JPH0123484B2 - - Google Patents
Info
- Publication number
- JPH0123484B2 JPH0123484B2 JP11072583A JP11072583A JPH0123484B2 JP H0123484 B2 JPH0123484 B2 JP H0123484B2 JP 11072583 A JP11072583 A JP 11072583A JP 11072583 A JP11072583 A JP 11072583A JP H0123484 B2 JPH0123484 B2 JP H0123484B2
- Authority
- JP
- Japan
- Prior art keywords
- laser
- thin film
- ptfe
- sample gas
- excited
- 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
Links
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 239000010409 thin film Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 102100040550 FXYD domain-containing ion transport regulator 4 Human genes 0.000 claims description 2
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 claims description 2
- 108010070092 corticosteroid hormone-induced factor Proteins 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
本発明は、ポリテトラフルオロエチレン（以
下、「PTFE」という）薄膜をレーザーによつて
製造する方法に関する。
PTFE薄膜で表面を被覆することにより摩擦を
減じたり、表面の不活性化、酸化防止又は不導体
化、表面エネルギーの低減化を計ることが行われ
ている。例えば、精密機械のコーテイング、潮解
性結晶の吸湿防止、ヒユーズ抵抗器の製造、半導
体装置の製造、電気光学用電極基板の製造などに
利用されている。
PTFE薄膜を基板上で製造する方法としては、
プラズマ重合法（N.Morosoff ＆ H.
Yasuda：J.Appl.Polym.Sci.23，3449（1979）参
照）、スパツタコーテイング法（H.Biederman，
S.M.Ojha and L.Holland：Thin Solid Films，
41，329（1977）参照）、蒸着法（J.A.Lane：
Brighton College of Technol.Project Rep.
（1967））参照）などが知られている。
しかし、これら周知の方法は、基板上の所望の
特定部分のみにポリマーを形成させたり、複雑な
ポリマーのパターンを作るためには不適当であ
る。特公昭49―41268号に開示されているように
マスクを用いてパターンを作ることは可能である
が、非常に微小部分のみの被覆や、非常に複雑な
パターンの被覆を行うには不都合である。
本発明は、固体表面の所望の特定部分に選択的
にPTFE薄膜を被覆することのできるレーザーを
利用したPTFE薄膜の製法を提供することを目的
とする。
この目的は、固体表面近傍の試料ガスを照射し
て主成するCF2ラジカル又は励起されたC2F4を、
該固体表面のレーザー照射部分において選択的に
重合させることによつて達成される。
こゝで、用いられる試料ガスとしては、
CHF3，CHClF2，CHBrF2，CHIF2，CCl2F2，
CBr2F2，CI2F2，C2F4，C2HF5，C2HClF4，
C2HBrF4，C2HIF4，ｎ―C3F6，ｃ―C3F6，ｎ―
C4F8，ｃ―C4F8などがある。
更に、こゝで用いるレーザーはパルス発振、連
続発振いずれでもよく、CO2レーザー、エキシマ
レーザー、N2レーザー、Arイオンレーザーなど
が用いられる。
以下、添付図面を参照して本発明を詳しく説明
する。第１図において、１はレーザー、２はレン
ズ、３は光学結晶の窓材、４はガス容器、５は試
料ガス、６はCF2ラジカル又は励起C2F4分子生成
領域、７はPTFE薄膜、８は基板である。
レーザー光を基板８の表面近傍の試料ガス５に
照射し、次の光化学反応を用いてCF2ラジカル又
は励起C2F4分子を生成させる。
試料ガスレーザー光
―――――→
：CF2又はC2F4 * ……(1)
こゝで、＊は振動又は電子励起種を示し、試料
ガスとしては上記したCHF3……ｃ―C4F8などで
ある。
生成したCF2ラジカル又は励起されたC2F4は、
レーザー照射された基板上に選択的に付着し、次
の重合反応が起る。
nCF2→―CF2―CF2―CF2 ……(2)
又はnC2F4→―CF2―CF2―CF2 ……(3)
結果として、レーザー光の照射された部分のみ
PTFE薄膜が生成される。以下、実施例について
述べる。
試料ガスとしてCHF3を45Torr容器内に封入
し、KBrを基板として焦点距離7.5cmのレンズ集
光して、TEA型CO2レーザー光（波数1075cm-1、
パルスエネルギー0.8J）で数十パルス照射したと
ころ基板上のレーザー光照射部分に白色のPTFE
薄膜が生成した。反応は次のように進行する。
CHF3nhυ
―――→
：CF2＋HF (1)（気相）
ｎ（：CF2）→PTFE (2)（表面）
生成した薄膜の質量分析の結果を第２図に示す。
図中に示したような分解フラグメントが認めら
れ、分解パターンが既知のPTFEのパターンと一
致することから、確かにPTFE薄膜が生成してい
ることが判つた。
以上詳述したように、本発明は試料ガスを照射
して生成するCF2ラジカル又は励起されたC2F4
を、レーザーを照射した領域のみに選択的に重合
させてPTFE薄膜を形成する方法であるので、上
記した種々の応用分野に極めて有用である。
なお、本発明の説明では基板表面にPTFE薄膜
を形成する場合を例にとつて証明したが、本発明
は板状に限らず、種々の目的に応じた固体の表面
にPTFE薄膜を形成できることはいうまでもな
い。 DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polytetrafluoroethylene (hereinafter referred to as "PTFE") thin film using a laser. The surface is coated with a PTFE thin film to reduce friction, inactivate the surface, prevent oxidation or make it nonconductive, and reduce surface energy. For example, it is used for coating precision instruments, preventing moisture absorption of deliquescent crystals, manufacturing fuse resistors, manufacturing semiconductor devices, manufacturing electro-optic electrode substrates, etc. The method for manufacturing PTFE thin film on a substrate is as follows:
Plasma polymerization method (N.Morosoff & H.
Yasuda: J.Appl.Polym.Sci. 23 , 3449 (1979)), sputter coating method (H.Biederman,
SMOjha and L.Holland: Thin Solid Films,
41, 329 (1977)), vapor deposition method (JALane:
Brighton College of Technol.Project Rep.
(1967))) are known. However, these known methods are unsuitable for forming a polymer only on a desired specific portion of a substrate or for creating a complex polymer pattern. Although it is possible to create a pattern using a mask as disclosed in Japanese Patent Publication No. 49-41268, it is inconvenient to cover only extremely small areas or to cover extremely complex patterns. . An object of the present invention is to provide a method for producing a PTFE thin film using a laser that can selectively coat a desired specific portion of a solid surface with a PTFE thin film. The purpose is to irradiate the sample gas near the solid surface to generate mainly CF 2 radicals or excited C 2 F 4 .
This is achieved by selectively polymerizing the laser irradiated portion of the solid surface. Here, the sample gas used is:
CHF 3 , CHClF 2 , CHBrF 2 , CHIF 2 , CCl 2 F 2 ,
CBr 2 F 2 , CI 2 F 2 , C 2 F 4 , C 2 HF 5 , C 2 HClF 4 ,
C 2 HBrF 4 , C 2 HIF 4 , n-C 3 F 6 , c-C 3 F 6 , n-
Examples include C 4 F 8 and c-C 4 F 8 . Further, the laser used here may be either pulse oscillation or continuous oscillation, and CO 2 laser, excimer laser, N 2 laser, Ar ion laser, etc. are used. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. In Figure 1, 1 is a laser, 2 is a lens, 3 is an optical crystal window material, 4 is a gas container, 5 is a sample gas, 6 is a CF 2 radical or excited C 2 F 4 molecule generation region, 7 is a PTFE thin film , 8 is a substrate. The sample gas 5 near the surface of the substrate 8 is irradiated with laser light, and CF 2 radicals or excited C 2 F 4 molecules are generated using the following photochemical reaction. Sample gas laser light――――――→: CF 2 or C 2 F 4 * …(1) Here, * indicates a vibrational or electronically excited species, and the sample gas is the above-mentioned CHF 3 … c— For example, C 4 F 8 . The generated CF 2 radical or excited C 2 F 4 is
It selectively adheres to the laser-irradiated substrate, and the next polymerization reaction occurs. nCF 2 →―CF 2 ―CF 2 ―CF 2 ……(2) or nC 2 F 4 →―CF 2 ―CF 2 ―CF 2 ……(3) As a result, only the part irradiated with the laser beam
A PTFE thin film is produced. Examples will be described below. CHF 3 was sealed in a 45 Torr container as a sample gas, and the light was focused by a lens with a focal length of 7.5 cm using KBr as a substrate to generate TEA type CO 2 laser light (wave number 1075 cm -1 ,
After several tens of pulses were irradiated with a pulse energy of 0.8 J), white PTFE appeared on the laser beam irradiated area on the substrate.
A thin film was formed. The reaction proceeds as follows. CHF 3 nhυ ---→ :CF 2 +HF (1) (gas phase) n (: CF 2 )→PTFE (2) (surface) Figure 2 shows the results of mass spectrometry of the formed thin film.
Decomposition fragments as shown in the figure were observed, and the decomposition pattern matched the known pattern of PTFE, indicating that a PTFE thin film was indeed formed. As described in detail above, the present invention is directed to CF 2 radicals generated by irradiating a sample gas or excited C 2 F 4
This method forms a PTFE thin film by selectively polymerizing only the area irradiated with laser, so it is extremely useful in the various application fields mentioned above. In addition, in the explanation of the present invention, the case where a PTFE thin film is formed on the surface of a substrate is used as an example to prove the case, but the present invention is not limited to a plate shape, and it is possible to form a PTFE thin film on the surface of a solid material for various purposes. Needless to say.
第１図は本発明を実施するために用いた装置の
一例を示す。第２図は本発明の実施例で得られた
PTFE薄膜の質量分析結果を示すグラフである。
図中の符号：１……レーザー、４……ガス容
器、５……試料ガス、６……CF2ラジカル又は励
起C2F4分子生成領域、７……PTFE薄膜、８……
基板。
FIG. 1 shows an example of the apparatus used to carry out the invention. Figure 2 was obtained in an example of the present invention.
It is a graph showing the mass spectrometry results of a PTFE thin film. Codes in the figure: 1...Laser, 4...Gas container, 5...Sample gas, 6... CF2 radical or excited C2F4 molecule generation region, 7...PTFE thin film, 8...
substrate.
Claims (1)
CCl2F2，CBr2F2，CI2F2，C2F4，C2HF5，
C2HClF4，C2HBrF4，C2HIF4，ｎ―C3F6，ｃ―
C3F6，ｎ―C4F8，ｃ―C4F8のうちのいずれか１
つの、固体表面近傍の試料ガスに、レーザー光を
照射して生成するCF2ラジカル又は励起された
C2F4を、該固体表面のレーザー照射部分におい
て選択的に重合させることを特徴とするレーザー
を用いたポリテトラフルオロエチレン薄膜の製造
方法。 ２ 前記のレーザーがパルス又は連続発振のCO2
レーザー、エキシマレーザー、N2レーザー、Ar
イオンレーザーである特許請求の範囲第１項に記
載のレーザーを用いたポリテトラフルオロエチレ
ン薄膜の製造方法。[Claims] 1 CHF 3 , CHClF 2 , CHBrF 2 , CHIF 2 ,
CCl 2 F 2 , CBr 2 F 2 , CI 2 F 2 , C 2 F 4 , C 2 HF 5 ,
C 2 HClF 4 , C 2 HBrF 4 , C 2 HIF 4 , n―C 3 F 6 , c―
Any one of C 3 F 6 , n-C 4 F 8 , c-C 4 F 8
CF2 radicals or excited CF2 radicals are generated by irradiating a sample gas near the solid surface with laser light.
A method for producing a polytetrafluoroethylene thin film using a laser, characterized in that C 2 F 4 is selectively polymerized in a laser-irradiated portion of the solid surface. 2 The above laser is pulsed or continuous wave CO 2
Laser, excimer laser, N2 laser, Ar
A method for producing a polytetrafluoroethylene thin film using the laser according to claim 1, which is an ion laser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11072583A JPS601207A (en) | 1983-06-20 | 1983-06-20 | Production of thin polytetrafluoroethylene film using laser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11072583A JPS601207A (en) | 1983-06-20 | 1983-06-20 | Production of thin polytetrafluoroethylene film using laser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS601207A JPS601207A (en) | 1985-01-07 |
| JPH0123484B2 true JPH0123484B2 (en) | 1989-05-02 |
Family
ID=14542905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11072583A Granted JPS601207A (en) | 1983-06-20 | 1983-06-20 | Production of thin polytetrafluoroethylene film using laser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS601207A (en) |
-
1983
- 1983-06-20 JP JP11072583A patent/JPS601207A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS601207A (en) | 1985-01-07 |
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