JPH0624804A - Formation of water repelling film of carbon containing fluorine - Google Patents
Formation of water repelling film of carbon containing fluorineInfo
- Publication number
- JPH0624804A JPH0624804A JP17570092A JP17570092A JPH0624804A JP H0624804 A JPH0624804 A JP H0624804A JP 17570092 A JP17570092 A JP 17570092A JP 17570092 A JP17570092 A JP 17570092A JP H0624804 A JPH0624804 A JP H0624804A
- Authority
- JP
- Japan
- Prior art keywords
- water
- bond
- film
- repellent
- fluorine
- 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.)
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- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、撥水膜などとして利用
される炭素フッ素複合層からなる被膜を形成する方法に
関する。得られた撥水膜は、自動車のフロントガラスな
どに利用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a film composed of a carbon-fluorine composite layer used as a water repellent film or the like. The obtained water-repellent film can be used for windshields of automobiles.
【０００２】[0002]
【従来の技術】従来より、例えば反応管として利用され
る炭素被膜付きガラスとして、石英ガラスと、この石英
ガラスの表面に形成された炭素被膜と、からなるものが
知られている（特開平2-188447号公報）。この炭素被膜
は、例えば水素ガスで還元処理された石英ガラスの表面
に、炭素被膜形成原料を含むキャリアガスを供給するこ
とにより形成することができる。2. Description of the Related Art Conventionally, as a glass with a carbon coating used as, for example, a reaction tube, there is known a glass comprising a quartz glass and a carbon coating formed on the surface of the quartz glass (Japanese Patent Laid-Open No. Hei 2). -188447 publication). This carbon coating can be formed, for example, by supplying a carrier gas containing a carbon coating forming raw material to the surface of quartz glass that has been subjected to reduction treatment with hydrogen gas.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、炭素被
膜は撥水性を有するものの、水との接触角は約９０度で
あり自動車用撥水ガラスとしては撥水性が不十分であ
る。また炭素被膜とガラスとの付着性が不十分であり、
炭素被膜の剥離が生じ易いという不具合もあった。そこ
で本願発明者らは、鋭意研究の結果、先に炭素フッ素複
合層からなる炭素被膜付きガラスを出願している（特願
平3-172212号）。この発明によれば、炭素被膜中にフッ
素原子が導入されているため、極めて高い撥水性が得ら
れる。However, although the carbon coating has water repellency, the contact angle with water is about 90 degrees, which is insufficient as water repellency glass for automobiles. In addition, the adhesion between the carbon coating and the glass is insufficient,
There is also a problem that the carbon coating is easily peeled off. Then, as a result of earnest research, the inventors of the present application have previously applied for a glass with a carbon coating comprising a carbon-fluorine composite layer (Japanese Patent Application No. 3-172212). According to this invention, since the fluorine atom is introduced into the carbon coating, extremely high water repellency can be obtained.
【０００４】ところで上記先願に係る発明では、炭素被
膜中にフッ素原子を導入するのにＣＦ4 ，Ｃ2 Ｆ2 ，Ｃ
3 Ｆ6 などの化合物のガスを用い、炭素源とともにＰＶ
Ｄ法あるいはＣＶＤ法にて成膜することとしている。し
かしながらこの方法では、被膜中へのフッ素導入効率が
低く、撥水性を向上させるために多量のフッ素原子を被
膜中に導入しようとすると、炭素の堆積速度を小さくし
なければならず多大な時間が必要となる。In the invention according to the above-mentioned prior application, CF 4 , C 2 F 2 , C is used to introduce fluorine atoms into the carbon coating.
Using a gas of a compound such as 3 F 6 , PV with a carbon source
The film is formed by the D method or the CVD method. However, in this method, the efficiency of introducing fluorine into the film is low, and if a large amount of fluorine atoms are to be introduced into the film in order to improve water repellency, the deposition rate of carbon must be reduced and it takes a lot of time. Will be needed.
【０００５】本発明はこのような事情に鑑みてなされた
ものであり、上記特願平3-172212号に記載された発明を
さらに改良し、被膜中へのフッ素原子の導入効率を向上
させることを目的とする。The present invention has been made in view of the above circumstances, and further improves the invention described in Japanese Patent Application No. 3-172212 to improve the efficiency of introducing fluorine atoms into the coating film. With the goal.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決する本発
明のフッ素含有炭素撥水膜の形成方法は、Ｃ−Ｆ結合を
もつとともに炭素との結合であってその結合エネルギー
がＣ−Ｆ結合の結合エネルギーより小さい結合をもつ化
合物のガスをフッ素源として用い、炭素源とともにＰＶ
Ｄ法またはＣＶＤ法により成膜することを特徴とする。The method for forming a fluorine-containing carbon water-repellent film of the present invention, which solves the above-mentioned problems, has a C—F bond and is a bond with carbon whose bond energy is a C—F bond. A gas of a compound having a bond smaller than the bond energy of
It is characterized in that the film is formed by the D method or the CVD method.
【０００７】フッ素源として用いられる化合物とは、Ｃ
−Ｆ結合をもち、かつ炭素との結合であってその結合エ
ネルギーがＣ−Ｆ結合の結合エネルギーより小さい結合
をもつ。炭素との結合であって、Ｃ−Ｆ結合より小さい
結合エネルギーの結合としては、Ｃ−Ｈ結合，Ｃ−Ｃｌ
結合，Ｃ−Ｂｒ結合，Ｃ−Ｉ結合などがある。したがっ
てこれらの結合をもつ化合物としては、ＣＨＦ3 ，ＣＨ
2 Ｆ2 ，ＣＨ3 Ｆ，ＣＦ3 Ｃｌ，ＣＦ2 Ｃｌ2 ，ＣＦ3
Ｂｒ，ＣＦ3 Ｉなど種々の化合物が挙げられる。短時間
で高い撥水性を得るためには、一分子中のフッ素原子の
数が多いものを用いることが好ましい。The compound used as the fluorine source is C
It has a -F bond and a bond with carbon, the bond energy of which is smaller than that of the C-F bond. A bond with carbon, which has a bond energy smaller than that of a C-F bond, includes a C-H bond and a C-Cl bond.
There are a bond, a C-Br bond, a C-I bond and the like. Therefore, as a compound having these bonds, CHF 3 , CH
2 F 2 , CH 3 F, CF 3 Cl, CF 2 Cl 2 , CF 3
Various compounds such as Br and CF 3 I can be mentioned. In order to obtain high water repellency in a short time, it is preferable to use one having a large number of fluorine atoms in one molecule.
【０００８】[0008]
【作用】例えばＣＦ4 ガスをフッ素源として用いてスパ
ッタリングした場合、ＣＦ4 は各Ｃ−Ｆ結合の結合強度
は同一であるため、プラズマ中でＣとＦとに完全に分解
するものと考えられる。そのためフッ素が炭素被膜中に
導入されにくいものと考えられる。When, for example, CF 4 gas is used as a fluorine source and is sputtered, CF 4 is considered to be completely decomposed into C and F in plasma because each C—F bond has the same bond strength. . Therefore, it is considered that fluorine is difficult to be introduced into the carbon coating.
【０００９】一方本発明の形成方法では、フッ素源にＣ
−Ｆ結合の結合エネルギーより小さい結合をもつ化合物
を用いている。したがってプラズマ中では弱い結合が先
ず切断され、ＣＦ3 ラジカル、ＣＦ2 ラジカル、ＣＦラ
ジカルなどが生成され易く、またプラズマ化効率も高く
なるために、フッ素が炭素被膜中へ導入され易くなるも
のと考えられる。On the other hand, in the forming method of the present invention, the fluorine source is C
A compound having a bond smaller than the bond energy of the -F bond is used. Therefore, it is thought that weak bonds are first broken in plasma, CF 3 radicals, CF 2 radicals, CF radicals, etc. are easily generated, and plasma efficiency is also increased, so that fluorine is easily introduced into the carbon coating. To be
【００１０】[0010]
【実施例】以下、実施例により具体的に説明する。 （実施例１）２元ＲＦマグネトロンスパッタリング装置
の真空槽に、ガラス基板と、ＳｉＯ 2 ターゲットと、Ｃ
ターゲットとを配置した。そして真空槽を２×１０-3Ｐ
ａ以下まで減圧し、ガラス基板を３００℃に加熱した。
次いでＡｒガスを真空槽内の圧力が０．１Ｐａとなるま
で導入し、図１に示すように初期はＳｉＯ2 ターゲット
のみに印加し、次いでＳｉＯ2 ターゲットの印加電圧を
低くするとともにＣターゲットの印加電圧を高くし、後
期はＣターゲットのみに印加するようにして、スパッタ
リング成膜を行った。EXAMPLES The present invention will be specifically described below with reference to examples. (Example 1) Binary RF magnetron sputtering apparatus
Glass substrate and SiO 2Target and C
Arranged with the target. And the vacuum chamber is 2 × 10-3P
The pressure was reduced to a or less and the glass substrate was heated to 300 ° C.
Next, Ar gas was added until the pressure in the vacuum chamber became 0.1 Pa.
Introduced in, and as shown in FIG.2target
Applied to only then SiO 22The applied voltage of the target
Lower the voltage applied to the C target and lower
In the period, sputter by applying only to the C target.
A ring film was formed.
【００１１】次いでＡｒガス中に２０ｖｏｌ％のＣＨＦ
3 ガスを混合させ、それを真空槽内の圧力が０．１Ｐａ
となるように導入し、基板ホルダに２００ＷのＲＦ電力
を印加してガラス基板近傍にプラズマを発生させ、上記
で得られた膜表面の表面フッ素化処理を行って撥水膜と
し、撥水ガラスを製造した。この撥水ガラスの撥水膜表
面から深さ方向の各元素の分布をＡＥＳ（オージェ電子
分光分析）により定量分析したところ、図２に示すよう
にガラス基板10表面から順に、約１００ÅのＳｉＯ2 層
11と、ＳｉＯ2 とＣからなり表面へ近づくほどＣのモル
分率が高くなる約３００Åの混合層12と、約１００Åの
Ｃ層13とから構成されていた。そしてＣ層13の表面部分
にはＦ元素が存在し、撥水化されていることがわかる。 （実施例２）各ターゲットに印加する電圧を図３に示す
ように変化させ、かつＡｒガスにＣＨＦ3 ガスを２０ｖ
ｏｌ％混合した混合ガスを導入したこと以外は実施例１
と同様にしてスパッタリング成膜した。そして特別な表
面フッ素化処理を行うことなくそのまま撥水ガラスとし
た。そして実施例１と同様にＡＥＳにより各元素の分布
を定量分析し、結果を図４に示す。Next, 20 vol% CHF in Ar gas
3 gases are mixed, and the pressure in the vacuum chamber is 0.1 Pa
Then, RF power of 200 W is applied to the substrate holder to generate plasma in the vicinity of the glass substrate, and the surface of the film obtained above is fluorinated to form a water-repellent film. Was manufactured. The water repellent distribution of each element in the depth direction from the water-repellent film surface of glass was quantitatively analyzed by AES (Auger electron spectroscopy), in this order from the glass substrate 10 surface as shown in FIG. 2, from about 100 Å SiO 2 layer
11, a SiO 2 and C mixed layer 12 of about 300 Å in which the mole fraction of C increases toward the surface, and a C layer 13 of about 100 Å. It can be seen that the F element is present on the surface portion of the C layer 13 and is made water repellent. (Example 2) The voltage applied to each target was changed as shown in FIG. 3, and CHF 3 gas was 20 v for Ar gas.
Example 1 except that a mixed gas mixed with ol% was introduced.
A film was formed by sputtering in the same manner as in. The water-repellent glass was used as it was without any special surface fluorination treatment. Then, the distribution of each element was quantitatively analyzed by AES in the same manner as in Example 1, and the results are shown in FIG.
【００１２】図４よりこの撥水膜では、ガラス基板20表
面から順に、ＳｉＯ2 とＦからなり約１００Åの第１混
合層21と、ＳｉＯ2 とＦ及びＣからなり表面へ近づくほ
どＣのモル分率が高くなる約３００Åの第２混合層22
と、ＣとＦからなり約１００Åの第３混合層23とから構
成され、内部まで撥水化されていることがわかる。した
がって、この撥水膜では、表面部分が磨耗して削られて
も撥水性が確保されるため、高い耐久性を有している。 （実施例３）ＳｉＯ2 ターゲットの代わりにＡｌ2 Ｏ3
ターゲットを用い、各ターゲットに印加する電圧を図５
に示すように変化させ、かつＡｒガスにＣＨＦ3 ガスを
２０ｖｏｌ％混合した混合ガスを導入したこと以外は実
施例１と同様にしてスパッタリング成膜し、特別な表面
フッ素化処理を行うことなくそのまま撥水ガラスとし
た。そして実施例１と同様にＡＥＳにより各元素の分布
を定量分析し、結果を図６に示す。[0012] In this water-repellent film than 4, in order from the glass substrate 20 surface, a first mixed layer 21 of about 100Å made of SiO 2 and F, the closer to the surface consists of SiO 2 and F and C C mol The second mixed layer of about 300 Å that increases the fraction 22
And the third mixed layer 23 composed of C and F and having a thickness of about 100 Å, and it is understood that the inside is made water repellent. Therefore, the water-repellent film has high durability because the water-repellent property is secured even when the surface portion is worn and scraped. (Example 3) Al 2 O 3 instead of the SiO 2 target
Using the target, the voltage applied to each target is shown in FIG.
Except that the mixed gas in which CHF 3 gas was mixed in an amount of 20 vol% was introduced into Ar gas was sputter-deposited in the same manner as in Example 1 and was directly subjected to no special surface fluorination treatment. Water repellent glass was used. Then, as in Example 1, the distribution of each element was quantitatively analyzed by AES, and the results are shown in FIG.
【００１３】図６よりこの撥水膜では、ガラス基板30表
面から順に、Ａｌ2 Ｏ3 とＦからなり約１００Åの第１
混合層31と、Ａｌ2 Ｏ3 とＦ及びＣからなり表面へ近づ
くほどＣのモル分率が高くなる約３００Åの第２混合層
32と、ＣとＦからなり約１００Åの第３混合層33とから
構成され、内部まで撥水化されていることがわかる。し
たがって、この撥水膜では、表面部分が磨耗して削られ
ても撥水性が確保されるため、高い耐久性を有してい
る。 （実施例４）各ターゲットに印加する電圧を図７に示す
ように変化させ、かつＡｒガスにＣＨＦ3 ガスを２０ｖ
ｏｌ％混合した混合ガスを導入したこと以外は実施例１
と同様にしてスパッタリング成膜し、特別な表面フッ素
化処理を行うことなくそのまま撥水ガラスとした。そし
て実施例１と同様にＡＥＳにより各元素の分布を定量分
析し、結果を図８に示す。As shown in FIG. 6, the water-repellent film is composed of Al 2 O 3 and F in order from the surface of the glass substrate 30 and has a first thickness of about 100 Å.
Mixed layer 31 and second mixed layer of about 300Å consisting of Al 2 O 3 and F and C, in which the mole fraction of C increases toward the surface.
It can be seen that it is composed of 32 and the third mixed layer 33 composed of C and F and having a thickness of about 100 Å, and that the inside is made water repellent. Therefore, the water-repellent film has high durability because the water-repellent property is secured even when the surface portion is worn and scraped. (Example 4) The voltage applied to each target was changed as shown in FIG. 7, and CHF 3 gas was 20 v as Ar gas.
Example 1 except that a mixed gas mixed with ol% was introduced.
A film was formed by sputtering in the same manner as described above, and the water-repellent glass was used as it was without any special surface fluorination treatment. Then, as in Example 1, the distribution of each element was quantitatively analyzed by AES, and the results are shown in FIG.
【００１４】図８よりこの撥水膜では、ガラス基板40表
面にＳｉＯ2 とＣ及びＦからなり約２００Åの混合層41
が形成され、内部まで撥水化されていることがわかる。
したがって、この撥水膜でも、表面部分が磨耗して削ら
れても撥水性が確保されるため、高い耐久性を有してい
る。 （実施例５）各ターゲットに印加する電圧を図３に示す
ように変化させ、かつＡｒガスにＣＨ2 Ｆ2 ガスを２０
ｖｏｌ％混合した混合ガスを導入したこと以外は実施例
１と同様にしてスパッタリング成膜した。そして特別な
表面フッ素化処理を行うことなくそのまま撥水ガラスと
した。そして実施例１と同様にＡＥＳにより各元素の分
布を定量分析し、結果を図９に示す。As shown in FIG. 8, in this water repellent film, a mixed layer 41 of SiO 2 and C and F of about 200 Å is formed on the surface of the glass substrate 40.
It can be seen that the water-repellent material is formed even inside.
Therefore, even with this water repellent film, the water repellency is ensured even when the surface portion is worn and scraped off, and thus has high durability. (Example 5) The voltage applied to each target was changed as shown in FIG. 3, and the CH 2 F 2 gas was changed to 20 as Ar gas.
A film was formed by sputtering in the same manner as in Example 1 except that a mixed gas mixed with vol% was introduced. The water-repellent glass was used as it was without any special surface fluorination treatment. Then, as in Example 1, the distribution of each element was quantitatively analyzed by AES, and the results are shown in FIG.
【００１５】図９よりこの撥水膜では、ガラス基板50表
面から順に、ＳｉＯ2 とＦからなり約１００Åの第１混
合層51と、ＳｉＯ2 とＦ及びＣからなり表面へ近づくほ
どＣのモル分率が高くなる約３００Åの第２混合層52
と、ＣとＦからなり約１００Åの第３混合層53とから構
成され、内部まで撥水化されていることがわかる。した
がって、この撥水膜では、表面部分が磨耗して削られて
も撥水性が確保されるため、高い耐久性を有している。 （実施例６）ＲＦプラズマＣＶＤ装置に、実施例１にお
ける表面フッ素化処理前の炭素薄膜付きガラスを基板と
して配置し、１０-3Ｐａ以下まで減圧する。その後反応
ガスとして、ＣＨＦ3 とＣＨ4 の混合ガス（ＣＨＦ3 ／
ＣＨ4 ＝９／１）を０．２Ｐａになるように導入する。
その後４００ＷのＲＦ電力を投入し、６０分間の成膜を
行った。そして実施例１と同様にＡＥＳにより各元素の
分布を定量分析し、結果を図１０に示す。[0015] In this water-repellent film than 9, in order from the glass substrate 50 surface, a first mixed layer 51 of about 100Å made of SiO 2 and F, the closer to the surface consists of SiO 2 and F and C C mol The second mixed layer 52 of about 300 Å which increases the fraction
And the third mixed layer 53 composed of C and F and having a thickness of about 100 Å, and it is understood that the inside is made water repellent. Therefore, the water-repellent film has high durability because the water-repellent property is secured even when the surface portion is worn and scraped. (Example 6) The glass with a carbon thin film before the surface fluorination treatment in Example 1 is placed as a substrate in an RF plasma CVD apparatus, and the pressure is reduced to 10 -3 Pa or less. Then, as a reaction gas, a mixed gas of CHF 3 and CH 4 (CHF 3 /
CH 4 = 9/1) is introduced so that the pressure becomes 0.2 Pa.
After that, RF power of 400 W was applied to form a film for 60 minutes. Then, the distribution of each element was quantitatively analyzed by AES in the same manner as in Example 1, and the results are shown in FIG.
【００１６】図１０よりこの撥水膜は、ガラス基板60表
面から順に、約１００ÅのＳｉＯ2層61と、ＳｉＯ2 及
びＣからなり表面へ近づくほどＣのモル分率が高くなる
約３００Åの混合層62と、約１００ÅのＣ層63と、Ｃと
Ｆからなり約１０００Åの複合層64とから構成され、内
部まで撥水化されていることがわかる。したがって、こ
の撥水膜では、表面部分が磨耗して削られても撥水性が
確保されるため、高い耐久性を有している。 （比較例１）実施例１における表面フッ素化処理前の炭
素薄膜付きガラスを比較例１の撥水ガラスとした。この
撥水ガラスの撥水膜中の元素組成は、Ｆが存在しないこ
と以外は実施例１と同様である。 （比較例２）各ターゲットに印加する電圧を図３に示す
ように変化させ、かつＡｒガスにＣＦ4 ガスを２０ｖｏ
ｌ％混合した混合ガスを導入したこと以外は実施例１と
同様にしてスパッタリング成膜し、特別な表面フッ素化
処理を行うことなくそのまま撥水ガラスとした。そして
実施例１と同様にＡＥＳにより各元素の分布を定量分析
し、結果を図１１に示す。As shown in FIG. 10, this water-repellent film is a mixture of a SiO 2 layer 61 of about 100 Å in order from the surface of the glass substrate 60, and a mixture of about 300 Å which is composed of SiO 2 and C and has a higher mole fraction of C as it gets closer to the surface. It can be seen that the layer 62, the C layer 63 of about 100 Å, and the composite layer 64 of C and F of about 1000 Å are made water repellent to the inside. Therefore, the water-repellent film has high durability because the water-repellent property is secured even when the surface portion is worn and scraped. Comparative Example 1 The glass with a carbon thin film before the surface fluorination treatment in Example 1 was used as the water repellent glass in Comparative Example 1. The elemental composition of the water-repellent film of this water-repellent glass is the same as in Example 1 except that F does not exist. (Comparative Example 2) The voltage applied to each target was changed as shown in FIG. 3, and CF 4 gas was 20 vo for Ar gas.
A film was formed by sputtering in the same manner as in Example 1 except that a mixed gas mixed with 1% was introduced, and the water-repellent glass was used as it was without any special surface fluorination treatment. Then, as in Example 1, the distribution of each element was quantitatively analyzed by AES, and the results are shown in FIG.
【００１７】図１１よりこの撥水膜では、ガラス基板70
表面から順に、ＳｉＯ2 とＦからなり約１００Åの第１
混合層71と、ＳｉＯ2 とＦ及びＣからなり表面へ近づく
ほどＣのモル分率が高くなる約３００Åの第２混合層72
と、ＣとＦからなり約１００Åの第３混合層73とから構
成され、内部まで撥水化されていることがわかる。した
がって、この撥水膜では、表面部分が磨耗して削られて
も撥水性が確保されるため、高い耐久性を有している。 （評価）上記各実施例及び比較例の撥水ガラスの撥水膜
の水との接触角を測定し、結果を表１に示す。またサン
シャインウェザオメータ（６３℃水有り）で２０００時
間促進試験を行い、その後の撥水膜の水との接触角を測
定し、結果を表１に示す。さらに、撥水膜の表面を３０
０ｇ／ｃｍ2 の荷重で３０００回往復する条件で、乾燥
したネル布で摩擦し、撥水膜の剥離の有無を調べた結果
も合わせて表１に示す。As shown in FIG. 11, in this water repellent film, the glass substrate 70 is used.
The first from about 100Å consisting of SiO 2 and F in order from the surface
The mixed layer 71 and the second mixed layer 72 of SiO 2 and F and C, which has a mole fraction of C which increases toward the surface, of approximately 300Å.
It can be seen that the inner part is made water repellent and is composed of C and F and the third mixed layer 73 of about 100 liters. Therefore, the water-repellent film has high durability because the water-repellent property is secured even when the surface portion is worn and scraped. (Evaluation) The contact angle with water of the water-repellent film of the water-repellent glass of each of the above Examples and Comparative Examples was measured, and the results are shown in Table 1. Further, a 2000-hour accelerated test was carried out with a sunshine weatherometer (with water at 63 ° C.), and the contact angle of the water-repellent film with water was measured thereafter, and the results are shown in Table 1. Furthermore, the surface of the water-repellent film is
Table 1 also shows the results of examining the presence or absence of peeling of the water-repellent film by rubbing with a dry flannel cloth under the condition of reciprocating 3000 times with a load of 0 g / cm 2 .
【００１８】[0018]
【表１】 表１より、各実施例と比較例２の撥水ガラスでは、Ｆが
導入されているため、比較例１の炭素薄膜よりなる撥水
膜をもつ撥水ガラスに比べて撥水性に優れている。また
比較例１では、促進耐候性試験１０００時間で接触角が
６０度に低下したが、他のものは２０００時間経過後も
十分な撥水性を有している。[Table 1] From Table 1, since the water-repellent glass of each Example and Comparative Example 2 contains F, it is superior in water repellency to the water-repellent glass having the water-repellent film made of the carbon thin film of Comparative Example 1. . Further, in Comparative Example 1, the contact angle decreased to 60 degrees in 1000 hours of the accelerated weather resistance test, but the others have sufficient water repellency even after 2000 hours.
【００１９】また含Ｆガスの種類が異なること以外は同
条件で成膜された実施例２、実施例５及び比較例２を比
較してみると、初期及び促進後とも実施例２及び実施例
５の方が高い撥水性を示している。これは、例えば実施
例２のＣＨＦ3 のＣ−Ｈ結合がＣ−Ｆ結合より結合エネ
ルギーが小さいため、実施例２では成膜時にＣ−Ｈ結合
が選択的に切断され、ＣＦ3 ラジカルが生成したこと、
及びプラズマ効率も高くなったことから、炭素中へのフ
ッ素の複合化効率が比較例２に比べて向上したことを示
している。Comparing Example 2, Example 5 and Comparative Example 2 which were formed under the same conditions except that the type of F-containing gas was different, Example 2 and Example were obtained both at the initial stage and after the promotion. No. 5 has higher water repellency. This is because, for example, the C—H bond of CHF 3 in Example 2 has a smaller binding energy than that of the C—F bond, so that in Example 2, the C—H bond is selectively broken during film formation to generate a CF 3 radical. What you did
Also, since the plasma efficiency was also increased, it indicates that the efficiency of compounding fluorine into carbon was improved as compared with Comparative Example 2.
【００２０】図４、図９、図１１を比較してみると、膜
中のＦの原子濃度はＣＨＦ3 ＞ＣＨ 2 Ｆ2 ＞ＣＦ4 とな
り、上記機構が裏付けられている。Comparing FIG. 4, FIG. 9 and FIG.
The atomic concentration of F is CHF3> CH 2F2> CFFourTona
The above mechanism is supported.
【００２１】[0021]
【発明の効果】すなわち本発明のフッ素含有炭素撥水膜
の形成方法によれば、膜中のフッ素の導入効率が高いた
め、高い撥水性を有する炭素被膜を容易にかつ確実に形
成することができる。That is, according to the method for forming a fluorine-containing carbon water-repellent film of the present invention, since the efficiency of introducing fluorine into the film is high, a carbon coating having high water repellency can be easily and reliably formed. it can.
【図１】実施例１における撥水膜形成時の、各ターゲッ
トへの電圧印加条件を示すグラフである。FIG. 1 is a graph showing voltage application conditions to each target when forming a water-repellent film in Example 1.
【図２】実施例１で形成された撥水膜の、深さ方向の原
子組成を示すグラフである。FIG. 2 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 1.
【図３】実施例２及び比較例２における撥水膜形成時
の、各ターゲットへの電圧印加条件を示すグラフであ
る。FIG. 3 is a graph showing voltage application conditions to each target when forming a water repellent film in Example 2 and Comparative Example 2.
【図４】実施例２で形成された撥水膜の、深さ方向の原
子組成を示すグラフである。FIG. 4 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 2.
【図５】実施例３における撥水膜形成時の、各ターゲッ
トへの電圧印加条件を示すグラフである。FIG. 5 is a graph showing voltage application conditions to each target when forming a water-repellent film in Example 3.
【図６】実施例３で形成された撥水膜の、深さ方向の原
子組成を示すグラフである。FIG. 6 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 3.
【図７】実施例４における撥水膜形成時の、各ターゲッ
トへの電圧印加条件を示すグラフである。FIG. 7 is a graph showing voltage application conditions to each target when forming a water repellent film in Example 4.
【図８】実施例４で形成された撥水膜の、深さ方向の原
子組成を示すグラフである。FIG. 8 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 4.
【図９】実施例５で形成された撥水膜の、深さ方向の原
子組成を示すグラフである。FIG. 9 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 5.
【図１０】実施例６で形成された撥水膜の、深さ方向の
原子組成を示すグラフである。FIG. 10 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Example 6.
【図１１】比較例２で形成された撥水膜の、深さ方向の
原子組成を示すグラフである。11 is a graph showing the atomic composition in the depth direction of the water repellent film formed in Comparative Example 2. FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 田嶋 一郎 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 (72)発明者 石井 昌彦 愛知県愛知郡長久手町大字長湫字横道41番 地の１ 株式会社豊田中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Tajima, Nagakute-cho, Aichi-gun, Aichi Prefecture, 1-41, Yokoshiro, Toyota Central Research Institute Co., Ltd. 41, Yokoshiro Road Inside Toyota Central Research Institute Co., Ltd.
Claims (1)
もに炭素との結合であってその結合エネルギーが該炭素
−フッ素結合の結合エネルギーより小さい結合をもつ化
合物のガスをフッ素源として用い、炭素源とともにＰＶ
Ｄ法またはＣＶＤ法により成膜することを特徴とするフ
ッ素含有炭素撥水膜の形成方法。1. A gas of a compound having a carbon-fluorine (CF) bond and a bond with carbon, the bond energy of which is smaller than the bond energy of the carbon-fluorine bond, is used as a fluorine source. PV with carbon source
A method for forming a fluorine-containing carbon water-repellent film, which comprises forming the film by the D method or the CVD method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17570092A JPH0624804A (en) | 1992-07-02 | 1992-07-02 | Formation of water repelling film of carbon containing fluorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17570092A JPH0624804A (en) | 1992-07-02 | 1992-07-02 | Formation of water repelling film of carbon containing fluorine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0624804A true JPH0624804A (en) | 1994-02-01 |
Family
ID=16000721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17570092A Pending JPH0624804A (en) | 1992-07-02 | 1992-07-02 | Formation of water repelling film of carbon containing fluorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0624804A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068128A1 (en) * | 2004-12-21 | 2006-06-29 | Zeon Corporation | Optical device |
| KR20200093512A (en) | 2020-07-30 | 2020-08-05 | 차양수 | Fermentation and destruction apparatus for feed waste |
-
1992
- 1992-07-02 JP JP17570092A patent/JPH0624804A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006068128A1 (en) * | 2004-12-21 | 2006-06-29 | Zeon Corporation | Optical device |
| KR20200093512A (en) | 2020-07-30 | 2020-08-05 | 차양수 | Fermentation and destruction apparatus for feed waste |
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