KR100558965B1 - Controlling method of Thermo-optic coefficient of Inorganic-Organic Hybrid Materials for Thermo-Optic Waveguide Devices - Google Patents

Abstract

The present invention provides a thermo-optic optical waveguide device made of an inorganic-organic hybrid material. The inorganic-organic hybrid material according to the present invention is an inorganic-organic hybrid having a network structure, which is prepared by the sol-gel method and has a network structure including an organic atom capable of crosslinking or modification with an oxygen atom bonded to silicon or a crosslinkable organic monomer in the structure. It is characterized by including a material. According to the present invention, it is easy to control the size according to the mixing ratio, size and structure of the inorganic and organic compounds in the hybrid material. From this, a thermo-optic optical waveguide device suitable for the application can be manufactured.

Description

Controlling method of Thermo-optic coefficient of Inorganic-Organic Hybrid Materials for Thermo-Optic Waveguide Devices}

The present invention relates to a method for controlling the thermo-optic coefficient of an inorganic-organic hybrid material for manufacturing a thermo-optic waveguide device.

The thermo-optic effect is a phenomenon in which the refractive index changes according to the temperature change of the material (dn / dT), and it is used to heat the optical switch, the optical modulator, the variable optical attenuator, the optical variable filter, the optical drop multiplexer, and the optical cross connector. An optical optical waveguide device is fabricated. In recent years, a temperature-independent Awave Waveguide device is fabricated using the thermo-optic effect of an optical waveguide material to prevent the change of the characteristics of an optical device according to the ambient temperature with the development of a wavelength division transmission system in optical communication.

As a conventional technique related to the present invention, according to Japanese Patent Application Laid-Open No. Hei 6-34924, an optical phase in which a quartz glass optical waveguide having a core portion and a cladding portion surrounding the core portion is provided on a silicon substrate and a thin film heater is disposed in the vicinity thereof. Disclosed is a Mach-Zehnder type thermo-optic switch capable of fabricating a modulator to switch optical paths.

According to Japanese Patent No. 2000-241781, a polymer optical waveguide having a core portion and a clad portion surrounding the core portion on a substrate and a thin film heater are installed on the upper portion of the optical waveguide, and the thin film heater is heated to improve the refractive index of a portion near the core portion. A polymer thermo-optical device is disclosed that has a light path switching function and a variable wavelength selection function of light that has changed and guided the core.

In addition, Professor Y.Kokubun of Japan produced a temperature-independent Awave Waveguide that uses the thermo-optic effect of materials to prevent the characteristics of the optical device from changing according to the ambient temperature. This is based on the fact that the optical path does not change with temperature in the case of an optical waveguide having a quartz glass core and a polymer material clad ( Electron. Lett. , Vol. 34, No. 4, p. 367 (1998). )). However, in the case of quartz glass and polymers, the range of thermo-optic coefficients is limited, which makes it difficult to manufacture a complete temperature independent optical waveguide and has a disadvantage of complicated design.

As described above, the conventional thermo-optic optical waveguide device uses quartz glass or polymer and has the following characteristics.

1. Quartz-based glass: It is manufactured by vapor deposition such as Flame Hydrolysis Deposition (FHD) and Chemical Vapor Deposition (CVD), and has low light loss (<0.01dB / cm), connection loss and It has excellent thermal and chemical stability. However, the quartz glass optical waveguide requires a high temperature manufacturing process of 1000 ° C. or more and expensive manufacturing equipment, and has a problem of causing birefringence due to polarization due to thermal stress of the high temperature process. In addition, since the heat transfer rate is low and the thermal optical coefficient has a low value of about 10 ^-5 / ℃, the operating power required for driving the device is very large and the reaction time is slow.

2. Polymers: Polymers can be easily controlled and synthesized by molecular chemistry and the manufacturing process is simple and low temperature, so it is economical and can be applied to various processes. In addition, it has a large thermo-optic coefficient of about -10 ^-4 / ℃, so that the device can be driven with low power and the manufacturing method is simple. However, in practice, optical waveguide loss due to vibration in the molecular structure, polarization-dependent birefringence, and thermal There is limited application because of instability.

The technical problem to be achieved by the present invention is to improve the shortcomings of the quartz glass and polymer used to fabricate the conventional thermo-optic optical waveguide device, the thermo-optic coefficient is easy to control, wide size, excellent brightness The present invention provides a method for controlling the thermo-optic coefficient of an inorganic-organic hybrid material having a thermooptic optical waveguide device which exhibits breakage chamber and thermal stability.

The present invention for achieving the above object includes an inorganic-organic hybrid material having a negative thermo-optic coefficient and having a network structure crosslinked with silicon atoms in the structure or an organic monomer capable of crosslinking or modification, Thermo-optic coefficient control of the thermo-optic waveguide device fabricating inorganic-organic hybrid material, characterized in that the thermo-optic coefficient is controlled by adjusting the inorganic-organic composition in the mesh structure or the mesh structure constituting the inorganic-organic hybrid material. It includes a method.

The inorganic-organic hybrid material of the present invention can be prepared using silicon compounds represented by the following general formulas 1 to 3 as starting materials.

<Formula 1>

(OR ¹ ) _n Si-R ² _m (n + m = 4)

<Formula 2>

(OR ¹ ) _n Si- (XR ³ ) _m (n + m = 4)

<Formula 3>

R ⁴ SiCl ₃

In general formulas 1 to 3, R ¹ is a straight-chain or branched chain alkyl group such as methyl, ethyl, propyl, or butyl having 1 to 10 carbon atoms or a hydrogen atom in which these groups are hydrolyzed, and R ² is a straight chain having 1 to 4 carbon atoms. Or a branched alkyl group, a phenyl group, a phenyl alkoxy group, or an amine group. In addition, n is a natural number of 1-4, m represents the integer of 0-3.

X is a carbon chain having 3 to 6 carbon atoms and R ³ represents a substance containing a vinyl group, a glycidoxy group, a methacryl group or a fluoride atom substituted in a carbon chain having 4 to 8 carbon atoms.

R ⁴ is a fluoride valence in a carbon chain having 1 to 10 carbon atoms, or a straight or branched alkyl group or a hydrogen atom, a phenyl group, a phenyl alkoxy group, an amine group, a vinyl group, a glycidoxy group or a methacryl group or a carbon chain having 4 to 8 carbon atoms. Substituted material.

Examples of specific compounds belonging to the general formulas (1) to (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltripropoxysilane, Vinyltriacetoxysilane, vinyldimethoxyethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltripropoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3 -Aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyldimethoxysilane, 3-acryloxypropyldiethoxysilane, 3-acryloxypropyldipropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, N -(2-aminoethyl-3-aminoprop Phil) -trimethoxysilane (DIAMO), N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, N- (2-aminoethyl-3-aminopropyl) -tripropoxysilane, N -(2-aminoethyl-3-aminopropyl) -tributoxysisilane, trimethoxysilylpropyldiethylenetriamine (TRIAMO), triethoxysilylpropyldiethylenetriamine, tripropoxysilylpropyldiethylenetri Amine, tributoxysilylpropyldiethylenetriamine, 2-glycidoxyethylmethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxypropyl Trimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 3-glycidoxyethylmethyldimethoxysilane, 3 Glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldi Methoxysilane, 2-glycidoxypropylethyldiethoxysilane, 2-glycidoxypropylethyldimethoxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Ethoxycyclohexyl) ethyltriethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltripropoxysilane, 2-chloropropyltributoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, 3,3,3, -trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, methyltrichlorosilane, ethyltrichlorosilane , Phenyltrichlorosilane, vinyltrichlorosilane, hexyltrichlorosilane or decyltrichlorosilane.

The first method of preparing the inorganic-organic hybrid material according to the present invention is to prepare a mixed solution of water and alcohol of the material represented by the above general formulas (1) to (3), and preferably by adding an acid or a base catalyst to hydrolysis and Condensation reaction. The silanes represented by Formulas 1 and 2 are prepared through a gelation process in which an oxide having a high molecular weight is transferred from a sol state to a gel state through a continuous reaction of hydrolysis and condensation reactions represented by Formula 1 below.

As the organic monomer capable of intermolecular crosslinking in the material of Formula 2, when a vinyl group, glycidoxy group, and methacryl group are included, an organic polymerization reaction represented by Chemical Formula 3 is included. It is preferable when the organic group substituted in the silicone is a vinyl group and a methacryl group (preferably methacryloxy group) and the like. The organic polymerization reaction is carried out by adding a thermal and photo organic polymerization initiator in the form of free radicals and positive and negative ions. Let's do it. When glycidoxy group is included, organic polymerization may be preferably performed through a ring opening reaction using aluminum alkoxide, titanium alkoxide, zirconium alkoxide, amine group or the like.

<Formula 1>

[Hydrolysis]

M (OR) _x + xH ₂ O ↔M (OH) _x + xROH

[Condensation]

≡M (OH) + (HO) M≡ ↔ ≡MOM≡ + H ₂ O

               [Water condensation]

≡M (OR) + (HO) M≡ ↔ ≡M-O-M≡ + ROH

              [Alcohol condensation]

According to a second method of preparing an inorganic-organic hybrid material according to the present invention, reactants such as silicon chloride, methyltrichlorosilane, ethyltrichlorosilane, and phenyltrichlorosilane represented by the general formula (3) are preferably used with silicon alkoxide or alkyl ether. Includes preparing a inorganic-organic hybrid material having a polymer oxide structure through a reaction represented by the following Chemical Formula 2 using a catalyst such as metal chloride, for example, zirconium chloride, titanium chloride, tin chloride, and the like.

<Formula 2>

RSiCl ₃ + 0.75 Si (OR`) <sub>4</sub> → [RSi <sub>1.75</sub> O <sub>3</sub> ] <sub>n</sub> + 3R`Cl

0.75SiCl ₄ + RSi (OR`) <sub>3</sub> → [RSi <sub>1.75</sub> O <sub>3</sub> ] <sub>n</sub> + 3R`Cl

RSiCl ₃ + RSi (OR`) <sub>3</sub> → [R <sub>2</sub> Si <sub>2</sub> O <sub>3</sub> ] <sub>n</sub> + 3R`Cl

2RSiCl ₃ + 3R` <sub>2</sub> O → [R <sub>2</sub> Si <sub>2</sub> O <sub>3</sub> ] <sub>n</sub> + 6R`Cl

RSiCl ₃ + Si (OR`) <sub>4</sub> → [RSi <sub>2</sub> O <sub>3</sub> -OR`] _n + 3R`Cl

SiCl ₄ + RSi (OR`) <sub>3</sub> → [RSi <sub>2</sub> O <sub>3</sub> -Cl] <sub>n</sub> + 3R`Cl

R ′ in Formula 2 is a straight or branched alkyl group having 1 to 10 carbon atoms, and R is a straight or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, a phenyl group, a phenyl alkoxy group, an amine group, a vinyl group, or a glycidoxy group. Or a substance containing a methacryl group or a fluoride atom substituted in a carbon chain having 4 to 8 carbon atoms.

A third method of preparing an inorganic-organic hybrid material according to the present invention is a process of reacting silicon oxide particles (for example, silica sol) dispersed in water or alcohol with materials represented by the general formulas (1) and (2). It includes. The silica sol includes silicon oxide particles having a size of 5 to 20 nm surface-treated to prevent reaction between the particles and water or an alcohol solvent having an acid or base pH to disperse them. Silica sol and the silanes represented by Formulas 1 and 2 may be prepared through hydrolysis and condensation reactions represented by Formula 1.

The inorganic-organic hybrid material according to the present invention can be produced by the above three methods and can change the structure and properties of the final material according to the type of organic material added. In the inorganic-organic hybrid material, the organic material plays a role of a network former and a network modifier in a network structure largely crosslinked with oxygen atoms. For example, organic materials that cannot bond with other organic monomers or inorganic network such as phenyl group or amine group serve as modifiers in the inorganic-organic hybrid material. If the added organic substance is an organic substance such as glycidoxy group, methacryl group, or vinyl group, it can act as a crosslinking agent to form a new bond through bonding with other organic monomers or other organic substances in the inorganic network structure. .

<Formula 3>

O ₃ ≡Si-R + R`-Si≡O <sub>3</sub> → O <sub>3</sub> ≡Si-RR`-Si≡O ₃

O ₃ ≡Si-R + R + R + R`-Si≡O <sub>3</sub> → O <sub>3</sub> ≡Si-RRRR`-Si≡O ₃

R, R` in Formula 3 is an organic monomer capable of crosslinking and has an unsaturated hydrocarbon such as a double bond or a triple bond or an unstable ring structure. Representative examples of such bonds or structures include vinyl groups, methacryl groups, glycidoxy groups, and the like.

In the inorganic-organic hybrid material according to the present invention, the thermo-optic coefficient exhibits a negative value and can be adjusted to a range that cannot be obtained with quartz glass and polymer, which are conventional optical waveguide materials. That is, the inorganic-organic hybrid material can adjust the thermo ^- optic coefficient in a wide range of about -0.2x10 ^-4 / ℃ to -3x10 ^-4 / ℃. Inorganic-organic hybrid materials are prepared in solution, so they can be easily varied in starting concentration, and the ratio of the inorganic network structure and organics can be adjusted from the starting concentration. For example, if tetramethoxysilane and phenyltrimethoxysilane are used as starting materials, the more tetramethoxysilane, the more the end product will have an inorganic network structure, and the more phenyltrimethoxysilane, the more organic matter. The refractive index and thermo-optic coefficient of the final product can be adjusted by controlling the ratio of the inorganic network structure and the organic material by the starting material. The adjustment of the thermo-optic coefficient increases in the negative direction as the ratio of organic matter in the inorganic-organic hybrid material increases.

The inorganic-organic hybrid material according to the present invention can adjust the thermo-optic coefficient through the selection of the starting material. When the organic material in the starting material acts as a modifier, the larger the molecular weight of the organic material is, the higher the thermo-optic coefficient is in the negative direction. For example, when the modified organic material is an ethyl group than when the methyl group, the thermo-optic coefficient shows a larger negative value.

In addition, when the inorganic-organic hybrid material according to the present invention contains an organism capable of organic polymerization, after addition of a suitable initiator, the polymerization or crosslinking reaction between organic groups is carried out by irradiation of strong light such as heat or ultraviolet ray. The thermo-optic coefficient can be adjusted. The polymerization or crosslinking of these organisms increases the organic mesh of the inorganic-organic hybrid material and the thermo-optic coefficient increases in the positive direction.

In the present invention, since the inorganic-organic hybrid material is prepared in the liquid phase, it is possible to easily and uniformly add inorganic or organic substances having special physical properties. Not only the thermo-optic coefficient is adjusted by the properties of the added inorganic or organic material, but additional properties can be given. For example, when aluminum alkoxide, germanium alkoxide and zirconium alkoxide are added, the thermo-optic coefficient may increase in the positive direction and also increase the refractive index, the intensity, the photosensitivity, and the like. In addition, when the silane or organic monomer substituted with a fluorine atom is added, the thermo-optic coefficient may be increased to a negative value, and the optical waveguide loss and refractive index may be reduced. When the silica, boehmite, alumina, and zirconia metal oxide particles are dispersed in a solvent such as water or alcohol in the inorganic-organic hybrid material, the thermo-optic coefficient of the inorganic-organic hybrid material increases in the positive direction, and the refractive index, strength It can also increase.

The inorganic-organic hybrid material according to the present invention has the advantage of being able to form a film by a relatively easy coating process such as spin coating method, dip coating method, bar coating method because it is prepared from the liquid state and easy to change the viscosity. The thickness of the coating film can be adjusted by changing the viscosity, and a uniform coating film can be obtained. The coating film is composed of a high refractive index core portion and a low refractive index upper and lower cladding portion surrounding the core portion, and at least one region of the core portion and the clad portion includes an inorganic-organic hybrid material according to the present invention and differs in thermooptic coefficient. An optical waveguide can be manufactured. By using such an optical waveguide, it is possible to manufacture a thermo-optic device that can control the characteristics of the light to be guided.

 Hereinafter, the content of the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention and should not be construed that the scope of the present invention is limited to these examples.

<Example 1>

12 hours in which 0.1N HCl was added to phenyltrimethoxysilane (PhTMS) in a 1: 3 molar ratio, and 0.1N HCl was added to tetramethoxy orthosilicate (TMOS) in a 1: 2 molar ratio. Stirring was carried out to carry out the sol-gel reaction. The molar ratio of phenyltrimethoxysilane and tetramethoxy orthosilicate at the time of mixing was adjusted as shown in Table 1 to adjust the composition of the coating film finally obtained. The mixed solution was extracted with methanol in the solution for 20 minutes while maintaining a temperature of 60 degrees Celsius in a vacuum evaporator.

The final solution was coated onto a silicon substrate using a spin coater and then heat treated at 180 degrees Celsius for 12 hours. The thickness of the coated film has a thickness of 3 ~ 4㎛, and the thermal stress (thermal stress) acts on the coating film during cooling, gradually cooling to the temperature of 150 ℃, 120 ℃, 80 ℃, 40 ℃ step by step the final coating film Was prepared.

Table 1 below shows the thermo-optic coefficient according to the molar ratio (PhTMS / TMOS) of phenyltrimethoxysilane and tetramethoxy orthosilicate. The thermo-optic coefficient was measured as a refractive index change with temperature after linearly approximating the value of the refractive index measured in the temperature range of 30 to 100 degrees Celsius by forming a film to be measured on a silicon substrate and installing a thermal control device on the prism coupler. (App.Phy. Lett., Vol. 81, No. 8, pp. 1438-14 (2002))

TABLE 1

PhTMS / TMOS Thermo-optic Coefficient (x10 ^-4 / ℃) 0.5 -1.35 One -1.84 2 -2.15 3 -2.56 4 -3.01

<Example 2>

0.1N HCl was added to 3-methacryloxypropyltrimethoxysilane (MPTS) in a 1: 3 molar ratio and 0.1N HCl was added to perfluoroalkylsilane (PFAS) in a 1: 2 molar ratio. The solution was mixed and stirred for 24 hours to conduct a sol-gel reaction. During mixing, the molar ratio of 3-methacryloxypropyltrimethoxysilane and perfluoroalkylsilane was adjusted as shown in Table 2 to adjust the composition of the coating film finally obtained. The subsequent process was carried out in the same manner as in Example 1 and the thickness of the coated film was 7 ~ 10㎛. Table 2 below shows the thermo-optic coefficient according to the molar ratio (PFAS / MPTS) of 3-methacryloxypropyltrimethoxysilane and perfluoroalkylsilane.

TABLE 2

PFAS / MPTS Thermo-optic Coefficient (x10 ^-4 / ℃) 0.5 -2.11 One -2.34 2 -2.60 3 -2.82 4 -3.02

<Example 3>

Methyl silicon trichloride (MSTC) and tetraethyl orthosilicate (TEOS) were stirred for 30 minutes in a nitrogen atmosphere with low moisture. At this time, the molar ratio of methylsilicon trichloride and tetraethyl orthosilicate was adjusted as shown in Table 3 to adjust the composition of the coating film finally obtained. Iron chloride (FeCl ₃ ) was added as a catalyst of the reaction at 1% by weight of the total silicon, followed by stirring at a temperature of 35 ° C. for 12 hours to perform a sol-gel reaction. The subsequent process was carried out in the same manner as in Example 1 and the thickness of the coated film was 8 ~ 10㎛. Table 3 shows the thermo-optic coefficients according to the molar ratio (MSTC / TEOS) of methyl silicon trichloride and tetraethyl orthosilicate.

TABLE 3

MSTC / TEOS Thermo-optic Coefficient (x10 ^-4 / ℃) 0.5 -0.70 One -0.89 2 -1.19 3 -1.44 4 -1.61

<Example 4>

0.1N HCl was added to 3-methacryloxypropyltrimethoxysilane (MPTS) in a 1: 3 molar ratio, and 0.1N HCl was added to tetramethoxy orthosilicate (TMOS) in a 1: 2 molar ratio. After the solution was mixed and stirred for 12 hours, the mixed solution was extracted in methanol in the solution for 20 minutes while maintaining the temperature at 60 ° C. in a vacuum evaporator. And benzoyl peroxide, an acrylic organic polymerization initiator, was added in an amount of 3% by weight of the silicon atom, followed by stirring for 1 hour. The final solution was coated on a silicon substrate using a spin coater, and then the amount of ultraviolet irradiation was adjusted as shown in Table 4 to adjust the degree of organic polymerization. After the heat treatment was performed in the same manner as in Example 1. Table 4 shows the thermo-optic coefficient according to the amount of ultraviolet radiation.

TABLE 4

UV dose (J / cm ² ) Thermo-optic Coefficient (x10 ^-4 / ℃) 0 -1.75 2.7 -1.67 13.5 -1.60 27 -1.47 81 -1.37 162 -1.18

<Example 5>

A solution containing 0.1N HCl in a 1: 3 molar ratio to 3-glycidoxypropyltrimethoxysilane (GPTS) and a solution containing 0.1N HCl in a 1: 2 molar ratio to tetramethoxy orthosilicate (TMOS) The mixture was stirred for 12 hours, and then aluminum 2-butoxide, an epoxy organic polymerization initiator, was added, followed by stirring for 3 hours. At this time, the amount of aluminum 2-butoxide was adjusted as shown in Table 5 to adjust the epoxy organic polymerization degree. The mixed solution was extracted with methanol in the solution while maintaining the temperature at 60 ° C. in a vacuum evaporator. The subsequent process was performed in the same manner as in Example 4. Table 5 shows the thermo-optic coefficient according to the degree of epoxy organic polymerization.

TABLE 5

Aluminum 2-butoxide (wt%) Thermo-optic Coefficient (x10 ^-4 / ℃) 0 -1.81 One -1.59 3 -1.42 5 -1.33 10 -1.27

<Example 6>

To the 3-methacryloxypropyl trimethoxysilane (MPTS) was added a solution of 0.1N HCl in a 1: 3 molar ratio and the silica sol stabilized at pH 3 was stirred for 5 hours. The molar ratio of 3-methacryloxypropyltrimethoxysilane and silica sol upon mixing was adjusted as indicated in Table 6 below. Coating and heat treatment of the final solution was carried out in the same manner as in Example 1. Table 6 shows the thermo-optic coefficients according to the molar ratio (MPTS / silica sol) of 3-methacryloxypropyltrimethoxysilane and silica sol.

TABLE 6

MPTS / Silicazol Thermo-optic Coefficient (x10 ^-4 / ℃) 0.5 -0.22 One -0.54 2 -0.81 3 -1.17 4 -1.34

<Example 7>

The molar ratio of 3-methacryloxypropyltrimethoxysilane (MPTS) and diphenylsilanediol (DPDS) was adjusted and mixed as indicated in Table 7 below, and the solution was stirred for 30 minutes. Barium hydroxide (Ba (OH) ₂ ) was slowly added to the stirred solution as 5 wt% of the total silicon atoms as a catalyst of the reaction, and then reacted at a temperature of 60 ° C. for 3 hours using a vacuum evaporator. The final solution was prepared in the final membrane as in Example 3 using a bar coater. Coating and heat treatment of the final solution was carried out in the same manner as in Example 1. Table 6 shows thermooptic coefficients according to the molar ratio (DPDS / MPTS) of 3-methacryloxypropyltrimethoxysilane and diphenylsilanediol.

TABLE 7

DPDS / MPTS Thermo-optic Coefficient (x10 ^-4 / ℃) 0.5 -2.07 One -2.23 2 -2.50 3 -2.69 4 -2.88

As described above, the thermo-optic waveguide material according to the present invention facilitates the design and fabrication of thermo-optic waveguide devices by controlling thermo-optic coefficients in a wider range than conventional quartz-based glass and polymer materials. To improve the effect.

Claims (15)

Including an inorganic-organic hybrid material having a negative thermo-optic coefficient, and having a mesh structure crosslinked with an oxygen atom bonded to silicon in the structure or an organic monomer capable of crosslinking or modification, and constitutes the inorganic-organic hybrid material. Thermo-optic coefficient control method of the thermo-optic waveguide device fabrication inorganic-organic hybrid material, characterized in that for controlling the thermo-optic coefficient by adjusting the inorganic-organic composition in the network structure or the network structure The method of claim 1, The inorganic-organic hybrid material of the inorganic-organic hybrid material for manufacturing a thermo-optic optical waveguide device, characterized in that the compound represented by the following formula (1) is formed through a hydrolysis and condensation reaction in the presence of an acid or a base catalyst Thermo optical coefficient control method (OR ¹ ) _n Si-R ² _m (n + m = 4) (1) In the above, R ¹ is a straight or branched chain alkyl group or hydrogen atom having 1 to 10 carbon atoms, R ² is a straight or branched chain alkyl group having 1 to 4 carbon atoms, a phenyl group, a phenyl alkoxy group, an amine group, n is a natural number of 1 to 4, m is an integer between 0 and 3. delete The method of claim 1, The inorganic-organic hybrid material of the inorganic-organic hybrid material for manufacturing a thermo-optic optical waveguide device, characterized in that the compound represented by the following formula (2) is a compound formed by the hydrolysis and condensation reaction in the presence of an acid or a base catalyst. Thermo optical coefficient control method (OR ¹ ) _n Si- (XR ³ ) _m (n + m = 4) (2) In the above, R ¹ is a linear or branched alkyl group or hydrogen atom having 1 to 10 carbon atoms, X is a carbon chain having 3 to 6 carbon atoms, R ³ is a vinyl group, glycidoxy group, methacryl group or 4 to 8 carbon atoms Substituted fluoride atoms in individual carbon chains, n is a natural number from 1 to 4, m is an integer from 0 to 3. delete The method of claim 1, The inorganic-organic hybrid material is a compound obtained by reacting an organic halogen silane represented by the following formula (3) with a silicon alkoxide or alkyl ether: thermo-optic coefficient control of an inorganic-organic hybrid material for manufacturing a thermo-optic optical waveguide device Way. R ⁴ SiCl ₃ (3) R ⁴ is a linear or branched alkyl group having 1 to 10 carbon atoms or a hydrogen atom, a phenyl group, a phenyl alkoxy group, an amine group, a vinyl group, a glycidoxy group, a methacryl group, or a 4 to 8 carbon chain in a carbon chain. Substituted Substituted Substances. The method of claim 6, Thermo-optic coefficient control method of inorganic-organic hybrid material for thermo-optic waveguide device fabrication characterized by metal chloride delete The method of claim 1, The inorganic-organic hybrid material is an inorganic-organic hybrid for fabricating a thermo-optic optical waveguide device obtained by reacting silicon oxide particles dispersed in water or alcohol with at least one compound represented by the following formula (1) or (2): Method for controlling the thermo-optic coefficient of a material. (OR ¹ ) _n Si-R ² _m (n + m = 4) (1) R ¹ is a straight or branched chain alkyl group having 1 to 10 carbon atoms or a hydrogen atom. R <^2> is a C1-C4 linear or branched alkyl group, a phenyl group, a phenyl alkoxy group, and an amine group. n is a natural number between 1 and 4, and m is an integer between 0 and 3. (OR ¹ ) _n Si- (XR ³ ) _m (n + m = 4) (2) R ¹ is a straight or branched chain alkyl group having 1 to 10 carbon atoms or a hydrogen atom. X is a carbon chain having 3 to 6 carbon atoms. R ³ is a substance containing a vinyl group, glycidoxy group, methacryl group or a fluoride atom substituted in a carbon chain having 4 to 8 carbon atoms. n is a natural number between 1 and 4, and m is an integer between 0 and 3. delete delete delete delete delete delete