JP2706705B2 - Method for producing organic thin film by ultraviolet laser - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a single-layer or multilayer organic thin film on the surface of a polymer molded article, the surface of a substrate, or both using an ultraviolet laser. Specifically, the present invention irradiates the surface of the polymer molded article with an ultraviolet laser beam to improve the structural properties and functionality of the surface without leaving residual impurities on the polymer surface, and then apply the laser irradiation surface A method for selectively immobilizing an organic compound having a vinyl group or an allyl group, further, alternately introducing an organic compound having a vinyl group, an allyl group, an aryl group or an ethynyl group,
The present invention relates to a novel thin film manufacturing method in which a reaction is performed in the order of introduction to form a multilayer film on a laser irradiation surface. Further, the present invention provides a method of immobilizing an organic compound on a substrate surface, which is formed by depositing a polymer decomposition fragment (fragment) generated by irradiating an ultraviolet laser beam onto a polymer molded article on a solid substrate in a vacuum atmosphere,
And a method for forming a multilayer film.

[0002]

The surface processing of the Related Art polymeric molded article, which radiation before, the surface modification method using plasma irradiation has been proposed (e.g., Park et polymer Ronbunshu 49, N
o. 5p405, Iwasaki et al. 1 p
21), all discuss only immobilization of a single component and are not developed into a multilayer film. Also,
In plasma irradiation, the activation of the surface of the polymer molded article varies on the surface of the molded article, and (1) there is no reproducibility of the obtained modified product. (2) It is difficult to control the position selectivity of surface modification. There was such a problem. The modification by radiation not only modifies the surface but also changes the properties of the bulk polymer body. There were drawbacks such as.

Next, an example of research using an ultraviolet laser will be described. Ablation (direct etching) using an excimer laser that oscillates high-intensity pulsed light in the ultraviolet region is being actively studied as a precise microfabrication method for polymers from both basic and applied aspects. The present inventors have previously reported (1) formation of a microstructure applicable to a liquid crystal alignment film on a polymer surface by ablation (H. Niino, A. Yabe, et al., Jp.
n. J. Appl. Phys. , 28 , L2225 (1
989); Appl. Phys. , 55 , 510 (19
89); ibid. , 54 , 2159 (1989); i.
bid. , 57 , 2368 (1990); Photo
chem. Photobiol. A. Chem. , 65 ,
303 (1992)) and (2) Electroless plating with irradiation position selection can be performed by using the change in surface potential (H. Niino, A. Yabe, et al., A).
ppl. Phys. Lett. , 60 2697 (19
92)). These are based on periodic changes in surface shape and generation of ion species.

[0004] Lazaré et al. (S. Lazare an
dR. Srinivasan, Journal of
Physical Chemistry, Vol. 9
0,2124 (1986)), reported that when a polymer film surface was irradiated with a high-intensity ultraviolet laser such as an excimer laser, the irradiated surface was easily modified immediately after irradiation, and new functional groups were generated. ing. Also, S.I. Lazaré et al. Describe that optical processing of a polymer surface with an ultraviolet laser is a quick and easy method for observing the surface state. As described above, optical processing of a polymer surface using an ultraviolet laser can be accurately and efficiently performed. Furthermore, by controlling the irradiation conditions, the structural characteristics, chemical properties and functionality of the irradiated resin surface can be improved, so that various surface reactions can be performed with good control. However, they have not examined whether or not a reaction intermediate has been formed on the laser irradiation surface, and have not made any proposals on the industrial utility and utility of the surface treatment.

Further, deposition of polymer decomposed fragments (fragments) generated by irradiating a polymer molded article with ultraviolet laser light on a solid substrate such as glass in a vacuum atmosphere is described in S.K. Hansen et al. (SG Hansenand TE Robit)
aile, Appl. Phys. Lett. , 52 .
81. (1988)). However, they have not studied the chemical reactivity of the sediment, and have not made any suggestions on the industrial utility or utilization of the sediment surface.

Further, as a method of depositing an organic compound on the surface of a solid substrate using an ultraviolet laser, a chemical vapor deposition method (Chemical Vapor Deposition) is used.
on (CVD)) (for example, Hirotaka Hirotaka, Applied Physics, 57.1985 (1988)). This laser CV
D is a method completely different from the present invention because the introduction of the organic compound and the laser irradiation are performed simultaneously, or the introduction of the organic compound is performed first.

Further, as a method of forming a multilayer film, (a) a vapor deposition method including molecular beam epitaxy (MBE),
(B) Chemical vapor deposition (CVD) and (c) sputtering have been proposed. In the vapor deposition method including MBE, for example, Hoshi et al. Attempted to form a two-layer film on a KBr substrate using two kinds of phthalocyanine derivatives (lutetium and aluminum) (H. Hoshi, et a).
l. , J. et al. Appl. Phys. 67 . 6871 (19
90)). In this method, a two-layer film is produced by heating an organic compound forming a thin film under a high vacuum into a molecular beam by heating, and changing the organic compound reaching the substrate. It is a completely different method. In addition, in the CVD method and the sputtering method, the method of scattering an organic compound is a method of producing a multilayer film by using a laser, heat, or high-energy particles as an excitation source, and scattering alternately activated substances on a substrate. It is based on the same idea as the MBE vapor deposition method, and is fundamentally different from the present invention.

[0008]

The surface processing (fixing of a single component and the formation of a multilayer film) on a polymer molded article has been attempted in the above-mentioned method. (1) In order to obtain a high-quality film, The equipment becomes complicated (high vacuum system).
(2) Lack of reproducibility. Therefore, development of a new surface processing technology has been desired.

The present inventors have repeatedly studied a polymer processing method using an ultraviolet laser having features such as high intensity, monochromaticity, and directivity. As a result, by irradiating the ultraviolet laser, the surface of the polymer molded product was improved. The existence of a reaction intermediate having a chemical reactivity such as a radical in the polymer decomposition fragment (fragment) was found by a test using an electron spin resonance method. From this, a method of using this reaction intermediate having chemical reactivity to immobilize an organic compound having a vinyl group or an allyl group by a radical mechanism only at a site activated by ultraviolet laser light in a selective manner. I found it. In addition, the present inventors have also found the possibility of forming a multilayer film at an activated site by using a plurality of substances (such as an organic compound having a vinyl group, an allyl group, or an ethynyl group) to be introduced. The present invention has been made based on these findings.

The present invention has been made in view of the above-mentioned points, and has as its object to provide an optical processing method for a polymer molded article and / or a solid substrate by irradiating an ultraviolet laser to obtain excellent characteristics of the optical processing method. Without lowering, the organic compound such as a vinyl derivative, an allyl derivative, etc. is immobilized on the surface of the polymer molded article or / and the solid substrate in a position-selective manner,
Another object of the present invention is to provide a novel method for producing a multilayer film by continuously fixing a plurality of organic compounds.

[0011]

In order to achieve the above object, the method of the present invention comprises irradiating a surface of a polymer molded article with an ultraviolet laser in a vacuum chamber, and then applying a vinyl group or a vinyl group on the surface. It is characterized in that an organic compound having an allyl group is reacted to form an organic thin film on the surface of a polymer molded article. The surface of the polymer molded article is irradiated with an ultraviolet laser, and then the surface is treated with a general formula (I) H ₂ C） CHR ₁ (I) (wherein R ₁ is a halogen atom, a cyano group, a substituted carbonyl group) , An organic compound having a vinyl group represented by a substituted or unsubstituted aldehyde group, a carboxyl group, or a carbamoyl group);
I) H ₂ C ＝ CHCH ₂ R ₂ (II) (wherein R ₂ is a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted aryl group, an aldehyde group, a carboxyl group, a carbamoyl group) The organic compound having an allyl group represented by the formula (1) is reacted to form an organic thin film on the surface of the polymer molded article.

Another method of the present invention is to irradiate the surface of a polymer molded article with an ultraviolet laser in a vacuum chamber, and then arbitrarily select an organic compound having a vinyl group, an allyl group or an ethynyl group, and remove these organic compounds. It is characterized in that it is successively introduced on the surface and reacted in the order of introduction to form a multilayer film on the surface of the polymer molded article. The surface of the polymer molded article is irradiated with an ultraviolet laser, and then the surface is treated with a general formula (III) H ₂ C ＝ CHR ₃ (III) (where R ₃ is a halogen atom, a cyano group, a substituted carbonyl group) Or a substituted or unsubstituted alkyl group, aryl group, aldehyde group, carboxyl group, or carbamoyl group), or an organic compound having a general formula (II) H ₂ C ＝ CHCH ₂ R ₂ (II (Wherein R ₂ represents a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted alkyl group, an aryl group, an aldehyde group, a carboxyl group, or a carbamoyl group) the organic compound having a or the general formula _{(IV) HC≡CR 4 (IV)} ( provided that wherein R ₄ is a halogen atom, a cyano group, a substituted carbonyl group, lay be substituted Organic compounds having an ethynyl group represented by an unsubstituted alkyl group, an aryl group, an aldehyde group, a carboxyl group, or a carbamoyl group) are arbitrarily selected, and these are sequentially introduced on the surface, and in the order of introduction. The reaction is performed to form a multilayer film on the surface of the polymer molded article.

Another method of the present invention is to irradiate the surface of a polymer molded article with an ultraviolet laser beam in a vacuum chamber,
The produced polymer decomposed fragments are deposited on a substrate, and then an organic compound having a vinyl group or an allyl group is reacted on the surface of the deposited substrate to form an organic thin film. Irradiate the surface of the polymer molded article with ultraviolet laser light,
The generated polymer-decomposed fragments are deposited on a substrate, and then the general formula (I) H ₂ C ＝ CHR ₁ (I) (where R ₁ is a halogen atom, a cyano group Represents a substituted carbonyl group, a substituted or unsubstituted aldehyde group, a carboxyl group or a carbamoyl group), or an organic compound having a vinyl group represented by the general formula (I
I) H ₂ C ＝ CHCH ₂ R ₁ (II) (wherein, R ₁ represents a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted aldehyde group, a carboxyl group, or a carbamoyl group. ) Is reacted with an organic compound having an allyl group to form an organic thin film.

Still another method of the present invention is to irradiate the surface of a polymer molded article with an ultraviolet laser beam in a vacuum chamber to deposit the generated polymer decomposed fragments on a solid substrate. It is characterized in that an organic compound having a vinyl group, an allyl group or an ethynyl group is arbitrarily selected, sequentially introduced into the surface, and reacted in the order of introduction to form a multilayer film. The surface of the polymer molded article is irradiated with an ultraviolet laser beam to deposit the generated polymer decomposed fragments on a solid substrate, and then the general formula (III) H ₂ C ＣCHR ₃ (III) (Where R ₃ represents a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted alkyl group, an aryl group, an aldehyde group, a carboxyl group, or a carbamoyl group). Or an organic compound having the general formula (II) H ₂ C ＝ CHCH ₂ R ₂ (II) (wherein R ₂ is a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted alkyl group, aldehyde group, a carboxyl group, a carbamoyl group.) the organic compound having an allyl group represented by or the general formula _{(IV) HC≡CR 4 (IV)} ( provided that wherein R ₄ Represents an ethynyl group represented by a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted alkyl group, an aryl group, an aldehyde group, a carboxyl group or a carbamoyl group. These are sequentially introduced into the surface, and reacted in the order of introduction to form a multilayer film.

In the above method, it is desirable that the ultraviolet laser irradiation conditions are set at a vacuum of 1 Torr or less, and the organic compound introduction conditions are set to a temperature at which the introduced organic compound desorbs from the surface of the polymer molded article. Further, it is preferable that the ultraviolet laser irradiation condition is set to a vacuum of 1 Torr or less, and the organic compound introduction condition is set to a temperature not more than a temperature at which the introduced organic compound desorbs from the polymer decomposed fragment.

When the pressure in the vacuum chamber exceeds 1 Torr during the irradiation with the ultraviolet laser, the active species (radical species) formed on the surface of the polymer molded article and / or the film on which the polymer decomposed fragments are deposited by the ultraviolet laser irradiation. ) Is inactivated. In addition, it is preferable that the inside of the vacuum chamber be an inert gas atmosphere during the irradiation with the ultraviolet laser.
In this case, there is an advantage that the active species (radical species) generated on the surface of the polymer molded article and / or the film on which the polymer decomposed fragments are deposited by the ultraviolet laser irradiation are present in a stable state. When the introduced organic compound exceeds the temperature at which the introduced organic compound desorbs from the surface of the polymer molded article or the polymer decomposed fragment, the surface of the polymer molded article or the polymer formed by the irradiation of the ultraviolet laser is irradiated. There is a disadvantage that the organic compound is not sufficiently supplied to the active species (radical species) generated in the decomposed fragment.

Next, based on FIG.
An example in which an organic thin film is formed on the surface of a polymer film 0 (for example, a polymer film) will be described. Reference numeral 12 denotes a vacuum chamber which is maintained at, for example, 83K and 3 × 10 ^-5 Torr. When the polymer molded article 10 is irradiated with an ultraviolet laser from the opening of the mask 14 (state 1), active species (radical species) 16 are generated on the surface of the polymer molded article 10 (state 2). Next, when the organic compound (single component or multiple components) is introduced in a gaseous or solution state (state 3), an immobilization reaction occurs between the organic compound and the active species 16 to form an organic thin film 18. (State of 4.). In addition,
At this point, no ultraviolet laser irradiation has been performed. Thereafter, unreacted substances in the vacuum chamber 12 are removed. At this time, the inside of the vacuum chamber 12 is, for example, 3
00K, 3 × 10 ⁻⁵ Torr.

Next, an example in which an organic thin film is formed on the surface of the substrate 20 (for example, a quartz substrate) will be described with reference to FIG. ^Reference numeral 12 denotes a vacuum chamber which is maintained at, for example, 3 × 10 ^-5 Torr and 300K. When the polymer molded article 10 (for example, a polymer film) is irradiated with an ultraviolet laser (for example, KrF laser) (state 1), a polymer decomposed fragment (fragment) 22 is generated from the surface of the polymer molded article 10, Attached to the surface of the substrate 20
accumulate. Next, when the organic compound (single component or multi-component) is introduced in a gaseous or solution state (state 2), an immobilization reaction occurs between the organic compound and the polymer-decomposed fragment, and An organic thin film is generated. In addition, when introducing an organic compound, irradiation of an ultraviolet laser is not performed. By adjusting the introduction direction of the organic compound, it is also possible to form an organic thin film on both the substrate 20 and the polymer molded article 10.

As the polymer molded product, a film, a sheet, a fiber, a fiber reinforced resin, a resin molded product and the like are used.
Materials for polymer molded products include amorphous, crystalline, aromatic,
Any non-aromatic polymer may be used. Preferred polymers include, for example, polyphenylene sulfide, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyimide, polyester, polyolefin, polyacrylate, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, Polytrifluoroethylene or epoxy resin,
Synthetic resins composed of these copolycondensates or mixtures can be mentioned. The substrate (substrate) for depositing the polymer decomposition fragments may be any of an organic material, an inorganic material, and a metal material.

As the ultraviolet laser, particularly preferably,
XeF (351 nm), XeCl (308 nm), KrF
(248 nm), ArF (193 nm) or F2 (15
7 nm) excimer laser and the like. Also, in a Nd +: YAG laser, a dye laser, a Kr ion laser, an Ar ion laser or a copper vapor laser, the fundamental oscillation wavelength light is converted by a nonlinear optical element or the like.
A laser converted into a laser in the ultraviolet region can also be used. Also, FEL (free electron laser) can be used. The laser fluence varies depending on the polymer material, but the pulse width is about 0.1 mJ / cm with nanoseconds.
A high intensity laser of ² / pulse or more is desirable.

Examples of the substance to be introduced include acrylic acid, acrylonitrile, acrolein, acrylamide, acryloyl chloride and the like as the compound represented by the general formula (I). Representative compounds of the general formula (II) include allyl acetic acid, allyl chloride, allyl amine, allyl aldehyde, allyl cyanide and the like. Alternatively, a substance obtained by chemically modifying an arbitrary organic compound with a vinyl group or an allyl group may be used. Compounds that do not have a sufficient vapor pressure in a vacuum are brought into a solution state (a solvent may be any as long as it is stable to free radicals).

Next, the behavior of the radical species will be described. Irradiation with ultraviolet laser generates radical species on the surface of the polymer molded article or on the solid substrate on which polymer decomposed fragments are deposited (FIG. 4), thereby increasing the high chemical reactivity. As for this reactivity, radicals react with oxygen in the air when left in the air and instantly lose their chemical reactivity (FIG. 5). Maintain high chemical reactivity of radical species by maintaining the laser irradiation surface and polymer decomposition fragment deposition surface in a vacuum atmosphere, inert atmosphere, and low temperature state to extend the life of free radicals, which are reaction intermediates It becomes possible.

The conditions for laser irradiation and substance introduction are as follows. Atmosphere: Under a vacuum of 10 ⁻³ Torr or less, under an inert atmosphere such as helium, argon, or nitrogen. Temperature: The organic compound to be introduced is on the surface of the polymer molded article or /
Or lower than the temperature at which desorption occurs from the surface of the polymer-degraded fragment (preferably maintained at a low temperature of 150K or lower). In addition, when the low-temperature state is used, it is possible to accurately determine the amount of the introduced molecule by using it together with the measurement of the ultraviolet absorption spectrum. It is also possible to perform adsorption for several layers.

As for thin film molding, there are a case of immobilization of a single component and a case of immobilization of multiple components (multilayer film) as follows. Irradiated with a single component immobilized KrF laser (248 nm) (10 ^-5 Torr,
83K) It is confirmed by X-ray photoelectron spectroscopy (XPS) F _1s peak that trifluoroethyl acrylate (fluorine mark) is immobilized on polyethylene naphthalate (PEN) thin film (manufactured by casting method). Was done. Here, the use of trifluoroethyl ester, which is a fluorine-substituted compound, facilitates confirmation of the reaction of the compound with the polymer by reacting a compound having an element (fluorine) not present in the polymer. This is the reason (FIGS. 6 and 7). Multicomponent immobilization (multilayer film) A Pr thin film (manufactured by a casting method) is irradiated with a KrF laser (248 nm), and trifluoroethyl acrylate is first introduced on the surface, and then dibromopropyl acrylate is added to the surface. When introduced (10 ^-5 Torr,
83K). In the spectrum after immobilization, a peak based on fluorine of trifluoroethyl acrylate (F _1s ) and a peak based on bromine of dibromopropyl acrylate (Br _3d ) appear, and P
A plurality of vinyl derivatives (an acrylic acid derivative having a carboxyl group substituted as a functional group) are immobilized on the surface of the EN thin film. That is, it was confirmed that a multilayer film was formed on the surface. The reason why the compound containing fluorine and bromine was used was to confirm the reaction on the surface, as described above.

The fixing mechanism of the organic thin film is as follows. In the method of the present invention, only the irradiation of ultraviolet laser light is performed on the surface of the polymer molded article before the introduction of the organic compound, so that the active species (radical species) are generated on this occasion, and the active site is a vinyl group or an allyl group. It is considered that it reacted with an organic compound having a group. That is, it is considered that the active species (radical species) generated by the irradiation of the ultraviolet laser light attack the vinyl group or the allyl group, and the organic compound is immobilized via the carbon radical. In immobilizing a plurality of organic compounds, the introduced organic compound is adsorbed on carbon radicals (a kind of living polymer) generated by the introduction of the first component, and attacks the functional group of the second component. Is considered to have caused immobilization.

The following can be considered as application examples of the present invention. Water and oil repellency of the surface; chemical modification with an organic compound containing fluorine, for example, trifluoroethyl acrylate, etc. may be performed. Hydrophilization of the surface; chemical modification with an organic compound such as acrylic acid. Manufacture of pyroelectric material (use of multilayer film) If an electron-donating compound is immobilized on the first component and an electron-withdrawing compound is immobilized on the second component (or vice versa), the multilayer film can have any polarization. If this is combined with any molecular orientation technique, it is possible to produce a substance having pyroelectric and piezoelectric properties. In addition, by irradiating a laser beam that has passed through a mask (metal pattern, etc.) corresponding to the portion of the surface of the polymer molded product that is desired to be modified, only the desired irradiated portion can be activated, and patterning is used. The present invention can also be applied to optical elements, optical waveguide fabrication, and organic electronic materials. Further, the membrane surface-treated by this method can be applied to a gas separation membrane for CO ₂ or the like. In the present invention, since the high molecular compound reacts by a non-thermal photochemical reaction by the ultraviolet laser, the surface treatment other than the irradiation site does not involve any thermal damage, and the surface treatment can be performed very selectively and effectively. In addition, a multilayer film can be formed.

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and the present invention may be practiced by appropriately changing the gist of the invention. Is possible. FIG. 3 shows a test apparatus used in the following examples. Reference numeral 12 denotes a vacuum chamber in which the polymer molded article 10 and the substrate 2 are provided.
0 is fixed. The inside of the vacuum chamber 12 is configured to be evacuated by a vacuum generating source including a rotary pump 24 and a diffusion pump 26 to be in a vacuum state. The ultraviolet laser light is applied to the polymer molded article 10 through the lens 28 and the laser inlet 30. Reference numeral 32 denotes an introduction tube, into which the compound 1 or the compound 2 is introduced into the vacuum chamber 12 via a flow meter 34 or 36, respectively. Reference numerals 38, 40, and 42 denote on-off valves, and reference numeral 44 denotes an emergency shutoff valve. In addition, vacuum chamber 1
An inert gas introduction pipe (not shown) is connected to 2.
The temperature control in the vacuum chamber 12 is performed by using, for example, liquid nitrogen cooling and resistance heating.

Example 1 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At a temperature of 85K, a KrF excimer laser (wavelength: 248 nm, half width about 20 ns) was irradiated with 10 shots at 140 mJ / cm ² / pulse to generate active species on the surface. Irradiated surface has 1-1 Diphenyl-2 pic
Radical measurement by electron spin resonance based on ryl-hydrazyl (DPPH) revealed that about 3 free radicals were generated per 1 nm ² . Thereafter, trifluoroethyl acrylate was introduced into the reactor, and was adsorbed on the irradiated surface in a predetermined amount. Immediately after the immobilization reaction, the temperature in the reaction vessel was raised to 300 K to remove unreacted monomers, and a surface-treated thin film was obtained. X
X-ray photoelectron spectroscopy (XPS) detected a fluorine-based peak in trifluoroethyl acrylate, confirming that the peak was immobilized only on the laser-irradiated surface.

Example 2 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At a temperature of 300K, a KrF excimer laser (wavelength: 248 nm, half width: about 20 ns) was 140 mJ / cm ^2.
Irradiation was performed for 10 shots / pulse, and the generated polymer decomposed fragments were deposited on a glass substrate. Thereafter, trifluoroethyl acrylate was introduced into the reactor on which the polymer decomposed fragments were deposited with the vacuum line and vacuum chamber closed, and kept at 300 K for 30 minutes to perform the immobilization reaction. Then, a surface-treated thin film was obtained. By X-ray photoelectron spectroscopy (XPS), a peak based on fluorine of acrylic acid trifluoroethyl ester was observed in the same manner as in Example 1, and it was confirmed that the peak was immobilized only on the laser-irradiated surface portion.

Example 3 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At a temperature of 85K, a KrF excimer laser (wavelength: 248 nm, half width about 20 ns) was irradiated for 10 shots at 140 mJ / cm ² / pulse, and the generated polymer decomposed fragments were deposited on a glass substrate. Thereafter, trifluoroethyl acrylate was introduced into the reactor, and was adsorbed on the irradiated surface in a predetermined amount. Immediately after the immobilization reaction, the temperature in the reaction vessel was raised to 300 K to remove unreacted monomers, thereby obtaining a surface-treated film. By X-ray photoelectron spectroscopy (XPS), a peak based on fluorine of acrylic acid trifluoroethyl ester was observed in the same manner as in Example 1, and it was confirmed that the peak was immobilized only on the laser-irradiated surface portion.

Example 4 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At a temperature of 85K, a KrF excimer laser (wavelength: 248 nm, half width about 20 ns) was irradiated with 10 shots at 140 mJ / cm ² / pulse to generate active species on the surface. Irradiated surface has 1-1 Diphenyl-2 pic
Radical measurement by electron spin resonance based on ryl-hydrrazyl (DPPH) revealed that about 3 free radicals were generated per 1 nm ² . Thereafter, trifluoroethyl acrylate is introduced into the reactor, and a predetermined amount is adsorbed on the irradiated surface. At this time, a fixation reaction to radicals generated in advance on the polymer surface occurs. Then, when dibromopropyl acrylate is continuously introduced, the radical species formed in the first component and the substance introduced next are mixed. The immobilization reaction progressed between them, and a multilayer film was formed. A peak based on fluorine of trifluoroethyl acrylate and a peak based on bromine of dibromopropyl acrylate were detected by X-ray photoelectron spectroscopy (XPS), indicating that the peak was immobilized only in the laser irradiation part. confirmed.

Example 5 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At room temperature, a KrF excimer laser (wavelength: 248 nm, half-width about 20 ns) was irradiated for 10 shots at 140 mJ / cm ² / pulse, and the generated polymer decomposed fragments were deposited on a glass substrate. With the vacuum chamber and the vacuum line closed, trifluoroethyl acrylate was introduced into the reactor into the deposit of polymer decomposed fragments, and kept at 300K for 30 minutes. At this time, the immobilization reaction to the generated radical occurs. Then, when dibromopropyl acrylate is continuously introduced, the immobilization reaction between the radical species formed in the first component and the substance introduced next is performed. Proceeded, and a multilayer film was generated. A peak based on fluorine of trifluoroethyl acrylate and a peak based on bromine based on dibromopropyl acrylate were observed in the same manner as in Example 4 by X-ray photoelectron spectroscopy (XPS). It was confirmed that only the part was fixed.

Example 6 A polyethylene naphthalate thin film formed on a sapphire substrate by a casting method was placed in a vacuum atmosphere (2 × 10 ⁻⁵ Torr).
r) At a temperature of 85K, a KrF excimer laser (wavelength: 248 nm, half width about 20 ns) was irradiated for 10 shots at 140 mJ / cm ² / pulse, and the generated polymer decomposed fragments were deposited on a glass substrate. Thereafter, trifluoroethyl acrylate was introduced into the reactor, and was adsorbed on the irradiated surface in a predetermined amount. At this time, an immobilization reaction to a radical generated in advance on the polymer surface occurs. Then, when dibromopropyl acrylate is continuously introduced, the first
The immobilization reaction proceeded between the radical species formed as the component and the substance introduced next, and a multilayer film was formed. Thereafter, the temperature in the reactor was increased to 300 K to remove unreacted monomers, and a surface-treated film was obtained. X-ray photoelectron spectroscopy (XP
By S), a peak based on fluorine of trifluoroethyl acrylate and a peak based on bromine based on dibromopropyl acrylate were observed in the same manner as in Example 4, and the peak was fixed only to the laser irradiation part. It was confirmed that.

[0034]

As described above, the present invention has the following effects. (1) High intensity, short pulse (for example, 20 ns), and
The use of an ultraviolet laser with high directivity enables high-speed activation of the surface of the polymer molded product, resulting in residual impurities (debris).
It is possible to cleanly and efficiently produce a precise and uniform organic thin film without leaving any residue. (2) It can be deposited only on a pattern formation site by laser irradiation. (3) Since the number of steps is small, the operation and the apparatus are simpler than those in the case of a conventional vapor deposition method including molecular beam epitaxy (MBE), CVD (laser, heat), or the like. (4) In the case of manufacturing a multilayer film, components constituting the multilayer film are introduced in a gaseous state (using a vapor pressure) or in a solution state. An organic multilayer film can be easily obtained. (5) By monitoring with an ultraviolet absorption spectrum, the amount of the organic compound introduced can be precisely controlled, and it is possible to develop an ultrathin film.

[Brief description of the drawings]

FIG. 1 illustrates an example of a method for producing an organic thin film using an ultraviolet laser according to the present invention, and is a process explanatory diagram in a case where an organic compound is immobilized on a polymer molding surface.

FIG. 2 illustrates another example of the method of the present invention, and is an explanatory diagram of steps in a case where a fragment deposit and an organic compound are immobilized on the surface of a solid substrate.

FIG. 3 is a system diagram of a test apparatus used in an example.

FIG. 4. Ablated PE
3 is an ESR (electron spin resonance) spectrum of an N (polyethylene naphthalate) film.

FIG. 5 is a graph showing the stability of active species (radical species) measured for PEN (polyethylene naphthalate) and showing the relationship between retention time and the number of radicals.

FIG. 6 shows the relationship between the binding energy and the count in an XPS (X-ray photoelectron spectroscopy) spectrum (before introducing an organic compound) after irradiation with an ultraviolet laser.

FIG. 7 shows the relationship between the binding energy and the count in an XPS (X-ray photoelectron spectroscopy) spectrum when trifluoroethyl ester is introduced into the surface after irradiation with an ultraviolet laser.

[Description of Signs] 10 Polymer molded product (polymer film) 12 Vacuum chamber 14 Mask 16 Active species 18 Organic thin film 20 Substrate 22 Polymer decomposed fragment (fragment)

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hiroyuki Shinno 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Tetsuori Ohana 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Yoshihisa Ishii, Examiner, National Institute of Materials Science and Technology (56) Reference JP-A-6-177974 (JP, A)

Claims (6)

(57) [Claims] In a vacuum chamber, a surface of a polymer molded article is irradiated with an ultraviolet laser in a vacuum chamber, and then the surface is treated with a general formula (I) H ₂ C = CHR ₁ (I) (wherein R ₁ is halogen atom, a cyano group, an organic compound having a substituted carbonyl group, a substituted or unsubstituted aldehyde group, a carboxyl group, a vinyl group represented by a carbamoyl group.), or the general formula (I
I) H ₂ C ＝ CHCH ₂ R ₂ (II) (wherein R ₂ is a halogen atom, a cyano group, a substituted
Carbonyl group, substituted or unsubstituted aryl
Group, aldehyde group, carboxyl group, carbamoyl group
Express. A method for producing an organic thin film using an ultraviolet laser, comprising reacting an organic compound having an allyl group represented by the formula (1 ) to form an organic thin film. 2. In a vacuum chamber, the surface of the polymer molded article is irradiated with an ultraviolet laser, and an organic compound having a vinyl group, an allyl group or an ethynyl group on the surface is arbitrarily selected, and these are sequentially applied to the surface. A method for producing an organic thin film using an ultraviolet laser, wherein the organic thin film is introduced and reacted in the order of introduction to form a multilayer film. 3. In a vacuum chamber, the surface of the polymer molded article is irradiated with an ultraviolet laser beam to deposit the generated polymer decomposed fragments on the substrate, and then the general formula (I) H ₂ C = CHR ₁ (I) (wherein, R ₁ represents a halogen atom, a cyano group, a substituted carbonyl group, a substituted or unsubstituted aldehyde group, a carboxyl group, or a carbamoyl group). An organic compound or a compound of the general formula (I
I) H ₂ C ＝ CHCH ₂ R ₁ (II) (wherein R ₁ is a halogen atom, a cyano group, a substituted
Carbonyl group, substituted or unsubstituted aldehyde
A carboxyl group or a carbamoyl group. )
A method for producing an organic thin film using an ultraviolet laser, comprising reacting an organic compound having an allyl group to produce an organic thin film. 4. In a vacuum chamber, the surface of the polymer molded article is irradiated with an ultraviolet laser beam to deposit the generated polymer decomposed fragments on a substrate, and then a vinyl group, an allyl group or an ethynyl group is formed on the surface of the deposited substrate. A method for producing an organic thin film using an ultraviolet laser, comprising arbitrarily selecting an organic compound having the compound, sequentially introducing the compound to the surface, and reacting the compounds in the order of introduction to form a multilayer film. 5. An ultraviolet laser irradiation condition under a vacuum of 1 Torr or less, and an introduction condition of an organic compound is a temperature at or below a temperature at which the introduced organic compound desorbs from the surface of the polymer molded article. 3. The method for producing an organic thin film according to 1 or 2. 6. An ultraviolet laser irradiation condition under a vacuum of 1 Torr or less, and an introduction condition of an organic compound is a temperature at or below a temperature at which the introduced organic compound desorbs from a polymer decomposition fragment deposit. Item 5. The method for producing an organic thin film according to item 3 or 4.