JPS63203757A - Method for annealing tin-added indium oxide film - Google Patents
Method for annealing tin-added indium oxide filmInfo
- Publication number
- JPS63203757A JPS63203757A JP3577387A JP3577387A JPS63203757A JP S63203757 A JPS63203757 A JP S63203757A JP 3577387 A JP3577387 A JP 3577387A JP 3577387 A JP3577387 A JP 3577387A JP S63203757 A JPS63203757 A JP S63203757A
- Authority
- JP
- Japan
- Prior art keywords
- annealing
- indium oxide
- film
- tin
- low
- 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.)
- Pending
Links
- 238000000137 annealing Methods 0.000 title claims abstract description 24
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 239000007789 gas Substances 0.000 abstract description 11
- 239000011521 glass Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Manufacturing Of Electric Cables (AREA)
- Liquid Crystal (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、液晶表示素子等の電極として広（用いられ
る透明導電膜を形成する九めの錫添加酸化インジウム膜
のアニール方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a method of annealing a tin-doped indium oxide film forming a transparent conductive film widely used as an electrode for liquid crystal display elements, etc. .
一般に、液晶表示装置や蛍光表示管には錫添加酸化イン
ジウム膜（以下、ＩＴＯ膜と称する）等で構成される透
明導電膜が用いられることが多−・。Generally, a transparent conductive film composed of a tin-doped indium oxide film (hereinafter referred to as an ITO film) or the like is often used in liquid crystal display devices and fluorescent display tubes.
これらのＩＴＯ膜はスノくツタ法、真空蒸着法、スプレ
ー法などに１って形成されるが、このままでは抵抗が高
く、電極どして使用でき々いので、このＩＴＯ膜をアニ
ールすることによって低抵抗化を行なっている。そして
アニールすることによって透過率も大きくなる。These ITO films are formed by the snow ivy method, vacuum evaporation method, spray method, etc., but as they are, they have a high resistance and cannot be used as electrodes, so by annealing this ITO film, Low resistance is achieved. Annealing also increases the transmittance.
しかしながら従来のアニール方法は低抵抗化することが
難かしいものが多く、水素雰囲気中では低抵抗化は可能
であるが、透過率は７０Ｘ程度のものしか得られず、ま
た数百Ｔｏｒｒ程度の多量の水素ガスを用いるので安全
性に問題がある。However, in many conventional annealing methods, it is difficult to reduce the resistance, and although it is possible to reduce the resistance in a hydrogen atmosphere, the transmittance can only be obtained at about 70 Since hydrogen gas is used, there is a safety problem.
このような間！ＩＩｉを解決する友めにこの発明は、減
圧水素雰囲気中でアニールを行なう工うにしたものであ
る。For a while like this! In order to solve the problem IIi, the present invention is designed to carry out annealing in a reduced pressure hydrogen atmosphere.
透過率が高く、低抵抗のＩＴＯ膜が形成される。 An ITO film with high transmittance and low resistance is formed.
第１図はこの発明の方法を適用する装置を示す図であり
、１は真空槽、２は排気口、３はアニ−ル用の雰囲気ガ
スを導入するガス導入口、４はアニールすべきＩＴＯ膜
を堆積したガラス基板、５は試料保持台、６はヒータ、
７は加熱用電源である。FIG. 1 is a diagram showing an apparatus to which the method of the present invention is applied, in which 1 is a vacuum chamber, 2 is an exhaust port, 3 is a gas inlet for introducing atmospheric gas for annealing, and 4 is an ITO to be annealed. A glass substrate on which a film is deposited, 5 a sample holding table, 6 a heater,
7 is a heating power source.
このように構成され念装置において、ガス導入口３′ｔ
−閉じ次後、真空槽１内の排気を行なう、所定の真空圧
に達した後、ガス導入口３ｊ？水素ガスを導入し、ガス
流量と排気口２の開度ｔ″調整ることに１って所定のガ
ス圧に設定する。そして、ヒータ６を加熱してガラス基
板４の温度を上昇させ、所定のアニール温度になつ九ら
その温度ｔ−一定時間、例えば１時間糧度保持し友後、
ヒータ６への通電を止めて自然冷却させる。この間、真
空槽１内は一定の水素ガス圧に保持しておく０以上の方
法で、ＩＴＯ膜をアニールすることができる。In the device constructed in this way, the gas inlet 3't
- After closing, the vacuum chamber 1 is evacuated, and after reaching a predetermined vacuum pressure, the gas inlet 3j? Hydrogen gas is introduced, and a predetermined gas pressure is set by adjusting the gas flow rate and the opening degree t'' of the exhaust port 2.Then, the heater 6 is heated to raise the temperature of the glass substrate 4, and the gas pressure is set to a predetermined value. When the annealing temperature is reached, the temperature is maintained for a certain period of time, for example, 1 hour, and then
The power supply to the heater 6 is stopped and the heater 6 is allowed to cool naturally. During this time, the ITO film can be annealed by a method of 0 or more in which the inside of the vacuum chamber 1 is maintained at a constant hydrogen gas pressure.
第２図は、アニール温度をパラメータにして、ＩＴＯ膜
のシート抵抗と水素ガス圧との関係を示したものである
。ここで用いたＩＴＯ膜は、Ｉｎ−８ｎ １０ｗｔＸタ
ーゲットを使用し、Ａｒ＋０１雰囲気中の反応性スパッ
タ法でガラス基板上に堆積し次ものである。８２図に示
される工うに、水素ガス圧が５ ｍ Ｔｏｒｒ以上では
各温度において、シート抵抗が大幅に低下している。FIG. 2 shows the relationship between the sheet resistance of the ITO film and the hydrogen gas pressure using the annealing temperature as a parameter. The ITO film used here was deposited on a glass substrate by reactive sputtering in an Ar+01 atmosphere using an In-8n 10wtX target. As shown in Figure 82, the sheet resistance significantly decreases at each temperature when the hydrogen gas pressure is 5 m Torr or higher.
ま九、４５０〜５００℃程度の高いアニール温度を必要
とする従来の真空中アニールや窒素中アニールに比べ低
い温度範囲でシート抵抗が減少しており、基板の温度を
高くできない低融点のガラス基板や、アモルファス半導
体膜などにも低抵抗のＩＴＯ膜を形成することができる
。さらに、水素ガス圧を低くできることは大気圧での水
素中アニールに比べ水素使用量が少ないため、水素ガス
使用にともなう取扱いの点で非常に安全である。(9) Compared to conventional vacuum annealing or nitrogen annealing, which require a high annealing temperature of about 450 to 500°C, the sheet resistance is reduced in a lower temperature range, making it impossible to raise the substrate temperature on a glass substrate with a low melting point. A low-resistance ITO film can also be formed on an amorphous semiconductor film or the like. Furthermore, since the hydrogen gas pressure can be lowered, the amount of hydrogen used is smaller than in annealing in hydrogen at atmospheric pressure, which makes handling of hydrogen gas extremely safe.
つぎに簗３図はアニール温度３００℃におけるＩＴＯ膜
の可視域における透過率の水素ガス圧依存性を示してい
る。第３図かられかるように、水素ガス圧が５ｍＴｏｒ
ｒ〜２ Ｔｏｒｒの範囲で高い透過率が得られることが
わかる。２ Ｔｏｒｒでは水素の還元作用が大きく、Ｉ
ｎの析出が起こり始め、光が散乱される几め透過率が減
少する。また、水素ガス圧が低くなり、５ｍＴｏｒｒ以
下のところでは水素の還元作用が十分に行われず、この
九め、ＩＴＯ膜の吸収端が低波長域まで移動せず、し九
がって低波長域（５００ｎｍ以下）の透過率が減少する
ために透過率が小さくなる。この傾向は他のアニール温
度においても同じである。Next, Figure 3 shows the hydrogen gas pressure dependence of the transmittance in the visible range of the ITO film at an annealing temperature of 300°C. As can be seen from Figure 3, the hydrogen gas pressure was 5 mTorr.
It can be seen that high transmittance can be obtained in the range of r~2 Torr. At 2 Torr, the reducing effect of hydrogen is large, and I
Precipitation of n begins to occur, and the reduced transmittance through which light is scattered decreases. In addition, when the hydrogen gas pressure becomes low and below 5 mTorr, the reduction effect of hydrogen is not sufficiently performed. (500 nm or less), the transmittance decreases. This tendency is the same at other annealing temperatures.
つぎにＷｃ４図に水素ガス圧２ Ｔｏｒｒにおける透過
率のアニール温度依存性を示す、ＩＮ４Ｎ４図エフかな
工うに、アニール温度が２００℃〜４００℃の範囲で高
い透過率のＩＴＯＩｌｌ［ｔ−得ることができる。Next, Figure Wc4 shows the dependence of transmittance on annealing temperature at a hydrogen gas pressure of 2 Torr, and Figure F in IN4N4 shows that it is possible to obtain ITOIll [t-] with high transmittance at annealing temperatures in the range of 200°C to 400°C. can.
２００℃以下では温度が低いため、水素による還元作用
が十分行なわれず、ＩＴＯ膜中の酸素の拡散が遅くなり
、したがって、吸収端のシフト重が少なく、透過率が向
上しない、ま念４５０℃以上では水素による還元作用が
大きすぎる几めＩｎの析出が起こり、これにどもなって
広い波長範囲にわ次って透過率が減少してしまう、ま之
第２図に示さｉる工うに、２００℃〜４００℃のアニー
ル温度範囲では、シート抵抗も低くできる。ＩＴＯ膜中
の酸素が減少すると空孔が生じキャリアが電導するため
シート抵瓶が低くなるが、水素の還元作用に工り酸素の
減少が促進される０以上の１うに、低抵抗かつ高透過率
のＩＴＯ膜を得るには、アニール温度２００℃〜４００
℃水素ガス５ ｍ Ｔａｒｔ 〜２ Ｔｏｒｒの範囲が
適当であることがわかり念。さらに、水素ガス圧が低く
てすむ九め、安全性の点で優れて〜する。If the temperature is below 200℃, the reduction effect by hydrogen will not be sufficient, and the diffusion of oxygen in the ITO film will be slow, so the shift weight of the absorption edge will be small and the transmittance will not improve. In the process shown in Figure 2, the reduction effect caused by hydrogen causes the precipitation of concentrated In, which reduces the transmittance over a wide wavelength range. In the annealing temperature range of .degree. C. to 400.degree. C., sheet resistance can also be reduced. When the oxygen in the ITO film decreases, vacancies are created and carriers conduct, resulting in a lower sheet resistance. However, the reduction of oxygen is promoted by the reduction action of hydrogen. In order to obtain an ITO film with a high
It is understood that a range of 5 mTart to 2 Torr for hydrogen gas is appropriate. Furthermore, since the hydrogen gas pressure is low, it is superior in terms of safety.
以上説明し念工うにこの発明は減圧水素雰囲気中でかつ
低い温度でアニールを行なうようにしたので・抵抗であ
りま念高透過率のＩＴＯ膜を得ることができ、−さらに
減圧水素雰囲気中でのアニールであることから、安全性
の点でも優れているという効果を有する。As explained above, in this invention, annealing is performed in a reduced pressure hydrogen atmosphere and at a low temperature, so that an ITO film with high transmittance can be obtained without resistance. Since it is annealed, it has the effect of being excellent in terms of safety.
【図面の簡単な説明】
ＩＥＩ図はこの発明の方法を実施する装置を示す図、ｆ
ａ２図はシート抵抗の水素ガス圧依存特性仝示すグラフ
、第３図は透過率の水素ガス圧依存特性を示すグラフ、
第４図は透過率のアニール温度依存特性を示すグラフで
ある。
１・・・・真空槽、２・・・・排気口、３・・・・ガス
導入口、４・・・・ガラス基板、６・・・・ヒータ、７
・・・・加熱用電源。[BRIEF DESCRIPTION OF THE DRAWINGS] The IEI diagram is a diagram showing an apparatus for carrying out the method of the present invention, f
Figure a2 is a graph showing the hydrogen gas pressure dependence characteristics of sheet resistance, and Figure 3 is a graph showing the hydrogen gas pressure dependence characteristics of transmittance.
FIG. 4 is a graph showing the annealing temperature dependence of transmittance. 1... Vacuum chamber, 2... Exhaust port, 3... Gas inlet, 4... Glass substrate, 6... Heater, 7
...Heating power supply.
Claims (1)
ガス圧を５ｍＴｏｒｒ〜２Ｔｏｒｒの範囲とし、基板温
度を２００℃〜４００℃の範囲としてアニールすること
を特徴とする錫添加酸化インジウム膜のアニール方法。A method for annealing a tin-doped indium oxide film, the method comprising annealing a tin-doped indium oxide film at a hydrogen gas pressure in a range of 5 mTorr to 2 Torr and at a substrate temperature in a range of 200°C to 400°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3577387A JPS63203757A (en) | 1987-02-20 | 1987-02-20 | Method for annealing tin-added indium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3577387A JPS63203757A (en) | 1987-02-20 | 1987-02-20 | Method for annealing tin-added indium oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63203757A true JPS63203757A (en) | 1988-08-23 |
Family
ID=12451201
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3577387A Pending JPS63203757A (en) | 1987-02-20 | 1987-02-20 | Method for annealing tin-added indium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63203757A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0475028A (en) * | 1990-07-18 | 1992-03-10 | Canon Inc | Production of substrate for liquid crystal color display element |
| JP2013098241A (en) * | 2011-10-28 | 2013-05-20 | Kaneka Corp | Crystalline silicon solar cell and method for manufacturing the same |
-
1987
- 1987-02-20 JP JP3577387A patent/JPS63203757A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0475028A (en) * | 1990-07-18 | 1992-03-10 | Canon Inc | Production of substrate for liquid crystal color display element |
| JP2013098241A (en) * | 2011-10-28 | 2013-05-20 | Kaneka Corp | Crystalline silicon solar cell and method for manufacturing the same |
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