JPH0558171B2 - - Google Patents
Info
- Publication number
- JPH0558171B2 JPH0558171B2 JP59152499A JP15249984A JPH0558171B2 JP H0558171 B2 JPH0558171 B2 JP H0558171B2 JP 59152499 A JP59152499 A JP 59152499A JP 15249984 A JP15249984 A JP 15249984A JP H0558171 B2 JPH0558171 B2 JP H0558171B2
- Authority
- JP
- Japan
- Prior art keywords
- transparent
- thin film
- iridium
- metal
- torr
- 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.)
- Expired - Lifetime
Links
- 239000010409 thin film Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 16
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 16
- 239000010408 film Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 238000004544 sputter deposition Methods 0.000 claims description 10
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000002222 fluorine compounds Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、エレクトロクロミツク素子におけ
る、透明な酸化イリジウムからなるエレクトロク
ロミツク薄膜の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an electrochromic thin film made of transparent iridium oxide in an electrochromic device.
乾電池程度の電圧を印加することによつて発色
し、逆電圧を印加することによつて元の無色透明
に消色するエレクトロクロミツク（EC）表示装
置（以下、ECDと略す）は、日の字型のセブン
セグメントを用いた数字その他の表示手段として
利用すべく実用化にむけて盛んに研究されてい
る。その１つとして、WO3、MoO3等の還元発色
性EC物質を用いたECDがある。
Electrochromic (EC) display devices (hereinafter abbreviated as ECD), which develop color by applying a voltage similar to that of a dry cell battery, and fade back to their original colorless transparency by applying a reverse voltage, Active research is being carried out towards the practical use of this method as a means of displaying numbers and other things using letter-shaped seven segments. One of them is ECD using reduction color-forming EC substances such as WO 3 and MoO 3 .
これらのEC物質が発色するには、電子（e-）
とカチオン（X+）の同時注入が必要とされ、発
色・消色に伴う反応式は次のように考えられてい
る。 For these EC substances to develop color, electrons (e - ) are required
Simultaneous injection of cation and cation (X + ) is required, and the reaction equation for color development and decolorization is thought to be as follows.
消色時：WO3＋ne-＋nX+
↑↓ ↑↓
発色時：XnWO3
そして、カチオン（X+）としては、イオン半
径の小さく移動の容易なH+が主として使用され
ている。これらのカチオンは常時カチオンである
必要はなく、電圧が印加され電場が形成された時
にカチオンが発生すればよいので、特にH+の場
合には水がカチオン供給源として利用される。水
は電場の中で
H2O→H+＋OH-
に従つて分解する。水は極く微量で十分であるら
しく、大気中から自然にWO3層に取り込まれる
量の水分でしばしば間に合う。When decoloring: WO 3 +ne - +nX + ↑↓ ↑↓ When developing color: XnWO 3 And as the cation (X + ), H + , which has a small ionic radius and is easily mobile, is mainly used. These cations do not need to be cations all the time, but only need to be generated when a voltage is applied and an electric field is formed. Therefore, especially in the case of H + , water is used as a cation source. Water decomposes in an electric field as H 2 O→H + +OH - . Very small amounts of water appear to be sufficient, and the amount of water that is naturally drawn into the WO 3 layer from the atmosphere is often sufficient.
しかしながら、単にWO3層を一対の電極で挾
んで電圧を印加して発色させても、容易に消色す
ることができない。なぜならば、消色しようとし
て逆電圧を印加しても陰極に通じた電極側から電
子（e-）が流入してくるので、もしH+があれば、
WO3＋ne-＋nH+→HnWO3
の反応が起こつて着色するからである。 However, even if the WO 3 layer is simply sandwiched between a pair of electrodes and a voltage is applied to develop color, the color cannot be easily erased. This is because even if a reverse voltage is applied to erase the color, electrons (e - ) will flow in from the electrode side connected to the cathode, so if there is H + , WO 3 +ne - +nH + →HnWO 3 This is because a reaction occurs and the color changes.
そのため、WO3層と一方の電極との間に絶縁
層例えばSiO2、MgF2を設けたECDが提案された
（特公昭52−46098号）。このECDの絶縁層は、電
子の移動はできないが、OH-イオンの移動は自
由であり、このOH-イオンが電気を運び、絶縁
層と電極との間で
OH-→（1/2）H2O＋（1/4）O2↑＋e-
の反応に従つて電子を陽極側に放出しているもの
と思われる。 Therefore, an ECD was proposed in which an insulating layer such as SiO 2 or MgF 2 was provided between the WO 3 layer and one electrode (Japanese Patent Publication No. 52-46098). The insulating layer of this ECD cannot move electrons, but OH - ions can move freely, and these OH - ions carry electricity, causing OH - → (1/2)H between the insulating layer and the electrode. It seems that electrons are released to the anode side according to the reaction 2 O + (1/4) O 2 ↑ + e - .
つまり発色時には、 （陰極側） WO3＋ne-＋nH+→HnWO3 （陽極側） ｎ（OH-）→（ｎ／２）H2O ＋（ｎ／４）O2↑＋ne- という反応が推定され、消色時には、 （陽極側） HnWO3→WO3＋ne-＋nH+ （陰極側） nH2O＋ne-→nOH-＋（ｎ／２）H2↑ という反応が生じるものと推定される。 In other words, during color development, the reaction is estimated to be (cathode side) WO 3 +ne - +nH + →HnWO 3 (anode side) n(OH - ) → (n/2)H 2 O + (n/4)O 2 ↑+ne - It is estimated that the following reaction occurs during decolorization: (anode side) HnWO 3 →WO 3 +ne - +nH + (cathode side) nH 2 O+ne - →nOH - + (n/2)H 2 ↑.
これらの式からも明らかであるが、現実にも特
公昭52−46098号のECDは駆動により水が消費さ
れるので大気中から速やかに水が供給されないと
発色しなくなり、また、駆動に伴つてO2ガスや
H2ガスが放出されるので層間剥離を生じるとい
う欠点があつた。 As is clear from these equations, in reality, the ECD of Special Publication No. 52-46098 consumes water when it is driven, so unless water is quickly supplied from the atmosphere, it will not produce color. O 2 gas or
The disadvantage was that delamination occurred due to the release of H 2 gas.
そのため、WO3層の隣に「イオン良導体であ
る電子絶縁層／酸化発色性EC層」を設けた全固
体型ECDが提案された（特開昭56−4679号）。こ
れは酸化発色性EC層として水酸化イリジウムを
使用し、WO3の発色時に、陽極側で
Ir（OH）ｍ＋ｎ（OH-）
（無色透明）
↓
Ir（OH）ｌ・pH2O＋
――――――
↓
着色種
qH2O＋ｒ（e-）
と反応し、WO3の消色時に陰極側で
Ir（OH）ｌ・pH2O＋qH2O＋ｒ（e-）
↓
Ir（OHm＋ｎ（OH-）
と反応するものと考えられている。従つて、水が
再生されるので水が消費されず、またH2ガスや
O2ガスの発生もない。 Therefore, an all-solid-state ECD was proposed in which an ``electronic insulating layer that is a good ionic conductor/an oxidative color-developing EC layer'' was provided next to the three WO layers (Japanese Patent Application Laid-open No. 4679/1983). This uses iridium hydroxide as the oxidative color-forming EC layer, and when coloring WO 3 , Ir(OH)m+n(OH - ) (colorless and transparent) on the anode side ↓ Ir(OH)l・pH 2 O+ --- --- ↓ Reacts with colored species qH 2 O + r (e - ), and when WO 3 is decolored, Ir(OH)l・pH 2 O + qH 2 O + r (e - ) ↓ Ir (OHm + n (OH - ) Therefore, water is not consumed because it is regenerated, and H 2 gas and
No O2 gas is generated.
この場合、水酸化イリジウムは、一般の水酸化
物がそうであるように酸化物の水和物としてとら
えることができる。特に薄膜では大気中から容易
に水が浸入することから、水酸化物ではなく酸化
物と表現しても差し支えない。逆に酸化イリジウ
ム薄膜を入手しても大気中下では厳密な意味で水
酸化物と区別することは難しい。 In this case, iridium hydroxide can be regarded as a hydrate of an oxide, just like general hydroxides. Particularly in thin films, water easily penetrates from the atmosphere, so it may be referred to as an oxide rather than a hydroxide. On the other hand, even if you obtain an iridium oxide thin film, it is difficult to distinguish it from hydroxide in a strict sense in the atmosphere.
ところで、従来、透明な水酸化ないし酸化イリ
ジウム薄膜は、一旦金属イリジウムの薄膜を真空
蒸着、スパツタリングその他の真空薄膜形成技術
によつて形成した後、その薄膜を酸またはアルカ
リ水溶液中で陽極酸化することによつて製造して
いた。
By the way, transparent iridium hydroxide or iridium oxide thin films have conventionally been produced by first forming a thin film of metallic iridium by vacuum evaporation, sputtering or other vacuum thin film forming techniques, and then anodizing the thin film in an acid or alkaline aqueous solution. It was manufactured by.
従つて、２工程を必要とすることから、製造コ
ストが高く、製造時間が長くかかつていた。 Therefore, since two steps are required, the manufacturing cost is high and the manufacturing time is long.
また、陽極酸化のために下地に電極が必要とな
り、電極として透明電極（透過型ECDには必須
のもの）を選択した場合には、現在透明電極材料
として、低電気抵抗のものがないので、大面積の
金属イリジウム薄膜を陽極酸化しようとすると、
中心部の金属イリジウムが陽極酸化されずに、不
透明ないし透明な黒色のまま残つてしまい、その
ため大面積の透明な水酸化ないし酸化イリジウム
薄膜を得ることは、これまで不可能であつた。 In addition, an electrode is required on the base for anodic oxidation, and if a transparent electrode (essential for transmission type ECD) is selected as the electrode, there is currently no transparent electrode material with low electrical resistance. When attempting to anodize a large area of metallic iridium thin film,
The central metal iridium is not anodized and remains opaque to transparent black, so it has been impossible to obtain a large-area transparent iridium hydroxide or oxide thin film.
本発明の目的は、工程が１工程で済み、かつエ
レクトロクロミツク素子におけるエレクトロクロ
ミツク薄膜としての大面積の透明な酸化イリジウ
ム薄膜を製造できる方法を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a method that requires only one step and can produce a large-area transparent iridium oxide thin film as an electrochromic thin film in an electrochromic device.
本発明者らは、鋭意研究の結果、金属イリジウ
ムを「その酸化物もしくは弗化物が透明な他の金
属またはその酸化物もしくは弗化物」を共に特定
の酸素分圧及び成膜速度比の条件下に多元スパツ
タリングすることにより、透明な酸化イリジウム
薄膜を製造できる方法を見い出し、本発明を成す
に至つた。
As a result of intensive research, the present inventors have discovered that metallic iridium can be used with "other metals whose oxides or fluorides are transparent, or their oxides or fluorides" under specific oxygen partial pressures and film-forming rate ratios. The present inventors have discovered a method for producing a transparent iridium oxide thin film by multi-dimensional sputtering, and have accomplished the present invention.
しかして、本発明は、金属イリジウム（Ir）
を、他の金属(M)またはその酸化物もしくは弗化物
と共に、
O2分圧：５×10-3〜１×10-1Torr.
成膜速度比：Ir／Ｍ（重量比）＝0.02以上
の条件下で多元スパツタリングすることにより、
基板上にエレクトロクロミツク素子における、透
明な酸化イリジウムからなるエレクトロクロミツ
ク薄膜を製造する方法を提供する。 Therefore, the present invention is based on metal iridium (Ir).
together with other metals (M) or their oxides or fluorides, O 2 partial pressure: 5×10 -3 to 1×10 -1 Torr. Film formation rate ratio: Ir/M (weight ratio) = 0.02 or more By multidimensional sputtering under the conditions of
A method of manufacturing a transparent electrochromic thin film of iridium oxide in an electrochromic device on a substrate is provided.
本発明を実施するには、通常対向電極の形成さ
れた基板を用意する。しかしながら、他の金属(M)
の酸化物が導電性であつて得られる酸化イリジウ
ム薄膜がそれ自体導電性を示す場合には、特に対
向電極が形成されている必要はない。なお、対向
電極としては、SnO2、In2O3、ITO
（In2O3に５％程度のSnO2が混入したもの）、
ZnO等の透明導電性材料、Al、Ag、Au等の金属
材料が使用される。また対向電極の他に他の膜が
形成されていてもよい。 To carry out the present invention, a substrate on which a counter electrode is generally formed is prepared. However, other metals (M)
When the oxide of is conductive and the resulting iridium oxide thin film itself is conductive, it is not necessary to form a counter electrode. In addition, as the counter electrode, SnO 2 , In 2 O 3 , ITO (In 2 O 3 mixed with about 5% SnO 2 ),
Transparent conductive materials such as ZnO and metal materials such as Al, Ag, and Au are used. Further, other films may be formed in addition to the counter electrode.
このような基板を用い、本発明に従い金属Irを
他の金属Ｍまたはその酸化もしくは弗化物と共に
多元スパツタリングする。金属Irと共に使用され
る他の金属Ｍとしては、例えば、Sn、In、Ta、
Zn、Ti、Si、Mg、Ca、Ｗ、MoまたはSbなどが
挙げられる。これらの金属Ｍは既述のようにそれ
自体をターゲツトとせずに、その酸化物もしくは
弗化物をターゲツトとしてもよい。いずれにせ
よ、それらの金属Ｍの酸化物もしくは弗化物は無
色透明であり、酸化イリジウム薄膜を不透明にす
ることはない。
Using such a substrate, metal Ir is subjected to multi-element sputtering together with another metal M or its oxide or fluoride according to the present invention. Other metals M used together with metal Ir include, for example, Sn, In, Ta,
Examples include Zn, Ti, Si, Mg, Ca, W, Mo, and Sb. As described above, these metals M may not be used as targets per se, but their oxides or fluorides may be used as targets. In any case, these oxides or fluorides of metal M are colorless and transparent and do not make the iridium oxide thin film opaque.
スパツタリングの方法としては、高周波または
直流スパツタリングが用いられる。 As the sputtering method, high frequency or direct current sputtering is used.
スパツタリングは、真空槽内に基板を置いて、
一旦到達真空度：１×10-6〜５×10-6Torr程度
に真空にした後、スパツタリング時O2分圧：５
×10-3〜１×10-1TorrのO2ガスを流し、基板温
度を−200℃〜300℃程度の間で、成膜速度比を
Ir／Ｍ重量比換算で0.02以上に制御しながら行な
う。 Sputtering involves placing the substrate in a vacuum chamber.
Once the vacuum is reached to a degree of vacuum: 1×10 -6 to 5×10 -6 Torr, O 2 partial pressure during sputtering: 5
×10 -3 to 1 × 10 -1 Torr of O 2 gas was flowed, the substrate temperature was between -200°C to 300°C, and the deposition rate ratio was adjusted.
This is done while controlling the Ir/M weight ratio to be 0.02 or more.
この場合、もしO2分圧が５×10-3Torrより低
いと、
放電が不安定
膜が酸化不足によつて、可視光を吸収するよ
うになり、透明感がなくなる
などの欠点が出てくる。逆に１×10-1Torrより
高いと、
均一な構造の膜が成長し難くなる
付着が悪くなる。 In this case, if the O 2 partial pressure is lower than 5 x 10 -3 Torr, the discharge will be unstable.The film will absorb visible light due to insufficient oxidation, resulting in defects such as loss of transparency. come. On the other hand, if it is higher than 1×10 -1 Torr, it becomes difficult to grow a film with a uniform structure, and adhesion becomes poor.
などの欠点が出てくる。There are drawbacks such as.
また、成膜速度比がIr／Ｍ重量比換算で0.02未
満であると、電極反応が円滑に進まなくなり、そ
の結果EC性が低下する（反応電荷量が過小とな
る）。逆に、高すぎても透明感がなくなるので一
般に約10以下位が好ましい。 Furthermore, if the film formation rate ratio is less than 0.02 in terms of Ir/M weight ratio, the electrode reaction will not proceed smoothly, resulting in a decrease in EC properties (the amount of reaction charge will become too small). On the other hand, if it is too high, the transparency will be lost, so it is generally preferable to set it at about 10 or less.
こうして透明な酸化イリジウム薄膜が得られる
が、この薄膜は微多孔質構造を有しており、大気
中からまたは隣層から容易に水分を吸収し、その
結果ある意味でそれは水酸化物と呼べる状態にな
り得る。 In this way, a transparent thin film of iridium oxide is obtained, which has a microporous structure and easily absorbs moisture from the atmosphere or from adjacent layers, so that in a sense it can be called a hydroxide. It can be.
本発明に従つて得られる酸化イリジウム薄膜
は、Irの含有率が低下するに従い発色濃度は低下
するものの、O2ガスやH2ガスの発生抑止には効
果を有する。 The iridium oxide thin film obtained according to the present invention has the effect of suppressing the generation of O 2 gas and H 2 gas, although the color density decreases as the Ir content decreases.
酸化イリジウムの膜厚は任意であるが、ECD
に使用するには一般的に0.005μｍ〜１mm程度とす
る。 The iridium oxide film thickness is arbitrary, but ECD
Generally, the thickness is about 0.005 μm to 1 mm.
以下、実施例により、本発明を具体的に説明す
る。 Hereinafter, the present invention will be specifically explained with reference to Examples.
厚さ0.15μｍのITO透明導電性(E)の形成された
ガラス基板を用意し、導電層(E)の上に下記条件：
ターゲツト：金属Irと金属Snの２元系
到達真空度：１×10-6Torr
O2分圧：３×10-2Torr
基板温度：室温
成膜速度比：Ir／Sn（重量比）約1.0
下にRF（高周波）スパツタリングを行ない、膜
厚200Åの透明な酸化イリジウム薄膜(D)を形成さ
せた。
A glass substrate with a thickness of 0.15 μm on which ITO transparent conductive material (E) is formed is prepared, and the following conditions are applied on the conductive layer (E): Target: Binary system of metal Ir and metal Sn Ultimate degree of vacuum: 1× 10 -6 Torr O2 partial pressure: 3 x 10 -2 Torr Substrate temperature: room temperature Film formation rate ratio: Ir/Sn (weight ratio) approx. 1.0 RF (radio frequency) sputtering is performed below to form a transparent oxide film with a thickness of 200 Å. An iridium thin film (D) was formed.
次にその上に下記条件：
蒸発源：Ta2O5
到達真空度：５×10-6Torr
O2分圧：４×10-4Torr
基板温度：150℃
の下に真空蒸着により、膜厚5000Åの透明イオン
導電層(C)を形成させた。 Next, the film thickness is determined by vacuum evaporation under the following conditions: Evaporation source: Ta 2 O 5 Ultimate vacuum: 5 × 10 -6 Torr O 2 Partial pressure: 4 × 10 -4 Torr Substrate temperature: 150°C A transparent ion conductive layer (C) of 5000 Å was formed.
その上にさらに下記条件：
蒸発源：WO3
到達真空度：５×10-6Torr
Ar分圧：４×10-4Torr
基板温度：150℃
の下に真空蒸着により、膜厚5000Åの透明な非晶
質WO3層(B)を形成させた。 Furthermore, under the following conditions: Evaporation source: WO 3 Ultimate vacuum: 5 × 10 -6 Torr Ar partial pressure: 4 × 10 -4 Torr Substrate temperature: 150°C A transparent film with a thickness of 5000 Å was deposited under the following conditions: Three layers of amorphous WO (B) were formed.
最後にWO3層(B)の上に下記条件：
蒸発源：In2O3とSnO2との混合物
到達真空度：５×10-6Torr
O2分圧：３×10-4Torr
基板温度：150℃
の下に高周波イオンプレーテイングにより、膜厚
2500Åの透明表示電極(A)を形成させた。こうし
て、５層構造を有するECDが得られた。 Finally, apply the following conditions on the WO 3 layer (B): Evaporation source: mixture of In 2 O 3 and SnO 2 Ultimate vacuum: 5×10 -6 Torr O 2 partial pressure: 3×10 -4 Torr Substrate temperature : The film thickness is reduced by high frequency ion plating at 150℃.
A 2500 Å transparent display electrode (A) was formed. In this way, an ECD with a five-layer structure was obtained.
このECDをエポキシ樹脂で封止した後、電極
(A)、(E)を通じて＋1.4ボルトの発色電圧を印加す
ると、100ｍsecで発色し、発色時の透過率（Tc）
は波長λ＝600nｍで15％であり、この発色状態
は電圧印加を止めても保持された。次に、−1.4ボ
ルトの消色電圧を印加すると、50ｍsecで元の無
色透明に戻り、消色時の透過率（Tb）は85％で
あつた。 After sealing this ECD with epoxy resin, the electrode
When a coloring voltage of +1.4 volts is applied through (A) and (E), coloring occurs in 100 msec, and transmittance (Tc) when coloring occurs.
was 15% at wavelength λ=600 nm, and this coloring state was maintained even after the voltage application was stopped. Next, when a decoloring voltage of -1.4 volts was applied, the original colorless and transparent state was restored in 50 msec, and the transmittance (Tb) at the time of decolorization was 85%.
比較例 １
実施例で用いたガラス基板を用意し、その導電
層(E)の上に下記条件：
蒸発源：金属Ir
真空度：５×10-6Torr
Ar分圧：３×10-4Torr
基板温度：20℃
成膜速度：１×10-1Å／sec
の下に高周波イオンプレーテイングにより、膜厚
700Åの黒色の金属Ir薄膜を形成させた。Comparative Example 1 The glass substrate used in Example was prepared, and the following conditions were applied on the conductive layer (E): Evaporation source: Metal Ir Vacuum degree: 5 × 10 -6 Torr Ar partial pressure: 3 × 10 -4 Torr Substrate temperature: 20℃ Deposition rate: 1×10 -1 Å/sec by high frequency ion plating to increase the film thickness.
A 700 Å black metallic Ir thin film was formed.
その後、1N硫酸水溶液中で＋1.3、−0.5Vvs.
SCE交流電圧（0.5Hz）を印加して陽極酸化を行
ない、透明な酸化イリジウム薄膜(D)に変えた。 After that, +1.3, -0.5V vs. 1N sulfuric acid aqueous solution.
Anodic oxidation was performed by applying SCE AC voltage (0.5 Hz) to transform it into a transparent iridium oxide thin film (D).
酸化イリジウム薄膜(D)の上に実施例と同様に(C)
層、(B)層及び(A)層を積層してECDを作成し封止
したところ、得られたECDは発色電圧印加前か
ら、やや褐色に着色しており、大気中で±1.5ボ
ルトの0.5Hz交流電圧を500分印加しても、完全に
は無色透明にならなかつた。消色した後、発消色
テストを行つたところ、200ｍsecでTc＝20％、
150ｍsecでTb＝75％であつた。 Same as Example (C) on iridium oxide thin film (D)
When an ECD was created and sealed by laminating layers (B) and (A), the resulting ECD was colored slightly brown even before the coloring voltage was applied, and the voltage of ±1.5 volts in the atmosphere was slightly brown. Even after applying a 0.5Hz AC voltage for 500 minutes, it did not become completely colorless and transparent. After decoloring, a color development/decolorization test was performed and Tc = 20% at 200 msec.
Tb=75% at 150 msec.
以上のとおり、本発明によれば陽極酸化が不要
なので１工程でエレクトロクロミツク素子におけ
るエレクトロクロミツク薄膜としての大面積の透
明な酸化イリジウム薄膜が得られる。
As described above, according to the present invention, since anodic oxidation is not required, a transparent iridium oxide thin film having a large area as an electrochromic thin film in an electrochromic device can be obtained in one step.
また、得られる酸化イリジウム薄膜は、存在す
る大部分のIr原子がEC性に関与し、また耐久性
にすぐれている。そのほか、希少で高価なIrが節
約される利点もある。 Furthermore, in the obtained iridium oxide thin film, most of the Ir atoms present are involved in EC properties, and it has excellent durability. Another advantage is that rare and expensive Ir is saved.
Claims (1)
その酸化物もしくは弗化物と共に、 O2分圧：５×10-3〜１×10-1Torr. 成膜速度比：Ir／Ｍ（重量比）＝0.02以上 の条件下で多元スパツタリングすることにより、
基板上に、エレクトロクロミツク素子における、
透明な酸化イリジウムからなるエレクトロクロミ
ツク薄膜を製造する方法。 ２ 前記金属(M)が、Sn、In、Ta、Zn、Ti、Si、
Mg、Ca、Ｗ、MoまたはSb であることを特徴とする特許請求の範囲第１項記
載の方法。[Claims] 1 Metal iridium (Ir) together with another metal (M) or its oxide or fluoride, O 2 partial pressure: 5 × 10 -3 to 1 × 10 -1 Torr. Film formation rate By performing multi-dimensional sputtering under the condition of ratio: Ir/M (weight ratio) = 0.02 or more,
In the electrochromic device on the substrate,
A method for producing electrochromic thin films of transparent iridium oxide. 2 The metal (M) is Sn, In, Ta, Zn, Ti, Si,
The method according to claim 1, characterized in that the metal is Mg, Ca, W, Mo or Sb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59152499A JPS6129822A (en) | 1984-07-23 | 1984-07-23 | Production of thin transparent iridium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59152499A JPS6129822A (en) | 1984-07-23 | 1984-07-23 | Production of thin transparent iridium oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6129822A JPS6129822A (en) | 1986-02-10 |
| JPH0558171B2 true JPH0558171B2 (en) | 1993-08-25 |
Family
ID=15541796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59152499A Granted JPS6129822A (en) | 1984-07-23 | 1984-07-23 | Production of thin transparent iridium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6129822A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995013562A1 (en) * | 1993-11-12 | 1995-05-18 | Ppg Industries, Inc. | Iridium oxide film for electrochromic device |
| SE0103198D0 (en) | 2001-09-26 | 2001-09-26 | Andris Azens | Electrochromic film and device comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59180526A (en) * | 1983-03-30 | 1984-10-13 | Fujitsu Ltd | Electrochromic display element |
-
1984
- 1984-07-23 JP JP59152499A patent/JPS6129822A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59180526A (en) * | 1983-03-30 | 1984-10-13 | Fujitsu Ltd | Electrochromic display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6129822A (en) | 1986-02-10 |
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