JPH09291357A - Production of thin film/powder using mixed solid as raw material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase film forming rate or powder producing rate and to improve film quality or powder quality in a method for producing a thin film/ powder by irradiating a solid organic material with laser. SOLUTION: The mixture solid 16 prepared by adding and mixing at least one of a metal, a metallic compound and an inorganic compound of a 2nd component to and with an organic compound of a 1st component is arranged in a reaction chamber 14 and after the reaction chamber 14 is evacuated into an reduced pressure state of 10<-1> -10<-6> Pa, molecules are deposited on a capturing body 20 by heating and exciting the mixture solid 16 with the irradiation of infrared laser and/or ultraviolet laser to emitting the molecules. As the metal of the 2nd component, at least one of Co, Fe, Ni and Cu is used, as the metallic compound, at least one of a Co compound, Fe compound, a Ni compound and a Cu compound is used and as the inorganic compound, a ceramic is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a thin film or powder having functionality such as pyroelectric / piezoelectric property, gas separation property and / or gradient function from a mixed solid mainly containing an organic compound. Is prepared by adding and mixing the second component (a metal, a metal compound, an inorganic compound alone or a mixture thereof) to the organic compound which is the first component to form a molded body, and then irradiating the mixed solid with a laser to fly ( The present invention relates to a method for producing a thin film / powder in which ablated molecules or excited molecules are trapped on a trapping body placed in a reaction chamber to form a thin film or powder.

[0002]

2. Description of the Related Art Wet methods and dry methods are known as methods for producing organic thin films or organic powders. As one of the wet methods, as described in JP-A-2-203954, a compound having an amphipathic property is developed in a liquid phase to form a monomolecular film, and if necessary, heating / cooling treatment. Then, there is a method for manufacturing an organic thin film by the Langmuir-Projet method in which a thin film having a low pinhole density is manufactured by laminating it on a substrate. Further, a sol-gel method is also known in which hydrolysis and polycondensation reactions of various metal alkoxide compounds including tetraethoxysilane are simultaneously advanced. These wet methods are operations under normal pressure and have a different configuration from the present invention, which is an operation under vacuum.

The production of a thin film by the dry method has been carried out so far by a vacuum vapor deposition method, which heats a solid in a vacuum, decomposes it into gas molecules and re-disperses it, and again forms a thin film on a substrate. The basic idea is to condense as. On the other hand, the thin film / powder manufacturing method of the present invention uses a laser rich in space controllability and high energy density,
This is a different method of vaporizing and exciting molecules. As a method using a laser, ablation using an excimer laser that oscillates pulsed light in the ultraviolet region has been actively studied as a precise microfabrication method for polymers from both basic and applied viewpoints. The Shinano et al. Group has so far developed (1) formation of a fine structure applicable to a liquid crystal alignment film on a polymer surface by ablation (H. Nli.
no, A.N. Yave, et al. , Jpn. J. Ap
pl. Phys. , 28 , L2225 (1989); A
ppl. Phys. , 55 , 510 (1989); ib
id. , 54 , 2159 (1989); ibid. , 5
7 , 2368 (1990); Photochem. P
hotbiol. A. Chem. , 65 , 303 (19
92)) and (2) that the electroless plating with irradiation position selection can be performed by utilizing the change in surface potential (H. Nli).
no, A.N. Yave, et al. ,; Appl. Ph
ys. Lett. , 60 , 2697 (1992)) and explains that they are based on periodic surface shape changes and generation of ionic species.

S. Lazaré et al. (S. Lazare an
d R. Srinivasan, Journal of
Physical Chemistry, Vol. 9
0, 2124 (1986)), it is reported that when the polymer film surface is irradiated with an excimer laser, the irradiated surface is easily modified immediately after irradiation to generate a new functional group. Also, S.I. Lazareth et al. Say that the photomachining of the polymer surface with this ultraviolet laser is a quick and simple method for observing the surface condition. in this way,
Optical processing of a polymer surface using an ultraviolet laser can be processed with high accuracy and efficiency. Furthermore, it has been reported that by controlling the irradiation conditions, it is possible to improve the structural characteristics, chemical properties, and functionality of the irradiated resin surface, so that various surface reactions can be performed with good control. In the above method, a laser is used for surface modification of a substance and the like, and its application to formation of a thin film or the like has not been examined. Furthermore, as a method of depositing an organic compound on the surface of a solid substrate using an ultraviolet laser, that is, a thin film forming method, a chemical vapor deposition method (Chemical Vapor Deposition) is used.
(H. Hirose, Applied Physics, 57.1985 (1988)). However, in this laser CVD, introduction of a gaseous organic compound and laser irradiation are simultaneously performed, or introduction of a gaseous organic compound is performed first. On the other hand, the present invention uses a solid raw material, which is a completely different method.

[0005]

In the production of organic thin films and powders, the methods described above have been attempted, but they have the following drawbacks. That is, as a method of evaporating the organic matter, heating the organic matter can be mentioned. However, when exposed to a high temperature for a long time, the organic matter may be decomposed and carbonized. As measures against this, the present inventors have already proposed in Japanese Patent Application No. 6-331094 a method for forming a thin film with reduced decomposition and less compositional deviation due to laser irradiation. Some compounds have small absorption and heat conduction in the film, the laser intensity applied is not fully utilized, and the film formation rate is very slow. The present invention has been made in view of the above points, and its object is to achieve the first object.
As a second component, a metal, a metal compound, an inorganic compound or a mixture thereof is added to the solid organic compound that is a component,
After forming into a compact, the mixed raw material is irradiated with a laser in a reduced pressure atmosphere, and the flying molecules or excited molecules are trapped on the trapping body placed in the reaction chamber to generate a thin film or powder, thereby thermally conducting the raw material. Another object of the present invention is to provide a method for producing a thin film / powder using a mixed solid as a raw material, which is intended to increase the film formation rate to improve the film quality.

[0006]

In order to achieve the above object, a method of producing a thin film / powder using a mixed solid as a raw material according to the present invention comprises an organic compound as a first component, a metal as a second component, A mixed solid obtained by adding and mixing at least one of a metal compound and an inorganic compound is placed in the reaction chamber,
The reaction chamber is evacuated to a reduced pressure of 10 ^-1 to 10 ^-6 Pa, preferably 10 ^-3 to 10 ^-5 Pa, and then the mixed solid is irradiated with a laser to be heated and excited, It is configured so that the molecules are ejected and the molecules are deposited on the capturing body. When the pressure in the reaction chamber is less than the above range, molecules flying from the solid surface due to laser irradiation reattach to the surface of the solid raw material. On the other hand, when the amount exceeds the above range, it does not particularly affect the production of the thin film and the powder, but it takes a long time for vacuum evacuation and a high-performance vacuum evacuation device is required. In this method,
As a laser for irradiating mixed solids, 0.8-11 μm
It is preferable to use an infrared laser having a wavelength of.
Further, as a laser for irradiating a mixed solid, 0.2 to
It is preferable to use an ultraviolet laser having a wavelength of 0.45 μm.

As the organic compound as the first component, it is preferable to use at least one of an organic compound having a reactive functional group such as a vinyl group and an allyl group, an organic polymer and an organic compound having a liquid crystallinity. As a compound having a reactive functional group such as a vinyl group, 1-4 phenylenebis {4-
6 (acryloyloxy) hexyloxy} benzoate and the like. Also, as the organic polymer, PE
Examples thereof include T and PVDF, and examples of the organic compound having liquid crystallinity include paraazoxyanisole. As the metal that is the second component, it is preferable to use at least one of Co, Fe, Ni, and Cu.
Further, it is preferable to use at least one of a Co compound, an Fe compound, a Ni compound and a Cu compound as the second component metal compound. Further, as the inorganic compound which is the second component, it is preferable to use ceramics represented by AlN.

As the amount of the second component added, there is an optimum value depending on the material to be thin film or powder and the added substance. For example, when it is desired to obtain a thin film / powder containing only organic molecules with 1-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate, the addition amount of the second component such as Co particles is 0.05 to About 10 wt% is desirable. If the amount added to the organic compound is less than 0.05%, the heat source of the irradiated laser is not sufficiently transmitted to the raw material compound, and the molecule does not fly. On the other hand, if the addition amount exceeds 10 wt%,
This is because, even if the laser intensity is such that the particles of the second component such as Co do not fly, the particles are entrained together with the molecules of the raw material compound and taken into the film or the powder. On the other hand, when the second component such as the added metal is mixed in the thin film or in the powder, it can be achieved by increasing the addition amount or increasing the laser intensity. As a method of adding the second component to the raw material organic compound which is the first component, it is possible to easily mix by stirring and mixing, or by stirring while mashing with a mortar or the like. After that, a compression-molded body at about 1 ton / cm ² is used. Alternatively, a premixed material may be heated to the melting point of the organic compound to form an organic material-metal mixture.

As the laser, an infrared light laser (wavelength 0.8 to 11 μm) and an ultraviolet light laser (0.2 nm) are taken into consideration in consideration of the absorption wavelength and the degree of absorption of organic compounds and additives.
To 0.45 μm) can be used. As the infrared laser, Nd: YAG laser (excitation method can be lamp excitation, diode excitation, etc.), semiconductor laser, N
d: Glass laser, dye laser, chemical laser, alexandrite laser, carbon dioxide gas laser, F center laser, iodine laser, free electron laser and the like can be used. XeF as an ultraviolet laser
(351 nm), XeCl (308 nm), KrF (248
nm), ArF (193 nm), or F ₂ (157 nm) excimer laser. Nd: Y
AG laser, dye laser, Kr ion laser, A
Also in the r-ion laser or the copper vapor laser, it is possible to use a laser in which the fundamental oscillation wavelength light is converted into a laser in the ultraviolet region by a non-linear optical element or the like. A thin film or powder having a desired composition can be formed by adjusting the intensity of the laser when the laser is irradiated. As the capturing body of the substrate on which the thin film is formed, any of organic materials, inorganic materials and metallic materials can be used. Also, in order to capture the powder,
Paper, an inorganic material filter, or the like can be used as the capturing body.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications. FIG. 1 shows a first embodiment of the present invention. As shown in FIG. 1, the apparatus for carrying out the method of the present invention is connected to a vacuum exhaust system 10 including a vacuum pump, a measuring instrument, etc., and has a reaction chamber (film forming chamber) having a laser inlet 12 such as a quartz window. 14, a target holder 18 for mounting a mixed solid (target) 16 disposed in the reaction chamber 14, and a reaction chamber 14
A capture body (substrate) 20 for film formation, which is disposed in the interior and faces the target holder 18 through a space, and a capture body holder 22 for mounting the capture body 20.
And a laser oscillator 24 for irradiating the mixed solid 16 attached to the target holder 18 with a laser.
And, it consists of. Reference numeral 26 is a formed thin film. When the thin film is formed on the capturing body 20, the capturing body 20 is separated into three layers.
It is necessary to heat at 0 to 500 ° C., preferably 100 to 300 ° C. to promote the motion of excited / activated molecules. For this reason, a heating means is built in the capturing body 20, or
Alternatively, heating means is connected. That is, the capturing body holder 22 also has a function of a heating device.

FIG. 2 shows a second embodiment of the present invention. In the present embodiment, the powder 28 is manufactured instead of the thin film, and instead of the substrate, the capturing body 20a made of a porous material such as a cloth, paper or inorganic material filter is used as the capturing body. In this embodiment, the capturing body holder 2
2a does not need to have a heating function. Alternatively, the capturing body holder 22a may not be used, and only the capturing body 20a may be fixed in the reaction chamber 14. Other configurations and operations are the same as those in FIG.

FIG. 3 shows a third embodiment of the present invention. In the present embodiment, in addition to the configuration shown in FIG. 2, a capturing body 30 made of a porous body is provided on the upstream side of the vacuum exhaust system in the reaction chamber 14 so that the capturing body 30 can also capture powder. It is a thing. Other configurations and operations are similar to those in the case of FIG.

FIG. 4 shows a fourth embodiment of the present invention. In the present embodiment, in addition to the configuration shown in FIG.
And a laser oscillator 34 for irradiating a laser in the space between the mixed solid 16 and the capturing body 20 to promote the movement of the excited / activated molecule. 36 is a laser inlet, 38, 40, 4
2 is a reflection mirror. Laser oscillator 24, 32, 3
4 can be an infrared light laser oscillator or an ultraviolet light laser oscillator or a combination thereof. Other configurations and operations are the same as those in FIG.

FIG. 5 shows a fifth embodiment of the present invention. In the present embodiment, in addition to the configuration shown in FIG. 2, a laser oscillator 3 for irradiating the capturing body 20a with a laser is provided.
2 is provided, and a laser oscillator 34 for irradiating a laser to the space between the mixed solid 16 and the capturing body 20a is provided to promote the movement of excited / activated molecules. 36 is a laser inlet, 38, 4
Reference numerals 0 and 42 are reflection mirrors. Laser oscillator 24, 3
2, 34 can be an infrared laser oscillator or an ultraviolet laser oscillator or a combination thereof. Other configurations and operations are similar to those in the case of FIG.

FIG. 6 shows a sixth embodiment of the present invention. In the present embodiment, in addition to the configuration shown in FIG. 3, a laser oscillator 3 for irradiating the capturing body 20a with a laser is provided.
2 is provided, and a laser oscillator 34 for irradiating a laser to the space between the mixed solid 16 and the capturing body 20a is provided to promote the movement of excited / activated molecules. 36 is a laser inlet, 38, 4
Reference numerals 0 and 42 are reflection mirrors. Laser oscillator 24, 3
2, 34 can be an infrared laser oscillator or an ultraviolet laser oscillator or a combination thereof. Other configurations and operations are the same as those in FIG.

[0016]

EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited to the following examples. Example 1 A thin film was manufactured using the apparatus shown in FIG. That is,
A raw material organic compound (1
-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate) with Co particles (size 0.0
3 .mu.m) was added in an amount of 0.05 wt% to obtain a compression molded body, which was used as a laser irradiation body (mixed solid, target). Also, a plate made of calcium fluoride (size: 4 sides)
A 9.8 mm square with a thickness of 1 mm) was attached as a thin film forming substrate, and the film forming chamber was evacuated to 10 ⁻⁴ Pa by a vacuum pump to obtain a vacuum state. After that, the infrared light laser was irradiated to three places for 12 minutes under the following conditions to form a film. Laser wavelength: 1.064 μm (Nd: YA
Laser intensity: 210 mJ / cm ² · pulse Laser repetition frequency: 10 Hz Target-substrate distance: 90 mm (distance D in FIG. 4) Substrate temperature: 125 ° C. Target temperature: 30 ° C.

Comparative Example 1 In the above Example 1, a laser film forming test was carried out using a target to which Co particles were not added. Other conditions are the same as in the first embodiment.

FIG. 7 shows the raw material compound (1-4 phenylene bis {4-6 (acryloyloxy)) used in the film formation test.
2 shows a near-infrared spectrum of hexyloxy} benzoate). The wavelength of the Nd: YAG laser used in this test is 1.064 μm, which is 939 when converted to wavenumber.
It is 8 cm ^-1 , but no absorption is observed in this part. In the test described in Comparative Example 1 in which Co particles were not added, it took about 50 minutes to form a thin film on the capturing body. It is almost correlated with the change in the degree of vacuum in the film forming apparatus shown in FIG. On the other hand, when Co particles were added, as is clear from FIG. 9, flight of molecules from the raw material compound was confirmed with laser irradiation. FIG. 10 shows an infrared spectrum (IR) chart of the starting compound before the addition of the second component, and FIG. 11 shows an infrared spectrum (IR) chart of the obtained thin film. In the IR chart of the thin film, the intensity of the —CH═CH ₂ absorption band is lower than that of the raw material, and it can be seen that the polymer thin film is formed. FIG. 12 shows a photograph of the surface of the thin film (magnification: 40 times). It can be seen that the thin film has a smooth surface. Figure 13 shows energy dispersive X
The result of a line spectroscopy (EDS) is shown. The added Co particles were not detected in the produced thin film. Example 1
The thickness of the thin film was about 7 μm, and it was possible to shorten the film formation time to 1/30 compared with the case where a thin film of the same thickness was prepared in the additive-free system.

Example 2 A film forming test was carried out by changing the additive from Co particles to AlN particles (size of about 1 μm) in Example 1 above. Other conditions are the same as in the first embodiment. FIG. 14 shows an EDS chart. An Al peak derived from the added AlN was detected.

[0020]

As described above, the present invention has the following effects. (1) A metal, a metal compound or an inorganic compound alone or a mixture thereof is added to a raw material organic compound to be irradiated with laser to increase the thermal conductivity of the raw material organic compound. In addition, it is possible to improve the film quality or the powder quality.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an apparatus for carrying out a method for producing a thin film / powder using a mixed solid as a raw material according to a first embodiment of the present invention.

FIG. 2 is a schematic configuration diagram showing a second embodiment of the present invention.

FIG. 3 is a schematic configuration diagram showing a third embodiment of the present invention.

FIG. 4 is a schematic configuration diagram showing a fourth embodiment of the present invention.

FIG. 5 is a schematic configuration diagram showing a fifth embodiment of the present invention.

FIG. 6 is a schematic configuration diagram showing a sixth embodiment of the present invention.

FIG. 7 is a near-infrared (1-2.5 μm) spectrum diagram of 1-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate in Examples 1 and 2 and Comparative Example 1.

8 is a graph showing a degree of vacuum in a reaction chamber and a temperature change of a raw material compound (mixed solid) in Comparative Example 1. FIG.

9 is a graph showing the degree of vacuum in the reaction chamber and the temperature change of the raw material compound (mixed solid) in Example 1. FIG.

FIG. 10 is an infrared spectroscopic (2.5 to 25 μm) spectrum diagram of 1-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate.

FIG. 11 is an infrared spectrum chart of a thin film.

FIG. 12 is a surface photograph of a thin film (magnification: 40 times).

FIG. 13 is an energy dispersive X-ray spectroscopy (EDS) chart of the thin film in Example 1.

14 is an energy dispersive X-ray spectroscopy (EDS) chart of the thin film in Example 2. FIG.

[Explanation of symbols]

 10 Vacuum Evacuation System 12, 36 Laser Inlet 14 Reaction Chamber 16 Mixed Solid (Target) 18 Target Holder 20 Capture Body (Substrate) 20a, 30 Capture Body (Porous Body) 22, 22a Capture Body Holder 24, 32, 34 Laser Oscillator 26 Thin Film 28 Powder 38, 40, 42 Reflective Mirror

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[Procedure amendment]

[Submission date] July 5, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Brief description of drawings

[Correction method] Change

[Correction contents]

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an apparatus for carrying out a method for producing a thin film / powder using a mixed solid as a raw material according to a first embodiment of the present invention.

FIG. 2 is a schematic configuration diagram showing a second embodiment of the present invention.

FIG. 3 is a schematic configuration diagram showing a third embodiment of the present invention.

FIG. 4 is a schematic configuration diagram showing a fourth embodiment of the present invention.

FIG. 5 is a schematic configuration diagram showing a fifth embodiment of the present invention.

FIG. 6 is a schematic configuration diagram showing a sixth embodiment of the present invention.

FIG. 7 is a near-infrared spectrum (1-2.5 μm) spectrum diagram of 1-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate in Examples 1 and 2 and Comparative Example 1.

8 is a graph showing a degree of vacuum in a reaction chamber and a temperature change of a raw material compound (mixed solid) in Comparative Example 1. FIG.

9 is a graph showing the degree of vacuum in the reaction chamber and the temperature change of the raw material compound (mixed solid) in Example 1. FIG.

FIG. 10 is an infrared spectroscopy (2.5 to 25 μm) spectrum diagram of 1-4 phenylene bis {4-6 (acryloyloxy) hexyloxy} benzoate.

FIG. 11 is an infrared spectrum chart of a thin film.

FIG. 12 is a micrograph showing a thin film formed on a substrate (40 × magnification).

FIG. 13 is an energy dispersive X-ray spectroscopy (EDS) chart of the thin film in Example 1.

14 is an energy dispersive X-ray spectroscopy (EDS) chart of the thin film in Example 2. FIG.

[Explanation of Codes] 10 Vacuum Evacuation System 12, 36 Laser Inlet 14 Reaction Chamber 16 Mixed Solid (Target) 18 Target Holder 20 Capture Body (Substrate) 20a, 30 Capture Body (Porous Body) 22, 22a Capture Body Holder 24, 32, 34 Laser oscillator 26 Thin film 28 Powder 38, 40, 42 Reflecting mirror

Claims (8)

[Claims] 1. A mixed solid obtained by adding and mixing at least one of a metal, a metal compound and an inorganic compound, which is a second component, to an organic compound, which is a first component, is placed in a reaction chamber, and the inside of the reaction chamber is evacuated. Then 10 ^-1 to 10 ^-6
After reducing the pressure of Pa, the mixed solid is irradiated with a laser to be heated and excited to cause the molecules to fly out and deposit the molecules on the capturing body. Powder manufacturing method. 2. A laser for irradiating a mixed solid,
The method for producing a thin film / powder using a mixed solid as a raw material according to claim 1, wherein an infrared laser having a wavelength of 0.8 to 11 µm is used. 3. A laser for irradiating a mixed solid,
The method for producing a thin film / powder using a mixed solid as a raw material according to claim 1, wherein an ultraviolet laser having a wavelength of 0.2 to 0.45 μm is used. 4. The mixed solid according to claim 1, 2 or 3, wherein at least one of an organic compound having a reactive functional group, an organic polymer and an organic compound having a liquid crystallinity is used as the first component organic compound. Method of manufacturing thin film / powder as raw material. 5. Co, F as the second component metal
A thin film using the mixed solid as a raw material according to claim 1, wherein at least one of e, Ni and Cu is used.
Powder manufacturing method. 6. Co as the second component metal compound
A method for producing a thin film / powder using the mixed solid as a raw material according to claim 1, wherein at least one of a compound, an Fe compound, a Ni compound and a Cu compound is used. 7. The method for producing a thin film / powder using a mixed solid as a raw material according to claim 1, wherein ceramics is used as an inorganic compound as a second component. 8. The amount of the second component added is 0.05 to 10 wt%.
The method for producing a thin film / powder using the mixed solid according to any one of claims 1 to 7 as a raw material.