WO2020100710A1 - Pattern forming method, transistor manufacturing method, and film for pattern formation - Google Patents

Abstract

This pattern forming method for forming a pattern on a surface to be treated of an object is provided with: a step for forming an oxide film layer on the surface to be treated; a step for forming a compound-containing layer having a photosensitive deprotecting group by applying a compound-containing composition having the photosensitive deprotecting group onto the oxide film layer; a step for generating a latent image comprising a hydrophilic region and a water-repellent region by irradiating the compound-containing layer having the photosensitive deprotecting group with light with a predetermined pattern; and a step for disposing a pattern forming material in at least part of the hydrophilic region or at least part of the water-repellent region.

Description

Pattern forming method, transistor manufacturing method, and pattern forming film

The present invention relates to a pattern forming method, a transistor manufacturing method, and a pattern forming film.
The present application claims priority based on Japanese Patent Application No. 2018-215168 filed in Japan on Nov. 16, 2018, and the content thereof is incorporated herein.

In recent years, in the production of semiconductor devices, integrated circuits, fine devices such as devices for organic EL displays, etc., a method of forming a pattern having different surface characteristics on a substrate and utilizing the difference in the surface characteristics to create a fine device. Is proposed.

As a pattern forming method utilizing the difference in surface characteristics on the substrate, for example, there is a method of forming a hydrophilic region and a water repellent region on the substrate and applying an aqueous solution of a functional material to the hydrophilic region. According to this method, since the aqueous solution of the functional material spreads only in the hydrophilic region, a thin film pattern of the functional material can be formed.

A coupling agent has been used in recent years as a material capable of forming a hydrophilic region and a water repellent region on a substrate. Patent Document 1 describes a photodegradable coupling agent capable of significantly changing the contact angle before and after light irradiation. In order to improve the resolution of the pattern such as wiring, it is preferable to obtain a higher contrast between the hydrophilic region and the water repellent region.

JP, 2008-50321, A

One embodiment of the present invention is a pattern forming method for forming a pattern on a surface to be processed of an object, which includes a step of forming an oxide film layer on the surface to be processed, and a photosensitive layer on the oxide film layer. A step of applying a compound-containing composition having a protective group to form a compound-containing layer having a photosensitive deprotecting group, and irradiating the compound-containing layer having a photosensitive deprotecting group with a predetermined pattern of light to make it hydrophilic. A pattern forming method comprising: a step of forming a latent image including a region and a water repellent region; and a step of disposing a pattern forming material on at least a part of the hydrophilic region or at least a part of the water repellent region.
One embodiment of the present invention is a method for manufacturing a transistor having a gate electrode, a source electrode, and a drain electrode, wherein at least one electrode of the gate electrode, the source electrode, and the drain electrode is 1 is a method for manufacturing a transistor, including a step of forming by a pattern forming method according to one embodiment of the invention.
One embodiment of the present invention is a pattern-forming film in which an object, an oxide film layer, and a compound-containing layer having a photosensitive deprotecting group are laminated in this order.

It is a schematic diagram which shows the whole structure of a substrate processing apparatus. It is a figure which shows the schematic process of a pattern formation method. It is a figure which shows an example of the schematic process of the manufacturing method of a transistor. It is an optical microscope image of the printed wiring manufactured in the example. It is an optical microscope image of the printed wiring manufactured in the comparative example.

<Pattern forming method>
The present embodiment is a pattern forming method for forming a pattern on a surface to be processed of an object. The pattern forming method of the present embodiment comprises a step of forming an oxide film layer on the surface to be treated, and applying a compound containing composition having a photosensitive deprotecting group on the oxide film layer to form a photosensitive deprotecting group. A step of forming a compound-containing layer having, a step of irradiating the compound-containing layer having a photosensitive deprotecting group with a predetermined pattern of light to form a latent image composed of a hydrophilic region and a water-repellent region, and at least the hydrophilic region. Disposing a pattern forming material on at least a part of the water repellent region.

According to the pattern forming method of the present embodiment, it is possible to form a pattern with high resolution. In this embodiment, the case where the compound having a photosensitive deprotecting group is a fluorine compound will be described, but the present invention is not limited to this.

[Process of forming oxide film]
In this embodiment, an oxide film layer is formed on the surface to be processed of the object. The material forming the oxide film layer is preferably one or more inorganic oxides selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , SiON, ZnO, MgO, and TiO ₂ .

As a method for forming the oxide film layer, any one or more methods selected from physical vapor deposition (PVD), chemical vapor deposition (CVD), and atomic layer deposition (ALD) are used. Preferably.

Further, the method of forming the oxide film layer is not limited to the above-mentioned embodiment, and a wet film forming method may be used. For example, when a SiO ₂ film is formed by a wet film formation method, a silicon compound such as alkoxysilane or silazane, or polysiloxane or polysilazane in which these are oligomerized is applied to a substrate, and an organic component is removed by heating or ashing. The film may be formed by doing so. When the silicon compound is applied to the substrate, the silicon compound may be diluted with water or an organic solvent and then applied. The coating method is not particularly limited, and a general method such as spin coating or dip coating can be adopted. When forming another metal oxide film, a metal alkoxide may be used as a raw material instead of the above silicon compound.

In this embodiment, the thickness of the oxide film layer formed is preferably 2 nm to 1000 nm. If the thickness of the oxide film layer is smaller than the above lower limit value, it tends to be difficult to control the film thickness uniformly depending on the film forming method. When the thickness of the oxide film layer exceeds the above upper limit, the oxide film layer tends to be hard and it is difficult to obtain flexibility.

In the present embodiment, when the object is a substrate, the oxide film layer may be formed on only one side of the substrate, or the oxide film layer may be formed on both sides.

Generally, when an oxide film layer is formed, multiple OH groups are generated on the surface. Also in this embodiment, by forming an oxide film layer on the surface to be processed of the object, a plurality of OH groups are generated on the surface, so that the reactivity with the fluorine compound-containing composition applied in the subsequent step is improved. However, the fluorine compound-containing composition is more likely to bond to the surface to be treated.

That is, when the oxide film layer is provided, it is expected that the amount of the fluorine compound-containing composition bonded to the surface to be treated will be larger than that in the case where the oxide film layer is not provided. Therefore, the water repellency of the fluorine compound-containing composition can be sufficiently exhibited, and the contact angle on the surface of the object can be improved. This makes it possible to enhance the water repellency of the surface to be processed of the object and obtain a higher wettability contrast with the hydrophilic region formed in the step of forming a latent image described later.

[Step of forming fluorine compound-containing layer]
The method for forming the fluorine compound-containing layer is not particularly limited as long as X bound to the reactive Si in the general formula (1) described later is a method for binding to the substrate, and a dipping method or a chemical treatment method is used. Known methods such as the above can be used.

[Process of generating latent image]
This step is a step of irradiating the surface on which the fluorine compound-containing layer is formed with a predetermined pattern of light to selectively expose the surface to form a latent image composed of a hydrophilic region and a water repellent region. According to this step, in the fluorine compound in the exposed area, a group having water repellency (protecting group) is eliminated to generate a group having relative hydrophilicity, and a hydrophilic region is formed. In the unexposed area, this detachment does not occur and remains in the water repellent area.
Since the group having the water-repellent property is dissociated and the residue (amino group) having the hydrophilic property is generated, a latent image composed of the hydrophilic region and the water-repellent region can be formed after the light irradiation.

In this step, the light to be irradiated is preferably ultraviolet light. The irradiation light preferably includes light having a wavelength included in the range of 200 nm to 450 nm, and more preferably includes light having a wavelength included in the range of 320 nm to 450 nm. It is also preferable to irradiate light including light having a wavelength of 365 nm. Light having these wavelengths can efficiently decompose the protective group of the compound used in the present embodiment. Light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, sodium lamps; gas lasers such as nitrogen, liquid lasers of organic dye solutions, solid-state lasers containing inorganic earth crystals containing rare earth ions, etc. Can be mentioned.

Further, as a light source other than a laser capable of obtaining monochromatic light, light having a specific wavelength obtained by extracting a broadband line spectrum or continuous spectrum using an optical filter such as a bandpass filter or a cutoff filter may be used. A high-pressure mercury lamp or an ultra-high-pressure mercury lamp is preferable as the light source because a large area can be irradiated at one time.
In the pattern forming method of the present embodiment, light can be emitted arbitrarily within the above range, but it is particularly preferable to emit light energy having a distribution corresponding to the circuit pattern.

The exposure process is not particularly limited, and one exposure may be performed or multiple exposures may be performed. Further, when a transparent object is processed, the exposure may be performed from the object side or the fluorine compound-containing layer side. From the viewpoint of further shortening the exposure process, the exposure is preferably performed once.

In the present embodiment, the formation of an oxide film layer on the surface to be processed of the object can suppress the permeation of chemical substances and gases. Therefore, it is possible to obtain an effect that it is possible to protect the laminated structure such as wiring and electrodes that can be formed after this step from chemical substances and gas.

[Arbitrary post-exposure heating step]
In this embodiment, heating may be performed after the exposure. Examples of the heating method include an oven, a hot plate, and an infrared heater. The heating temperature may be 40 ° C to 200 ° C, or 50 ° C to 120 ° C.

[Arbitrary cleaning process]
In the present embodiment, a cleaning process may be provided after the exposure process or the heating process. Examples of the cleaning method include immersion cleaning, spray cleaning and ultrasonic cleaning. As the cleaning liquid, a polar solvent such as water or alcohol or a nonpolar solvent such as toluene may be used, or a mixed solution thereof or a liquid containing an additive such as a surfactant may be used. Further, after the cleaning, a drying process such as gas spraying or heating may be provided.

[Step of placing pattern forming material]
This step is a step of disposing the pattern forming material in the hydrophilic region or the water repellent region generated in the process of generating the latent image. As described above, since the fluorine compound-containing layer is provided on the oxide film layer, the fluorine compound-containing layer exhibits sufficient water repellency in the present embodiment. That is, since the hydrophilic region and the water-repellent region have a high wettability contrast, the pattern forming material is less likely to remain in the water-repellent region, and is favorably arranged in the hydrophilic region.

As the pattern forming material, a wiring material (metal solution) in which particles such as gold, silver, copper and alloys thereof are dispersed in a predetermined solvent, or a precursor solution containing the above metal, an insulator (resin), Examples include electronic materials obtained by dispersing semiconductors, organic EL light emitting materials and the like in a predetermined solvent, resist solutions, and the like.

In the pattern forming method of this embodiment, the pattern forming material is preferably a conductive material, a semiconductor material or an insulating material. Further, these pattern forming materials are preferably liquid conductive materials, liquid semiconductor materials, or liquid insulating materials.

The liquid conductive material may be 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 one of gold, silver, copper, palladium, nickel and ITO, as well as oxides thereof, fine particles of conductive polymers and superconductors, and the like are used.

The conductive fine particles can be used by coating the surface with an organic substance in order to improve the dispersibility.

The dispersion medium is not particularly limited as long as it can disperse the above conductive fine particles and does not cause aggregation. For example, in addition to water, alcohols such as methanol, ethanol, propanol, butanol, n-heptane, n-octane, decane, dodecane, 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- Examples thereof include ether compounds such as methoxyethyl) ether and p-dioxane, and polar compounds such as propylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide and cyclohexanone. Among these, water, alcohols, hydrocarbon compounds, and ether compounds are preferable from the viewpoints of dispersibility of fine particles, stability of dispersion liquid, and ease of application to a droplet discharge method (inkjet method). As more preferable dispersion media, water and hydrocarbon compounds can be mentioned.

As the liquid semiconductor material, an organic semiconductor material dispersed or dissolved in a dispersion medium can be used. As the organic semiconductor material, a π-electron conjugated polymer material whose skeleton is composed of conjugated double bonds is desirable. Typically, a soluble polymer material such as polythiophene, poly (3-alkylthiophene), polythiophene derivative, and pentacene can be used.

Liquid insulating materials include polyimide, polyamide, polyester, acrylic, PSG (phosphorus glass), BPSG (phosphorus glass), polysilazane SOG, silicate SOG (Spin on Glass), alkoxy silicate SOG, and siloxane polymer. A typical example is an insulating material in which SiO ₂ having a Si—CH ₃ bond or the like is dispersed or dissolved in a dispersion medium.

In this step, as a method for disposing the pattern forming material, a droplet discharge method, an inkjet method, a spin coating method, a roll coating method, a slot coating method, or the like can be applied.

Note that this step is not limited to the method described above, and may be performed by an electroless plating step in which an electroless plating catalyst is placed in a hydrophilic region or a water repellent region and electroless plating is performed. Details of the electroless plating process will be described later.

The target object is not particularly limited. In the present embodiment, the material of the object is, for example, a metal, a crystalline material (for example, a single crystalline material, a polycrystalline material and a partially crystalline material), an amorphous material, a conductor, a semiconductor, an insulator, a fiber, a glass, Ceramics, zeolites, plastics, thermosetting and thermoplastic materials (eg optionally doped: polyacrylates, polycarbonates, polyurethanes, polystyrenes, cellulosic polymers, polyolefins, polyamides, polyimides, polyesters, polyphenylenes, polyethylene, polyethylene terephthalate, polypropylene) , Ethylene vinyl copolymer, polyvinyl chloride, etc.). Further, the object may be an optical element, a coated substrate, a film, etc., which may have flexibility.

Here, the term "flexible" refers to the property of being able to bend the substrate without breaking or breaking even if a force of about its own weight is applied to the substrate. Further, flexibility also includes the property of bending by a force of about its own weight. Further, the flexibility changes depending on the material, size, thickness, environment such as temperature, etc. of the substrate. As the substrate, one strip-shaped substrate may be used, but a plurality of unit substrates may be connected to form a strip-shaped substrate.
In this embodiment, the object is preferably a substrate made of a resin material.

In the pattern forming method of this embodiment, the pattern can be a circuit pattern for an electronic device.

-Fluorine compound-containing composition The fluorine compound-containing composition used in the present embodiment will be described. The fluorine compound-containing composition preferably contains a fluorine compound represented by the following formula (1). The fluorine compound represented by the following formula (1) is a compound that acts as a silane coupling agent.
In the fluorine compound represented by the following formula (1), the group exhibiting water repellency is decomposed (desorbed) by exposure to produce a group exhibiting hydrophilicity. Therefore, the surface of the object to be treated can be changed from water-repellent to hydrophilic by the action of exposure.

[In the general formula (1), X represents a halogen atom or an alkoxy group, R ¹ represents a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and R ^f1 , R ^f2 Are each independently an alkoxy group, a siloxy group, or a fluorinated alkoxy group, and n represents an integer of 0 or more. ]

In the general formula (1), X is a halogen atom or an alkoxy group. Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but X is preferably an alkoxy group rather than a halogen atom. n represents an integer and is preferably an integer of 1 to 20 and more preferably an integer of 2 to 15 from the viewpoint of easy availability of starting materials.

In the general formula (1), R ¹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
As the alkyl group for R ^1, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and isobutyl. Group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like.

Examples of the cyclic alkyl group include groups in which one or more hydrogen atoms have been removed from polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.
In this embodiment, R ¹ is preferably a hydrogen atom, a methyl group or an ethyl group.

In the general formula (1), R ^f1 and R ^f2 are each independently an alkoxy group, a siloxy group, or a fluorinated alkoxy group.
In the general formula (1), the alkoxy group, siloxy group or fluorinated alkoxy group of R ^f1 and R ^f2 is preferably an alkoxy group having 3 or more carbon atoms, which is partially fluorinated. Or may be a perfluoroalkoxy group. In the present embodiment, it is preferably a partially fluorinated fluorinated alkoxy group.

In the present embodiment, examples of the fluorinated alkoxy group for R ^f1 and R ^f2 include a group represented by —O— (CH ₂ ) _n ^f1 — (C _n ^f2 F _2n ^f2 ₊₁ ). The n ^f1 is an integer of 0 or more, and the n ^f2 is an integer of 0 or more.
In this embodiment, n ^f1 is preferably 0 to 30, more preferably 0 to 15, and particularly preferably 0 to 5.
Further, in the present embodiment, n ^f2 is preferably 0 to 30, more preferably 0 to 15, and particularly preferably 1 to 5.

In the general formula (1), n is an integer of 0 or more. In the present embodiment, n is preferably 1 or more, and more preferably 3 or more.

Specific examples of the fluorine compound represented by the general formula (1) are shown below.

The above-mentioned fluorine compound can be produced by the method described in International Publication No. WO 2015/029981.

An example of chemical modification in this step is shown below. In the following formula, X, R ¹ , R ^f1 , R ^f2 , and n are the same as the description of R ¹ , R ^f1 , R ^f2 , and n in the general formula (1).

The fluorine compound represented by the formula (1) is dissolved in an organic solvent such as hexafluoroxylene to obtain a fluorine compound-containing composition.
The compound concentration of the fluorine compound in the fluorine compound-containing composition is not particularly limited, and is preferably 0.05 mM to 1.0 mM in terms of molar concentration (M), more preferably 0.075 mM to 0.5 mM, and 0.085 mM to 0. 0.2 mM is particularly preferred.

Hereinafter, the pattern forming method of the present embodiment will be described with reference to the drawings.
In the pattern forming method of this embodiment, when a flexible substrate corresponding to a so-called roll-to-roll process is used, a substrate processing apparatus 100 as a roll-to-roll apparatus as shown in FIG. 1 is used. It may be used to form a pattern.

As illustrated in FIG. 1, the substrate processing apparatus 100 performs processing on a substrate supply unit 2 that supplies a belt-shaped substrate (for example, a belt-shaped film member) S and a surface (a surface to be processed) Sa of the substrate S. The substrate processing unit 3, the substrate recovery unit 4 for recovering the substrate S, the fluorine compound coating unit 6, the exposure unit 7, the mask 8, the pattern material coating unit 9, and a control unit CONT for controlling these units. And have. The substrate processing unit 3 can perform various kinds of processing on the surface of the substrate S after the substrate S is delivered from the substrate supply unit 2 and before the substrate S is recovered by the substrate recovery unit 4.
The substrate processing apparatus 100 can be suitably used when a display element (electronic device) such as an organic EL element or a liquid crystal display element is formed on the substrate S.

Note that, although FIG. 1 illustrates a method using a photomask to generate a desired pattern light, this embodiment can be suitably applied to a maskless exposure method that does not use a photomask. it can. Examples of the maskless exposure method for generating pattern light without using a photomask include a method using a spatial light modulator such as a DMD and a method of scanning spot light like a laser beam printer.

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

As the substrate S to be processed in the substrate processing apparatus 100, for example, a resin film or a foil such as stainless steel can be used. For example, the resin film is a polyolefin resin, a polysilicone resin, a polyethylene resin, a polypropylene resin, a polyester resin, an ethylene vinyl copolymer resin, a polyvinyl chloride resin, a cellulose resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polystyrene resin, acetic acid. A material such as vinyl resin can be used.

The substrate S preferably has a small coefficient of thermal expansion so that its dimensions do not change even if it receives heat of about 200 ° C., for example. For example, the dimensional change can be suppressed by annealing the film. In addition, an inorganic filler can be mixed with the resin film to reduce the coefficient of thermal expansion. Examples of the inorganic filler include titanium oxide, zinc oxide, alumina, silicon oxide and the like. Further, the substrate S may be a single body of ultra-thin glass having a thickness of about 100 μm manufactured by a float method or the like, or a laminated body in which the resin film or aluminum foil is attached to the ultra-thin glass.

The dimension of the substrate S in the width direction (short direction) is, for example, about 1 m to 2 m, and the dimension in the length direction (long direction) is, for example, 10 m or more. Of course, this size is merely an example, and the size is not limited to this. For example, the dimension of the substrate S in the Y direction 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 so as to have flexibility. Here, the term "flexible" refers to the property of being able to bend the substrate without breaking or breaking even if a force of about its own weight is applied to the substrate. Further, flexibility also includes the property of bending by a force of about its own weight.
Further, the flexibility changes depending on the material, size, thickness, environment such as temperature, etc. of the substrate. As the substrate S, one strip-shaped substrate may be used, or a plurality of unit substrates may be connected to form a strip-shaped substrate.

The substrate supply unit 2 sends out and supplies the substrate S wound in a roll shape to the substrate processing unit 3, for example. In this case, the substrate supply unit 2 is provided with a shaft portion around which the substrate S is wound, a rotary drive device that rotates the shaft portion, and the like. In addition to this, for example, a cover portion that covers the substrate S in a rolled state may be provided. The substrate supply unit 2 is not limited to a mechanism that feeds the substrate S wound in a roll shape, but includes a mechanism that sequentially feeds the belt-shaped substrate S in its length direction (for example, a nip-type drive roller or the like). I wish I had it.

The substrate collecting unit 4 collects the substrate S, which has passed through the substrate processing apparatus 100, in a roll shape, for example. Similar to the substrate supply unit 2, the substrate collecting unit 4 is provided with a shaft for winding the substrate S, a rotary drive source for rotating the shaft, a cover unit for covering the collected substrate S, and the like. 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 rolled state, for example, the substrate S is collected in a stacked state. It doesn't matter.

The substrate processing unit 3 transfers the substrate S supplied from the substrate supply unit 2 to the substrate recovery unit 4, and forms a fluorine compound-containing layer on the surface Sa to be processed of the substrate S during the transfer process. A step of irradiating light of a pattern and a step of disposing a pattern forming material are performed. The substrate processing section 3 includes a coating section 6 for coating a material for forming a fluorine compound-containing layer on the surface Sa to be processed of the substrate S, an exposure section 7 for irradiating light, a mask 8, and pattern material coating. The unit 9 and the transfer device 20 including the drive roller R that sends the substrate S under the condition corresponding to the processing mode are provided.

The coating unit 6 and the pattern material coating unit 9 include a droplet coating device (for example, a droplet discharge coating device, an inkjet coating device, a spin coating coating device, a roll coating coating device, a slot coating coating device, etc.). Is mentioned.

Each of these devices is appropriately installed along the transportation path of the substrate S, and the panel of the flexible display 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 for performing the steps before and after the exposure section 7 (photosensitive layer forming step, photosensitive layer developing step, etc.) is provided inline as necessary.

<Transistor manufacturing method>
The present embodiment is a method of manufacturing a transistor having a gate electrode, a source electrode, and a drain electrode. In this embodiment, at least one of the gate electrode, the source electrode and the drain electrode is formed by the pattern forming method of the present invention.

In the present embodiment, a method of forming a wiring pattern by an electroless plating step in which a catalyst for electroless plating is placed in a hydrophilic region or a water repellent region and electroless plating is performed in the method for manufacturing a transistor will be described. The wiring pattern may be formed by applying a metal solution as described in [Step of placing pattern forming material].
According to this embodiment, for example, a wiring pattern can be formed by electroless plating by the following method. This will be described below with reference to FIG.

(First step)
First, an oxide film layer is formed on the surface of the substrate 11. Next, the fluorine compound-containing composition is applied onto the oxide film layer to form a fluorine compound-containing layer. In FIG. 2A, the compound layer 12 is a layer in which an oxide film and a fluorine compound-containing layer are laminated in this order.

As a method for forming the oxide film layer, one or more methods selected from physical vapor deposition (PVD), chemical vapor deposition (CVD), and atomic layer deposition (ALD) are used, and SiO 2 is formed. It is possible to form one or more inorganic oxides selected from the group consisting of ₂ , Al ₂ O ₃ , ZrO ₂ , SiON, ZnO, MgO, and TiO ₂ .

Further, the method of forming the oxide film layer is not limited to the above-mentioned embodiment, and a wet film forming method may be used. For example, when a SiO ₂ film is formed by a wet film formation method, a silicon compound such as alkoxysilane or silazane, or polysiloxane or polysilazane in which these are oligomerized is applied to a substrate, and an organic component is removed by heating or ashing. The film may be formed by doing so. When the silicon compound is applied to the substrate, the silicon compound may be diluted with water or an organic solvent and then applied.

Also, the application method is not particularly limited, and general methods such as spin coating and dip coating can be adopted. When forming another metal oxide film, a metal alkoxide may be used as a raw material instead of the above silicon compound.

As a method for applying the fluorine compound-containing composition, any of general film forming techniques such as physical vapor deposition (PVD), chemical vapor deposition (CVD), liquid phase epitaxy and the like may be used. . Among them, the liquid phase growth method is particularly preferable, and examples of the liquid phase growth method include a coating method (spin coating, dip coating, die coating, spray coating, roll coating, brush coating), a printing method (flexo printing, screen printing) and the like. Can be mentioned. Alternatively, a SAM film or an LB film may be used.

In this step, for example, a treatment of drying the solvent by heat or reduced pressure may be added.

(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 the means using a photomask, and means such as projection exposure using an optical system such as a lens or a mirror, maskless exposure using a spatial light modulator, a laser beam, or the like can be used. Note that the photomask 13 may be provided so as to be in contact with the compound layer 12 or may be provided so as not to be in contact with the compound layer 12.

(Third step)
Then, as shown in FIG. 2C, the compound layer 12 is irradiated with UV light through the photomask 13. As a result, the compound layer 12 is exposed in the exposed region of the photomask 13 and the hydrophilic region 14 is formed.

Note that UV light can irradiate a wavelength at which optimum quantum efficiency is exhibited due to the structure of the photosensitive group. For example, an i line of 365 nm can be used. Further, the exposure amount and the exposure time do not necessarily need to completely proceed with deprotection, and may be such that a part of deprotection occurs. In that case, in the plating step described later, the conditions (activity of the plating bath, etc.) can be appropriately changed according to the progress of deprotection.

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

An amino group is exposed on the surface of the hydrophilic region 14, but the amino group can capture and reduce the electroless plating catalyst. Therefore, the electroless plating catalyst is supplemented only on the hydrophilic region 14 to form the catalyst layer 15. Further, as the electroless plating catalyst, a catalyst capable of supporting a hydrophilic group such as an amino group generated by the decomposition of the protective group can be used.

(Fifth step)
As shown in FIG. 2E, electroless plating is performed to form the plating layer 16. The material of the plating layer 16 may be nickel-phosphorus (NiP) or copper (Cu).

In this step, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface and deposit 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. When the reduction is insufficient, it may be immersed in a reducing agent solution such as sodium hypophosphite or sodium borohydride to positively reduce the metal ion on the amine.

Further, a method of manufacturing a transistor using the plating 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 insulating layer 17 is formed on the compound layer 12 by covering the plating layer 16 of the electroless plating pattern formed by the above-described electroless plating pattern forming method by a known method. The insulating layer 17 is formed by using a coating liquid prepared by dissolving one or more resins such as an ultraviolet curable acrylic resin, epoxy resin, ene / thiol resin, and silicone resin in an organic solvent, and applying the coating liquid. You may form by this. The insulating layer 17 can be formed into a desired pattern by irradiating the coating film with ultraviolet rays through a mask provided with an opening corresponding to a region where the insulating layer 17 is to be formed.

(Seventh step)
As shown in FIG. 3B, the hydrophilic region 14 is formed in the portion where the source electrode and the drain electrode are formed in the same manner as the above-described first to third steps.

(Eighth step)
As shown in FIG. 3C, similarly to the fourth and fifth steps described above, the catalyst for electroless plating is supported on the hydrophilic region 14 to form the catalyst layer 15, and then the electroless plating is performed. By doing so, the plating layer 18 (source electrode) and the plating layer 19 (drain electrode) are formed. Note that nickel-phosphorus (NiP) and copper (Cu) are also used as the material of the plated layers 18 and 19, but a material different from that of the plated layer 16 (gate electrode) may be used.

(Ninth 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 formed by, for example, preparing a solution in which an organic semiconductor material soluble in an organic solvent such as TIPS pentacene (6,13-Bis (triisopropysilyltyl) 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). 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 preferably applied to the hydrophilized portion, and the semiconductor layer 21 is easily formed selectively. The semiconductor layer 21 is formed by adding one or more insulating polymers such as PS (polystyrene) and PMMA (polymethylmethacrylate) to the above solution, applying a solution containing the insulating polymer, and drying. May be. When the semiconductor layer 21 is formed in this manner, the insulating polymer is concentrated and formed below the semiconductor layer 21 (on the side of the insulator layer 17). When a polar group such as an amino group is present at the interface between the organic semiconductor and the insulating layer, the transistor characteristics tend to deteriorate, but by providing the organic semiconductor via the insulating polymer described above, It is possible to suppress deterioration of transistor characteristics. The transistor can be manufactured as described above.

The structure of the transistor is not particularly limited and can be appropriately selected according to the purpose. 2 to 3, the manufacturing method of the bottom contact / bottom gate type transistor has been described, but the same applies to the top contact / bottom gate type, top contact / top gate type and bottom contact / top gate type transistors. You may manufacture it. 2 to 3, the method of forming all of the gate electrode, the source electrode, and the drain electrode by the pattern forming method has been described in the present embodiment, but only the gate electrode is formed by the pattern forming method in the present embodiment. It may be formed, or only the source electrode and the drain electrode may be formed in the present embodiment by the pattern forming method.

<Pattern forming film>
The present embodiment is a film for pattern formation in which an oxide film layer and a compound-containing layer having a photosensitive deprotecting group are laminated in this order. In the present embodiment, the case where the compound having a photosensitive deprotecting group is a fluorine compound will be described, but the present invention is not limited to this.

The pattern forming film of the present embodiment includes an oxide film layer and a fluorine compound-containing layer in this order. Therefore, by selectively exposing through a mask or the like, in the exposed portion, the group exhibiting water repellency is decomposed (desorbed), and the group exhibiting hydrophilicity is generated.
According to the film for forming a pattern of the present embodiment, a desired pattern including a hydrophilic region and a water repellent region can be formed by selectively exposing the film.

In this embodiment, the oxide film layer preferably contains at least one inorganic oxide selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , SiON, ZnO, MgO, and TiO ₂ .

In the film for pattern formation of the present embodiment, the compound contained in the fluorine compound-containing layer is preferably a compound which produces an amino group when the protective group is decomposed.

In the film for pattern formation of the present embodiment, the compound contained in the fluorine compound-containing layer is preferably the fluorine compound represented by the general formula (1).

In the film for pattern formation of the present embodiment, the substrate used is preferably made of a resin material. As the resin material that can be preferably used, the same resin material as the resin material of the substrate described in the pattern forming method of the present invention can be used.
In the film for pattern formation of the present embodiment, the substrate used is preferably flexible.

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

<Example 1>
[Oxide film formation process]
A commercially available polyethylene terephthalate (PET) substrate having a SiO ₂ vapor deposition film was prepared.

[Surface treatment process]
- polyethylene terephthalate (PET) substrate was cut (5 cm × 5 cm) with a cleaning process SiO ₂ deposited film on the substrate, to obtain a test substrate. The obtained test substrate piece was dipped in a cleaning container containing 100 ml of isopropyl alcohol, and ultrasonically cleaned at 28 kHz for 1 minute. Furthermore, after drying with a nitrogen flow, cleaning was performed with an atmospheric pressure plasma device.

Preparation of Fluorine Compound-Containing Composition A 0.1% by mass hexafluoroxylene solution of the following compound (F1) was prepared to give a fluorine compound-containing composition. The following compound (F1) was produced by the method described in WO 2015/029981.

[Step of forming fluorine compound-containing layer]
The washed test substrate was immersed in a container containing the prepared composition containing a fluorine compound, and the container was heated at 60 ° C. for 60 minutes. The test substrate was taken out from the fluorine compound-containing composition, immersed in a cleaning container containing chloroform and rinsed. Then, the test substrate was immersed in a cleaning container containing acetone, and ultrasonic cleaning was performed at 28 kHz for 3 minutes. After drying with a nitrogen stream, the formed test substrate was heated at 90 ° C. for 1 minute.

[Process of generating latent image]
Next, a test substrate on which the F1 layer was entirely deposited was exposed to light having a wavelength of 365 nm at 500 mJ / cm ² through a photomask (L / S = 100 μm / 100 μm) to expose the F1 layer to form a pattern.
The exposed test substrate was immersed in a cleaning container containing chloroform for rinsing. Then, the test substrate was immersed in a cleaning container containing acetone, and ultrasonic cleaning was performed at 28 kHz for 3 minutes. After drying with a nitrogen stream, the formed test substrate was heated at 90 ° C. for 1 minute.

[Step of placing pattern forming material]
Then, the silver nanometal ink (manufactured by Bando Kagaku Co., Ltd., solid content concentration 40% by mass) was introduced into a printing tester having a doctor blade, an anilox roller, and an inking roller by using a pipettor, and the exposed substrate was inked did. The metal wiring was produced on the substrate by firing the ink applied on the substrate at room temperature.

<Example 2>
The polyethylene terephthalate (PET) substrate having a SiO ₂ vapor deposition film of Example 1 was changed to a polyethylene naphthalate (PEN) substrate having a SiO ₂ CVD film, the same treatment was performed, and after exposure of 2000 mJ / cm ^2, exposure was carried out by printing. Metal wiring was produced.

<Example 3>
The SiO ₂ vapor deposition film of Example 1 was changed to an Al ₂ O ₃ ALD film, the same treatment was carried out, and after exposing at 1000 mJ / cm ² , metal wiring was produced by printing.

<Example 4>
The polyethylene terephthalate (PET) substrate having the SiO ₂ vapor deposition film of Example 1 was changed to a polyethylene naphthalate (PEN) substrate having an Al ₂ O ₃ ALD film, the same treatment was carried out, and after 500 mJ / cm ² exposure, Metal wiring was produced by printing.

<Comparative Example 1>
The polyethylene terephthalate (PET) substrate having the SiO ₂ vapor-deposited film of Example 1 was replaced with a polyethylene terephthalate (PET) substrate, the same treatment was carried out, and after 2000 mJ / cm ² exposure, metal wiring was produced by printing.

<Comparative example 2>
The polyethylene terephthalate (PET) substrate having the SiO ₂ vapor deposition film of Example 1 was changed to a polyethylene naphthalate (PEN) substrate, the same treatment was carried out, and after exposing at 2000 mJ / cm ² , metal wiring was produced by printing.

[Evaluation of printed wiring]
FIG. 4A shows an image of an optical microscope (VHX-900, manufactured by Keyence Corporation) on which printed wiring processing was performed in Example 1. FIG. 4 (b) shows the same example as that of Example 2, FIG. 4 (c) shows Example 3, and FIG. 4 (d) shows the same example as that obtained in Example 4.
FIG. 5A shows a substrate obtained as a result of performing the printed wiring process in Comparative Example 1 and FIG.

As shown in the figure, in Comparative Examples 1 and 2, the metal layer was formed on almost the entire surface of the substrate, but in Examples 1 to 4, excellent fine printed wiring was formed in every detail. It was confirmed that even in a low temperature process of ℃ or less, wiring can be formed on a flexible substrate very easily without using a resist.

S ... substrate
CONT ... Control unit Sa ... Surface to be processed
2 ... Substrate supply unit
3 ... Substrate processing unit
4 ... Board recovery unit
6 ... Compound coating part
7 ... Exposure unit
8 ... Mask
9 ... Pattern material application section
100 ... Substrate processing apparatus

Claims (14)

1. A pattern forming method for forming a pattern on a surface to be processed of an object,
   Forming an oxide film layer on the surface to be processed,
   On the oxide film layer, a step of applying a compound-containing composition having a photosensitive deprotecting group to form a compound-containing layer having a photosensitive deprotecting group,
   Irradiating the compound-containing layer having the photosensitive deprotecting group with a predetermined pattern of light to form a latent image composed of a hydrophilic region and a water-repellent region,
   A step of disposing a pattern forming material on at least a part of the hydrophilic area or at least a part of the water repellent area.
2. The pattern forming method according to claim 1, wherein, in the step of forming the latent image, a region of the compound-containing layer having the photosensitive deprotecting group, which is irradiated with the predetermined pattern light, becomes relatively hydrophilic. ..
3. The pattern forming method according to claim 1 or 2, wherein the photosensitive deprotecting group has fluorine.
4. The oxide film layer contains at least one inorganic oxide selected from the group consisting of SiO ₂ , Al ₂ O ₃ , ZrO ₂ , SiON, ZnO, MgO, and TiO ₂ . The method for forming a pattern according to item 1.
5. In the step of forming the oxide film layer, the oxide film layer is formed by any one or more methods selected from chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD). Item 5. The pattern forming method according to any one of Items 1 to 4.
6. 5. The pattern forming method according to claim 1, wherein in the step of forming the oxide film layer, the oxide film layer is formed by applying a raw material containing a metal alkoxide to remove an organic component. ..
7. The pattern forming method according to any one of claims 1 to 6, wherein the predetermined pattern corresponds to a circuit pattern for an electronic device.
8. The pattern forming method according to claim 1, wherein the object is a substrate made of a resin material.
9. The pattern forming method according to any one of claims 1 to 8, wherein the pattern forming material includes a conductive material, a semiconductor material, or an insulating material.
10. The pattern forming method according to claim 9, wherein the conductive material is conductive fine particles.
11. 9. The step of disposing the pattern forming material includes an electroless plating step of disposing an electroless plating catalyst in the hydrophilic region or the water repellent region and performing electroless plating. The method for forming a pattern according to.
12. A method for manufacturing a transistor having a gate electrode, a source electrode, and a drain electrode, comprising:
    A method of manufacturing a transistor, comprising a step of forming at least one electrode of the gate electrode, the source electrode, and the drain electrode by the pattern forming method according to claim 1.
13. A film for pattern formation, in which an object, an oxide film layer, and a compound-containing layer having a photosensitive deprotecting group are laminated in this order.
14. The pattern forming film according to claim 13, wherein the photosensitive deprotecting group has fluorine.

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