JPH08134638A - Method for forming titanium oxide film - Google Patents
Method for forming titanium oxide filmInfo
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- JPH08134638A JPH08134638A JP27133594A JP27133594A JPH08134638A JP H08134638 A JPH08134638 A JP H08134638A JP 27133594 A JP27133594 A JP 27133594A JP 27133594 A JP27133594 A JP 27133594A JP H08134638 A JPH08134638 A JP H08134638A
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- Prior art keywords
- titanium oxide
- film
- oxide film
- sputtering
- back pressure
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、チタン酸化物膜の成膜
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a titanium oxide film.
【０００２】[0002]
【従来の技術】チタン酸化物は可視域で透明な膜材料で
あり、かつ、屈折率が大きいため、光学多層膜の設計
上、非常に有用な材料である。このため、透明低屈折率
材料のシリカとともに各種の光学多層膜の構成材料とし
て盛んに用いられている。また、最近では、建築用や自
動車用の熱線反射ガラス用のコーティング材料としても
用いられている。2. Description of the Related Art Titanium oxide is a material that is transparent in the visible region and has a large refractive index, and is therefore a very useful material in the design of optical multilayer films. Therefore, it is widely used as a constituent material of various optical multilayer films together with transparent low refractive index material silica. Recently, it has also been used as a coating material for heat-reflecting glass for buildings and automobiles.
【０００３】従来のチタン酸化物膜は真空蒸着法やマグ
ネトロンスパッタリング法で成膜されている。チタン酸
化物膜を光学薄膜などに用いる場合には、真空蒸着法で
成膜するのが一般的であるが、膜厚分布が大きいため、
小さい部品に成膜するには適するものの、大面積の基板
に成膜するのは難しいという問題があった。また、マグ
ネトロンスパッタリング法では膜厚均一性は良いが、成
膜速度が遅くコストアップになるという欠点があった。A conventional titanium oxide film is formed by a vacuum vapor deposition method or a magnetron sputtering method. When a titanium oxide film is used as an optical thin film, it is generally formed by a vacuum evaporation method, but since the film thickness distribution is large,
Although it is suitable for forming a film on a small part, there is a problem that it is difficult to form a film on a large area substrate. Further, although the magnetron sputtering method has good film thickness uniformity, it has a drawback that the film formation rate is slow and the cost is increased.
【０００４】そこで、膜厚均一性のよいマグネトロンス
パッタリング法で高速成膜を行う方法として、ターゲッ
トにＴｉＯx （０＜ｘ＜２）を使用し、スパッタリング
ガスとして不活性ガスのみを用いた成膜方法が提案され
た（特願平６−２４４２０号）。Therefore, as a method for performing high-speed film formation by a magnetron sputtering method having good film thickness uniformity, TiO x (0 <x <2) is used as a target and only inert gas is used as a sputtering gas. A method was proposed (Japanese Patent Application No. 6-24420).
【０００５】しかし、この成膜方法は、成膜チャンバの
背圧の変化、つまり、残留水分圧の変化により、成膜速
度が変化する。これは、この領域の背圧は残留水分圧と
ほぼ等しいからである。また、ターゲットに酸素欠陥が
あるために、残留水分圧が十分でない場合、基板上に形
成される膜は可視光を吸収する膜になってしまうという
問題点があった。However, in this film forming method, the film forming rate changes due to a change in the back pressure of the film forming chamber, that is, a change in the residual water pressure. This is because the back pressure in this area is approximately equal to the residual water pressure. Further, since the target has oxygen defects, when the residual water pressure is not sufficient, the film formed on the substrate becomes a film that absorbs visible light.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、均一に、大
面積で、安定かつ高速で成膜が可能な、透明チタン酸化
物膜の成膜方法の提供を目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for forming a transparent titanium oxide film, which enables uniform, large-area, stable and high-speed film formation.
【０００７】[0007]
【課題を解決するための手段】本発明は、ＴｉＯx ター
ゲット（０＜ｘ＜２）を用いスパッタリングによりチタ
ン酸化物膜を成膜する方法において、スパッタリングガ
ス中に水分を調整し導入することを特徴とするチタン酸
化物膜の成膜方法を提供する。According to the present invention, in a method for forming a titanium oxide film by sputtering using a TiO x target (0 <x <2), it is necessary to adjust and introduce water into a sputtering gas. A method for forming a characteristic titanium oxide film is provided.
【０００８】図１は、本発明を行うために用いる装置の
基本的構成を示す。１は導電性ＴｉＯx ターゲットを示
す。このターゲットの製作方法としては、焼結法、また
は溶射法が通常採用されるが、得られるターゲットが導
電性を示すならば、特にその製造方法は限定されない。
２は直流マグネトロンスパッタ用電源を示し、通常の直
流電源であればよい。水を入れたタンク９は恒温槽１０
の中に入っており一定温度に保たれている。FIG. 1 shows the basic configuration of the apparatus used to carry out the present invention. Reference numeral 1 represents a conductive TiO x target. As a method for manufacturing this target, a sintering method or a thermal spraying method is usually adopted, but the manufacturing method is not particularly limited as long as the target obtained exhibits conductivity.
Reference numeral 2 denotes a DC magnetron sputtering power source, which may be a normal DC power source. The tank 9 containing water is a constant temperature bath 10.
It is kept inside and kept at a constant temperature.
【０００９】ＡｒガスがＡｒガスボンベ１４からマスフ
ローコントローラ１２を通って水タンク９に導入され、
Ａｒガスが水のキャリアガスとなり、水とＡｒがニード
ルバルブ８を通じて成膜チャンバ４内に導入される。な
お、キャリアガスとしてはＡｒガスに限定されず、その
他の不活性ガスも用い得る。また、成膜チャンバ４への
水の導入において、Ａｒガスをキャリアガスとして用い
ず、恒温槽１０内の水蒸気を、直接、成膜チャンバ４に
導入することもできる。Ar gas is introduced into the water tank 9 from the Ar gas cylinder 14 through the mass flow controller 12.
Ar gas serves as a carrier gas for water, and water and Ar are introduced into the film forming chamber 4 through the needle valve 8. The carrier gas is not limited to Ar gas, and other inert gas may be used. Further, when introducing water into the film forming chamber 4, it is possible to directly introduce the water vapor in the constant temperature bath 10 into the film forming chamber 4 without using Ar gas as a carrier gas.
【００１０】前記構成においては、水導入パイプは、内
面における水の凝結を防ぐため、ヒータ１１により恒温
槽の温度以上に加熱されることが望ましい。In the above structure, the water introducing pipe is preferably heated by the heater 11 to a temperature equal to or higher than the temperature of the constant temperature bath in order to prevent water from condensing on the inner surface.
【００１１】導入すべき水の導入量は、主には、スパッ
タリングガス中の水分圧により決まり、ターゲットのＴ
ｉＯX （０＜ｘ＜２）のｘの値、また、成膜装置によっ
ても、若干異なる。例えば、ターゲットのＴｉＯx のｘ
の値が小さいとき、成膜装置の排気速度が速いとき、あ
るいは、成膜装置の真空室容量が小さいときなどは、水
の導入量を多くする必要がある。The amount of water to be introduced is mainly determined by the water pressure in the sputtering gas, and
The value of x of iO x (0 <x <2) and the film forming apparatus are slightly different. For example, x of TiO x target
Is small, the evacuation speed of the film forming apparatus is high, or the vacuum chamber capacity of the film forming apparatus is small, it is necessary to increase the amount of water introduced.
【００１２】したがって、同一ターゲット、同一成膜装
置のもとで、Ａｒのみのスパッタリングを行い、背圧に
対する成膜速度、膜質の関係を調べた後、成膜速度が速
く、かつ、透明なチタン酸化物膜が得られる水の導入量
を決定する。Therefore, after sputtering only Ar under the same target and the same film forming apparatus and examining the relationship between the film forming speed and the film quality with respect to the back pressure, the film forming speed is high and transparent titanium is used. The amount of water introduced to obtain the oxide film is determined.
【００１３】実際の成膜時におけるスパッタリングガス
中の水分圧の調整方法としては、スパッタリングガス中
の水分量そのものを質量分析計７で読みとりながら、所
望の成膜速度や膜質になる水分圧になるようにニードル
バルブ８で調整する方法が最も直接的であり、実用的で
もある。As a method of adjusting the water pressure in the sputtering gas during the actual film formation, the water content itself in the sputtering gas is read by the mass spectrometer 7, and the water pressure at which the desired film formation speed and film quality are obtained is obtained. The method of adjusting with the needle valve 8 is the most direct and practical.
【００１４】他の方法として、予め、成膜速度や膜質と
スパッタリング中のプラズマの発光強度との関係を調べ
ておき、さらに、スパッタリングガス中の水分圧とスパ
ッタリング中のプラズマの発光強度の関係を調べた後
に、所望の成膜速度や膜質に対応するプラズマの発光強
度が一定になるようにニードルバルブ８の開閉を調整す
ることで、結果として水分圧を一定に保つ方法などがあ
る。As another method, the relationship between the film forming speed and film quality and the emission intensity of plasma during sputtering is investigated in advance, and the relationship between the water pressure in the sputtering gas and the emission intensity of plasma during sputtering is investigated. After the examination, there is a method in which the water pressure is kept constant by adjusting the opening and closing of the needle valve 8 so that the plasma emission intensity corresponding to the desired film formation rate and film quality becomes constant.
【００１５】この場合にモニタ信号として使用可能なプ
ラズマの発光種は、背圧中の水によるＨ2 Ｏ、ＯＨ、Ｈ
の発光とＴｉＯx ターゲットの構成原子であるＴｉの発
光などが挙げられる。In this case, the luminescent species of plasma that can be used as a monitor signal are H 2 O, OH, H due to water in the back pressure.
And the emission of Ti which is a constituent atom of the TiO x target.
【００１６】また、他の方法として、水晶振動子式の膜
厚計をチャンバ内の適当な位置に配置し、測定された成
膜速度が一定になるようにニードルバルブ８の開閉を調
整してもよい。As another method, a quartz oscillator type film thickness meter is arranged at an appropriate position in the chamber, and the opening / closing of the needle valve 8 is adjusted so that the measured film forming rate becomes constant. Good.
【００１７】また、以上のいずれの方法においてもニー
ドルバルブ８は加熱可能なマスフローコントローラに置
き換えることができる。In any of the above methods, the needle valve 8 can be replaced with a heatable mass flow controller.
【００１８】また、前述の構成において、別系統のＡｒ
ガスを直接真空室内に導入できるマスフローコントロー
ラ１３が接続されていると、成膜チャンバ内の圧力を容
易に一定にできるので望ましい。Further, in the above-mentioned structure, another system of Ar
It is desirable that the mass flow controller 13 that can directly introduce the gas into the vacuum chamber is connected because the pressure in the film forming chamber can be easily made constant.
【００１９】[0019]
【作用】前述したように、酸素欠陥を持つＴｉＯx （０
＜ｘ＜２）が導電性を示すことから不活性ガスのみによ
る直流マグネトロンスパッタリング法により、高速成膜
が行えることが提案されている。しかし、スパッタリン
グガスである不活性ガス中に酸化性ガスが混入しなけれ
ば、ＴｉＯx ターゲットが酸素欠陥を有するため、基板
上に形成される膜は可視光を吸収する膜になる。As described above, TiO x (0
Since <x <2) indicates conductivity, it has been proposed that high-speed film formation can be performed by the DC magnetron sputtering method using only an inert gas. However, if the oxidizing gas is not mixed into the inert gas that is the sputtering gas, the TiO x target has oxygen defects, and thus the film formed on the substrate becomes a film that absorbs visible light.
【００２０】本発明者らは、成膜時に、スパッタリング
ガスとして、水分を含有するスパッタリングガスを用い
ることにより、透明なチタン酸化物膜を、背圧によら
ず、一定の成膜速度で、しかも高速で形成できることを
見いだした。The inventors of the present invention use a sputtering gas containing water as a sputtering gas at the time of film formation, so that a transparent titanium oxide film can be formed at a constant film formation rate regardless of back pressure. We found that it can be formed at high speed.
【００２１】スパッタリングガス中に導入する水分の量
が水分圧で、１０-5Ｔｏｒｒより小さいと透明なチタン
酸化物膜を得られにくくなり、１０-3Ｔｏｒｒより大き
いと成膜速度が遅くなるので、スパッタリングガス中に
導入する水分の量は、水分圧で１０-5〜１０-3Ｔｏｒｒ
の範囲であることが望ましい。If the amount of water introduced into the sputtering gas is less than 10 -5 Torr due to the water pressure, it is difficult to obtain a transparent titanium oxide film, and if it is more than 10 -3 Torr, the film forming rate becomes slow. The amount of water introduced into the sputtering gas is 10 -5 to 10 -3 Torr in terms of water pressure.
Is desirably within the range.
【００２２】[0022]
［実施例１］図１は直流マグネトロンスパッタ装置の概
略図であって、４は成膜チャンバであり、３はガラス基
板、２は直流電源である。ターゲットとしては、焼結法
により作成したＴｉＯx （ｘ＝１．９７）ターゲットを
用いた。[Embodiment 1] FIG. 1 is a schematic view of a DC magnetron sputtering apparatus, in which 4 is a film forming chamber, 3 is a glass substrate, and 2 is a DC power source. As the target, a TiO x (x = 1.97) target prepared by a sintering method was used.
【００２３】まず、成膜チャンバ４を成膜前の背圧が
４．０×１０-4Ｔｏｒｒを示すまで、排気口５から排気
した（工程１）。First, the film forming chamber 4 was evacuated through the exhaust port 5 until the back pressure before film formation was 4.0 × 10 -4 Torr (step 1).
【００２４】次に、質量分析計７で水分圧をモニタしな
がら、Ａｒガスを導入した水タンクからＡｒと水の混合
ガスを、スパッタリングガス中の水分圧が５×１０-5Ｔ
ｏｒｒになるようにニードルバルブ８で調整した。その
後、チャンバ内圧力が２×１０-3Ｔｏｒｒになるように
マスフローコントローラ１３を通してＡｒを導入した
（工程２）。Next, while monitoring the moisture pressure with the mass spectrometer 7, the mixed gas of Ar and water was introduced from the water tank into which the Ar gas was introduced, and the moisture pressure in the sputtering gas was 5 × 10 -5 T.
The needle valve 8 was adjusted so as to be orr. Then, Ar was introduced through the mass flow controller 13 so that the pressure in the chamber became 2 × 10 −3 Torr (step 2).
【００２５】その後、直流電源２で電力を２ｋＷ投入
し、チタン酸化物膜を基板３に成膜した（工程３）。After that, 2 kW of power was applied by the DC power supply 2 to form a titanium oxide film on the substrate 3 (step 3).
【００２６】得られたチタン酸化物膜の膜厚（Å）を測
定し、単位搬送時間（ｍｉｎ／ｍ）、単位電力（ｋ
Ｗ）、および単位搬送回数（ｐａｓｓ）当たりの成膜速
度（以下、単位成膜速度という）を算出した。The thickness (Å) of the obtained titanium oxide film was measured, and the unit transport time (min / m) and the unit power (k)
W) and the film formation rate per unit number of conveyance (pass) (hereinafter, referred to as unit film formation rate) were calculated.
【００２７】続いて、排気時間を変えて、背圧を３．５
×１０-4Ｔｏｒｒ〜１．１×１０-5Ｔｏｒｒの範囲で変
化させ、上記同様にしてチタン酸化物膜を成膜し、背圧
と単位成膜速度（Å．ｍ／ｍｉｎ）／（ｋＷ．ｐａｓ
ｓ）との関係を調べた。Subsequently, the back pressure is set to 3.5 by changing the exhaust time.
A titanium oxide film was formed in the same manner as above by changing the pressure in the range of × 10 -4 Torr to 1.1 × 10 -5 Torr, and the back pressure and unit film formation rate (Å.m / min) / (kW .Pas
The relationship with s) was investigated.
【００２８】なお、成膜前後で背圧は変化するので、成
膜後の背圧をガスの導入を止めた状態で測定し、成膜前
後の背圧の平均をとり、得られた平均値を本実施例にお
ける背圧とした。Since the back pressure changes before and after film formation, the back pressure after film formation is measured with gas introduction stopped, and the back pressure before and after film formation is averaged to obtain an average value. Was the back pressure in this example.
【００２９】また、成膜中に背圧が変化し、スパッタリ
ングガス中の水分圧が変化した場合には、それに応じて
水を導入することで、常にスパッタリングガス中の水分
圧が５×１０-5Ｔｏｒｒとなるように維持しながら成膜
を行った。When the back pressure changes during the film formation and the water pressure in the sputtering gas changes, water is introduced in accordance with the change so that the water pressure in the sputtering gas is always 5 × 10 −. Film formation was performed while maintaining the pressure at 5 Torr.
【００３０】図２における（□印）が、単位成膜速度と
背圧との関係である。図２より、本実施例によれば、単
位成膜速度は背圧によらず高速、かつ、一定で安定して
いることがわかる。また、得られた膜はすべて透明なチ
タン酸化物膜であった。The mark (□) in FIG. 2 shows the relationship between the unit film forming rate and the back pressure. From FIG. 2, it can be seen that according to the present embodiment, the unit film formation rate is high regardless of the back pressure, and is constant and stable. The obtained films were all transparent titanium oxide films.
【００３１】［比較例１］実施例１における工程２にお
いて、Ａｒボンベ１４から流れてくるＡｒガスの流量を
マスフローコントローラ１３で調整し、圧力計６が２×
１０-3Ｔｏｒｒを示すまで導入した以外は、実施例１と
同様にしてチタン酸化物膜を成膜し、実施例１と同様
に、単位成膜速度と背圧との関係を調べた。[Comparative Example 1] In step 2 of Example 1, the flow rate of Ar gas flowing from the Ar cylinder 14 was adjusted by the mass flow controller 13, and the pressure gauge 6 was adjusted to 2 ×.
A titanium oxide film was formed in the same manner as in Example 1 except that the titanium oxide film was introduced up to the level of 10 −3 Torr, and the relationship between the unit film forming rate and the back pressure was examined in the same manner as in Example 1.
【００３２】図２における（○印）および（●印）が、
単位成膜速度と背圧との関係であり、（○印）は透明
膜、（●印）は可視光を吸収する膜であったことを示
す。図２より、単位成膜速度が背圧によらずほぼ一定に
なる領域では、膜が可視光を吸収する膜となり透明なチ
タン酸化物膜は得られないことがわかる。また、透明な
チタン酸化物膜が得られる領域では、単位成膜速度が背
圧に対して急激な変化を示し、安定したチタン酸化物膜
の成膜が行えないことがわかる。(O) and (●) in FIG.
The relationship between the unit film forming rate and the back pressure is shown. (○) indicates a transparent film, and (●) indicates a visible light absorbing film. From FIG. 2, it can be seen that in the region where the unit film formation rate is almost constant regardless of the back pressure, the film becomes a film that absorbs visible light and a transparent titanium oxide film cannot be obtained. Further, in the region where a transparent titanium oxide film is obtained, the unit film formation rate shows a rapid change with respect to the back pressure, and it can be seen that stable titanium oxide film formation cannot be performed.
【００３３】［実施例２］実施例１において、水分圧を
１×１０-4Ｔｏｒｒとした以外は、実施例１と同様にし
て、単位成膜速度と背圧との関係を調べた。Example 2 The relationship between the unit film forming rate and the back pressure was examined in the same manner as in Example 1 except that the water pressure was 1 × 10 −4 Torr.
【００３４】図３における（□印）が、単位成膜速度と
背圧との関係である。図３には比較例１の結果も併せて
示す。図３より、本実施例によれば、単位成膜速度は背
圧によらず、高速、かつ、一定で安定していることがわ
かる。また、得られた膜はすべて透明なチタン酸化物膜
であった。The symbol (□) in FIG. 3 shows the relationship between the unit film forming rate and the back pressure. FIG. 3 also shows the results of Comparative Example 1. From FIG. 3, it can be seen that according to the present embodiment, the unit film formation rate is high, constant, and stable regardless of the back pressure. The obtained films were all transparent titanium oxide films.
【００３５】［実施例３］実施例１の工程２において、
プラズマの発光強度をモニタした以外は実施例１と同様
にして、単位成膜速度と背圧との関係を調べた。[Embodiment 3] In step 2 of Embodiment 1,
The relationship between the unit film forming rate and the back pressure was examined in the same manner as in Example 1 except that the emission intensity of plasma was monitored.
【００３６】このとき、モニタした発光種は、Ｔｉ（４
５４ｎｍ）である。このときのＴｉの発光強度は５５
（任意目盛）であり、その値を維持するようにＡｒと水
との混合ガスをニードルバルブ８で調整した。At this time, the luminescent species monitored are Ti (4
54 nm). The emission intensity of Ti at this time is 55
(Arbitrary scale), and the mixed gas of Ar and water was adjusted by the needle valve 8 so as to maintain the value.
【００３７】図４における（□印）が、単位成膜速度と
背圧との関係である。図４には比較例１の結果も併せて
示す。図４より、本実施例によれば、単位成膜速度は背
圧によらず、高速、かつ、一定で安定していることがわ
かる。すなわち、スパッタリング中のプラズマ発光強度
を一定に保つことでも安定成膜ができることがわかる。
また、得られた膜はすべて透明なチタン酸化物膜であっ
た。The mark (□) in FIG. 4 shows the relationship between the unit film forming rate and the back pressure. The results of Comparative Example 1 are also shown in FIG. From FIG. 4, it can be seen that according to the present example, the unit film formation rate is high, constant, and stable regardless of the back pressure. That is, it can be seen that stable film formation can also be achieved by keeping the plasma emission intensity during sputtering constant.
The obtained films were all transparent titanium oxide films.
【００３８】［比較例２］実施例１において、水を導入
するかわりに、典型的な酸化性ガスである酸素を導入し
た。すなわち、スパッタリングガス中の酸素分圧を一定
に保ち、単位成膜速度と背圧との関係を調べた。Comparative Example 2 Instead of introducing water in Example 1, oxygen, which is a typical oxidizing gas, was introduced. That is, the oxygen partial pressure in the sputtering gas was kept constant and the relationship between the unit film forming rate and the back pressure was investigated.
【００３９】実施例１の工程２において、質量分析計７
で酸素分圧をモニタしながら、スパッタリングガス中の
酸素分圧が３×１０-5Ｔｏｒｒになるようにマスフロー
コントローラで調整し、その後、チャンバ内圧力が２×
１０-3ＴｏｒｒになるようにＡｒ流量を調整した以外
は、実施例１と同様にして背圧を変化させながら、成膜
を行った。In Step 2 of Example 1, the mass spectrometer 7
While monitoring the oxygen partial pressure with, adjust the oxygen partial pressure in the sputtering gas to 3 × 10 −5 Torr with a mass flow controller, and then adjust the chamber internal pressure to 2 ×.
Film formation was performed in the same manner as in Example 1 except that the Ar flow rate was adjusted to 10 −3 Torr while changing the back pressure.
【００４０】図５における（□印）が、単位成膜速度と
背圧との関係である。図５には比較例１の結果も併せて
示す。３×１０-5Ｔｏｒｒの酸素を導入した本比較例に
おいては、背圧によらず透明なチタン酸化物膜が得られ
た。しかし、単位成膜速度の背圧依存性は、依然として
解消されないことがわかる。The symbol (□) in FIG. 5 shows the relationship between the unit film forming rate and the back pressure. FIG. 5 also shows the results of Comparative Example 1. In this comparative example in which 3 × 10 −5 Torr of oxygen was introduced, a transparent titanium oxide film was obtained regardless of the back pressure. However, it can be seen that the back pressure dependency of the unit film formation rate is still unsolved.
【００４１】［比較例３］比較例２において、スパッタ
リングガス中の酸素分圧を１×１０-4Ｔｏｒｒとした以
外は、比較例２と同様にして単位成膜速度と背圧との関
係を調べた。[Comparative Example 3] The relationship between the unit film forming rate and the back pressure was obtained in the same manner as in Comparative Example 2 except that the oxygen partial pressure in the sputtering gas was changed to 1 × 10 -4 Torr. Examined.
【００４２】図６における（□印）が、単位成膜速度と
背圧との関係である。図６には比較例１の結果も併せて
示す。１×１０-4Ｔｏｒｒの酸素を導入した本比較例に
おいては、単位成膜速度の背圧依存性はなくなるが、成
膜速度は著しく遅くなることがわかる。The mark (□) in FIG. 6 shows the relationship between the unit film forming rate and the back pressure. FIG. 6 also shows the results of Comparative Example 1. In this comparative example, in which 1 × 10 −4 Torr of oxygen was introduced, it is found that the unit film forming rate does not have the back pressure dependency, but the film forming rate is remarkably slow.
【００４３】このように、酸化性ガスに酸素を用いた場
合は、安定に高速成膜することはきわめて困難であるこ
とがわかる。As described above, when oxygen is used as the oxidizing gas, stable high-speed film formation is extremely difficult.
【００４４】[0044]
【発明の効果】本発明の方法を用いれば、マグネトロン
スパッタリング法により、大面積で均一な透明なチタン
酸化物膜を、高速かつ安定して形成できる。According to the method of the present invention, a uniform and transparent titanium oxide film having a large area can be stably formed at a high speed by the magnetron sputtering method.
【図１】本発明を行うために用いる装置の概略図。FIG. 1 is a schematic diagram of an apparatus used to carry out the present invention.
【図２】実施例１および比較例１における単位成膜速度
と背圧との関係を示す図。FIG. 2 is a diagram showing a relationship between a unit film forming rate and back pressure in Example 1 and Comparative Example 1.
【図３】実施例２における単位成膜速度と背圧との関係
を示す図。FIG. 3 is a diagram showing a relationship between a unit film forming rate and back pressure in Example 2.
【図４】実施例３における単位成膜速度と背圧との関係
を示す図。FIG. 4 is a diagram showing a relationship between a unit film forming rate and back pressure in Example 3.
【図５】比較例２における単位成膜速度と背圧との関係
を示す図。5 is a diagram showing a relationship between a unit film forming rate and back pressure in Comparative Example 2. FIG.
【図６】比較例３における単位成膜速度と背圧との関係
を示す図。FIG. 6 is a diagram showing a relationship between a unit film forming rate and back pressure in Comparative Example 3.
１：ＴｉＯx ターゲット ２：直流電源 ３：ガラス基板 ４：成膜チャンバ ５：真空排気口 ６：圧力計 ７：質量分析計 ８：ニードルバルブ ９：水タンク １０：恒温槽 １１：ヒータ １２：マスフローコントローラ １３：マスフローコントローラ １４：Ａｒボンベ1: TiO x target 2: DC power supply 3: Glass substrate 4: Film forming chamber 5: Vacuum exhaust port 6: Pressure gauge 7: Mass spectrometer 8: Needle valve 9: Water tank 10: Constant temperature bath 11: Heater 12: Mass flow Controller 13: Mass flow controller 14: Ar cylinder
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２３Ｃ 14/08 Ｅ 8939−4Ｋ (72)発明者 大崎 壽 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 (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical indication C23C 14/08 E 8939-4K (72) Inventor Satoshi Osaki 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory
Claims (4)
スパッタリングによりチタン酸化物膜を成膜する方法に
おいて、スパッタリングガス中に水分を調整し導入する
ことを特徴とするチタン酸化物膜の成膜方法。1. A method of forming a titanium oxide film by sputtering using a TiO x target (0 <x <2), wherein moisture is adjusted and introduced into a sputtering gas. Deposition method.
の量は、水分圧で１０-5〜１０-3Ｔｏｒｒの範囲である
ことを特徴とする請求項１記載のチタン酸化物膜の成膜
方法。2. The method for forming a titanium oxide film according to claim 1, wherein the amount of water introduced into the sputtering gas is in the range of 10 −5 to 10 −3 Torr in terms of water pressure. .
中の水分量を質量分析計で読みとりながら行うことを特
徴とする請求項１または２記載のチタン酸化物膜の成膜
方法。3. The method for forming a titanium oxide film according to claim 1, wherein the moisture pressure is adjusted while reading the amount of moisture in the sputtering gas with a mass spectrometer.
よびＴｉの少なくとも１種のプラズマ発光種をモニタし
ながら行うことを特徴とする請求項１〜３いずれか１項
記載のチタン酸化物膜の成膜方法。4. The adjustment of the water pressure is performed while monitoring at least one plasma emission species of H 2 O, OH, H and Ti. Method for forming titanium oxide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27133594A JPH08134638A (en) | 1994-11-04 | 1994-11-04 | Method for forming titanium oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27133594A JPH08134638A (en) | 1994-11-04 | 1994-11-04 | Method for forming titanium oxide film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08134638A true JPH08134638A (en) | 1996-05-28 |
Family
ID=17498627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27133594A Pending JPH08134638A (en) | 1994-11-04 | 1994-11-04 | Method for forming titanium oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08134638A (en) |
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| JPH11236666A (en) * | 1998-02-25 | 1999-08-31 | Murata Mfg Co Ltd | Film forming device and production of dielectric film |
| JP2000282231A (en) * | 1999-03-29 | 2000-10-10 | Murata Mfg Co Ltd | Sputtering device and formation of dielectric film |
| JP2000297367A (en) * | 1999-04-12 | 2000-10-24 | Canon Inc | Metal oxide thin film deposition method |
| US6468402B1 (en) | 1996-01-05 | 2002-10-22 | Bekaert Vds | Process for coating a substrate with titanium dioxide |
| US6544890B2 (en) | 1999-02-26 | 2003-04-08 | Nec Corporation | Process for fabricating semiconductor device having silicide layer with low resistance and uniform profile and sputtering system used therein |
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1994
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|---|---|---|---|---|
| US6468402B1 (en) | 1996-01-05 | 2002-10-22 | Bekaert Vds | Process for coating a substrate with titanium dioxide |
| US6511587B2 (en) | 1996-01-05 | 2003-01-28 | Bekaert Vds | Sputtering targets and method for the preparation thereof |
| JPH11236666A (en) * | 1998-02-25 | 1999-08-31 | Murata Mfg Co Ltd | Film forming device and production of dielectric film |
| US6544890B2 (en) | 1999-02-26 | 2003-04-08 | Nec Corporation | Process for fabricating semiconductor device having silicide layer with low resistance and uniform profile and sputtering system used therein |
| JP2000282231A (en) * | 1999-03-29 | 2000-10-10 | Murata Mfg Co Ltd | Sputtering device and formation of dielectric film |
| JP2000297367A (en) * | 1999-04-12 | 2000-10-24 | Canon Inc | Metal oxide thin film deposition method |
| JP2003135952A (en) * | 2001-11-01 | 2003-05-13 | Nec Corp | Plasma treating system and plasma treating method |
| US7294404B2 (en) | 2003-12-22 | 2007-11-13 | Cardinal Cg Company | Graded photocatalytic coatings |
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| USRE43817E1 (en) | 2004-07-12 | 2012-11-20 | Cardinal Cg Company | Low-maintenance coatings |
| US7483226B2 (en) | 2004-09-27 | 2009-01-27 | Nidec Copal Corporation | ND filter, manufacturing method thereof, and aperture device |
| US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
| JP2011093112A (en) * | 2009-10-27 | 2011-05-12 | Mitsubishi Shindoh Co Ltd | Transparent laminated film |
| US20230203636A1 (en) * | 2012-05-04 | 2023-06-29 | Viavi Solutions Inc. | Reactive sputter deposition of dielectric films |
| US12545987B2 (en) * | 2012-05-04 | 2026-02-10 | Viavi Solutions Inc. | Reactive sputter deposition of dielectric films |
| CN104480442A (en) * | 2014-12-05 | 2015-04-01 | 中国科学院电工研究所 | Method for preparing transparent conductive film containing aluminum zinc hydroxide |
| CN104480441A (en) * | 2014-12-05 | 2015-04-01 | 中国科学院电工研究所 | Method for preparing hydrogen-containing zinc aluminum oxide transparent conducting film by using metal alloy target |
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