was measured. FIG. 6 shows the change in resistance increase rate with time.
【0062】図6より明らかなように、SZO膜および
CrON膜が存在することによって耐久性が格段に向上
する。As is apparent from FIG. 6, the presence of the SZO film and the CrON film significantly improves the durability.
【0063】[実施例7]実施例1の工程2〜3におい
て、GZO膜の膜厚を600Å、TiN膜をWO3-X 膜
(一部還元されたタングステン酸化物膜)に替えた以外
は実施例1と同様にして、ガラス/PVB/SZO/W
O3-X /GZO/ガラスなる構成の合わせガラスの透明
発熱体を作製した。[Embodiment 7] In steps 2 to 3 of Embodiment 1, the thickness of the GZO film is changed to 600Å and the TiN film is changed to the WO 3-X film (a partially reduced tungsten oxide film). Glass / PVB / SZO / W in the same manner as in Example 1.
A transparent heating element of laminated glass having a structure of O 3−x / GZO / glass was prepared.
【0064】還元気味の条件で成膜されたタングステン
酸化物膜は一般に波長約1μmの光を選択的に吸収ない
し反射して遮熱性能に優れることが知られている。本実
施例においては、WO3-X 膜の成膜にあたっては、スパ
ッタ成膜室内の水分圧が、3.2×10-5Torr、ス
パッタガスはArとO2 との混合ガス、ターゲットは金
属タングステンとし、直流スパッタリングを行った。こ
の際、スパッタガス中のO2 は少なめとし、タングステ
ン酸化物膜が水を取り込んで赤外光の吸収を生じるよう
に条件を調整した。It is known that a tungsten oxide film formed under a reducing condition generally selectively absorbs or reflects light having a wavelength of about 1 μm and is excellent in heat shielding performance. In this example, when forming a WO 3-X film, the water pressure in the sputtering film formation chamber was 3.2 × 10 -5 Torr, the sputtering gas was a mixed gas of Ar and O 2, and the target was a metal. Direct current sputtering was performed using tungsten. At this time, the amount of O 2 in the sputtering gas was made small, and the conditions were adjusted so that the tungsten oxide film could take in water and absorb infrared light.
【0065】本実施例においては、GZO膜は600
Å、WO3-X 膜を200Å、SZO膜を200Åとし
た。作製された透明発熱体について、100℃、2ヶ月
間の高温耐久性試験を行い、抵抗上昇率を測定した。図
7に、抵抗上昇率の経時変化を示す。In this embodiment, the GZO film is 600
Å, the WO 3-X film was 200 Å, and the SZO film was 200 Å. The produced transparent heating element was subjected to a high temperature durability test at 100 ° C. for 2 months, and the resistance increase rate was measured. FIG. 7 shows the change over time in the rate of increase in resistance.
【0066】図7より明らかなように、SZO膜および
WO3-X 膜が存在することによって耐久性が格段に向上
する。As is clear from FIG. 7, the presence of the SZO film and the WO 3-X film markedly improves the durability.
【0067】[0067]
【表1】 [Table 1]
【0068】[0068]
【発明の効果】本発明の透明発熱体は、低コストで、高
い信頼性と耐久性を有し、かつ優れた熱線遮断性能を有
する。The transparent heating element of the present invention has low cost, high reliability and durability, and excellent heat ray shielding performance.
【図1】実施例2の透明発熱体の高温耐久性を示すグラ
フFIG. 1 is a graph showing the high temperature durability of the transparent heating element of Example 2.
【図2】実施例3の透明発熱体の高温耐久性を示すグラ
フFIG. 2 is a graph showing the high temperature durability of the transparent heating element of Example 3.
【図3】実施例4の透明発熱体の高温耐久性の成膜圧力
依存性を示すグラフFIG. 3 is a graph showing the film forming pressure dependency of the high temperature durability of the transparent heating element of Example 4.
【図4】実施例4の透明発熱体の高温耐久性を示すグラ
フFIG. 4 is a graph showing high temperature durability of the transparent heating element of Example 4.
【図5】実施例5の透明発熱体の高温耐久性を示すグラ
フFIG. 5 is a graph showing high temperature durability of the transparent heating element of Example 5.
【図6】実施例6の透明発熱体の高温耐久性を示すグラ
フFIG. 6 is a graph showing high temperature durability of the transparent heating element of Example 6.
【図7】実施例7の透明発熱体の高温耐久性を示すグラ
フFIG. 7 is a graph showing high temperature durability of the transparent heating element of Example 7.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 一夫 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Sato 1150, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (2)
が0.1〜15原子%であるZnOを主成分とする透明
導電膜がコートされてなる透明発熱体であって、該透明
導電膜の上層には、SiとZrの複合酸化物膜および特
定のオーバーコート膜が形成され、該特定のオーバーコ
ート膜は、Cr、Ti、ZrおよびHfからなる群から
選ばれる少なくとも1種の金属の、窒化物膜、酸窒化物
膜と、Ti、W、Mo、Nb、TaおよびVからなる群
から選ばれる少なくとも1種の金属の低級酸化物膜の中
から選択される膜であることを特徴とする透明発熱体。1. A transparent heating element comprising a transparent substrate and a transparent conductive film mainly composed of ZnO having a Ga content relative to Zn of 0.1 to 15 atomic%, which is coated on the transparent substrate. A complex oxide film of Si and Zr and a specific overcoat film are formed on the upper layer of the film, and the specific overcoat film is at least one metal selected from the group consisting of Cr, Ti, Zr and Hf. Of a nitride film, an oxynitride film, and a lower oxide film of at least one metal selected from the group consisting of Ti, W, Mo, Nb, Ta, and V. Characteristic transparent heating element.
f、YおよびLaからなる群から選ばれる少なくとも1
種の金属を含有することを特徴とする請求項1記載の透
明発熱体。2. The transparent conductive film is made of Si, Ti, Zr, H.
at least 1 selected from the group consisting of f, Y and La
The transparent heating element according to claim 1, wherein the transparent heating element contains a kind of metal.
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JP (1) | JPH08151233A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006025470A1 (en) * | 2004-08-31 | 2006-03-09 | Sumitomo Metal Mining Co., Ltd. | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article using same, and infrared shielding article |
JPWO2006090806A1 (en) * | 2005-02-24 | 2008-07-24 | 積水化学工業株式会社 | Gallium-containing zinc oxide |
WO2009084442A1 (en) * | 2007-12-27 | 2009-07-09 | Asahi Glass Company, Limited | Heat reflecting glass and process for producing heat reflecting glass |
JP2010526758A (en) * | 2007-05-09 | 2010-08-05 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Transparency for vehicles heated by alternating current |
EP3203809A4 (en) * | 2014-09-29 | 2018-06-06 | LG Chem, Ltd. | Heating element and manufacturing method therefor |
US11105959B2 (en) | 2004-08-31 | 2021-08-31 | Sumitomo Metal Mining Co., Ltd. | Electroconductive particle, visible light transmitting particle-dispersed electrical conductor and manufacturing method thereof, transparent electroconductive thin film and manufacturing method thereof, transparent electroconductive article that uses the same, and infrared-shielding article |
-
1994
- 1994-11-24 JP JP6290067A patent/JPH08151233A/en not_active Withdrawn
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006025470A1 (en) * | 2004-08-31 | 2006-03-09 | Sumitomo Metal Mining Co., Ltd. | Conductive particle, visible light transmissive particle dispersed conductor, method for producing same, transparent conductive thin film, method for producing same, transparent conductive article using same, and infrared shielding article |
US8980135B2 (en) | 2004-08-31 | 2015-03-17 | Sumitomo Metal Mining Co., Ltd. | Electroconductive particle, visible light transmitting particle-dispersed electrical conductor and manufacturing method thereof, transparent electroconductive thin film and manufacturing method thereof, transparent electroconductive article that uses the same, and infrared-shielding article |
US11105959B2 (en) | 2004-08-31 | 2021-08-31 | Sumitomo Metal Mining Co., Ltd. | Electroconductive particle, visible light transmitting particle-dispersed electrical conductor and manufacturing method thereof, transparent electroconductive thin film and manufacturing method thereof, transparent electroconductive article that uses the same, and infrared-shielding article |
JPWO2006090806A1 (en) * | 2005-02-24 | 2008-07-24 | 積水化学工業株式会社 | Gallium-containing zinc oxide |
JP2010526758A (en) * | 2007-05-09 | 2010-08-05 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド | Transparency for vehicles heated by alternating current |
WO2009084442A1 (en) * | 2007-12-27 | 2009-07-09 | Asahi Glass Company, Limited | Heat reflecting glass and process for producing heat reflecting glass |
EP3203809A4 (en) * | 2014-09-29 | 2018-06-06 | LG Chem, Ltd. | Heating element and manufacturing method therefor |
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