JP5036256B2 - Organic inorganic composite material - Google Patents

Description

  The present invention relates to an organic-inorganic composite material.

In recent years, various electronic devices using organic semiconductors have been proposed (see, for example, Patent Documents 1 and 2). In many of these electronic devices, an organic material layer is provided on the surface of an inorganic material. In order to exhibit the property of forming a uniform layer over a large area, which is an advantage of using an organic material, the uniformity and stability of the interface between the inorganic material and the organic material are important. Conventionally, when applying an organic material to inorganic material surface such as SiO _2, the uniformity of the organic material layer has fallen into compromised by the presence of hydroxyl groups in the washing step. In addition, due to the hydroxyl group formed on the inorganic substrate, a water adsorption layer is formed between the organic material layer and the inorganic material layer, and a decrease in adhesion at the interface between the organic material layer and the inorganic material layer has been a problem. .
JP-A-5-55568 JP 2005-101493 A

  This invention is made | formed in view of said point, and it aims at providing the organic inorganic composite material which improved the water resistance of the interface of an organic material layer and an inorganic material layer.

  In order to achieve the above object, the present invention is characterized by the following measures.

The organic-inorganic composite material of the present invention is an organic-inorganic composite material including an inorganic material layer and an organic material film provided on the inorganic material layer, wherein the inorganic material has a hydroxyl group, and the material of the organic material film is silicon The organic material film is a film in which the benzene terminal-derived benzene ring is exposed on the surface of the organic material film, and the surface of the benzene terminal-derived benzene ring in the organic material film interval Ri der than 3.0Å or less 2.8 Å, further comprising an organic material layer on the organic material film, an organic-inorganic composite material.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the organic inorganic composite material which improved the water resistance of the interface of an organic material and an inorganic material.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  In the organic-inorganic composite material of the present invention, an organic material film in which a benzene ring having a surface interval of 2.8 to 3.0 mm is exposed on an inorganic substrate made of an inorganic material.

  FIG. 1 is a cross-sectional view of the organic-inorganic composite material of the present invention.

  Referring to FIG. 1, the organic-inorganic composite material 10 includes an inorganic substrate 11 and an organic material film 12.

  Specifically, the inorganic substrate 11 includes silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum oxide, tin oxide, vanadium oxide, barium strontium titanate, zirconium barium titanate, lead zirconate titanate. Inorganic insulating films such as lead lanthanum titanate, strontium titanate, barium titanate, magnesium barium fluoride, bismuth tantalate niobate, and yttrium oxide can be used.

As a production method, for example, a CVD method, a plasma CVD method, a plasma polymerization method, a vapor deposition dry process, a spray coating method, a spin coating method, a dip coating method, an ink jet method, a casting method, a blade coating method, and a bar coating method. The wet process by application | coating etc. is mentioned. Furthermore, coating type SiO ₂ can also be used.

  The organic material film 12 is provided on the inorganic substrate 11 and has a structure in which a benzene ring 13 having a surface interval of 2.8 to 3.0 mm is exposed on the film surface.

  The material of the organic material film 12 is, for example, trichlorosilane, dichlorosilane, monochlorosilane, trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxysilane, monoethoxysilane, monobutoxysilane, dibutoxysilane, And a film containing a halogen atom and a silicon terminal containing a substituted or unsubstituted alkoxy and a compound containing a benzene ring at the other terminal, such as monobutoxysilane, is formed by chemical adsorption. Specific examples of these compounds include phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenoxytrichlorosilane, phenoxytrimethoxysilane, phenoxytriethoxysilane, phenethyltrichlorosilane, phenethyltrimethoxysilane, and phenethyltrimethyl. Examples include ethoxysilane, 4-phenylbutyltrichlorosilane, and 4-phenylbutyltriethoxysilane.

  The above-mentioned compound is formed on the inorganic substrate 11 by a chemical adsorption method. The above compound is dissolved in a solvent such as dichloromethane, tetrahydrofuran, chloroform, toluene, dichlorobenzene, and xylene. The inorganic substrate 11 is dipped in the solution of the above compound and then dried to form a film on the inorganic substrate 11 with the above compound. In order to form the organic material film 12 composed of the benzene rings 13 having a surface interval of 2.8 to 3.0 mm, it is desirable to irradiate ultrasonic waves when the inorganic substrate 11 is immersed in a solution.

  Moreover, it is preferable to dissolve the above-mentioned silane compound in the above-mentioned solvent so as to have a concentration in the range of 0.1 mM to 1000 mM. If it is 0.1 mM or less, the immersion time becomes too long, and if it is 100 mM or more, the film surface consisting of the benzene rings 13 having a surface interval of 2.8 to 3.0 mm is uniform due to self-condensation of silane compounds. Not formed. More preferably, the concentration of the silane compound is in the range of 1 mM to 10 mM.

  The structure of the organic material film 12 can be confirmed by quantitative determination of carbon content by X-ray photoelectron spectroscopy, confirmation of functional groups by infrared absorption spectroscopy, and periodic structure of a monomolecular film by X-ray diffraction. For example, X-ray diffraction can be measured using a grazing incidence X-ray diffraction (GIXD) method in SPring-8 BL13XU. The measurement conditions for GIXD are an X-ray incident angle of 0.1 °, an extraction angle of 0.1 °, and an incident light energy of 12 KeV.

Example 1
FIG. 2 is a characteristic diagram showing the measurement results of the small-angle incident X-ray diffraction of Example 1 of the present invention.

The inorganic substrate is manufactured by thermally oxidizing the 30 mm square B-doped silicon substrate surface to form a 200 nm thick SiO ₂ insulating film. The inorganic substrate is immersed in a toluene solution containing 5 mM phenyltrichlorosilane for 30 minutes, and at the same time, ultrasonic irradiation is performed. Then, the organic-inorganic composite material in which the organic material film | membrane was provided on the inorganic substrate was produced by drying an inorganic substrate.

  Referring to FIG. 2, in-plane periodic structure analysis of a thin film is possible by GIXD measurement. In FIG. 1, the vertical axis represents the X-ray diffraction intensity, and the horizontal axis represents the diffraction parameter q (where q = 4π sin θ / λ, 2θ: diffraction angle, λ: wavelength). In normal GIXD analysis, the horizontal axis is indicated by the diffraction angle 2θ. However, in this measurement, considering the balance between sample degradation and measurement accuracy, the measurement wavelength of 12 KeV is used instead of the CuKα line used in normal GIXD measurement, so even with the same spacing. Since signals are observed at different 2θ positions, a diffraction parameter q that does not depend on the measurement wavelength is used on the horizontal axis.

As a result of structural analysis of the substrate treated as described above by GIXD, an X-ray intensity peak was shown at 22.31 nm ⁻¹ . From this result, it was confirmed that it has a periodic structure of a benzene ring with a plane spacing of 2.9 mm. Moreover, since the half width of the above-mentioned peak is ± 0.1 mm or less, it was also confirmed that a highly uniform thin film was formed on this inorganic substrate.

  3 is a cross-sectional view of the organic-inorganic composite material of Example 1. FIG.

  Referring to FIG. 3, the organic-inorganic composite material 20 includes an inorganic substrate 21, an organic material film 22, and an organic material layer 24. Since the inorganic substrate 21 and the organic material film 22 have the same configuration as that of the inorganic substrate 11 and the organic material film 12 described in FIG. 1, detailed description thereof is omitted here.

  The organic material layer 24 uses a polymer having an average molecular weight of 75,000, which is represented by [1] and represented by the following compound 1, and is about 1.0% by weight of tetrahydrofuran / paraxylene = 8/2 (volume / volume). A solution made of a mixed solvent is spin-coated on the surface of the benzene ring 13 exposed on the organic material film 12 and dried to produce a film thickness of 30 nm.

  <Compound 1>

上述の通り作製した有機材料層２４を有する無機基板２１を、純水中に３０分浸漬させた。その結果、無機基板２１上からの有機材料層２４の剥離は確認されなかった。

The inorganic substrate 21 having the organic material layer 24 produced as described above was immersed in pure water for 30 minutes. As a result, peeling of the organic material layer 24 from the inorganic substrate 21 was not confirmed.

(Comparative Example 1)
The inorganic substrate is manufactured by thermally oxidizing the 30 mm square B-doped silicon substrate surface to form a 200 nm thick SiO ₂ insulating film. The silicon substrate is immersed in a toluene solution containing 0.05 mM phenyltrichlorosilane for 5 minutes. Then, the organic material layer was produced by drying a silicon substrate.

  The substrate subjected to the above-described treatment was subjected to structural analysis by GIXD in the same manner as in Example 1. As a result, a benzene ring structure having a surface separation of 2.9 mm was not confirmed.

  The inorganic substrate having the organic material layer described above was immersed in pure water for 30 minutes. As a result, peeling of the organic material layer from the inorganic substrate was confirmed.

  According to Example 1, the organic material layer and the inorganic material layer are provided by providing, at the interface between the inorganic material layer and the organic material layer, an organic material film in which a benzene ring having a face interval of 2.8 to 3.0 mm is exposed. It becomes possible to improve the water resistance of the interface.

It is sectional drawing of the organic inorganic composite material of this invention. It is a characteristic view which shows the small angle incident X-ray-diffraction measurement result of Example 1 of this invention. 1 is a cross-sectional view of an organic-inorganic composite material of Example 1. FIG.

Explanation of symbols

10, 20 Organic-inorganic composite material 11, 21 Inorganic substrate 12, 22 Organic material film 13, 23 Benzene ring 14, 24 Organic material layer

Claims (2)

In an organic-inorganic composite material including an inorganic material and an organic material film provided on the inorganic material,
The inorganic material has a hydroxyl group;
The material of the organic material film includes a silicon end and a benzene end,
The organic material film is a film in which a benzene ring derived from the benzene terminal is exposed on the surface of the organic material film,
In the organic material film, the surface separation of the benzene-terminus derived from benzene ring Ri der than 3.0Å or less 2.8 Å,
Further comprising an organic material layer on the organic material film,
Organic inorganic composite material. 2. The organic-inorganic composite material according to claim 1, wherein the inorganic material includes an oxide of silicon, and the organic material film includes a compound having a silicon atom and a benzene ring.

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