WO2020045078A1 - Transistor production method - Google Patents

Abstract

Provided is a transistor production method involving steps in which: a gate electrode is formed upon a target using a conductive material; an insulating film is formed upon the gate electrode; a light-responsive film is formed upon the insulating film using a material containing a compound having a light-responsive nitrobenzyl group; the light-responsive film is selectively exposed to cause the dissociation of the light-responsive group in the exposed portions and form a pattern comprising hydrophilic exposed portions and a water-repellent unexposed portion; a conductive material is disposed on the exposed portions to form a source electrode and a drain electrode; a modified layer is formed wherein the surface energy of the unexposed portion has been reduced; and a semiconductor layer is formed upon the modified layer.

Description

Method for manufacturing transistor

The present invention relates to a method for manufacturing a transistor.
Priority is claimed on Japanese Patent Application No. 2018-161268 filed on August 30, 2018, the content of which is incorporated herein by reference.

In recent years, in the production of semiconductor devices, integrated circuits, and fine devices such as organic EL display devices, patterns having different surface characteristics are formed on a substrate, and fine devices such as thin film transistors are formed by utilizing the difference in surface characteristics. A method of creating one has been proposed. As a material for forming a pattern having different surface characteristics, for example, a photodegradable coupling agent disclosed in Patent Document 1 is known. From the viewpoint of improving the performance of a transistor, a transistor with improved electric characteristics is demanded.

JP 2008-50321 A

One embodiment of the present invention is to form a gate electrode using a conductive material over an object, form an insulating film over the gate electrode, and use a compound having a photoresponsive nitrobenzyl group on the insulating film. Forming a photo-responsive film using the material containing, selectively exposing the photo-responsive film to dissociate the photo-responsive group of the exposed portion, a hydrophilic exposed portion, and a water-repellent unexposed Forming a pattern consisting of a non-exposed portion, forming a source electrode and a drain electrode by arranging a conductive material in the exposed portion, forming a modified layer having a reduced surface energy of the unexposed portion, Forming a semiconductor layer on a layer.

FIG. 1 is a schematic diagram illustrating an overall configuration of a substrate processing apparatus suitable for a method of manufacturing a transistor according to an embodiment. FIG. 7 is a diagram illustrating an example of a schematic process of a method for manufacturing a transistor. FIG. 7 is a diagram illustrating an example of a schematic process of a method for manufacturing a transistor. FIG. 7 is a diagram illustrating an example of a schematic process of a method for manufacturing a transistor.

<Transistor manufacturing method>
This embodiment is a method for manufacturing a transistor.
In the present embodiment, first, a gate electrode is formed on a target using a conductive material, and an insulating film is formed on the gate electrode.
Next, a photoresponsive film is formed on the insulating film using a material containing a compound having a photoresponsive nitrobenzyl group.
Next, the photoresponsive film is selectively exposed to dissociate the photoresponsive groups in the exposed portions, thereby forming a pattern including a hydrophilic exposed portion and a water-repellent unexposed portion.
Next, a conductive material is disposed on the exposed portion to form a source electrode and a drain electrode.
Further, a modified layer in which the surface energy of the unexposed portion is reduced is formed, and a semiconductor layer is formed on the modified layer.

When a hydrophilic group such as a carboxy group, amino group, or hydroxyl group is present in contact with the channel region of a transistor, these polar groups attract carriers flowing through the channel region, preventing the flow of carriers. Is easy to occur. When a carrier trap is generated, the behavior of the transistor is not stable, and for example, a problem such as occurrence of hysteresis in element characteristics is likely to occur.
By the way, a material containing a compound having a photoresponsive nitrobenzyl group is used because the wettability of the substrate surface can be suitably modified. When this compound is used, a nitrobenzyl group exists in an unexposed portion. On the other hand, a hydrophilic group such as an amino group exists in a portion where the photodegradable group is decomposed by exposure.

ア ミ ノ Among the hydrophilic groups, the amino group is a functional group having a high surface free energy. Due to the high hydrophilicity, adsorption of moisture and impurities occurs, which can cause defects and deterioration of the device. If the surface free energy of the material to be laminated on the upper layer is significantly different from the surface free energy, desired adhesion, crystallinity and orientation may not be obtained.

In the present embodiment, an object is to provide a method for manufacturing a transistor with favorable characteristics even when a material including a compound having a photoresponsive nitrobenzyl group is used.

The method for manufacturing a transistor according to the present embodiment includes a first pattern forming step of forming a gate electrode, an insulating film forming step, a second pattern forming step of forming a source electrode and a drain electrode, and a modified layer forming step. It is preferable to provide in order.
Hereinafter, each step of the present embodiment will be described.

<< First pattern formation process >>
First, steps up to the formation of a pattern including a hydrophilic exposed portion on an object will be described.
The first pattern forming step is a step of forming a pattern on an object and arranging a conductive material on the pattern to form a gate electrode.
The first pattern forming step preferably includes a step of forming a photoresponsive film on the object, an exposing step, and a conductive material arranging step in this order.

Step of Forming Photoresponsive Film on Object First, as shown in FIG. 2A, a photoresponsive film 12 containing a compound having a photoresponsive nitrobenzyl group is formed on the surface of a substrate 11. I do.
It is preferable that the photoresponsive film 12 is formed by being applied on an object. The compound having a photoresponsive ditrobenzyl group contained in the photoresponsive film will be described later.

As a coating method, any of general film forming techniques such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and liquid phase growth may be used. Among them, the liquid phase growth method is particularly preferable. Examples of the liquid phase growth method include a coating method (spin coating, dip coating, die coating, spray coating, roll coating, brush coating), and a printing method (flexographic printing, screen printing). No. Further, it may be a SAM film or an LB film.

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

-Exposure Step After forming a photo-responsive film on the object, a predetermined pattern of light is irradiated to selectively expose. By the exposure step, the compound in the exposed portion is deprived of a group having a water repellency (protective group) to form a group having a hydrophilic property, and a hydrophilic region is formed in the exposed portion. In the unexposed portion, the detachment does not occur, and the water-repellent region remains.
Since the group having water repellency is dissociated, and a residue (amino group) having hydrophilic property is generated, a latent image including a hydrophilic area and a water repellent area can be generated after light irradiation.

Specifically, as shown in FIG. 2B, a photomask 13 having an exposure region of a predetermined pattern is prepared. The exposure method is not limited to a method using a photomask, but may be a method such as a projection exposure using an optical system such as a lens or a mirror, a maskless exposure using a spatial light modulator, a laser beam, or the like. Note that the photomask 13 may be provided so as to be in contact with the photoresponsive film 12 or may be provided so as not to be in contact therewith.
Thereafter, as shown in FIG. 2C, the photoresponsive film 12 is irradiated with UV light via the photomask 13. As a result, the photoresponsive film 12 is exposed in the exposed area of the photomask 13 and the hydrophilic area 14 is formed.

ＵＶ The UV light can be applied at a wavelength at which the optimum quantum efficiency is exhibited by the structure of the photosensitive group. For example, there is an i-line of 365 nm. Further, the exposure amount and the exposure time do not necessarily have to completely proceed with deprotection, but may be such that deprotection occurs partially. At this time, in the plating step described below, conditions (eg, activity of the plating bath) according to the degree of progress of deprotection can be appropriately changed.

に お い て In this step, the light to be irradiated is preferably ultraviolet light. The light to be irradiated preferably contains light having a wavelength in the range of 200 to 450 nm, and more preferably contains light having a wavelength in the range of 320 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 protecting 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, and sodium lamps; gas lasers such as nitrogen, liquid lasers of organic dye solutions, and solid-state lasers containing rare earth ions in inorganic single crystals. No.

In addition, as a light source other than a laser that can obtain monochromatic light, light of 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. Since a large area can be irradiated at one time, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp is preferable as the light source.
In the pattern forming step of this embodiment, light can be arbitrarily irradiated within the above range, but it is particularly preferable to irradiate light energy having a distribution corresponding to the circuit pattern.

(4) The exposure step is not particularly limited, and a single exposure may be performed or a plurality of exposures may be performed. When processing a transparent object, exposure may be performed from the object side. From the viewpoint of further shortening the exposure step, it is preferable to perform the exposure once.

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

[Optional cleaning process]
In the present embodiment, a cleaning step may be provided after the exposure step or after the heating step. Examples of the cleaning method include immersion cleaning, spray cleaning, and ultrasonic cleaning. As the washing liquid, a polar solvent such as water or alcohol, or a non-polar solvent such as toluene may be used, or a mixed solution thereof or a solvent containing an additive such as a surfactant may be used. After the cleaning, a drying step by gas blowing, heating, or the like may be provided.

[Placement process]
This step is a step of disposing a conductive material in the hydrophilic region generated in the exposure step. Through this step, a gate electrode is manufactured.

First, as shown in FIG. 2D, a catalyst for electroless plating is applied to the hydrophilic region 14 to form a catalyst layer 15.

触媒 A catalyst for electroless plating is a catalyst for reducing metal ions contained in a plating solution for electroless plating, and includes silver and palladium. When displacement plating or self-catalytic plating is performed as electroless plating, metal fine particles such as copper, nickel, and gold can be used instead of the above catalyst. The amino group is exposed on the surface of the hydrophilic region 14, and the amino group can capture and reduce the above-described catalyst for electroless plating. Therefore, the electroless plating catalyst is supplemented only on the hydrophilic region 14 to form the catalyst layer 15. As the electroless plating catalyst, a catalyst capable of carrying a hydrophilic group such as an amino group generated by decomposition of a protective group can be used.

Next, as shown in FIG. 2E, the substrate 11 is immersed in an electroless plating bath to reduce metal ions on the catalyst surface, thereby depositing a plating layer 16. Examples of the material of the plating layer 16 include nickel-phosphorus (NiP) and copper (Cu). Since the catalyst layer 15 supporting a sufficient amount of the 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, the metal ions on the amine may be positively reduced by immersion in a reducing agent solution such as sodium hypophosphite or sodium borohydride.

に よ り Through the above steps, the conductive material can be arranged in the hydrophilic region.

In addition, in this step, the conductive material can be arranged in the hydrophilic region by applying a pattern forming material composed 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, oxides thereof, and fine particles of a conductive polymer or a superconductor are used.

These conductive fine particles can be used by coating the surface with an organic substance or the like in order to improve 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, 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- (Methoxyethyl) ether, ether compounds such as p-dioxane, propylene carbonate, γ- Butyrolactone, N- methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, can be exemplified polar compounds such as cyclohexanone. Of these, water, alcohols, hydrocarbon compounds, and ether compounds are preferred in view of the dispersibility of the fine particles and the stability of the dispersion, and the ease of application to the droplet discharge method (inkjet method). More preferred dispersion media include water and hydrocarbon compounds.

有機 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 a conjugated double bond is desirable. Typically, soluble polymer materials such as polythiophene, poly (3-alkylthiophene), polythiophene derivatives, and pentacene are given.

液滴 As a method of disposing the pattern forming material, a droplet discharging method, an ink jet method, a spin coating method, a roll coating method, a slot coating method, and the like can be applied.

[Object]
The 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 monocrystalline, polycrystalline and partially crystalline material), an amorphous material, a conductor, a semiconductor, an insulator, a fiber, glass, Ceramics, zeolites, plastics, thermosetting and thermoplastic materials (eg, optionally doped: polyacrylate, polycarbonate, polyurethane, polystyrene, cellulose polymer, polyolefin, polyamide, polyimide, polyester, polyphenylene, polyethylene, polyethylene terephthalate, polypropylene , Ethylene-vinyl copolymer, polyvinyl chloride, etc.). Further, the target object may be an optical element, a painted substrate, a film, or the like, and these may have flexibility.

可 撓 Here, the term “flexible” refers to a property that the substrate can be bent 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. The flexibility varies depending on the material, size, thickness, environment such as temperature, and the like of the substrate. Note that a single band-shaped substrate may be used as the substrate, but a plurality of unit substrates may be connected to form a band.

<< Insulation film formation process >>
As shown in FIG. 3A, an insulating layer 17 is formed on the photoresponsive film 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. I do. The insulating layer 17 is made of, for example, a coating solution obtained by dissolving at least one resin such as an ultraviolet-curable acrylic resin, an epoxy resin, an en-thiol resin, a silicone resin, and an imide resin in an organic solvent. May be applied. By irradiating the coating film with ultraviolet rays through a mask provided with an opening corresponding to a region where the insulator layer 17 is formed, the insulator layer 17 can be formed in a desired pattern. The material of the insulating film is not limited to the organic material, but may be an inorganic material. Further, a metal oxide precursor such as an organic silane may be used. The method for forming the insulating film is not limited to the above coating method, and a known film forming technique such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) may be used.

<< Second pattern formation process >>
A second pattern forming step for forming a source electrode and a drain electrode will be described.
As shown in FIG. 3B, the hydrophilic region 14 is formed on the insulator layer 17 at the portion where the source electrode and the drain electrode are formed in the same manner as in the first pattern forming method described above.

As shown in FIG. 3C, in the same manner as in the first pattern forming method described above, the electroless plating catalyst is supported on the hydrophilic region 14 formed on the insulator layer 17, and the catalyst layer 15 is formed. After the formation, the plating layer 18 (source electrode) and the plating layer 19 (drain electrode) are formed by performing electroless plating. Note that nickel-phosphorus (NiP) and copper (Cu) are also examples of the material of the plating layers 18 and 19, but they may be formed of a material different from that of the plating layer 16 (gate electrode). In the second pattern forming step, the source electrode and the drain electrode may be formed using the pattern forming material described in the first pattern forming step.

≪Modified layer formation process≫
In the present embodiment, a modified layer in which the surface energy of the unexposed portion formed in the second pattern forming step is reduced is formed.
In the present embodiment, "reducing the surface energy" means that the contact angle with water before and after the formation of the modified layer is modified to a large value.

The step of forming the modified layer preferably includes a light irradiation step and a surface treatment step of performing a surface treatment with a photoresponsive surface treatment agent in this order.
The water-repellent region 12A in FIG. 3D is a layer containing a compound having a photoresponsive nitrobenzyl group. The modified layer forming step is a step of reducing the surface energy of the water-repellent region 12A. The surface energy of the water-repellent region 12A is made lower than the state where the nitrobenzyl group before the modification exists. Accordingly, carrier traps can be suppressed, and further, the adhesion to the material to be laminated on the upper layer and the crystallinity and orientation can be improved.

Light Irradiation Step In the modified layer forming step, as shown in FIG. 3D, the water repellent area 12A is irradiated with light. By irradiating the water-repellent region 12A with light, the nitrobenzyl group of the nitrobenzyl compound is decomposed, and a hydrophilic group such as an amino group is exposed. Thereby, the hydrophilic region 12B shown in FIG. 4A is formed.

に お い て In this step, the light to be irradiated is preferably ultraviolet light. The light to be irradiated preferably contains light having a wavelength in the range of 200 to 450 nm, and more preferably contains light having a wavelength in the range of 320 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 protecting 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, and sodium lamps; gas lasers such as nitrogen, liquid lasers of organic dye solutions, and solid lasers containing rare earth ions in inorganic single crystals. No. In the light irradiation step, the nitrobenzyl group does not always need to be completely decomposed in the exposed area, and at least a part of the nitrobenzyl group in the exposed area may be decomposed.

In addition, as a light source other than a laser that can obtain monochromatic light, light of 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. Since a large area can be irradiated at one time, a high-pressure mercury lamp or an ultra-high-pressure mercury lamp is preferable as the light source.
In the pattern forming method of the present embodiment, light can be arbitrarily irradiated within the above range, but it is particularly preferable to irradiate light energy having a distribution corresponding to the circuit pattern.

-Surface treatment step This step is a step of protecting the hydrophilic groups exposed in the light irradiation step with a surface treatment agent. As the surface treating agent used in this step, a surface treating agent such as a silane compound containing a phenyl group or a fluorine atom, or a phosphonic oxide can be used. Further, the surface treatment layer formed by the surface treatment step may be a layer formed from a self-assembled monomolecular SAM film material. When a self-assembled monomolecular SAM film material is used, electron-rich functional groups such as phenyl groups and fluorine atoms can be arranged on the surface of the insulating film by molecular orientation. Thus, the interface between the insulating film and the semiconductor layer becomes rich in electrons. Due to charge repulsion from the electron-rich insulating film interface, a hole-rich layer (positive charge) can be generated at the semiconductor-side interface.

It is also possible to obtain a surface containing two or more compounds by using two or more different surface treatment agents. In this case, for example, the exposure amount and the exposure time are controlled in the above-described light irradiation step, and a part of the nitrobenzyl group in the exposure region is decomposed. Then, after the exposed hydrophilic group is treated with a surface treating agent, a second light irradiation step is performed to decompose the remaining nitrobenzyl group that has not been decomposed. Next, the surface containing two or more compounds is obtained by treating the hydrophilic group exposed in the second light irradiation step with a different surface treatment agent.

Specific examples of the compound contained in the surface treatment agent used in the present embodiment include carboxylic acid compounds shown in the following (1) -1 and (1) -2, and compounds shown in (2) -1 and (2) -2. Succinimide compounds, silazane compounds shown in (3) -1 and (3) -2, chlorosilane compounds shown in (4) -1 to (4) -3, and (5) -1 and (5) -2 Sulfone compounds shown below.

As a method for performing the surface treatment, a known method such as a dipping method and a chemical treatment method can be used. Note that an activator or a condensing agent for promoting the reaction may be used. Further, a washing process may be appropriately performed to avoid the adhesion due to physical adsorption.
By performing the surface treatment with the surface treatment agents containing the compounds listed above, the surface treatment portion 12c is formed as shown in FIG. 4B.

The effect of forming the surface treatment portion 12c will be described using a p-type semiconductor as an example.
By forming the surface treatment portion 12c, it is possible to suppress or eliminate the effect of carrier traps due to defects in the insulating film and hydrophilic groups. Thereby, it is possible to improve the carrier mobility and the sub-threshold characteristic.

Further, at the interface between the insulating film and the semiconductor, the accumulation density of positive charges generated on the organic semiconductor side is improved, so that the on / off ratio can be improved. At this time, the gate voltage required to turn on the ON state changes depending on the dipole, that is, the strength of the charge distribution in the molecule. That is, it is possible to control the threshold voltage by selecting the surface modifier.
The change in surface charge due to surface treatment also lowers the surface free energy, which promotes molecular reorientation and crystallization at the time of polymer / low molecular weight organic semiconductor film formation, thereby improving transistor characteristics. .

4) As shown in FIG. 4C, 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, for example, by preparing a solution in which an organic semiconductor material soluble in an organic solvent such as TIPS pentacene (6,13-Bis (triisopropylsilylethyl) pentacene) is dissolved in the organic solvent, and forming the plating layer 18 (source). It may be formed by coating 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 making the portion corresponding to the channel of the transistor hydrophilic, the above solution is suitably applied to the hydrophilic portion, and the semiconductor layer 21 can be easily formed selectively. The semiconductor layer 21 is formed by adding at least one kind of insulating polymer such as PS (polystyrene) or PMMA (polymethyl methacrylate) to the above solution, and applying and drying a solution containing the insulating polymer. You may. When the semiconductor layer 21 is formed in this manner, the insulating polymer is concentrated below the semiconductor layer 21 (on the insulator layer 17 side). When 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 decrease, but by providing the organic semiconductor via the insulating polymer described above, Deterioration of transistor characteristics can be suppressed. As described above, a transistor can be manufactured.

The structure of the transistor is not particularly limited, and can be appropriately selected depending on the purpose. 2 to 4, the method of manufacturing a bottom-contact / bottom-gate transistor has been described. However, the same applies to a top-contact / bottom-gate transistor, a top-contact / top-gate transistor, and a bottom-contact / top-gate transistor. May be manufactured.

Hereinafter, an example of a pattern forming method according to the present embodiment will be described with reference to the drawings.
In the pattern forming method of the present embodiment, when a flexible substrate corresponding to a so-called roll-to-roll process is used, the substrate processing apparatus 100 which is a roll-to-roll apparatus as shown in FIG. The pattern may be formed by using the above.

As shown in FIG. 1, the substrate processing apparatus 100 performs processing on a substrate supply unit 2 that supplies a band-shaped substrate (for example, a band-shaped film member) S and a surface (processed surface) Sa of the substrate S. A substrate processing unit 3, a substrate recovery unit 4 for recovering the substrate S, a coating unit 6 of a compound having a photoresponsive nitrobenzyl group, an exposure unit 7, a mask 8, a pattern material coating unit 9, And a control unit CONT for controlling each unit. 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 S is collected by the substrate collection 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.

Although FIG. 1 illustrates a method using a photomask to generate a desired pattern light, the present embodiment can be suitably applied to a maskless exposure method using no photomask. it can. Examples of a 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 a spot light like a laser beam printer.

In the pattern forming method according to the present embodiment, an XYZ coordinate system is set as shown in FIG. 1, and the following description will be made using the XYZ coordinate system as appropriate. In the XYZ coordinate system, for example, an X axis and a Y axis are set along a horizontal plane, and a Z axis is set upward along a vertical direction. The substrate processing apparatus 100 transports 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 band-shaped substrate S is set in the Y-axis direction.

(4) As the substrate S to be processed in the substrate processing apparatus 100, for example, a foil (a foil) such as a resin film or stainless steel can be used. For example, the resin film may be made of a material such as 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, and the like. Can be used.

It is preferable that the substrate S 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, dimensional changes can be suppressed by annealing the film. Further, the thermal expansion coefficient can be reduced by mixing the inorganic filler with the resin film. Examples of the inorganic filler include titanium oxide, zinc oxide, alumina, and silicon oxide. The substrate S may be a single piece of ultra-thin glass having a thickness of about 100 μm manufactured by a float method or the like, or may be a laminate in which the above-described resin film or aluminum foil is bonded to the ultra-thin glass.

The size of the substrate S in the width direction (short direction) is, for example, about 1 m to 2 m, and the size in the length 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 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 to have flexibility. Here, the term "flexible" refers to a property that the substrate can be bent 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.
The flexibility varies depending on the material, size, thickness, environment such as temperature, and the like of the substrate. Note that, as the substrate S, a single band-shaped substrate may be used, but a configuration in which a plurality of unit substrates are connected to form a band may be used.

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 around which the substrate S is wound, a rotation driving device for rotating the shaft, and the like. In addition, for example, a configuration in which a cover or the like that covers the substrate S wound in a roll shape may be provided. The substrate supply unit 2 is not limited to a mechanism that sends out the substrate S wound in a roll shape, but includes a mechanism (for example, a nip-type driving roller or the like) that sequentially sends out the band-like substrate S in the length direction. I just need.

The substrate recovery unit 4 recovers the substrate S that has passed through the substrate processing apparatus 100, for example, by winding it into a roll. Similar to the substrate supply unit 2, the substrate recovery unit 4 includes a shaft for winding the substrate S, a rotation drive source for rotating the shaft, a cover for covering the recovered substrate S, and the like. When the substrate S is cut into a panel in the substrate processing unit 3, the substrate S is collected in a state different from the state of being wound in a roll, 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 forms a photoresponsive film on the processing target surface Sa of the substrate S during the transport process. A step of irradiating the pattern with light and a step of disposing a pattern forming material are performed. The substrate processing section 3 includes an application section 6 for applying a material for forming a photoresponsive film to the surface to be processed Sa of the substrate S, an exposure section 7 for irradiating light, a mask 8, and a pattern material application. It has a unit 9 and a transfer device 20 including a driving roller R for sending the substrate S under conditions corresponding to the form of processing.

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

These devices are appropriately provided along the transport path of the substrate S, and a panel of a flexible display or the like can be produced by a so-called roll-to-roll method. In the present embodiment, it is assumed that the exposure unit 7 is provided, and an apparatus for performing the processes before and after the process (the photosensitive layer forming process, the photosensitive layer developing process, etc.) is provided inline as necessary.

≪Compound≫
The compound having a photoresponsive nitrobenzyl group used in the present embodiment is preferably a fluorine-containing compound represented by the following general formula (1).

[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 and R ^f2 Is 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. X is preferably an alkoxy group rather than a halogen atom. n represents an integer and is preferably an integer of 1 to 20, more preferably an integer of 2 to 15, from the viewpoint of 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.
The alkyl group for R ¹ is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and the like. 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 a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, and a tetracycloalkane.
In the present 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 and is partially fluorinated. Or a perfluoroalkoxy group. In the present embodiment, a partially fluorinated alkoxy group is preferable.

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 ). ^Nf1 is an integer of 0 or more, and ^nf2 is an integer of 0 or more.
In the present embodiment, n ^f1 is preferably 0 to 30, more preferably 0 to 15, and particularly preferably 0 to 5.
In the present embodiment, ^nf2 is preferably from 0 to 30, more preferably from 0 to 15, and particularly preferably from 1 to 8.

ＮIn 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.

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

The above-mentioned fluorine-containing compound can be produced by the method described in WO 2015/029981.

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

S: substrate, CONT: control unit, Sa: surface to be processed, 2: substrate supply unit, 3: substrate processing unit, 4: substrate recovery unit, 6: fluorine-containing compound application unit, 7: exposure unit, 8: mask, 9: pattern material application unit, 100: substrate processing device

Claims (10)

1. Form a gate electrode using a conductive material on the object,
   Forming an insulating film on the gate electrode,
   Forming a photoresponsive film using a material containing a compound having a photoresponsive nitrobenzyl group on the insulating film;
   Selectively exposing the photoresponsive film to dissociate the photoresponsive group in the exposed portion, forming a pattern comprising a hydrophilic exposed portion and a water-repellent unexposed portion, Forming a source electrode and a drain electrode by disposing a conductive material, forming a modified layer having reduced surface energy of the unexposed portion, and forming a semiconductor layer on the modified layer. A method for manufacturing a transistor.
2. The method according to claim 1, wherein the step of forming the modified layer further includes a light irradiation step and a surface treatment step of performing a surface treatment with a photoresponsive surface treatment agent.
3. The method according to claim 1 or 2, wherein the pattern is a circuit pattern for an electronic device.
4. (4) The method for producing a transistor according to any one of (1) to (3), wherein the compound is a compound that generates an amino group when the protective group is decomposed.
5. The method according to any one of claims 1 to 4, wherein the material for forming the pattern includes a liquid conductive material or a liquid semiconductor material.
6. 6. The method of manufacturing a transistor according to claim 1, wherein the light for the exposure includes light having a wavelength in a range of 200 nm to 450 nm.
7. The method of manufacturing a transistor according to any one of claims 1 to 6, wherein the object is a substrate made of a resin material.
8. (8) The method of manufacturing a transistor according to any one of (1) to (7), wherein the object is a flexible substrate.
9. 9. The pattern according to claim 1, wherein the pattern includes a hydrophilic area and a water-repellent area, and includes an electroless plating step of arranging an electroless plating catalyst in the hydrophilic area or the water-repellent area and performing electroless plating. 2. A method for manufacturing a transistor according to claim 1.
10. The method according to claim 9, wherein in the electroless plating step, the electroless plating catalyst is disposed in the hydrophilic region.

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