JP4455039B2 - Method for forming Si-based organic / inorganic hybrid film - Google Patents

Description

  The present invention relates to a method for forming an organic / inorganic hybrid film, and more particularly to a vapor phase growth method for a Si-based organic / inorganic hybrid film.

  In recent years, organic-inorganic hybrid materials have attracted attention (33th Japan Society of Applied Physics, School B, “The Forefront of Organic Devices and Their Development: Part 1 Materials”, published on September 2, 2003, 33- 45, Yoshiki Nakajo, “Possibility of organic-inorganic hybrid materials” (JSAP Catalog Number: AP031333)). Here, the organic / inorganic hybrid means a combination of an organic material and an inorganic material. However, it has been proposed that the mixture is nano-order or molecular order, especially organic / inorganic hybrid, in distinction from a simple mixture such as a composite material known conventionally.

  Such organic / inorganic hybrid materials can be expected to have various characteristics that cannot be obtained with organic polymers or inorganic substances alone. For example, an organic / inorganic hybrid material such as plastic that is flexible but has excellent mechanical strength and heat resistance can be expected.

  Silica can be used as the most typical example of the inorganic component contained in the organic / inorganic hybrid material. In this case, no matter how finely the silica gel is pulverized, it is impossible to pulverize it to the molecular level. However, molecular dispersion is possible by using the sol-gel method. More specifically, the sol-gel method includes hydrolysis of silicate followed by condensation reaction of silanol groups. Therefore, an organic / inorganic hybrid material in which an organic polymer and silica gel are molecularly dispersed can be synthesized by allowing an organic polymer to coexist in such a sol-gel reaction.

FIG. 8 conceptually illustrates an example of an organic / inorganic hybrid material in which such an organic polymer and silica gel are molecularly dispersed. The organic polymer (Polymer) molecules are dispersed in the matrix of silica (SiO ₂ ). It shows the state.
The 33rd Japan Society of Applied Physics, School B, “Organic devices and the forefront of their development: Part 1 Materials”, published on September 2, 2003, pp. 33-45

  In the organic / inorganic hybrid material formed by using the sol-gel method as described above, the silica molecule and the polymer molecule are maintained by hydrogen bonds. FIG. 9 illustrates an example of the chemical structure of an organic / inorganic hybrid material in which silica molecules and polymer molecules are maintained by hydrogen bonds. In FIG. 9, an arrow represents a hydrogen bond.

  As is well known, hydrogen bonds are weak bonds compared to ordinary covalent bonds. Therefore, even if the organic / inorganic hybrid material by the sol-gel method has flexibility, it is considered difficult to have a sufficiently high strength, for example. Moreover, since the hydrogen bond in such an organic-inorganic hybrid material can react with water vapor | steam and oxygen in air | atmosphere, the hybrid material may deteriorate with time.

  Furthermore, since the sol-gel method is performed in a liquid, it is difficult to form an organic / inorganic hybrid film by directly applying the sol-gel method on the surface of a semiconductor electronic device or an organic electronic device. is there. On the other hand, when an organic / inorganic hybrid film formed by a sol-gel method is formed as a film, the film is generally formed by applying the obtained organic / inorganic hybrid material on a base. In that case, it is not easy to obtain sufficiently strong bondability at the interface between the substrate surface such as glass or polymer film and the organic / inorganic hybrid material. Moreover, when forming a film by the apply | coating method, it is difficult to control the film thickness by nano order.

In view of the situation of the organic / inorganic hybrid film forming method according to the prior art as described above, the present invention is to form an organic / inorganic hybrid film having various excellent characteristics easily and at low cost by the vapor phase growth method. It is an object.

  In the method for forming a Si-based organic / inorganic hybrid film according to one embodiment of the present invention, a heating filament and a substrate disposed opposite to the filament are provided in a reaction vessel, and an organic containing an ethylene bond (double bond) is provided. A vapor of at least one compound selected from alkylsilane, alkoxysilane, and aminosilane is introduced into the reaction vessel toward the heating filament together with the vapor of the compound (hereinafter also referred to as “ethylene bond-containing organic compound”), Thereby, a Si-based organic / inorganic hybrid film containing at least carbon and silicon is formed on the substrate.

In a method for forming a Si-based organic / inorganic hybrid film according to another aspect of the present invention, a substrate is provided in a reaction vessel, and together with hydrocarbon vapor as an organic compound containing an ethylene bond, alkylsilane, alkoxysilane, and aminosilane Si-based organic / inorganic hybrid film containing at least carbon and silicon by introducing a vapor of at least one compound selected from the above into a reaction vessel and plasma-exciting the introduced vapor to cause a chemical reaction Is formed on a substrate.

  In the case of forming a film using plasma excitation, during the film formation, one or more gases selected from nitrogen, hydrogen, helium, neon, argon, and xenon are also introduced into the reaction vessel. It is preferable.

  The ethylene bond-containing organic compound preferably also includes a benzene nucleus, more preferably includes a portion in which at least one of a vinyl group and a vinylene group and the benzene nucleus are adjacently bonded, and further preferably styrene.

  Before starting the formation of the Si-based organic / inorganic hybrid film, one or more gases selected from oxygen, nitrogen, hydrogen, helium, neon, argon, xenon, and methane are introduced into the reaction vessel, and the gas It is preferable to generate the plasma in the reaction vessel and clean the surface of the substrate with the plasma. As the substrate, glass or a polymer film can be used.

  The Si-based organic / inorganic hybrid film obtained by the above forming method is characterized in that the chemical skeleton structure contains at least carbon and silicon. The skeleton structure of the Si-based organic / inorganic hybrid film can further include at least one of oxygen and nitrogen.

  According to the present invention, it is possible to provide a Si-based organic / inorganic hybrid film having various excellent characteristics by a vapor phase growth method simply and at low cost.

(Embodiment 1)
In general, when an organic compound is heated to a high temperature, it is generally considered that the reaction proceeds in a direction in which the molecule decomposes. However, the present inventor introduces a vapor mixture of an organic compound containing an ethylene bond and a vapor of an organic compound containing Si (hereinafter also referred to as “organic Si compound”) toward a high-temperature filament. It has been found that a synthetic reaction occurs along with a decomposition reaction to synthesize a Si-based organic / inorganic hybrid film. Such a synthesis reaction caused by the action of the high-temperature filament is hereinafter also abbreviated as “heat synthesis” in the present specification.

  The chemical mechanism of the heat synthesis of such a Si-based organic / inorganic hybrid film is not necessarily clear, but the following mechanism can be assumed. First, it is considered that an organic compound containing an ethylene bond generates a chemically very active radical by a decomposition reaction by interaction with a high-temperature filament. In addition, it is considered that the organic Si compound also generates radicals by a decomposition reaction due to interaction with the high temperature filament. Then, it is presumed that a Si-based organic / inorganic hybrid film can be synthesized when these radicals react to form a stable C—Si bond.

In the usual case where a polymer is synthesized by polymerizing a monomer, a polymerization initiator is required. In the case of synthesizing the Si-based organic / inorganic hybrid film in the present invention, hydrogen radicals generated by the interaction with the high-temperature filament, CH _n (n = 1, 2, 3) or SiH _n (n = 1, 2, , 3) can be presumed to have a similar effect to the polymerization initiator.

  By the way, it is preferable that the ethylene bond-containing organic compound used in the heat synthesis of Embodiment 1 also contains a benzene nucleus. Moreover, the benzene nucleus is preferably present near the ethylene bond. This is because, due to the interaction between the double bond contained in the benzene nucleus and the ethylene bond, more active radicals can be expected at the time of thermal decomposition. As a typical example of an organic compound containing an ethylene bond and a benzene nucleus close to each other, styrene can be preferably used.

  On the other hand, as the organic Si compound, alkylsilane, alkoxysilane, aminosilane, or the like can be used. Monomethylsilane, dimethylsilane, etc. can be preferably used as examples of alkylsilane, dimethyldimethoxysilane, etc. can be preferably used as examples of alkoxysilane, and trisdimethylaminosilane, etc. can be preferably used as examples of aminosilane. Can do.

  FIG. 1 is a schematic block diagram illustrating a film forming apparatus that can be used in the method for forming a Si-based organic / inorganic hybrid film by heat synthesis according to the first embodiment. This film forming apparatus includes a reaction vessel 1 having a gas inlet 1a and an exhaust 1b. In the reaction vessel 1, a stage 4 is provided for supporting the heating filament 2 and the substrate or substrate 3 facing it. The filament 2 is connected to a power source 5 outside the reaction vessel 1. As can be seen from FIG. 1, in the heat synthesis of the first embodiment, the Si-based organic / inorganic hybrid film can be formed by a very simple and low-cost film forming apparatus.

  As a first specific example of heating and synthesizing a Si-based organic / inorganic hybrid film using the film forming apparatus of FIG. 1, a mixture of dimethylsilane gas and styrene gas is placed in a reaction vessel 1 in which a substrate 3 of a silicon single crystal wafer is placed. Gas was introduced, and the mixed gas pressure was set to 13300 Pa (100 Torr). When the W filament 2 was heated to 1800 ° C., a rapid synthesis reaction occurred in a short time of about 5 minutes, and a Si-based organic / inorganic hybrid film was formed on the silicon substrate 3. The crystallinity of the obtained Si-based organic / inorganic hybrid film was examined by X-ray diffraction, but no X-ray diffraction showing the crystallinity of the film was observed. That is, it is considered that an amorphous Si-based organic / inorganic hybrid film is formed in the present invention.

The graph of FIG. 4 shows the infrared transmittance in FTIR (Fourier transform infrared spectroscopy) of the obtained Si-based organic / inorganic hybrid film. That is, the horizontal axis of this graph represents the wave number (cm ⁻¹ ) of transmitted light, and the vertical axis represents the transmittance (%) (note that the horizontal axis represents a scale of 1 in a wave number region of 2000 cm ⁻¹ or more. / 2). And the trough part in the curve in a graph is a wave number part with a large infrared absorption, and has produced the absorption corresponding to a specific chemical bond. As can be seen from the representative chemical bonding examples illustrated in this graph, the obtained Si-based organic / inorganic hybrid film has Si—C bonds, Si—H _n (n = 1, 2, 3) bonds, C—H _n (n = 1, 2, 3) bond and the like are included. Therefore, as a chemical structure of this hybrid film, in view of the composition of the raw material gas, C and Si are contained in the skeleton structure in an amorphous state, and these floating bonds (dangling bonds) are terminated by H (terminate). ).

  The graph of FIG. 5 shows the PL (photoluminescence) characteristics of the Si-based organic / inorganic hybrid film obtained by the heat synthesis of the first specific example. That is, the horizontal axis of this graph represents the wavelength (nm) of PL light, and the vertical axis represents the PL intensity (arbitrary unit). The PL characteristics were measured by irradiation with ultraviolet light having a wavelength of 325 nm from a He—Cd laser device. As can be seen from this graph, the obtained Si-based organic / inorganic hybrid film has a characteristic of emitting almost white PL light although it is slightly greenish. Emission of white PL light in this manner is considered to suggest that the hybrid film contains chemical bonds of various energy levels corresponding to the chemical structure.

  Further, the Si-based organic / inorganic hybrid film according to the first specific example was left in the atmosphere for several months, but its PL emission characteristics hardly changed. This is because the Si-based organic / inorganic hybrid film according to the first embodiment is chemically very stable as compared with the conventional organic / inorganic hybrid material maintained by hydrogen bonding as shown in FIG. It is thought that it is a perfect film.

  As a second specific example of heat synthesis in the first embodiment, a mixed gas of dimethylsilane gas and styrene gas is introduced into a reaction vessel 1 in which a substrate 3 made of a PET (polyethylene terephthalate) film is arranged, and the mixed gas pressure is increased. Was set to 26600 Pa (200 Torr). When the W filament 2 was heated to 2000 ° C., a rapid synthesis reaction occurred in a short time of about 5 minutes, and a Si-based organic / inorganic hybrid film was formed on the PET film substrate 3. When the PL characteristics of the Si-based organic / inorganic hybrid film according to the second specific example were measured, characteristics similar to those in the graph of FIG. 5 were obtained.

  What should be noted in this second specific example is that the PET film substrate 3 was not thermally deformed during a short synthesis reaction even though the W filament was heated to a high temperature of 2000 ° C. It is. In this case, the substrate support 4 is made of stainless steel, and no cooling means is taken. A PET film has a low glass transition temperature of about 75 ° C. (in a film having an amorphous degree of about 95%), and an Si-based organic / inorganic hybrid film on an organic film having such a low glass transition temperature. It is thought that the method which can form is very useful industrially. Of course, in the method for forming a Si-based organic / inorganic hybrid film by heat synthesis according to the first embodiment, it can be formed on an organic film having a low glass transition temperature, so that quartz glass, Pyrex (registered trademark), soda glass, etc. Needless to say, the film can be formed on the glass substrate.

(Embodiment 2)
The present inventor not only applies a high-temperature filament to a mixed vapor containing an organic compound vapor containing an ethylene bond and an organic Si compound vapor, but also applies a plasma to the mixed vapor. It has been found that a Si-based organic / inorganic hybrid film can be synthesized. Such a synthesis reaction caused by the action of plasma is hereinafter also abbreviated as “plasma synthesis” in the present specification.

  The chemical mechanism of such plasma synthesis is that radicals are generated by the plasma excitation from the vapors of the organic compound containing an organic bond and the vapor of the organic Si compound by the action of the high-temperature filament instead of the radicals. Only in this respect, the subsequent reaction mechanism can be considered as in the case of the heat synthesis.

  FIG. 2 is a schematic block diagram illustrating a film forming apparatus that can be used in the method for forming a Si-based organic / inorganic hybrid film by plasma synthesis according to the second embodiment. This film forming apparatus includes a reaction vessel 1 having a gas inlet 1a and an exhaust 1b. In the reaction vessel 1, a pair of mesh electrodes 6 a and 6 b for generating plasma and a base 4 for supporting a substrate or substrate 3 facing the mesh electrodes 6 a and 6 b are provided. The plasma generating electrodes 6 a and 6 b are connected to a power source 7 outside the reaction vessel 1. As can be seen from FIG. 2, even in the plasma synthesis of the second embodiment, the Si-based organic / inorganic hybrid film can be formed by a very simple and low-cost film forming apparatus.

  As a method for generating plasma, plasma can be generated by glow discharge generated by applying a DC (direct current) voltage to the pair of mesh electrodes 6a and 6b. In the case of this DC excitation plasma, the power source 7 may include a simple DC power source. On the other hand, as a plasma generation method, RF excitation plasma can also be generated by applying an RF (high frequency) voltage to the pair of mesh electrodes 6a and 6b. In the case of this RF plasma, the power source 7 may include a high frequency power source.

(Reference form 1)
Next, Reference Embodiment 1 closely related to the present invention will be described below. In the first embodiment, when using plasma synthesis as in the second embodiment, the inventor synthesizes a Si-based organic / inorganic hybrid film without necessarily using an ethylene-bonded organic compound vapor. I also found that I can do it. The reason can be considered that far higher density radicals can be generated by plasma excitation than in the case where radicals are generated by interaction with a high temperature filament.

As a first specific example of plasma synthesis of a Si-based organic / inorganic hybrid film in the first embodiment using the film forming apparatus of FIG. 2, a flow rate of 10 sccm is provided in a reaction vessel 1 in which a glass substrate 3 is disposed. Dimethylsilane gas and nitrogen gas at a flow rate of 10 sccm were introduced, and the pressure of the mixed gas was set to 13.3 Pa (0.1 Torr). Then, when a DC glow discharge plasma is generated by applying a DC voltage of 400 V to the pair of mesh electrodes 6a and 6b, the Si—C—N film is about 100 nm on the glass substrate 3 in a short time of about 3 minutes. Formed in thickness.

  When forming a Si-based organic / inorganic hybrid film by plasma synthesis, in addition to the organic Si compound vapor, an additional gas selected from hydrogen, nitrogen, methane, helium, neon, argon, xenon, etc. These gases are also referred to as “additional gases”) are preferably introduced into the reaction vessel 1.

  In general, many organic Si compounds are liquid or solid at room temperature. Therefore, in order to efficiently introduce the vapor of the organic Si compound into the reaction vessel 1, the additional gas can be made to act as a carrier gas. Further, in order to introduce only the vapor of the organic Si compound into the reaction vessel 1 to generate a high-density plasma, a high-power plasma generation power source is required. However, by introducing an additional gas into the reaction vessel 1 as well, stable high-density plasma can be easily generated, and decomposition of the organic Si compound by plasma can be promoted. Further, when it is desired that the Si-based organic / inorganic hybrid film also contains N atoms, additional nitrogen gas can be used as an N atom supply source, and additional methane is a C atom supply source. It can also be used as In addition, when it is desired that atoms from the additional gas are not incorporated into the Si-based organic / inorganic hybrid film, an inert gas such as helium, neon, or argon can be preferably used.

Similarly, as a second specific example of plasma synthesis of the Si-based organic / inorganic hybrid film in the first embodiment using the film forming apparatus of FIG. 2, trisdimethyl is placed in a reaction vessel 1 in which a glass substrate 3 is disposed. Aminosilane (Si (N (CH ₃ ) ₂ ) ₃ H) gas was introduced together with nitrogen gas, and the pressure of the mixed gas was set to 400 Pa (3 Torr). Then, when a DC glow discharge plasma was generated by applying a DC voltage of 540 V to the pair of mesh electrodes 6a and 6b, the Si—C—N film on the glass substrate 3 was about 200 nm thick in about 10 minutes. Been formed. Although trisdimethylaminosilane contains N atoms for the Si—C—N film, it is preferably introduced into the reaction vessel 1 together with nitrogen gas for stable generation of plasma. The nitrogen gas can also act as a carrier gas.

Further, as a third specific example of plasma synthesis of the Si-based organic / inorganic hybrid film in the first embodiment using the film forming apparatus of FIG. 2, the inside of the reaction vessel 1 in which the substrate 3 of the silicon single crystal wafer is disposed. Then, tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ) gas was introduced together with nitrogen gas, and the pressure of the mixed gas was set to 1.33 Pa (0.01 Torr). Then, when a plasma was generated by applying a high frequency power of 300 W at a frequency of 13.56 MHz to the pair of mesh electrodes 6a and 6b, an Si—O—C—N-based film was formed on the silicon single crystal substrate 3 in about 30 minutes. A thickness of about 100 nm was formed.

In the fourth specific example of plasma synthesis of the Si-based organic / inorganic hybrid film in the first embodiment, pretreatment of the surface of the substrate 3 is introduced. First, in the film forming apparatus of FIG. 2, nitrogen gas was introduced into the reaction vessel 1 in which the PET film substrate 3 was placed, and the gas pressure was set to 13.3 Pa (0.1 Torr). Then, a high frequency power of 300 W at a frequency of 13.56 MHz was applied to the pair of mesh electrodes 6a and 6b to generate plasma, and the PET substrate surface was cleaned by exposing it to the plasma for 10 minutes.

  Immediately thereafter, tetraethoxysilane gas was introduced into the reaction vessel 1 together with nitrogen gas, and the pressure of the mixed gas was set to 1.33 Pa (0.01 Torr). Then, when a plasma was generated by applying a high frequency power of 300 W at a frequency of 13.56 MHz to the pair of mesh electrodes 6a and 6b, the Si—O—C—N film was formed on the PET film substrate 3 in about 120 minutes. A thickness of 500 nm was formed.

The graph of FIG. 6 similar to FIG. 4 shows the infrared transmittance in FTIR of the Si-based organic / inorganic hybrid film obtained in the fourth specific example of the first embodiment . As can be seen from the representative chemical bonding examples illustrated in this graph, the obtained Si-based organic / inorganic hybrid film has Si—C bond, Si—O bond, C—H _n (n = 1, 2). , 3) Includes bonds. Therefore, as a chemical structure of this hybrid film, in view of the composition of the raw material gas, C, Si, O, and N are included in the skeleton structure in an amorphous state, and their floating bonds (dangling bonds) are It is thought that it is terminated by H.

In the fourth specific example of the first embodiment , nitrogen is used as a gas for surface purification by plasma (hereinafter referred to as “plasma purification gas”), but the plasma purification gas is not limited to nitrogen. A gas selected from oxygen, hydrogen, methane, helium, neon, argon and the like can be used. In general, the surface of the substrate 3 often adsorbs contaminants, moisture, oxygen, etc. in the atmosphere. In such a case, the generation start of the Si-based organic / inorganic hybrid film on the substrate 3 is delayed, or the bonding property between the substrate and the film is lowered. Therefore, before forming the Si-based organic / inorganic hybrid film on the substrate 3, it is preferable to purify and activate the surface of the substrate 3 using a plasma purification gas.

  For example, when the glass substrate 3 is used, since the surface thereof is covered with Si—O bonds, it is preferable to purify with a plasma of oxygen or hydrogen. In this case, it may be possible to activate the glass surface by cutting a part of the Si—O bond with plasma. In the case of the substrate 3 made of a polymer film, the surface thereof is covered with C—H bonds, and it is considered that oxygen and water molecules in the atmosphere are adsorbed, so that it can be purified with hydrogen or methane plasma. preferable. In this case, a part of the C—H bond may be cut with plasma to activate the organic film surface. Further, when N atoms are planned to be incorporated into the Si-based organic / inorganic hybrid film, nitrogen gas can be preferably used as the plasma purification gas. This is because in that case, it is convenient that nitrogen gas as a plasma purification gas can be continuously introduced into the reaction vessel 1 as an additional gas during film formation by plasma synthesis.

(Embodiment 3 )
FIG. 3 is a schematic block diagram illustrating a film forming apparatus that can be used in the method for forming a Si-based organic / inorganic hybrid film by heat synthesis according to the third embodiment. The film forming apparatus of FIG. 3 is similar to the apparatus of FIGS. 1 and 2, but the apparatus of FIG. 3 is provided with both a heating filament 2 and a pair of mesh electrodes 6a and 6b for generating plasma in a reaction vessel 1. It is different in what is being done.

  If the film forming apparatus as shown in FIG. 3 is used, even in the case of forming a Si-based organic / inorganic hybrid film by heat synthesis using a heating filament as in the first embodiment, the substrate is formed before the film formation. 3 surface can be purified with plasma.

  As exemplified in the various embodiments as described above, according to the present invention, an amorphous Si-based organic / inorganic hybrid film that contains at least C and Si and can also contain O and / or N can be easily used. And it can be formed at low cost. Such Si-based organic / inorganic hybrid films are considered to contain at least C and Si in the chemical skeleton structure and may also contain O and / or N from the results of FTIR and PL measurements.

  FIG. 7 shows, as an example, a schematic three-dimensional network of an atomic arrangement in a Si-based organic / inorganic hybrid film containing C, Si, and O in the skeleton structure. In this figure, the circles with left-sloped hatching represent Si atoms, the circles with right-sloped hatching represent O atoms, and the circles with cross-hatching represent C atoms. And white circles represent H atoms. That is, in the Si-based organic / inorganic hybrid film, the atoms of C, Si, and O form a network having a skeleton structure by covalent bonds, and the dangling bonds of these atoms are terminated by H atoms. It is done. Such a chemical structure is completely different from the structure of a conventional organic / inorganic hybrid material in which organic molecules and inorganic molecules are dispersed through hydrogen bonds as shown in FIG. It will be understood.

  As described above, according to the present invention, a Si-based organic / inorganic hybrid film having a chemical structure different from that of a conventional organic / inorganic hybrid material can be provided simply and at low cost by a vapor phase growth method. Such Si-based organic / inorganic hybrid films can be used for various applications as functional films.

It is a typical block diagram which shows an example of the film-forming apparatus which can be utilized for the formation method of Si type organic / inorganic hybrid film | membrane by this invention. It is a typical block diagram which shows the other example of the film-forming apparatus which can be utilized for the formation method of the Si type organic and inorganic hybrid film by this invention. It is a typical block diagram which shows the further another example of the film-forming apparatus which can be utilized for the formation method of Si type organic / inorganic hybrid film | membrane by this invention. It is a graph which shows the infrared transmittance in FTIR of an example of the Si type organic and inorganic hybrid film | membrane obtained by this invention. It is a graph which shows the PL characteristic of an example of the Si type organic and inorganic hybrid film | membrane obtained by this invention. It is a graph which shows the infrared transmittance | permeability in FTIR of the other example of the Si type organic / inorganic hybrid film | membrane obtained by this invention. It is a model figure which shows an example of the chemical structure of Si type | system | group organic / inorganic hybrid film | membrane obtained by this invention. It is a schematic diagram which shows an example of the dispersion | distribution state of the organic molecule in the conventional Si type organic and inorganic hybrid material. It is a figure which shows an example of chemical formula containing the hydrogen bond between an organic molecule and silica in the conventional Si type organic and inorganic hybrid material.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 Reaction container, 1a Gas introduction port, 1b Exhaust port, 2 Heating filament, 3 Base | substrate or board | substrate, 4 Support stand, Power supply for heating filament, 6a, 6b A pair of mesh electrode, 7 Power supply for plasma generation.

Claims (8)

A heating filament and a substrate disposed opposite the filament are provided in the reaction vessel,
Introducing a vapor of at least one compound selected from alkylsilane, alkoxysilane, and aminosilane together with a vapor of an organic compound containing an ethylene bond into the reaction vessel toward the heating filament;
Thereby, a Si-based organic / inorganic hybrid film comprising at least carbon and silicon is formed on the substrate. A substrate is provided in the reaction vessel,
Introducing a vapor of at least one compound selected from alkylsilane, alkoxysilane, and aminosilane into the reaction vessel together with a vapor of hydrocarbon as an organic compound containing an ethylene bond;
The vapor introduced into the reaction vessel is plasma-excited to cause a chemical reaction,
Thereby, a Si-based organic / inorganic hybrid film comprising at least carbon and silicon is formed on the substrate.   The Si-based organic / inorganic hybrid according to claim 2, wherein at least one gas selected from nitrogen, hydrogen, helium, neon, argon, and xenon is also introduced into the reaction vessel together with the vapor. Method for forming a film.   The method for forming a Si-based organic / inorganic hybrid film according to claim 1 or 2, wherein the ethylene bond-containing organic compound also contains a benzene nucleus.   5. The method for forming a Si-based organic / inorganic hybrid film according to claim 4, wherein the ethylene bond-containing organic compound includes a portion in which at least one of a vinyl group and a vinylene group is adjacently bonded to a benzene nucleus.   6. The method for forming a Si-based organic / inorganic hybrid film according to claim 5, wherein the ethylene bond-containing organic compound is styrene. Before starting the formation of the Si-based organic / inorganic hybrid film,
Introducing one or more gases selected from oxygen, nitrogen, hydrogen, helium, neon, argon, xenon, and methane into the reaction vessel;
Generating a plasma of the gas in the reaction vessel,
The method for forming a Si-based organic / inorganic hybrid film according to any one of claims 1 to 6, wherein the surface of the substrate is purified by the plasma.   8. The method for forming a Si-based organic / inorganic hybrid film according to claim 1, wherein the substrate is made of glass or a polymer film.

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