WO2019073878A1 - Compound, pattern forming substrate, photodegradable coupling agent, pattern forming method, and transistor production method - Google Patents

Abstract

This compound is represented by general formula (1) (in the formula: X represents a halogen or an alkoxy group; R1 is any one group selected from C1-5 alkyl groups, groups represented by formula (R2-1), and groups represented by formula (R2-2); R2 is a group represented by formula (R2-1) or (R2-2); n0 is an integer of 0 or higher; n1 is an integer in the range of 0-5; and n2 is a natural number in the range of 1-5).

Description

Compound, substrate for pattern formation, photodegradable coupling agent, method for pattern formation, and method for manufacturing transistor

The present invention relates to a compound, a pattern formation substrate, a photocleavable coupling agent, a pattern formation method, and a method of manufacturing a transistor.
The present application claims priority based on Japanese Patent Application No. 2017-197501, filed on Oct. 11, 2017, and Japanese Patent Application No. 2018-045274, filed on Mar. 13, 2018, The contents are incorporated herein.

In recent years, in the manufacture of fine devices such as semiconductor devices, integrated circuits, devices for organic EL displays, etc., a method of forming patterns having different surface characteristics on a substrate and creating the fine devices using the difference in the surface characteristics Has been proposed.
As a method of forming a pattern utilizing differences in surface characteristics on a substrate, for example, there is a method of forming a hydrophilic region and a water repellent region on a substrate and applying an aqueous solution of a functional material to the hydrophilic region. In this method, since the aqueous solution of the functional material wets and spreads only in the hydrophilic region, a thin film pattern of the functional material can be formed.
As a material capable of forming a hydrophilic region and a water repellent region on a substrate, for example, Patent Document 1 describes a fluorine-containing compound whose contact angle can be changed before and after light irradiation. However, from the viewpoint of environmental persistence, a material not containing fluorine is desired.

Patent No. 4997765 gazette

A first aspect of the present invention is a compound represented by the following general formula (1).

[Wherein, X represents a halogen atom or an alkoxy group, R ¹ represents an alkyl group having 1 to 5 carbon atoms, a group represented by the following formula (R2-1), or a group represented by the following formula (R2-2) R ² is a group represented by the following formula (R2-1) or (R2-2), n0 is an integer of 0 or more, and n1 is 0 to The integer of 5, n2 is a natural number of 1 to 5. ]

[Wherein, R ²¹ and R ²² each independently represent an alkyl group of 1 to 5 carbon atoms, and n is a natural number. The wavy line means a bond. ]

A second aspect of the present invention is a patterning substrate having a surface chemically modified with the compound of the first aspect of the present invention.
A third aspect of the present invention is a photocleavable coupling agent comprising the compound of the first aspect of the present invention.
A fourth aspect of the present invention is a pattern forming method for forming a pattern on the surface to be treated of an object, wherein the step of chemically modifying the surface to be treated using the compound of the first aspect of the present invention And irradiating the chemically modified surface to be treated with light of a predetermined pattern to form a latent image comprising a hydrophilic area and a water repellent area, and disposing a pattern forming material on the hydrophilic area or the water repellent area. And a process of forming a pattern.
A fifth aspect of the present invention is a pattern forming method for forming a pattern on a surface to be treated of an object, wherein the compound to be treated is chemically modified using the compound of the first aspect of the present invention. And irradiating a light of a predetermined pattern onto the chemically modified surface to be treated to generate a latent image consisting of a hydrophilic area and a water repellent area, and arranging an electroless plating catalyst in the hydrophilic area, And a step of performing electrolytic plating.
A sixth aspect of the present invention is a method of manufacturing a transistor having a gate electrode, a source electrode, and a drain electrode, wherein at least one of the gate electrode, the source electrode, and the drain electrode is It is a manufacturing method of a transistor including the process formed with the pattern formation method of the 4th mode or the 5th mode of the above.

It is a schematic diagram which shows the whole structure of a substrate processing apparatus. It is a figure which shows the general | schematic process of the pattern formation method. It is a figure which shows an example of the general | schematic process of the manufacturing method of a transistor. It is a figure which shows the result of the XPS spectrum before and behind light irradiation. It is a figure which shows the result of the XPS spectrum before and behind light irradiation. It is a figure which shows the result of the XPS spectrum before and behind light irradiation. It is a figure which shows the result of the XPS spectrum before and behind light irradiation. It is a figure which shows the result of the XPS spectrum before and behind light irradiation.

<Compound>
The first embodiment of the present invention is a compound represented by the following general formula (1). The compound of the present embodiment has a siloxane-based water repellent group. When the surface of an object such as a substrate is modified using the compound of the present embodiment, the surface of the object can be modified to be water repellent. In addition, when light is irradiated after modification, the water repellent group is eliminated, a hydrophilic group is generated, and the surface of the object can be modified to be hydrophilic.
The compound of the present embodiment can be substituted for the fluorine-based compound which has been conventionally used for reforming to water repellency, and further exhibits the liquid repellency and releasability unique to siloxane-based water repellent groups. It is considered possible.

[Wherein, X represents a halogen atom or an alkoxy group, R ¹ represents an alkyl group having 1 to 5 carbon atoms, a group represented by the following formula (R2-1), or a group represented by the following formula (R2-2) R ² is a group represented by the following formula (R2-1) or (R2-2), n0 is an integer of 0 or more, and n1 is 0 to The integer of 5, n2 is a natural number of 1 to 5. ]

[Wherein, R ²¹ and R ²² each independently represent an alkyl group of 1 to 5 carbon atoms, and n is a natural number of 1 to 5]. The wavy line means a bond. ]

{X}
X is a halogen atom or an alkoxy group. The halogen atom represented by X can include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but X is preferably an alkoxy group rather than a halogen atom. n0 represents an integer of 0 or more, and is preferably an integer of 1 to 20, and more preferably an integer of 2 to 15 from the viewpoint of the availability of starting materials.

{R ¹ }
In the general formula (1), R ¹ is an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (R2-1) or (R2-2).
Examples of the alkyl group having 1 to 5 carbon atoms of R ¹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.

{N1, n2}
In the general formula (1), n1 is an integer of 0 to 5, and in the case of the disubstituted type described later, n1 is preferably a natural number of 1 to 5, more preferably 2 to 4, and particularly preferably 3. In the case of 1-substituted type, 0 is preferable. n2 is a natural number of 1 to 5, preferably 2 to 4, and more preferably 3.

{Group represented by Formula (R2-1) or (R2-2)}
Examples of the group represented by R ¹ and R ² in the general formula (1) include groups represented by the following formula (R2-1) or (R2-2).

[Wherein, R ²¹ and R ²² each independently represent an alkyl group of 1 to 5 carbon atoms, and n is a natural number. The wavy line means a bond. ]

In formulas (R2-1) or (R2-2), R ²¹ and R ²² each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include the groups described for R ¹ above, among which a methyl group, an isopropyl group or a tert-butyl group is preferable. N in the formula (R2-2) is a natural number, preferably 1 to 200, preferably 1 to 150, and more preferably 1 to 120.

In the following, when a group represented by the formula (R2-1) is contained as a group represented by R ¹ and R ² is referred to as “branched type” and a group represented by R ¹ and R ² is a group represented by formula (R2-2 The case having a group represented by) may be described as "straight chain type". In addition, when R ¹ is an alkyl group is described as “monosubstituted type”, and when R ¹ is a group represented by formula (R2-1) or (R2-2) as “disubstituted type” It may be explained.

In the compound represented by the general formula (1) of the present embodiment, by adjusting the groups to be introduced into R ¹ and R ² , monosubstituted branched type, monosubstituted chain type, disubstituted branched type, disubstituted It includes compounds of linear type.

Below, the specific example of a compound represented by General formula (1) is described.

«Method for producing compound»
The compound represented by General formula (1) of this embodiment can be manufactured by the following method.
In the following description of the production method, the descriptions regarding R ¹ , R ²¹ and R ²² are the same as above.

[Manufacturing method 1]
Intermediate compound 14 'can be obtained by reacting the intermediate compound 14 represented by the following formula with a siloxane compound. Intermediate compound 14 may be produced by the method described in the examples described later, for example, as described in H. Nakayama et al. , Colloids Surf. B, 2010, 76, 88-97.

[Wherein, R ¹ and R ²¹ are each independently an alkyl group having 1 to 5 carbon atoms. ]

A compound (1) of this embodiment can be obtained by further reacting a siloxane compound with the obtained intermediate compound 14 '.

[Wherein, R ¹ and R ²¹ are each independently an alkyl group having 1 to 5 carbon atoms. X represents a halogen atom or an alkoxy group, and n0 is an integer of 0 or more. ]

[Manufacturing method 2]
The compound represented by general formula (1) of 1-substituted linear type can also be manufactured by the following method. Specifically, an intermediate compound 13 represented by the following formula is reacted with a siloxane compound to obtain an intermediate compound 15.

[Wherein, R ¹ and R ²² are each independently an alkyl group having 1 to 5 carbon atoms. ]

The resulting intermediate compound 15 can be reacted with squamimidyl carbonate to obtain an intermediate compound 15 '.

[Wherein, R ¹ and R ²² are each independently an alkyl group having 1 to 5 carbon atoms. ]

The resulting intermediate compound 15 'is further reacted with a siloxane compound to obtain the compound (1) of the present embodiment.

[Wherein, R ¹ and R ²¹ are each independently an alkyl group having 1 to 5 carbon atoms. X represents a halogen atom or an alkoxy group, and n0 is an integer of 0 or more. ]

[Manufacturing method 3]
The compound represented by the disubstituted general formula (1) can be produced by the following method.
Specifically, each of the siloxane compounds can be reacted with an intermediate compound 25 represented by the following formula to obtain an intermediate compound 25 ′.

[Wherein, R ²¹ represents an alkyl group having 1 to 5 carbon atoms. ]

Wherein R ¹ is an alkyl group having 1 to 5 carbon atoms. ]

A compound (1) of the present embodiment can be obtained by further reacting a siloxane compound with the obtained intermediate compound 25 '.

Wherein R ¹ is an alkyl group having 1 to 5 carbon atoms. X represents a halogen atom or an alkoxy group, and n0 is an integer of 0 or more. ]

Wherein R ¹ is an alkyl group having 1 to 5 carbon atoms. X represents a halogen atom or an alkoxy group, and n0 is an integer of 0 or more. ]

<Board for pattern formation>
A second embodiment of the present invention is a substrate for pattern formation having a surface chemically modified using the compound of the first embodiment.
The surface of the substrate for pattern formation of this embodiment is modified using the compound of the first embodiment. For this reason, by selectively exposing through a mask or the like, a hydrophilic region is formed in the exposed area on the pattern forming substrate, and a water repellent area is formed in the unexposed area.
By applying the pattern forming material on the substrate on which the hydrophilic region and the water repellent region are formed, the pattern forming material can be selectively applied to the hydrophilic region formed in the exposed portion, and metal wiring Etc. can be formed.

The substrate is not particularly limited, and glass, quartz glass, silicon wafer, plastic plate, metal plate and the like are preferably mentioned. Moreover, you may use the board | substrate with which the metal thin film was formed on these board | substrates.

The shape of the substrate is not particularly limited, and a flat surface, a curved surface, or a flat surface having a partially curved surface is preferable, and a flat surface is more preferable. Further, the area of the substrate is also not particularly limited, and a substrate having a surface of a size as long as the conventional coating method can be applied can be adopted. Moreover, it is preferable to form the surface chemically modified using the compound of the first embodiment on one side of the planar substrate.

When modifying the surface of the substrate, it is preferable to pretreat the substrate surface. As a pretreatment method, pretreatment with a piranha solution or pretreatment with a UV-ozone cleaner is preferable.

<Photodegradable coupling agent>
The third embodiment of the present invention is a photocleavable coupling agent comprising the compound of the first embodiment.
The photodegradable coupling agent of the present embodiment includes a photodegradable group having a liquid repellent group, and an adhesion group linked to the photodegradable group via a functional group, and the liquid repellent group has a siloxane structure. In addition, the functional group is one that becomes a residue of an amino group after photolysis. Therefore, the photolytic coupling agent of the present embodiment can ensure a large difference in contact angle before and after light irradiation.

<Pattern formation method>
A fourth embodiment of the present invention is a pattern forming method for forming a pattern on a surface to be treated of an object, wherein the step of chemically modifying the surface to be treated using the compound of the first embodiment; Irradiating a light of a predetermined pattern onto the chemically modified surface to be treated to generate a latent image consisting of a hydrophilic area and a water repellent area; disposing a pattern forming material on the hydrophilic area or the water repellent area; And a pattern forming method comprising:

[Chemical modification process]
This step is a step of chemically modifying the surface to be treated using the compound of the first embodiment in the pattern forming method for forming a pattern on the surface to be treated of the object.

The object is not particularly limited, and, for example, metals, crystalline materials (for example, single crystalline, polycrystalline and partially crystalline materials), amorphous materials, conductors, semiconductors, insulators, optical elements, painted substrates , Fiber, glass, ceramics, zeolite, plastic, thermosetting and thermoplastic materials (eg, optionally doped: polyacrylate, polycarbonate, polyurethane, polystyrene, cellulose polymer, polyolefin, polyamide, polyimide, resin, polyester, polyphenylene Etc.), films, thin films, foils, etc.

In the pattern formation method of the present embodiment, it is preferable to form a circuit pattern for an electronic device on a flexible substrate.

In the present embodiment, as a flexible substrate to be an object, for example, a foil such as a resin film or stainless steel can be used. For example, the resin film may be made of polyethylene resin, polypropylene resin, polyester resin, ethylene vinyl copolymer resin, polyvinyl chloride resin, cellulose resin, polyamide resin, polyimide resin, polycarbonate resin, polystyrene resin, vinyl acetate resin, etc. It can be used.

The term "flexibility" as used herein refers to the property of being able to bend the substrate without breaking or breaking even when a force of about its own weight is applied to the substrate. In addition, the property of being bent by the force of its own weight is also included in the flexibility. Also, the flexibility varies depending on the material, size, thickness, environment such as temperature, etc. of the substrate. Note that although a single strip-shaped substrate may be used as the substrate, a plurality of unit substrates may be connected to form a strip.

In this step, it is preferable to chemically modify the entire surface or the specific region of the surface to be treated of the object using the compound of the first embodiment.

The method for chemically modifying the surface to be treated of the object is not particularly limited as long as the group represented by X in the general formula (1) is a method of binding to the substrate, and the immersion method, chemical treatment method Known methods such as can be used.

An example of the chemical modification in this process is shown.
The chemical modification in this step can be performed, for example, by reacting the compound represented by the general formula (1) with a substrate as shown below.

[Wherein, X represents a halogen atom or an alkoxy group, R ¹ is an alkyl group having 1 to 5 carbon atoms, a group represented by the above formula (R2-1) or (R2-2), and R ² is A group represented by the formula (R2-1) or (R2-2) n0 is a natural number. n1 is an integer of 0 to 5, and n2 is a natural number of 1 to 5. ]

[Latent image generation process]
This step is a step of exposing the chemically modified surface to be treated to generate a latent image consisting of a hydrophilic area and a water repellent area.

The light irradiated at the time of exposure is preferably ultraviolet light. The light to be irradiated preferably includes light having a wavelength within the range of 200 nm to 450 nm, and more preferably includes light having a wavelength within the range of 320 nm to 450 nm. It is also preferable to emit light including light with a wavelength of 365 nm. The light having these wavelengths can efficiently decompose the photolytic group. As a light source, low pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, xenon lamp, sodium lamp; gas laser such as nitrogen, liquid laser of organic dye solution, solid laser containing rare earth ion in inorganic single crystal, etc. It can be mentioned.
Further, as a light source other than a laser capable of obtaining monochromatic light, light of a specific wavelength obtained by extracting a wide-band line spectrum or a continuous spectrum using an optical filter such as a band pass filter or a cutoff filter may be used. A high pressure mercury lamp or an ultrahigh pressure mercury lamp is preferable as a light source because a large area can be irradiated at one time.
In the pattern formation method of the present embodiment, light can be emitted arbitrarily within the above range, but it is particularly preferable to emit light energy of distribution corresponding to the circuit pattern.

In this step, the group having water repellent performance is dissociated by irradiating a light of a predetermined pattern to the chemically modified surface to be treated, and residues having hydrophilic performance (amino group) are generated. Can produce a latent image consisting of hydrophilic and water repellent regions.

In this step, it is preferable to generate a latent image of a circuit pattern on the surface of the flexible substrate due to the difference in hydrophilicity and water repellency.

By irradiating a light having a predetermined pattern on a surface to be treated which is chemically modified below, a group having water repellent performance is dissociated as shown below to generate a residue having hydrophilic performance (amino group).

[Wherein, R ¹ is an alkyl group having 1 to 5 carbon atoms, a group represented by the above formula (R2-1) or (R2-2), and R ² is a group represented by the above formula (R2-1) or (R2 And a group represented by -2). n0 is a natural number. n1 is an integer of 0 to 5, and n2 is a natural number of 1 to 5. ]

[Step of arranging pattern forming material]
This step is a step of arranging a pattern forming material in the hydrophilic area or the water repellent area generated in the above-mentioned step.

Wiring material (metal solution) in which particles of gold, silver, copper or alloys thereof are dispersed in a predetermined solvent, or precursor solution containing the above-mentioned metal, insulator (resin), as a pattern forming material Examples thereof include electronic materials in which a semiconductor, an organic EL light emitting material and the like are dispersed in a predetermined solvent, and a resist solution.

In the pattern formation method of the present embodiment, the pattern formation material is preferably a conductive material, a semiconductor material, or an insulating material.

Examples of the conductive material include a pattern forming material made of a dispersion liquid in which conductive fine particles are dispersed in a dispersion medium. As the conductive fine particles, for example, metal fine particles containing any of gold, silver, copper, palladium, nickel and ITO, these oxides, and fine particles of conductive polymer and superconductor, etc. are used.

These conductive fine particles can also be used by coating an organic substance or the like on the surface in order to improve the dispersibility.

The dispersion medium is not particularly limited as long as it can disperse the above-mentioned conductive fine particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol and butanol, n-heptane, n-octane, decane, dodecane, tetradecane, tetradecane, toluene, xylene, cymene, durene, indene, dipentene, tetrahydronaphthalene, decahydro Hydrocarbon compounds such as naphthalene and cyclohexylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, 1,2-dimethoxyethane, bis (2- (2-) Ether compounds such as methoxyethyl) ether and p-dioxane, and further propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Among these, water, alcohols, hydrocarbon compounds, and ether compounds are preferable in terms of the dispersibility of the fine particles, the stability of the dispersion, and the ease of application to the droplet discharge method (ink jet method), As a more preferable dispersion medium, water and a hydrocarbon type compound can be mentioned.

As the semiconductor material, an organic semiconductor material composed of a dispersion liquid dispersed or dissolved in a dispersion medium can be used. As the organic semiconductor material, a low molecular weight material or a high molecular weight material of π electron conjugated system whose skeleton is composed of conjugated double bonds is desirable. Typically, soluble low molecular weight materials such as acenes such as pentacene, and thienoacenes such as benzothienobenzothiophene, and soluble high molecular weight materials such as polythiophene, poly (3-alkylthiophene) and polythiophene derivatives can be mentioned. Alternatively, a soluble precursor material may be used which is converted to the above-described semiconductor by heat treatment, and examples of the pentacene precursor include sulfinylacetamide pentacene and the like. The present invention is not limited to the organic semiconductor material, and an inorganic semiconductor material may be used.

Insulating materials are represented by polyimide, polyamide, polyester, acrylic, PSG (phosphor glass), BPSG (phosphoboron glass), polysilazane SOG, silicate SOG (Spin on Glass), alkoxysilicate SOG, and siloxane polymer. An insulating material comprising a dispersion in which SiO ₂ or the like having a Si—CH ₃ bond is dispersed or dissolved in a dispersion medium can be mentioned.

In this step, as a method of arranging a pattern forming material, a droplet discharge method, an inkjet method, a spin coat method, a roll coat method, a slot coat method, a dip coat method, or the like can be applied.

Hereinafter, the pattern formation method of the present embodiment will be described with reference to the drawings.
In the case of using a flexible substrate corresponding to a so-called roll-to-roll process in the pattern forming method of the present embodiment, a substrate processing apparatus 100 which is a roll-to-roll apparatus as shown in FIG. It may be used to form a pattern. The structure of the substrate processing apparatus 100 is shown in FIG.

As shown in FIG. 1, the substrate processing apparatus 100 performs processing on a substrate supply unit 2 that supplies a strip-shaped substrate (for example, a strip-shaped film member) S, and a surface (processed surface) Sa of the substrate S. The substrate processing unit 3, the substrate recovery unit 4 for recovering the substrate S, the application unit 6 of the compound of the first embodiment, the exposure unit 7, the mask 8, the pattern material application unit 9, and these units And a controller CONT to control. The substrate processing unit 3 can execute various processes on the surface of the substrate S after the substrate S is sent out from the substrate supply unit 2 and before the substrate recovery unit 4 recovers the substrate S.
This substrate processing apparatus 100 can be suitably used, when forming display elements (electronic device), such as an organic EL element and a liquid crystal display element, on a substrate S, for example.

Although FIG. 1 illustrates a method of using a photomask to generate desired pattern light, the present embodiment may be suitably applied to a maskless exposure method that does not use a photomask. it can. As a maskless exposure method of generating pattern light without using a photomask, a method of using a spatial light modulation element such as DMD, a method of scanning a spot light as in a laser beam printer, and the like can be mentioned.

In the pattern formation method of the present embodiment, an XYZ coordinate system is set as shown in FIG. 1, and the following description will be made using this XYZ coordinate system as appropriate. In the XYZ coordinate system, for example, an X axis and a Y axis are set along a horizontal surface, and a Z axis is set upward along the vertical direction. In addition, the substrate processing apparatus 100 transports the substrate S along the X axis as a whole from the minus side (− side) to the plus side (+ side). At that time, the width direction (short direction) of the strip-like substrate S is set in the Y-axis direction.

As a substrate S to be processed in the substrate processing apparatus 100, for example, a foil such as a resin film or stainless steel can be used. For example, the resin film may be made of polyethylene resin, polypropylene resin, polyester resin, ethylene vinyl copolymer resin, polyvinyl chloride resin, cellulose resin, polyamide resin, polyimide resin, polycarbonate resin, polystyrene resin, vinyl acetate resin, etc. It can be used.

The substrate S preferably has a small thermal expansion coefficient so that the dimensions do not change even if it receives heat of, for example, about 200.degree. For example, an inorganic filler can be mixed with a resin film to reduce the thermal expansion coefficient. Examples of the inorganic filler include titanium oxide, zinc oxide, alumina, silicon oxide and the like. Further, the substrate S may be a single layer of ultrathin glass having a thickness of about 100 μm manufactured by the float method or the like, or a laminate in which the above-mentioned resin film or aluminum foil is bonded to the ultrathin glass.

The dimension in the width direction (short direction) of the substrate S is, for example, about 1 m to 2 m, and the dimension in the longitudinal direction (long direction) is, for example, 10 m or more. Of course, this dimension is only an example, and is not limited to this. For example, the dimension in the Y direction of the substrate S may be 50 cm or less, or 2 m or more. Further, the dimension of the substrate S in the X direction may be 10 m or less.

The substrate S is preferably formed to have flexibility. The term "flexibility" as used herein refers to the property of being able to bend the substrate without breaking or breaking even when a force of about its own weight is applied to the substrate. In addition, the property of being bent by the force of its own weight is also included in the flexibility.
Also, the flexibility varies depending on the material, size, thickness, environment such as temperature, etc. of the substrate. Note that although a single strip-shaped substrate may be used as the substrate S, a plurality of unit substrates may be connected to form a strip.

The substrate supply unit 2 feeds and supplies, for example, the substrate S wound in a roll shape to the substrate processing unit 3. In this case, the substrate supply unit 2 is provided with a shaft portion around which the substrate S is wound, a rotation driving device which rotates the shaft portion, and the like. In addition to this, for example, a cover provided to cover the substrate S in a rolled state may be provided. The substrate supply unit 2 is not limited to a mechanism for delivering the substrate S wound in a roll, but includes a mechanism (for example, a nip type drive roller) for sequentially delivering the strip-like substrate S in its length direction. I hope there is.

The substrate recovery unit 4 rolls up and recovers the substrate S which has passed through the substrate processing apparatus 100, for example, in a roll shape. Similar to the substrate supply unit 2, the substrate recovery unit 4 is provided with a shaft for winding the substrate S, a rotational drive source for rotating the shaft, and a cover for covering the collected substrate S. When the substrate S is cut into a panel shape in the substrate processing unit 3, the substrate S is collected in a state different from the state of being wound in a roll shape, for example, the substrate S is collected in a stacked state. It does not matter.

The substrate processing unit 3 transports the substrate S supplied from the substrate supply unit 2 to the substrate recovery unit 4 and uses the compound of the first embodiment for the processing surface Sa of the substrate S in the process of transport. A step of chemically modifying, a step of irradiating light of a predetermined pattern onto the chemically modified treated surface, and a step of arranging a patterning material are performed. The substrate processing unit 3 applies a compound application unit 6 that applies the compound of the first embodiment to the surface to be processed Sa of the substrate S, an exposure unit 7 that emits light, a mask 8, and a pattern material application unit 9. And a transport device 20 including a drive roller R for feeding the substrate S under conditions corresponding to the form of processing.

The compound application unit 6 and the pattern material application unit 9 are droplet application devices (for example, droplet discharge type application devices, inkjet type application devices, spin coat type application devices, roll coat type application devices, slot coat type application devices, etc. Can be mentioned.

Each of these devices is appropriately provided along the transport path of the substrate S, and a flexible display panel or the like can be produced by a so-called roll-to-roll method. In the present embodiment, the exposure unit 7 is provided, and an apparatus that takes charge of steps before and after that (photosensitive layer forming step, photosensitive layer developing step, etc.) is also provided inline as necessary.

<Method of forming wiring pattern by electroless plating>
A fifth embodiment of the present invention is a pattern forming method for forming a pattern on the surface to be treated of an object, wherein the step of chemically modifying the surface to be treated using the compound of the first embodiment; A step of irradiating the modified surface to be treated with light of a predetermined pattern to form a latent image consisting of a hydrophilic area and a water repellant area; arranging an electroless plating catalyst in the hydrophilic area; And a step of performing the pattern formation method.
According to the present embodiment, for example, the wiring pattern can be formed by electroless plating by the following method. This will be described below with reference to FIG.

(First step)
First, as shown in FIG. 2A, the compound of the first embodiment is applied to form a compound layer 12.

As a coating method, any of general film forming techniques such as physical vapor deposition (PVD), chemical vapor deposition (CVD), liquid phase growth, and the like may be used. Among them, the liquid phase growth method is particularly preferable, and as the liquid phase growth method, for example, a coating method (spin coat, dip coat, die coat, spray coat, roll coat, brush coating), printing method (flexo printing, screen printing) etc. It can be mentioned. Alternatively, a SAM film or an LB film may be used.

In addition, in this process, you may add the process which dries a solvent by heat, pressure reduction, etc., for example.

(Second step)
Next, as shown in FIG. 2B, a photomask 13 having an exposure area of a predetermined pattern is prepared. The exposure method is not limited to a method using a photomask, and a method such as projection exposure using an optical system such as a lens or a mirror, a spatial light modulation element, maskless exposure using a laser beam or the like can be used. The photomask 13 may be provided in contact with the compound layer 12 or may be provided in non-contact with the compound layer 12.

(Third step)
Thereafter, as shown in FIG. 2C, the compound layer 12 is irradiated with UV light through the photomask 13. Thereby, the compound layer 12 is exposed in the exposure region of the photomask 13 to form the hydrophilic region 14.

In addition, UV light can be irradiated with the wavelength from which an optimal quantum efficiency is exhibited by the structure of photosensitive group. For example, there is i-line at 365 nm. Further, the exposure dose and the exposure time do not necessarily have to proceed completely with deprotection, and may be such an extent that some amino groups are generated. At that time, in the plating step described later, conditions (such as the activity of the plating bath) can be appropriately changed according to the progress of deprotection.

(4th step)
Next, as shown in FIG. 2D, a catalyst for electroless plating is applied to the surface to form a catalyst layer 15. The catalyst for electroless plating is a catalyst for reducing metal ions contained in a plating solution for electroless plating, and examples thereof include silver and palladium.

Although the amino group is exposed on the surface of the hydrophilic region 14, the amino group can capture and reduce the above-mentioned catalyst for electroless plating. Therefore, the electroless plating catalyst is captured only on the hydrophilic region 14 to form the catalyst layer 15. Further, as the electroless plating catalyst, one capable of supporting an amino group can be used.

(Fifth step)
As shown in FIG. 2E, electroless plating is performed to form a plating layer 16. Examples of the material of the plating layer 16 include nickel-phosphorus (NiP) and copper (Cu).

In this step, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface, thereby depositing the plating layer 16. At this time, since the catalyst layer 15 supporting a sufficient amount of catalyst is formed on the surface of the hydrophilic region 14, the plating layer 16 can be selectively deposited only on the hydrophilic region 14. If the reduction is insufficient, it may be immersed in a reducing agent solution such as sodium hypophosphite or sodium borohydride to actively reduce the metal ion on the amine.

According to the above steps, it is possible to form a wiring pattern on a predetermined substrate using the compound of the first embodiment.

<Method of Manufacturing Transistor>
Furthermore, a method of manufacturing a transistor using the plated layer 16 obtained in the fifth step as a gate electrode will be described with reference to FIG.

(Sixth step)
As shown in FIG. 3A, the plating layer 16 of the electroless plating pattern formed by the above-described method of forming an electroless plating pattern is covered by a known method to form the insulator layer 17 on the compound layer 12. The insulator layer 17 applies the coating solution using, for example, a coating solution in which one or more resins such as an ultraviolet curable acrylic resin, an epoxy resin, an ene / thiol resin, and a silicone resin are dissolved in an organic solvent. It may be formed by By irradiating the coating film with ultraviolet light through a mask provided with an opening corresponding to the region where the insulator layer 17 is to be formed, the insulator layer 17 can be formed into a desired pattern.

(The seventh step)
As shown in FIG. 3B, in the same manner as the first to third steps of the method of forming an electroless plating pattern described above, the hydrophilic region 14 is formed in the portion where the source electrode and the drain electrode are to be formed.

(Eighth step)
As shown in FIG. 3C, the catalyst for electroless plating is supported on the hydrophilic region 14 to form the catalyst layer 15 in the same manner as the fourth and fifth steps of the method for forming an electroless plating pattern described above. Thereafter, electroless plating is performed to form a plating layer 18 (source electrode) and a plating layer 19 (drain electrode). Although nickel-phosphorus (NiP) or copper (Cu) may be mentioned as a material of the plated layers 18 and 19, it may be formed of a material different from the plated layer 16 (gate electrode).

(9th step)
As shown in FIG. 3D, the semiconductor layer 21 is formed between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode). The semiconductor layer 21 is prepared, for example, by forming a solution in which an organic semiconductor material soluble in an organic solvent such as TIPS pentacene (6, 13-bis (triisopropylsilylethynyl) pentacene) is dissolved in the organic solvent, and the plating layer 18 (source It may be formed by applying and drying between the electrode) and the plating layer 19 (drain electrode). In addition, before forming the semiconductor layer 21, the compound layer 12 between the plating layer 18 (source electrode) and the plating layer 19 (drain electrode) may be exposed to be hydrophilic. By hydrophilizing the portion corresponding to the channel of the transistor, the solution is suitably applied to the hydrophilized portion, so that the semiconductor layer 21 can be selectively formed easily. The semiconductor layer 21 is formed by adding one or more kinds of insulating polymers such as PS (polystyrene) and PMMA (polymethyl methacrylate) to the solution, and applying and drying a solution containing the insulating polymer. May be Thus, when the semiconductor layer 21 is formed, the insulating polymer is formed in a concentrated manner below the semiconductor layer 21 (on the side of the insulator layer 17). If a polar group such as an amino group is present at the interface between the organic semiconductor and the insulator layer, the transistor characteristics tend to be degraded. However, by providing the organic semiconductor through the above-described insulating polymer, Deterioration of transistor characteristics can be suppressed. As described above, a transistor can be manufactured.

According to the method as described above, it is not necessary to separately provide a chemical resist or the like in the UV exposure process, and a simple process can be performed using only a photomask. Therefore, of course, the step of removing the resist layer is not necessary. In addition, the catalyst reduction ability of the amino group makes it possible to omit the catalyst activation treatment step that is usually required, and enables highly precise patterning while realizing significant cost reduction and time reduction. In addition, since a dip coating method can be used, it can be used very well even in roll-to-roll processes.

The structure of the transistor is not particularly limited and can be selected as appropriate depending on the purpose. Although the embodiment of FIGS. 2 to 3 has described a method of manufacturing a bottom contact / bottom gate type transistor, the same applies to top contact / bottom gate type, top contact / top gate type, bottom contact / top gate type transistors. It may be manufactured. In addition, although the aspect of FIGS. 2-3 demonstrated the method to form all of a gate electrode, a source electrode, and a drain electrode using the compound of 1st Embodiment, only a gate electrode is a 1st embodiment. It may be formed using a compound, or only the source electrode and the drain electrode may be formed using the compound of the first embodiment.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

<Synthesis of Compound 3a>
<< Step 1: Synthesis of 1- (4-allyloxy-3-methoxyphenyl) ethanone >>
Add 4-hydroxy-3-methoxyacetophenone (5.00 g, 30.1 mmol) to a 300 mL eggplant flask, dissolve in acetone (50 mL), add potassium carbonate (6.24 g, 45.1 mmol), and add 5 at room temperature. After stirring for a minute, allyl bromide (5.46 g, 45.1 mmol) was added and stirred at room temperature for 24 hours. After concentration, ethyl acetate (50 mL × 2) and pure water (50 mL) are added for extraction, and the organic layer is washed successively with saturated aqueous sodium carbonate solution (50 mL × 3) and saturated brine (50 mL × 2), and anhydrous magnesium sulfate The reaction mixture was dried, filtered and concentrated to give 6.09 g (29.5 mmol, 98%) of a pale yellow oil (Intermediate compound 11; 1- (4-allyloxy-3-methoxyphenyl) ethanone).

The identification result of the obtained intermediate compound 11 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 2.57 (3H, s), 3.94 (3H, s), 4.69 (2H, dt, J = 5.4, 1.5 Hz), 5.33 (1H, dq, J = 11, 1.3 Hz), 5.43 (1 H, dq, J = 17, 1.5 Hz), 6.09 (1 H, ddt, J = 17, 11, 5.4 Hz), 6.89 (1 H, d, J = 9.0 Hz), 7.52- 7.56 (2H, m).

Step 2: Synthesis of 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethanone
The above intermediate compound 11 (497 mg, 2.41 mmol) is added to a 50 mL eggplant flask and dissolved in acetic acid (3 mL), and fuming nitric acid (1 mL, 24.1 mmol) is slowly added dropwise on an ice bath. Stir for 30 minutes. Cold water (10 mL) is added and extraction is performed with ethyl acetate (10 mL × 3), and the organic layer is washed successively with saturated aqueous sodium hydrogen carbonate solution (10 mL) and saturated brine (10 mL × 2), dried over anhydrous magnesium sulfate, and filtered. Concentrated. Purification by silica gel column chromatography (hexane: ethyl acetate = 4: 1 → 2: 1), yellowish white solid (Intermediate compound 12; 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethanone) 345 mg ( 1.37 mmol, 57%) were obtained.

The identification result of the obtained intermediate compound 12 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 2.50 (3H, s), 3.98 (3H, s), 4.71 (2H, dt, J = 5.5, 1.4 Hz), 5.39 (1H, dq, J = 11, 1.3 Hz), 5.48 (1 H, dq, J = 17, 1.3 Hz), 6.07 (1 H, ddt, J = 17, 11, 5.4 Hz), 6. 76 (1 H, s), 7.62 (1 H, s).

Step 3: Synthesis of 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethanol
In a 50 mL recovery flask, the intermediate compound 12 (1.41 g, 5.61 mmol) obtained in the above step, tetrahydrofuran (10 mL), and methanol (10 mL) are placed, and sodium borohydride (637 mg, 16. 8 mmol) were added in small portions. The mixture was stirred at 0 ° C. for 20 minutes and then at room temperature for 40 minutes. After concentration, chloroform (10 mL × 3) and pure water (30 mL) are added for extraction, and the organic layer is washed with saturated brine (20 mL × 3), dried over anhydrous magnesium sulfate, filtered and concentrated. Intermediate compound 13; 1.40 g (5.54 mmol, 99%) of 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethanol was obtained.

The identification result of the obtained intermediate compound 13 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 1.56 (3 H, d, J = 6.3 Hz), 2. 29 (1 H, d, J = 3.7 Hz), 4.00 (3 H, s), 4. 67 (2 H, dt , J = 5.5, 1.4 Hz), 5.36 (1H, dq, J = 11, 1.3 Hz), 5.46 (1 H, dq, J = 17, 1.5 Hz), 5.57 (1 H, qd, J = 6.3, 3.7 Hz) , 6.07 (1 H, ddt, J = 17, 11, 5.4 Hz), 7.31 (1 H, s), 7. 59 (1 H, s).

<< Step 4: Synthesis of 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethyl N-succinimidyl carbonate >>
Intermediate compound 13 (2.50 g, 9.85 mmol) is put in a 200 mL two-necked eggplant flask and dissolved in dry acetonitrile (35 mL), and di (N-succinimidyl) carbonate (6.36 g, 24.8 mmol), triethylamine (4.05 g, 40.1 mmol) was added and stirred at room temperature for 17 hours under a nitrogen atmosphere. After concentration, add chloroform (150 mL, 60 mL × 2), pure water (200 mL) and 2N hydrochloric acid (10 mL) for extraction, wash the organic layer with saturated brine (100 mL × 3), dry over anhydrous magnesium sulfate, filter , Concentrated. Purification by silica gel column chromatography (hexane: ethyl acetate = 2: 1), yellowish white solid (Intermediate compound 14; 1- (4-allyloxy-5-methoxy-2-nitrophenyl) ethyl N-succinimidyl carbonate) 2. 97 g (7.54 mmol, 77%) were obtained.

The identification result of the obtained intermediate compound 14 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 1.76 (3H, d, J = 6.4 Hz), 2.80 (4H, s), 4.06 (3H, s), 4.67 (2H, dt, J = 5.5, 1.4 Hz), 5.37 (1H, dq, J = 11, 1.3 Hz), 5. 47 (1 H, dq, J = 17, 1.5 Hz), 6.07 (1 H, ddt, J = 17, 11, 5.4 Hz), 6.51 ( 1 H, q, J = 6.4 Hz), 7.08 (1 H, s), 7. 65 (1 H, s).

In this example, Intermediate Compound 14 was synthesized by the above method.
Nakayama et al. , Colloids Surf. B, 2010,
The intermediate compound 14 synthesized by the method described in 76, 88-97 may be used.

<< Step 5; Synthesis of 1- (5-methoxy-2-nitro-4- (3-tris (trimethylsiloxy) silylpropoxy) phenyl) ethyl N-succinimidyl carbonate >>
Intermediate compound 14 (300 mg, 0.761 mmol) is placed in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (6 mL), tris (trimethylsiloxy) silane (677 mg, 2.28 mmol), Karsted catalyst (5 drops) ) Was added and stirred at room temperature for 20 hours under a nitrogen atmosphere. After concentration, the residue is purified by silica gel column chromatography (hexane: ethyl acetate: tetramethoxysilane = 60: 20: 1 → 50: 50: 1) to give a yellow gum (intermediate compound 1a; 1- (5-methoxy-2-). It was obtained 281 mg (0.407 mmol, 53%) of nitro-4- (3-tris (trimethylsiloxy) silylpropoxy) phenyl N-succinimidyl carbonate).

The identification result of the obtained compound intermediate compound 1a is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.10 (27 H, s), 0.55-0.60 (2 H, m), 1. 76 (3 H, d, J = 6.5 Hz), 1.85-1.94 (2 H, m) , 2.80 (4H, s), 3.98-4.03 (2H, m), 4.04 (3H, s), 6.51 (1 H, q, J = 6.4 Hz), 7.07 (1 H, s), 7.62 (1 H, s).

<< Step 6: Synthesis of 1- (5-methoxy-2-nitro-4- (3-tris (trimethylsiloxy) silylpropoxy) phenyl) ethyl 3-trimethoxysilylpropyl carbamate >>
Intermediate compound 1a (100 mg, 0.145 mmol) is placed in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (1 mL), 3-aminopropyltrimethoxysilane (0.028 mL, 0.161 mmol) is added, and light shielding is performed under a nitrogen atmosphere. The mixture was then stirred at room temperature for 22 hours. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate: tetramethoxysilane = 60: 20: 1) to obtain 48 mg (0.0636 mmol, 44%) of light yellow gum.

The identification result of the obtained compound 3a of the present embodiment is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.10 (27 H, s), 0.54-0.65 (4 H, m), 1.58 (3 H, d, J = 6.5 Hz), 1.61-1. 68 (2 H, m) , 1.84-1.93 (2H, m), 3.10-3.18 (2H, m), 3.56 (9H, s), 3.95 (3H, s), 3.98-4.03 (2H, m), 4.95 (1H, t, J = 5.2 Hz), 6.37 (1 H, q, J = 6.4 Hz), 6.99 (1 H, s), 7.56 (1 H, s).
¹³ C NMR (CDCl ₃ / TMS, 100 MHz): δ 1.74 (9 C), 6.31, 10.3, 22.3, 23.0, 23.2, 43.3, 50.6 (3 C), 56.3, 68.8, 71.6, 108.0, 108.8, 139.6, 139.6, 139.6 147.4, 153.9, 155.3.

<Surface modification>
The thermally oxidized silicon wafer (SiO ₂ / Si substrate) was ultrasonically cleaned with methanol for 5 minutes, dried with a nitrogen stream, and then pretreated by UV irradiation with a UV-ozone cleaner for 1 hour.
Next, the compound 3a obtained by the above method was dissolved in dry toluene to prepare a 1 mM solution, the above-described pretreated substrate was placed, and immersed at room temperature for 20 hours under a nitrogen atmosphere. The substrate was rinsed with methanol, ultrasonically cleaned with methanol and chloroform for 5 minutes each, and dried with a nitrogen stream (Step 1 below).

<Light irradiation>
The modified substrate was irradiated with light having a wavelength of 365 nm and an illuminance of 15 J in the atmosphere via a filter with an extra-high pressure mercury lamp. The substrate was ultrasonically cleaned with chloroform for 5 minutes and dried with a stream of nitrogen (Step 2 below).

<Contact angle measurement>
Using a contact angle meter (Kyowa Interface Science Co., Ltd.), the static contact angle before and after light irradiation was measured using water, diiodomethane, and 1-bromonaphthalene as the lobe liquid according to the droplet method / θ / 2 method. The results are listed in Table 1. In Table 1 below, “before light irradiation” means immediately after the above step 1 and “after light irradiation” means immediately after the above step 2.

As a result shown in the above-mentioned Table 1, it was confirmed that the contact angle becomes small after light irradiation of the compound 3a which does not contain fluorine.

<XPS measurement>
The obtained modified substrate was compared before and after light irradiation by static contact angle measurement and X-ray photoelectron spectroscopy (hereinafter referred to as “XPS”). FIG. 4 shows XPS spectra before and after light irradiation.
It is considered that the surface of the substrate was modified because of the large contact angle after modification and the hydrophobicity.
In addition, XPS showed that after modification, the appearance of a peak derived from a nitro group was observed, and thus modification was possible.
It was confirmed that the contact angle decreased after the light irradiation. In addition, it was confirmed from XPS that the peak derived from the nitro group disappeared after light irradiation and the C (carbon) peak decreased, and that the photodegradable group was detached by light irradiation.

<Synthesis of Compound 3b>
<< Step 1; 1- (4- (3- (1,1,3,3,5,5,5-heptamethyltrisiloxanyl) propoxy) -5-methoxy-2-nitrophenyl) ethyl N-sk Synthesis of cinimidyl carbonate >>
Intermediate compound 14 (1.0 g, 2.53 mmol) is put in a 50 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (21 mL) to obtain 1,1,3,3,5,5,5-heptamethyltrisiloxane (1.13 g, 5.07 mmol) and a Karstedt catalyst (1.0 mL) were added, and the mixture was stirred at room temperature for 3 hours under a light-shielded nitrogen atmosphere. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate: tetramethoxysilane = 200: 100: 3) to obtain 0.597 g (0.968 mmol, 38%) of a yellow viscous material.

The identification result of the obtained intermediate compound 1b is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.03 (6 H, s), 0.09 (9 H, s), 0.12 (6 H, s), 0.62-0.69 (2 H, m), 1. 76 (3 H, d, J = 6.4 Hz), 1.86-1.95 (2H, m), 2.80 (4H, s), 3.99-4.05 (2H, m), 4.04 (3H, s), 6.51 (1 H, q, J = 6.4 Hz), 7.07 (1 H, s), 7.63 (1 H, s).

<< Step 2; Synthesis of 1- (4- (3- (1,1,3,3,5,5,5- heptmethyltrisilyloxyl) propoxy) -5-methoxy-2-nitrophenyl) ethyl 3-trimethoxysilylpropyl carbamate >>
Intermediate compound 1b (200 mg, 0.324 mmol) is placed in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (2 mL), 3-aminopropyltrimethoxysilane (0.085 mL, 0.486 mmol), triethylamine (0.113 mL, 0) .81 mmol) was added, and the mixture was stirred at room temperature for 13 hours with shielding light under a nitrogen atmosphere. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate: tetramethoxysilane = 50: 50: 1) to obtain 98 mg (0.144 mmol, 45%) of light yellow gum.

The identification result of the obtained compound 3b is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.03 (6H, s), 0.09 (9H, s), 0.11 (6H, s), 0.58-0.69 (4H, m), 1.53-1.69 (5H, m), 1.84-1.94 (2H, m), 3.06-3.21 (2H, m), 3.56 (9H, s), 3.95 (3H, s), 4.01 (2H, t, J = 7.2 Hz), 4.95 (1H , t, J = 5.8 Hz), 6.37 (1 H, q, J = 6.4 Hz), 6.99 (1 H, s), 7.56 (1 H, s).

<Synthesis of Compound 4a>
<< Step 1: Synthesis of 1- (3,4-diallyloxyphenyl) ethanone >>
In a 300 mL two-necked eggplant flask, 3,4-dihydroxyacetophenone (10.0 g, 65.7 mmol) is added and dissolved in acetone (145 mL), potassium carbonate (36.3 g, 263 mmol) is added, and stirred at room temperature for 1 hour After that, allyl bromide (37.4 g, 309 mmol) was added and refluxed for 2.5 hours. After concentration, ethyl acetate (150 mL × 3) and pure water (150 mL) are added for extraction, and the organic layer is washed with saturated brine (150 mL × 3), dried over anhydrous magnesium sulfate, filtered and concentrated. 15.2 g (65.2 mmol, 99%) of solid were obtained.

The identification result of the obtained intermediate compound 21 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 2.55 (3H, s), 4.65-4.70 (4H, m), 5. 29-5. 34 (2H, m), 5.41-5. 48 (2H, m), 6.03- 6.14 (2H, m), 6.88-6. 91 (1H, m), 7.53-7.56 (2H, m).

<< Step 2: Synthesis of 1- (4,5-diallyloxy-2-nitrophenyl) ethanone >>
Intermediate compound 21 (15.2 g, 65.2 mmol) is placed in a 300 mL eggplant flask and dissolved in acetic acid (60 mL), and fuming nitric acid (27.3 mL) is slowly added over 20 minutes on an ice bath to react After confirming the progress by TLC, it was poured into pure water (200 mL). The extract was extracted with chloroform (250 mL × 3), and the organic layer was washed successively with 5% aqueous sodium hydrogen carbonate solution (250 mL × 2) and saturated brine (250 mL × 2), dried over anhydrous magnesium sulfate, filtered and concentrated. Purification by silica gel column chromatography (hexane: ethyl acetate = 4: 1) gave a pale yellow solid. Recrystallization from ethanol gave 6.08 g (21.9 mmol, 34%) of needle-like pale yellow crystals.

The identification result of the obtained intermediate compound 22 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 2.49 (3H, s), 4.68-4.72 (4H, m), 5.35-5. 40 (2H, m), 5.42-5.51 (2H, m), 6.00- 6.12 (2H, m), 6.76 (1 H, s), 7.62 (1 H, s).

Step 3: Synthesis of 1- (4,5-diallyloxy-2-nitrophenyl) ethanol
Intermediate compound 22 (6.08 g, 21.9 mmol) is put in a 300 mL eggplant flask, dissolved in tetrahydrofuran (70 mL), methanol (30 mL) is added, and then sodium borohydride (2.90 g) on an ice bath , 76.7 mmol) was added in small portions and stirred at 0 ° C. for 1.5 hours. After concentration, ethyl acetate (100 mL × 3), pure water (100 mL) and 2N hydrochloric acid (15 mL) are added for extraction, and the organic layer is washed with saturated brine (150 mL × 2), dried over anhydrous magnesium sulfate, and filtered. Concentrated. The resulting yellow-brown solid was washed with hexane and suction filtered to obtain 5.51 g (19.7 mmol, 90%) of a yellow solid.

The identification result of the obtained intermediate compound 23 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 1.54 (3 H, d, J = 6.3 Hz), 2.27 (1 H, d, J = 3.6 Hz), 4.64-4. 76 (4 H, m), 5.32-5.38 (2H, m), 5.42-5. 50 (2H, m), 5.51-5. 57 (1 H, m), 6.02-6. 13 (2 H, m), 7.30 (1 H, s), 7. 59 (1 H, s).

<< Step 4: Synthesis of 1- (4,5-diallyloxy-2-nitrophenyl) ethyl N-succinimidyl carbonate >>
Intermediate compound 23 (2.86 g, 10.2 mmol) is put into a 300 mL two-necked eggplant flask and dissolved in dry acetonitrile (35 mL), di (N-succinimidyl) carbonate (4.46 g, 17.4 mmol), triethylamine (3.21 g, 31.7 mmol) was added and stirred at room temperature for 19 hours under a nitrogen atmosphere. After concentration, ethyl acetate (250 mL × 3) and pure water (250 mL) were added for extraction, and the organic layer was washed with saturated brine (250 mL × 3), dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography (hexane: ethyl acetate = 2: 1) to obtain 3.13 g (7.45 mmol, 73%) of a white yellow solid.

The identification result of the obtained intermediate compound 24 is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 1.74 (3H, d, J = 6.4 Hz), 2.80 (4H, s), 4.65-4.69 (2H, m), 4.73-4.86 (2H, m) , 5.33-5.41 (2H, m), 5.43-5.54 (2H, m), 6.01-6.16 (2H, m), 6.50 (1H, q, J = 6.4 Hz), 7.10 (1H, s), 7.65 (1H , s).

<< Step 5; Synthesis of 1- (2-nitro-4,5-bis (3-tris (trimethylsiloxy) silylpropoxy) phenyl) ethyl N-succinimidyl carbonate >>
Intermediate compound 24 (400 mg, 0.95 mmol) was placed in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (10 mL) to obtain tris (trimethylsiloxy) silane (1.41 g, 4.75 mmol), a Karstedt catalyst ( 10 drops were added and stirred at room temperature for 27 hours under nitrogen atmosphere. After concentration, the residue was purified by silica gel chromatography (hexane: ethyl acetate = 8: 1, containing 1% tetramethoxysilane) to obtain 314 mg (0.31 mmol, 33%) of a yellow gum.

The identification result of the obtained intermediate compound 2a is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.10-0.11 (54H, m), 0.54-0.65 (4H, m), 1.75 (3H, d, J = 6.4 Hz), 1.83-1.97 (4H, 4H, m) m), 2.80 (4H, s), 3.97-4.17 (4H, m), 6.52 (1 H, q, J = 6.6 Hz), 7.05 (1 H, s), 7.61 (1 H, s).

Step 6: Synthesis of 1- (2-nitro-4,5-bis (3-tris (trimethylsiloxy) silylpropoxy) phenyl) ethyl 3-trimethoxysilylpropyl carbamate >>
Intermediate compound 2a (147 mg, 0.145 mmol) is placed in a 30 mL two-necked eggplant flask, dissolved in dry tetrahydrofuran (7 mL), 3-aminopropyltrimethoxysilane (78 mg, 0.43 mmol), triethylamine (44 mg, 0.43 mmol) In addition, the mixture was stirred at room temperature for 13 hours under light shielding under a nitrogen atmosphere. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1, containing 1% of tetramethoxysilane) to obtain 64 mg (0.059 mmol, 41%) of a light yellow gum.

The identification result of the obtained compound 4a is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.09-0.12 (54H, m), 0.51-0.67 (6H, m), 1.52-1.66 (5H, m), 1.81-1.94 (4H, m), 3.03-3.22 (2H, m), 3.56 (9H, s), 3.93-4.05 (4H, m), 4.88 (1H, t, J = 5.9 Hz), 6.37 (1 H, q, J = 6.4 Hz), 6.97 (1H, s), 7.55 (1H, s).

<Synthesis of Compound 4b>
<< Step 1; 1- (4,5-Bis (3- (1,1,3,3,5,5,5-heptamethyltrisiloxanyl) propoxy) -2-nitrophenyl) ethyl N-succin Synthesis of imizyl carbonate »
Intermediate compound 24 (800 mg, 1.90 mmol) was put in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (15 mL), and 1,1,3,3,3,5,5,5-heptamethyltrisiloxane (1. 69 g (7.61 mmol) and a Karstedt catalyst (10 drops) were added and stirred at room temperature for 4 hours under nitrogen atmosphere. After concentration, the residue was purified by silica gel chromatography (hexane: ethyl acetate = 8: 1, containing 1% tetramethoxysilane) to obtain 527 mg (0.60 mmol, 32%) of a yellow gum.

The identification result of the obtained compound 2b is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.03 (6 H, s), 0.04 (6 H, s), 0.08 (9 H, s), 0.09 (9 H, s), 0.12 (6 H, s), 0.12 (6H, s), 0.63 to 0.73 (4H, m), 1.75 (3H, d, J = 6.4 Hz), 1.84-1.96 (4H, m), 2.80 (4H, s), 3.97-4.21 (4H, m) ), 6.48-6.55 (1 H, m), 7.05 (1 H, s), 7.61 (1 H, s).

<< Step 2; Synthesis of 1- (4,5-bis (3- (1,1,3,3,5,5,5-heptamethyltrisiloxyl) propoxy) -2-nitrophenyl) ethyl 3-trimethoxysilylpropyl carbamate >>
Intermediate compound 2b (500 mg, 0.578 mmol) is placed in a 30 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (10 mL), 3-aminopropyltrimethoxysilane (0.122 mL, 0.692 mmol), triethylamine (70 mg, 0.69 mmol) ) Was added, and the mixture was stirred at room temperature for 3 hours while shielding light under a nitrogen atmosphere. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 3: 1, containing 1% of tetramethoxysilane) to obtain 342 mg (0.368 mmol, 64%) of a light yellow gum.

The identification result of the obtained compound 4b is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.025 (6 H, s), 0.031 (6 H, s), 0.080 (9 H, s), 0.085 (9 H, s), 0.11 (6 H, s), 0.12 (6H, s), 0.58-0.71 (6H, m), 1.53-1.67 (5H, m), 1.82-1.94 (4H, m), 3.03-3.22 (2H, m), 3.56 (9H, s), 3.99 (2H, t, J = 7.0 Hz), 4.03 (2H, t, J = 7.0 Hz), 4.90 (1 H, t, J = 5.8 Hz), 6.37 (1 H, q, J = 6.4 Hz), 6.97 (1 H , s), 7.55 (1 H, s).

<Synthesis of Compound 4c>
<< Step 1: Synthesis of 1- (4,5-bis (3- (polydimethylsiloxanyl) propoxy) -2-nitrophenyl) ethyl N-succinimidyl carbonate >>
Intermediate compound 24 (1.01 g, 2.39 mmol) is put into a 200 mL two-necked eggplant flask and dissolved in dry tetrahydrofuran (30 mL), and polydimethylsiloxane (6.69 g, 6.19 mmol), the Karsted catalyst (10) Drop) was added and stirred at room temperature for 20 hours under nitrogen atmosphere. After concentration, the residue was purified by silica gel chromatography (hexane: ethyl acetate = 8: 1, containing 1% tetramethoxysilane) to obtain 630 mg (0.26 mmol, 11%) of a yellow gum.

The identification result of the obtained compound 2c is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.03-0.14 (156 H, m), 0.49-0.57 (4 H, m), 0.62-0.75 (4 H, m), 0.88 (6 H, t, J = 7.0) Hz), 1.24-1.38 (8H, m), 1.75 (3H, d, J = 6.4 Hz), 1.83-1.97 (4H, m), 2.80 (4H, s), 3.97-4.21 (4H, m), 6.48 -6.55 (1 H, m), 7.04 (1 H, s), 7.61 (1 H, s).

<< Step 2; Synthesis of 1- (4,5-bis (3- (polydimethylsilyl) propoxy) -2-nitrophenyl) ethyl 3-trimethoxysilylpropyl carbamate >>
Intermediate compound 2c (305 mg, 0.12 mmol) is placed in a 30 mL two-necked eggplant flask, dissolved in dry tetrahydrofuran (12 mL), 3-aminopropyltrimethoxysilane (66 mg, 0.37 mmol), triethylamine (37 mg, 0.37 mmol) In addition, the mixture was stirred at room temperature for 2.5 hours under light shielding under a nitrogen atmosphere. After concentration, the residue was purified by silica gel column chromatography (hexane: ethyl acetate = 2: 1, containing 1% tetramethoxysilane) to obtain 91 mg (0.036 mmol, 29%) of a yellow gum.

The identification result of the obtained compound 4c is shown below.
¹ H NMR (CDCl ₃ / TMS, 400 MHz): δ 0.02-0.14 (156 H, m), 0.49-0.57 (4 H, m), 0.58-0.71 (6 H, m), 0.88 (3 H, t, J = 7.0) Hz), 1.24-1.36 (8H, m), 1.52-1.65 (5H, m), 1.81-1.94 (4H, m), 3.03-3.23 (2H, m), 3.56 (9H, s), 3.98 (2H, m) t, J = 7.0 Hz), 4.03 (2 H, t, J = 7.0 Hz), 4. 89 (1 H, t, J = 5.7 Hz), 6.33-6. 40 (1 H, m), 6. 97 (1 H, s), 7.55 ( 1H, s).

<Surface modification>
The silicon wafer with thermal oxide film (SiO ₂ / Si substrate) is ultrasonically cleaned with pure water, acetone, methanol and chloroform for 5 minutes each, dried with a nitrogen stream, and then irradiated with UV for 1 hour with a UV-ozone cleaner. Pre-treated.
Next, the compounds 3b, 4a, 4b and 4c obtained by the above method were each dissolved in dry toluene to prepare a 1 mM (compound 4a, 4b and 4c was 0.1 mM) solution, and the above pretreatment was carried out. The substrate was placed, and immersed in a nitrogen atmosphere at room temperature for 20 hours (the compounds 4a and 4c were for 24 hours). The substrate was ultrasonically cleaned with chloroform for 5 minutes and dried with a stream of nitrogen (Step 1 below).

<Light irradiation>
The modified substrate was irradiated with light of wavelength 365 nm and illuminance 15 J (only compound 4 b was 10 J) through a filter with an extra-high pressure mercury lamp in the atmosphere. The substrate was ultrasonically cleaned with chloroform for 5 minutes and dried with a stream of nitrogen (Step 2 below).

<Contact angle measurement>
Using a contact angle meter (Kyowa Interface Science Co., Ltd.), water, diiodomethane, and 1-bromonaphthalene were respectively used as the probe liquid according to the droplet method / θ / 2 method to measure static contact angles before and after light irradiation. The results are shown in the table. In the following table, "before light irradiation" means immediately after the above step 1 and "after light irradiation" means immediately after the above step 2.

<XPS measurement>
It was evaluated by X-ray photoelectron spectroscopy (hereinafter referred to as "XPS"). FIG. 5 shows a substrate modified with compound 3b, FIG. 6 shows a substrate modified with compound 4a, FIG. 7 shows a substrate modified with compound 4b, and FIG. 8 shows XPS spectra before and after light irradiation on a substrate modified with compound 4c.

The obtained modified substrate was compared before and after light irradiation by static contact angle measurement and XPS.
It is considered that the surface of the substrate was modified because the contact angle was large after the modification and the water repellency was shown.
Moreover, compound 3b, 4a, 4c has confirmed the appearance of the peak derived from a nitro group after modification from XPS. Although a clear peak derived from a nitro group by XPS was not confirmed for the compound 4b, it is considered that this is because the film thickness is thin and sufficient sensitivity can not be obtained.
It was confirmed that the contact angle decreased after the light irradiation. Further, according to XPS, the compounds 3b, 4a and 4c were able to confirm the disappearance of the peak derived from the nitro group after light irradiation. Further, in any of the compounds, the C (carbon) peak decreased, and it was confirmed that the photodegradable group was eliminated by light irradiation.

S: Substrate CONT: Control unit Sa: Surface to be treated 2 ... Substrate supply unit 3 ... Substrate treatment unit 4 ... Substrate recovery unit 6 ... Compound application unit 7 .. Exposure unit 8: Mask 9: Pattern material application unit 100: Substrate processing device

Claims (14)

1. The compound represented by following General formula (1).
   

   

   [Wherein, X represents a halogen atom or an alkoxy group, R ¹ represents an alkyl group having 1 to 5 carbon atoms, a group represented by the following formula (R2-1), or a group represented by the following formula (R2-2) R ² is a group represented by the following formula (R2-1) or (R2-2), n0 is an integer of 0 or more, and n1 is 0 to The integer of 5, n2 is a natural number of 1 to 5. ]
   

   

   [Wherein, R ²¹ and R ²² each independently represent an alkyl group of 1 to 5 carbon atoms, and n is a natural number. The wavy line means a bond. ]
2. The compound according to claim 1, wherein R ²¹ or R ²² is any one of a methyl group, an isopropyl group and a tert-butyl group.
3. A substrate for pattern formation having a surface chemically modified with the compound according to claim 1 or 2.
4. A photocleavable coupling agent comprising the compound according to claim 1 or 2.
5. A pattern forming method for forming a pattern on a surface to be processed of an object, comprising:
   Chemically modifying the surface to be treated using the compound according to claim 1 or 2;
   Irradiating the chemically modified surface to be treated with light of a predetermined pattern to generate a latent image comprising a hydrophilic area and a water repellant area;
   And disposing a pattern forming material on the hydrophilic area or the water repellent area.
6. The pattern forming method according to claim 5, wherein the predetermined pattern corresponds to a circuit pattern for an electronic device.
7. The pattern forming method according to claim 5, wherein the pattern forming material includes a conductive material, a semiconductor material, or an insulating material.
8. The pattern forming method according to claim 7, wherein the conductive material comprises a conductive fine particle dispersion.
9. The pattern forming method according to claim 7, wherein the semiconductor material comprises an organic semiconductor material dispersion.
10. A pattern forming method for forming a pattern on a surface to be processed of an object, comprising:
    Chemically modifying the surface to be treated using the compound according to claim 1 or 2;
    Irradiating the chemically modified surface to be treated with light of a predetermined pattern to generate a latent image comprising a hydrophilic area and a water repellant area;
    And disposing an electroless plating catalyst in the hydrophilic region and performing electroless plating.
11. The pattern forming method according to any one of claims 5 to 10, wherein the object is a flexible substrate.
12. The pattern forming method according to any one of claims 5 to 11, wherein the object is made of a resin material.
13. The pattern forming method according to any one of claims 5 to 12, wherein the light includes light whose wavelength is included in a range of 200 nm to 450 nm.
14. A method of manufacturing a transistor having a gate electrode, a source electrode, and a drain electrode, comprising:
    A method of manufacturing a transistor, comprising the step of forming at least one of the gate electrode, the source electrode, and the drain electrode by the pattern forming method according to any one of claims 5 to 13.

Images