KR102108040B1 - Method of forming organic polymer semiconductor pattern by low-temperature solution process - Google Patents

Abstract

The present invention relates to a method of manufacturing an organic semiconductor polymer pattern using a low temperature solution process, more specifically, surface treatment of a first region of a substrate to change surface properties, and coating an emulsion containing an organic semiconductor polymer on a substrate It relates to a method of manufacturing an organic semiconductor pattern through a unit coating process after washing with alcohol.

Description

Method of forming organic polymer semiconductor pattern by low-temperature solution process

The present invention relates to a method of manufacturing an organic semiconductor polymer pattern using a low temperature solution process, more specifically, surface treatment of a first region of a substrate to change surface properties, and coating an emulsion containing an organic semiconductor polymer on a substrate It relates to a method of manufacturing an organic semiconductor pattern through a unit coating process after washing with alcohol.

Various flat panel display devices that can reduce weight and volume, which are disadvantages of the conventional cathode ray tube display, have been developed. Examples of display systems that have been developed to date include plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FEDs), and organic electroluminescent devices (OLEDs).

Among them, a liquid crystal display device to which a thin film transistor is applied is a display device manufactured using a semiconductor process, and has been widely used from a mobile device to a large area device. However, the liquid crystal display device has disadvantages such as high power consumption due to a rear light source and additional optical loss such as a polarizing filter, a prism sheet, and a diffuser plate, and a narrow viewing angle. A liquid crystal display device has a high dynamic range and an increase in contrast ratio with technology development, and is a high-efficiency and general-purpose display device, but has a disadvantage of no folding or bending property due to the characteristics of a flat panel display.

As the display industry gradually advances, the necessity of reducing the size and complexity of the display is increasing, and a flexible display capable of pursuing convenience with high performance of display quality in the mobile area is gradually receiving attention. In particular, as the development of wearable smart devices, the increase in space utilization through shape modification, and the demand for high portability have increased, the development of flexible display devices has become more important in flat display devices that have led the display market to date. In order to implement a flexible display, in developing an active driving device array, it is necessary to easily apply a low cost process and to have excellent device flexibility and durability.

One of the important fields in the development of the flexible display as described above is an organic electroluminescent device (OLED) using an organic semiconductor polymer. The organic semiconductor polymer is a conjugated organic polymer that exhibits semiconductor properties, since polyacetylene-based and polythiophene-based polymers have been developed, easy control of polymer properties, relatively simple synthesis method, simple film forming process, flexibility, conductivity Due to advantages such as low production cost, active research is being conducted in a wide range of fields as a new electronic material.

In order to apply organic semiconductor polymers to OLEDs, a patterning process must be used, and commercially available patterning processes include fine metal mask processes, ink-jet processes, and photolithography processes. And so on. The double fine metal mask process is a vacuum that deposits heat by applying heat to an organic material in a high vacuum state, and photolithography is described above in that it includes a series of complex processes such as photoresist coating, mask placement, exposure, photoresist removal, and etching. The process as described above is disadvantageous in that it is not environmentally friendly and the process cost is high.

In the case of the inkjet process, many studies have been conducted due to the advantages of realizing high resolution and being able to apply the pattern to a desired area, but there is a problem that the process speed is slow because the process is complicated and the area to be coated in a single coating process is small. . In addition, since the thin film is formed by the coating method of the DOD (drop on demand) method, there is still a problem of uniformity reduction due to the coffee ring effect.

Meanwhile, in order to use an organic semiconductor polymer for a display device, a technique such as spin coating on a substrate after dissolving a polymer material in a solvent, and patterning after evaporating the solvent may be applied. However, the process of patterning by coating is difficult to precisely pattern the organic semiconductor polymer selectively in a specific area desired, and since an organic solvent is used, damage to the lower pattern may occur, and there is a problem that is not environmentally friendly. In addition, even when sequentially coating different organic semiconductor polymers on a single substrate, there is a problem in that it is difficult to continuously and uniformly pattern different organic semiconductor polymers due to limitations in which the same organic solvent must be used. In order to solve the above problems, Korean Patent Publication No. 2018-0026012 discloses a technique for forming a polymer semiconductor thin film using water, which is an environmentally friendly solvent, to solve this problem. However, there is still a problem that it is difficult to precisely pattern the organic semiconductor polymer selectively in a specific region, and it is difficult to implement a reliable device due to low charge mobility due to the presence of residual surfactant.

Therefore, even if the organic semiconductor polymer is precisely patterned on a substrate by a simple process, and a plurality of different organic semiconductor polymers are sequentially patterned, there is no damage to the organic semiconductor polymer pattern already formed by the subsequent patterning process, and high charge mobility It is necessary to develop an environmentally friendly patterning process that can implement.

KR10-2018-0026012A

An object of the present invention is to provide a method of manufacturing an organic semiconductor polymer pattern having a high charge mobility by patterning an organic semiconductor polymer in a specific region in a simple process.

Another object of the present invention is to provide a simple and economical method of manufacturing an organic semiconductor polymer pattern in an atmospheric environment by using a non-vacuum process using an organic semiconductor polymer emulsion without using a vacuum process.

Another object of the present invention is that even if a plurality of different organic semiconductor polymers are sequentially patterned, the organic semiconductor polymer patterns already formed by a subsequent patterning process are not affected at all, and all of the plurality of different organic semiconductor polymer patterns are uniform and high quality. It is to provide a method of manufacturing an organic semiconductor polymer pattern capable of forming a thin film.

A method of manufacturing an organic semiconductor polymer pattern according to the present invention includes a first step of surface-treating a first area of a substrate having a first surface property with a second surface property; A second step of including an organic semiconductor polymer on the inner phase and coating an emulsion containing a surfactant on the substrate; And a third step of drying the coated substrate and washing with alcohol, wherein the first and second surface properties are hydrophilic or hydrophobic and different from each other.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the emulsion in the second step may be an oil-in-water emulsion.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the hydrophobic groups of the side chain and the surfactant of the organic semiconductor polymer may be homologs.

In the method for manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the linear carbon number CP of the side chain of the organic semiconductor polymer and the linear carbon number C _S of the hydrophobic group of the surfactant may satisfy the following relationship.

[Relationship 1]

0.8 <C _P / C _S <1.2

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the surfactant may be a (C10-C16) aliphatic cationic surfactant.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the unit coating process may further include performing in a region different from the first region of the hydrophilic substrate.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the alcohol may be (C2-C4) alcohol.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the thickness of the polymer pattern may be 10 to 100 nm.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the surface roughness (R _rms ) of the pattern may be 10 nm or less.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the first region of the substrate having the first surface property may be a self-assembled monolayer or hydrophobic polymer layer formed on the substrate.

In a method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the first step includes applying a self-assembled compound to a first region of a substrate having a first surface property, and the self-assembly The compound may be a compound containing any one or more functional groups selected from the group consisting of alcohols, amines, carboxylic acids and thiols.

In the method for manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the unit coating process is included two or more times, but the organic semiconductor polymer included in each unit coating process may be the same or different.

The present invention includes an organic semiconductor polymer pattern manufactured by the above-described manufacturing method.

The present invention includes an optoelectronic device including an organic semiconductor polymer pattern, and the optoelectronic device may be any one selected from OLED devices, surface lighting, e-paper, e-books, touch panels, and solar cells.

The method of manufacturing an organic semiconductor polymer pattern according to the present invention can provide an organic semiconductor polymer pattern and a photoelectric device having high charge mobility by patterning an organic semiconductor polymer in a specific process on a specific region of a substrate.

The method for manufacturing an organic semiconductor polymer pattern according to the present invention can use a non-vacuum process using an organic semiconductor polymer emulsion without using a vacuum process, and can provide an organic semiconductor polymer pattern and an optoelectronic device simply and economically in an atmospheric environment. have.

The method of manufacturing an organic semiconductor polymer pattern according to the present invention does not affect the organic semiconductor polymer pattern already formed by a subsequent patterning process at all, even if a plurality of different organic semiconductor polymers are sequentially patterned in a solution phase, All of the organic semiconductor polymer patterns can form a uniform high-quality thin film.

Even if the effects are not explicitly mentioned in the present invention, the effects described in the specification expected by the technical features of the present invention and the inherent effects thereof are treated as described in the specification of the present invention.

1 is a view showing the size distribution of emulsion particles measured by a dynamic light scattering method.
Figure 2 is a view showing a picture of the surface of the PNDI-TVT polymer pattern prepared by coating the emulsion particles on a substrate with a scanning electron microscope.
3 is a view showing FT-IR results of patterns before and after washing the organic semiconductor polymer pattern with alcohol.
4 is a diagram showing a GIXD image of a PNDI-TVT polymer pattern.
FIG. 5 (a) shows the n-type transfer characteristics of the PFET of the PNDI-TVT polymer pattern of the embodiment, and (b) shows the n-type of the PFET prepared by dissolving PNDI-TVT in dichlorobenzene and coating the substrate. It is a diagram showing transfer characteristics.
6 is an image patterning a plurality of different organic semiconductor polymers according to an embodiment.

Hereinafter, a method of manufacturing an organic semiconductor polymer pattern according to the present invention, an organic semiconductor polymer pattern and a photoelectric device manufactured therefrom will be described in detail with reference to the accompanying drawings.

The drawings described in this specification are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the presented drawings and may be embodied in other forms, and the drawings may be exaggerated to clarify the spirit of the present invention.

Unless otherwise defined in technical terms and scientific terms used in the present specification, those skilled in the art to which the present invention pertains have the meanings commonly understood, and the subject matter of the present invention in the following description and the accompanying drawings. Descriptions of well-known functions and configurations that may unnecessarily obscure are omitted.

As used herein, the singular form of the term may be interpreted as including the plural form unless otherwise specified.

In addition, in the specification and the appended claims, units used without specific mention are based on weight, and for example, units of% or ratio mean weight percent or weight ratio.

Also, in the specification and the appended claims, a homolog means a compound or a substituent of the same kind, and may mean a series of compounds or substituents having a similar structure. For example, methyl, ethyl, isopropyl, n-propyl, pentyl, heptyl, and the like are straight or branched chain alkyl groups, and ethenyl, propenyl, butenyl and the like are straight or branched chain alkenyl groups. It corresponds. In another example, phenyl, naphthyl, 4-methylphenyl, 3-ethylnaphthyl, pyrenyl, and the like are homologs as an aryl group.

In addition, in the specification and the appended claims, hydrophilic and hydrophobic means water-like properties and water-dislike properties, but when hydrophilicity and hydrophobicity are used simultaneously, it means a relative concept. As a specific example, in the case of a hydroxyl group (-OH) and an alkyl group, the hydroxyl group is a hydrophilic group and the alkyl group is a hydrophobic group, but in the case of an alkyl group and a fluorinated alkyl group, the alkyl group is a hydrophilic group and the fluorinated alkyl group is a hydrophobic group because the hydrophobicity of the fluorinated alkyl group is higher. Can be.

A method of manufacturing an organic semiconductor polymer pattern according to the present invention includes a first step of surface-treating a first area of a substrate having a first surface property with a second surface property; A second step of including an organic semiconductor polymer on the inner phase and coating an emulsion containing a surfactant on the substrate; And a third step of drying the coated substrate and washing with alcohol, wherein the first and second surface properties are hydrophilic or hydrophobic and different from each other.

The substrate may be a rigid substrate or a flexible substrate (flexible substrate), and if the device does not require flexible properties, a rigid substrate may be selected, and a flexible substrate may be preferably selected for use in a flexible display. When the substrate is a rigid substrate, a rigid substrate known in the art may be selected, and as one non-limiting example, it may be any one or more selected from the group consisting of a glass substrate, an ITO substrate, and a silicon (Si) substrate. The method of manufacturing the organic semiconductor polymer pattern according to the present invention has a higher usefulness in a flexible substrate that is vulnerable to heat because a high-temperature heat treatment process is unnecessary unlike the ITO transparent electrode in the manufacturing process. In the case of selecting a flexible substrate, a flexible photoelectric device can be implemented, and there is an advantage of mass production of the device in a short time through a printing process or a roll-to-roll process during the manufacturing process of the device. The material of the flexible substrate may be a polymer, and for example, non-limiting examples include polyethersulfone (PES), polyethylene terephthalate (PET), polycarbonate (PC), polyimide (PI), and polyethylene naphthalate (PEN). It may be any one or more selected from the group.

The substrate may have a first surface property, and the surface property of the substrate preferably has a uniform first surface property. At this time, since the first surface property may be hydrophilic or hydrophobic, the substrate having the first surface property may be a hydrophilic substrate having a hydrophilic surface property or a hydrophobic substrate having a hydrophobic surface property.

The first region of the substrate may be at least a partial region of the substrate, and may be a single region or a region in which a plurality of regions are regularly or irregularly spaced from each other and positioned on the substrate. Since the first area of the substrate is not surface-treated, the surface property of the first area is the same as the surface property of the substrate, and thus the first surface property is also made. The first surface property of the first region may be changed or modified to a second surface property through surface treatment, wherein the first surface property and the second surface property are different from each other. For example, the first region of the hydrophilic substrate has hydrophilicity, but the first region of the hydrophobic substrate can be changed or modified through surface treatment, and in another example, the first region of the hydrophobic substrate has hydrophobicity, but is One region can be modified or modified to be hydrophilic.

Changing or modifying the first surface property to the second surface property can be used without any known means, for example, polishing, chemical treatment, chemical vapor deposition, surface modification by plasma, surface coating of polymers, self-assembled monomolecular film Any one or more combinations selected from the group consisting of formation can be used.

The surface modification by chemical treatment may be to modify the first region using any one or more selected from the group consisting of acids, alkalis and oxidizing agents. The surface modification by polishing may be physically modifying the first region of the substrate using an abrasive.

The surface modification by chemical vapor deposition may be a vapor deposition method such as a chemical vapor deposition method or an atomic layer deposition method, and the precursor compound may be uniformly deposited on the substrate through the vapor deposition means. As an example, a precursor compound may be injected through an atomic layer deposition method to induce a self-limiting adsorption process on the substrate surface and modify the surface properties of the substrate through a surface reaction. The thickness of the thin film formed on the surface of the substrate can be easily adjusted according to the number of deposition cycles, and the detailed description of the precursor compound, the deposited material and the deposition conditions for modifying the surface properties are known, and thus detailed description thereof will be omitted. As a method of modifying the surface property of the first region by chemical vapor deposition, the surface property of the entire surface of the substrate is first modified by chemical vapor deposition, and then the surface property of the first region of the modified substrate is second. The surface treatment may be an aspect in which the surface treatment is performed through a known means, or an aspect in which the first surface property of the first region is modified to the second surface property by chemically depositing only the first area of the substrate to thereby cover the scope of the present invention. Of course it is included.

The surface modification by surface coating of the polymer may be to modify the first surface property of the substrate to the second surface property by forming a uniform polymer film by coating the polymer on the substrate. For example, by coating the hydrophobic polymer on the glass substrate, the surface properties of the entire substrate can be modified to be hydrophobic, and in another example, only the first region on the glass substrate is coated with the hydrophobic polymer so that the first region has hydrophobic properties. , Other regions of the substrate may have hydrophilic properties.

The surface modification by plasma may be, but is not limited to, oxygen (O2) or argon (Ar) plasma, and the surface property of the first region may be changed by exposing the plasma to the first region of the substrate. B. It is environmentally friendly in that it is a process that does not use a compound, and may be preferable in that it is possible to uniformly modify the first region without damaging the substrate. As a specific example, in the case of normal pressure plasma, it is economical because no vacuum device is used, and it may be more preferable to change the surface properties of the first region in that continuous processing is possible. As a non-limiting example, when only a first region is exposed on a glass substrate modified with a hydrophobic polymer or a hydrophobic compound, and then treated with oxygen plasma, the hydrophobic polymer or hydrophobic compound in the first region is removed so that the first region is hydrophilic. It has properties, and other regions of the substrate may have hydrophobic properties. As another example, when only the first region of the hydrophobic polymer substrate is exposed and then treated with oxygen plasma, the surface of the hydrophobic polymer in the first region is hydrophilized to have hydrophilic properties, and the other regions of the substrate not treated with oxygen plasma are It can have hydrophobic properties.

Surface modification by a self-assembled monomolecular film means modifying the surface of the substrate with a compound containing a functional group having reactivity on the substrate surface, and when treating the substrate with a compound containing a reactive functional group, the compound spontaneously forms a crystal structure. The surface properties of the substrate can be modified according to the hydrophobic or hydrophilic properties of the aligned and vertically oriented substituents of the substrate. As a non-limiting example, when only a first region is exposed on a hydrophilic glass substrate and then treated with a hydrophobic compound containing a reactive functional group, the first region has hydrophobic properties, and other regions of the substrate may have hydrophilic properties. have. Examples of the compound containing a reactive functional group capable of forming a self-assembled monomolecular layer include, for example, an alkylthiol-based compound, an arylthiol-based compound, an alkylsilane-based compound, an arylsilane-based compound, an alkylcarboxylic acid-based compound, and an arylcarboxylic acid-based compound. , An alkylamine-based compound, an arylamine-based compound, an alkylalcohol-based compound, an arylalcohol-based compound, an alkylphosphoric acid-based and an arylphosphoric acid-based compound, but it is not limited thereto.

As described above, the means for modifying the surface properties may be used in combination of two or more. As an example, the substrate may be modified with a self-assembled monomolecular film to produce a substrate having a first surface property, and then the surface property of the first area may be modified to a second surface property through plasma treatment only in the first area. In this case, when the substrate is a glass substrate, the first surface property means hydrophobicity, and the second surface property means hydrophilicity. As another modified example, the substrate is spin coated with a hydrophobic polymer to form a film, so that the surface properties of the substrate are prepared as substrates having the first surface properties, and subsequently the surface properties of the first area through plasma treatment only in the first area. It may be to modify the second surface properties. At this time, when the substrate is a flexible polymer substrate, the surface properties of the flexible polymer substrate may be hydrophilized before the surface treatment, the first surface property means hydrophobicity, and the second surface property means hydrophilicity.

The emulsion contains an organic semiconductor polymer in an inner phase (dispersed phase) and a surfactant to stabilize the interface of the inner phase. The emulsion may be prepared through a known emulsifying means, and may be prepared by mixing a solution in which an organic semiconductor polymer is dissolved in an organic solvent with water in an outer phase (continuous phase) and stirring vigorously. . In more detail, the emulsion may preferably be small and uniform in size, and for this, may include a step of uniformly dispersing the solution in which the organic semiconductor polymer is dissolved into fine droplets by stirring through an agitator and applying ultrasonic waves.

The organic solvent capable of dissolving the organic semiconductor polymer is not particularly limited, and for example, a known organic solvent that can be evaporated at a temperature of 100 ° C. or less can be used without limitation. For example, the organic solvent is chloroform, methylene chloride, dichloroethane, ethyl acetate, heptane, butyl acetate, n-butanol, hexane, cyclohexane, toluene, benzene, pentane, cyclopentane, butanol, dioxane, diethyl ether, methyl ethyl It may be one or more selected from the group consisting of ketones, but is not limited thereto.

The content of the organic semiconductor polymer dissolved in the organic solvent is not particularly limited, for example, the concentration of the organic semiconductor polymer in the solvent is 0.01 mg / ml to 100 mg / ml, or 0.1 mg / ml to 50 mg / ml, or 0.5 mg / ml to 20 mg / ml, specifically 1.0 mg / ml to 10 mg / ml, specifically 1.0 to 5.0 mg / ml, but is not limited thereto.

The emulsion may be a mini-emulsion, and the average particle diameter may be 10 to 500 nm, preferably 20 to 400 nm, more preferably 50 to 200 nm, and the average particle diameter and particle size distribution of the emulsion are dynamic. It can be measured and defined by dynamic light scattering. The particle size distribution of the emulsion may be monomodal or bimodal. A uniform and dense film can be obtained even in a monodisperse emulsion, but in the case of a bi-distribution emulsion, a more uniform and dense film can be obtained by placing the emulsion particles of small particle size in the gap between the emulsion particles of large particle size. have. As described above, the emulsion may be an oil-in-water emulsion containing an organic semiconductor polymer solution in the inner phase and water or an aqueous phase in the outer phase. The organic solvent is preferably removed by drying after preparation of the emulsion. can do. In order to remove the organic solvent present in the organic semiconductor polymer solution as the inner phase, it may be heated to a temperature below the boiling point of the organic solvent or induce evaporation under reduced pressure.

The volume ratio of the inner phase (disperse phase) to the outer phase (continuous phase) may be 0.01: 1 to 2: 1, preferably 0.1: 1 to 1.5: 1, more preferably 0.2: 1 to 1: 1, This is an example only and is not limited.

The organic semiconductor polymer emulsion from which the organic solvent has been removed may be coated on the substrate, and the organic semiconductor polymer emulsion may be selectively coated on a specific region of the hydrophilically modified substrate. The organic semiconductor polymer material itself has hydrophobicity, but the surface of the organic semiconductor polymer emulsion inner surface has hydrophilicity due to the hydrophilicity of the head group of the surfactant, so that the second step is a hydrophilic-hydrophilic interaction without the addition of additional patterning means. It can be spontaneously coated on the surface. As a more detailed example, when the first region of the substrate having a hydrophobic surface property is surface-treated with hydrophilicity, when the organic semiconductor polymer emulsion is applied on the substrate, the organic semiconductor polymer emulsion is selectively spontaneously hydrophilized to the first region. It can be positioned to form a pattern.

The surfactant is sufficient if the organic semiconductor polymer solution dispersed in fine droplets is contained in an amount such that it can stably be dispersed in water or the water phase as a continuous phase. If the surfactant is included in an excessive amount, charge mobility may be poor due to the residual surfactant, resulting in deterioration of device characteristics. In addition, the depletion force of the organic semiconductor polymer particles in the emulsion is excessively generated, and thus the aggregation between particles becomes severe, and a large cluster in which particles are aggregated before the unity between particles to form a film may be formed. On the other hand, if the surfactant is contained in an excessively small amount, a problem that the emulsion cannot be stabilized may occur. When preparing an emulsion through an emulsification process, the content of the surfactant is not particularly limited, and for example, without limitation, 0.1 mg / ml to 100 mg / ml, or 0.5 mg / ml to 50 mg / ml, or 1 to the water phase mg / mg to 50 mg / ml, preferably 5 mg / mg to 40 mg / ml, more preferably 10 mg / mg to 30 mg / ml.

More specifically, a minimum critical amount of surfactant may be present in consideration of the volume ratio of the dispersed phase to the volume of the continuous phase and the particle size of the fine droplets that are the dispersed phase, and most preferably, the surfactant needs to be included in the emulsion in the minimum critical amount. However, since emulsifying with a minimum critical amount of surfactant is very difficult to apply to the process, it is very difficult to actually apply it to the process. After preparing the emulsion with a somewhat excessive amount of surfactant, dialysis with micelles that are not present at the interface between the oil phase and the aqueous phase is performed. It must be removed in the same way. However, removing the surfactant through dialysis required a long time, and it was difficult to apply the actual process because the trauma had to be replaced with pure water continuously. Surprisingly, however, in the method of manufacturing the organic semiconductor polymer pattern according to the present invention, it was found that by coating the emulsion on the substrate and washing it with alcohol, virtually all of the residual surfactant can be effectively removed without causing any negative effects on the organic semiconductor polymer. Did. The meaning that substantially no residual surfactant is present in the organic semiconductor polymer pattern means that the surfactant is present or completely removed with a trace amount or impurity that does not affect the charge mobility. It may mean less than 100 ppm, specifically less than 10 ppm, more specifically less than 1 ppm based on the total weight of the polymer.

Before washing the organic semiconductor polymer pattern with alcohol, the surfactant may have high surface energy as it is included in the pattern, but as the surfactant is removed by alcohol washing, the pattern may have low surface energy. As the organic semiconductor polymer pattern has a low surface energy, adsorption of other impurities can be prevented, and even if a subsequent unit coating process is performed as described below, the pattern is formed by the emulsion or surfactant included in the subsequent unit coating process. It may not be adversely affected, such as being damaged.

In the method of manufacturing the organic semiconductor polymer pattern according to an example of the present invention, the alcohol included in the washing in the third step may be an aliphatic alcohol. By using an aliphatic alcohol, substantially all surfactants can be removed without adversely affecting the organic semiconductor polymer. The aliphatic alcohol may be (C1-C10) alcohol, preferably (C1-C6) alcohol, and more preferably (C2-C4) alcohol. By using the alcohol, the surfactant selectively acts to dissolve only the surfactant to remove the surfactant present in the pattern. For example, ethanol may be the most preferred alcohol, and in the case of ethanol, the microstructure and crystalline packing of the organic semiconductor polymer coated on the substrate are not damaged, and only the surfactant contained in the organic semiconductor polymer film is used. It is advantageous because it has an excellent effect in selectively dissolving to remove substantially all.

In the method of manufacturing the organic semiconductor polymer pattern according to an example of the present invention, the annealing step may be further included after the third step of alcohol washing. The annealing step may be performed under a warming condition, and may be performed in a range of 100 ° C to 300 ° C, preferably in a range of 150 ° C to 250 ° C, for 1 minute to 100 minutes, preferably May be performed for 5 to 20 minutes, but this is only an example and is not limited thereto. Through the annealing step, there is an advantage of realizing a level of performance similar to that of a device using an existing organic solvent through recovery of a unique crystal structure in an organic semiconductor.

The organic semiconductor polymer may be any one or more selected from the group consisting of a p-type organic semiconductor polymer, an n-type organic semiconductor polymer, and an ambipolar (bipolar) organic semiconductor polymer. As an example of the p-type organic semiconductor polymer, poly (3-hexylthiophene-2,5-diyl) (P3HT), poly [2,5-bis (3-tetradecylthiophen-2-yl) thieno [3,2-b] thiophene ] (PBTTT), poly [6,60-dibromo- (N, N0-2-decylnonadecyl) -isoindigo- (E) -1,2-di (selenophen-2-yl) ethene] (PIID-SVS) or poly -[2,5-bis (2-decyltetradecyl) pyrrolo [3,4-c] -pyrrole-1,4- (2H, 5H) -dione- (E) -1,2-bis (5- (thiophen- 2-yl) selenophen-2-yl) ethene] (PDPP-SVS), Poly [2,5-bis (2-hexyldecyl) phenylene-alt- [5,6-difluoro-4,7-di (thiophen-2) -yl) benzo [c] [1,2,5] thiadiazole]] (PPDT2FBT), and examples of the n-type organic semiconductor polymer include poly (naphthobisthiazole diimide) s (PNBTDIs) and Poly (2,5-bis) (2-octyldodecyl) -3,6-di (pyridin-2-yl) -pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione-alt-2,2'-bithiophene) ( PDBPyBT), poly ((N, N'-bis (2-octyldodecyl) -1,4,5,8-naphthalenedicarboximide-2,6-diyl) -alt-5,5 '-(2,20-bithiophene)) (PNDI2ODT2), poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl-9- (5- (2- (5-methylthiophen-2-yl) vinyl) thiophen-2-yl) benzo [lmn] [3,8] phenanthrolin e-1,3,6,8 (2H, 7H) -tetraone] (PNDI-TVT), and an example of the bipolar organic semiconductor polymer is poly [2,5-bis (2-decyltetradecyl) pyrrolo [3 , 4-c] pyrrole-1,4 (2H, 5H) -dione- (E)-[2,20-bithiophen] -5-yl-3- (thiophen-2-yl) acrylonitrile] (PDPP-CN- TVT), Poly ({4,8-bis [(2-ethylhexyl) oxy] benzo [1,2-b: 4,5-b '] dithiophene-2,6-diyl} {3-fluoro-2- [ (2-ethylhexyl) carbonyl] thieno [3,4-b] thiophenediyl}) (PTB7), Poly [N-9′-heptadecanyl-2,7-carbazole-alt-5,5- (4 ′, 7′- di-2-thienyl-2 ′, 1 ′, 3′-benzothiadiazole)], Poly [[9- (1-octylnonyl) -9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1 , 3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl] (PCDTBT), but this is only a non-limiting example and is not limited thereto.

In the method of manufacturing an organic semiconductor polymer pattern according to an example of the present invention, the side chain of the organic semiconductor polymer and the hydrophobic groups of the surfactant may be homologs. The main chain of the organic semiconductor polymer contains at least one aryl or heteroaryl in a structural unit and at the same time contains a hydrophobic group in a side chain bonded to the main chain. The hydrophobic group included in the side chain may be an alkyl group, an alkylene group, an alkynyl group, a siloxane group, an aryl group or a heteroaryl group, and the hydrophobic group may be further substituted with another substituent or hetero element. As a non-limiting example, the alkyl group further substituted with a hetero element may be a perfluoroalkyl group, and the hydrophobic group may have a straight or branched chain form.

Surfactant refers to a molecule having amphiphilicity and simultaneously having hydrophilicity and hydrophobicity in one molecule, thereby simultaneously having affinity for oil and water. The hydrophobic group of the surfactant is distributed into the oil phase and the hydrophilic group is distributed into the water phase, thereby reducing the surface tension at the interface between the water phase and the oil phase, thereby contributing to reducing the energy of the premise system. As described above, in order to stabilize the organic semiconductor polymer emulsion, the hydrophobic group of the surfactant is distributed toward the organic semiconductor polymer, and the hydrophobic group of the surfactant can interact with the organic semiconductor polymer. In detail, the hydrophobic group of the surfactant can be distributed into the inner phase of the emulsion, thereby enabling a more effective van der Waals interaction with the side chain having a higher flexibility than the main chain of the organic semiconductor polymer, and at this time, the side chain of the organic semiconductor polymer and the number of surfactants When the group is a homologue, it may be more effective for stability of the emulsion, small particle size, and uniform distribution of particle size. As a preferred example, the homologue may be an aliphatic hydrocarbon group, more preferably an alkyl group.

When the side chain of the organic semiconductor polymer and the hydrophobic group of the surfactant are homologs, it may be more advantageous for the packaging of the organic semiconductor polymer, and the organic semiconductor polymer may be spontaneously packed during the preparation of the emulsion and the evaporation of the solvent. As a specific example, when the hydrophobic group of the side chain and the surfactant of the organic semiconductor polymer is an aliphatic hydrocarbon group, high hydrophobic interaction, that is, high van der Waals interaction can be induced. That is, it is advantageous in that the aliphatic hydrocarbon group of the side chain of the organic semiconductor polymer and the aliphatic hydrocarbon group of the surfactant are well aligned with each other at the interface, thereby effectively stabilizing the emulsion, forming a small particle size of 100 nm or less, and uniformly distributing the particle size. In particular, it is preferable in that the packing of the organic semiconductor polymer can be effectively induced by protecting the organic semiconductor polymer from the foreign water phase by stabilizing the interface, and the crystallinity of the organic semiconductor polymer can be improved.

In the method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, the hydrophobic group of the side chain and the surfactant of the organic semiconductor polymer may be a straight chain or branched chain alkyl group, wherein the side chain of the organic semiconductor polymer is a straight chain alkyl group At this time, the carbon number C _P of the linear alkyl group and the carbon number C _S of the linear alkyl group of the hydrophobic group of the surfactant may satisfy the following relationship.

[Relationship 1]

0.5 <C _P / C _S <2

As another example, when the side chain of the organic semiconductor polymer is a branched chain alkyl group, the carbon number C _P of the linear alkyl group constituting the branched chain and the carbon number C _S of the linear alkyl group of the hydrophobic group of the surfactant may satisfy the relational expression (1). For example, when the branched chain alkyl group is-(CH ₂ ) _x -CH- (C _y H _{2y + 1} ) (C _z H _{2z + 1} ) and y <z, the number of branches of the alkyl group is 2 and each has a carbon number. Since it consists of a straight-chain alkyl group of y and a straight-chain alkyl group having x + z + 1 carbon atoms, the carbon number of the straight-chain alkyl group forming the bonsai chain alkyl group means x + z + 1.

In the relational expression 1, C _P / C _S may be preferably 0.75 to 1.5, and more preferably 0.8 to 1.2. When the straight-chain alkyl group of the organic semiconductor polymer and the straight-chain alkyl group of the carbon number and the hydrophobic group of the surfactant have a similar carbon number range, the packing of the organic semiconductor polymer can be induced more effectively, and the spontaneous packing of the organic semiconductor polymer The degree of crystallinity may be further improved, which may be desirable. Furthermore, when the organic semiconductor polymer is well aligned and packed on the emulsion, and subsequently coated on a substrate and washed with alcohol, the crystalline packing of the organic semiconductor polymer is not only well preserved, but also has excellent orientation, and a photoelectric device having high charge mobility There is an advantage that can be produced as.

In the method of manufacturing an organic semiconductor polymer pattern according to an example of the present invention, the surfactant may be a cationic surfactant. When the hydrophilic group of the surfactant contains a cationic group, the emulsion can be stabilized with a minimum critical amount, and it may be preferable in that substantially all surfactants can be removed in a subsequent alcohol washing step. The cationic group is not limited as long as it is a cationic group that may be included in the hydrophilic group of the surfactant, and for example, it may be any one selected from the group consisting of ammonium, sulfonium and phosphonium.

As a more specific example of the cationic surfactant, the cationic surfactant may be an aliphatic cationic surfactant, and the carbon number of the aliphatic hydrocarbon corresponding to the hydrophobic group of the aliphatic cationic surfactant is C6 to C24, preferably C8 to C20. , More preferably C10 to C16. As a non-limiting example, the aliphatic cationic surfactant is (C6-C24) alkyl cationic surfactant, preferably (C8-C20) alkyl cationic surfactant, more preferably (C10-C16) alkyl cationic surfactant Can be the best.

In a method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, a first step of surface-treating a first area of a substrate having a first surface property with a second surface property; A second step of including an organic semiconductor polymer on the inner phase and coating an emulsion containing a surfactant on the substrate; And a third step of drying the coated substrate and washing with alcohol; further comprising performing a unit coating process in a region different from the first region.

In the unit coating process, an organic semiconductor polymer pattern is formed in the first region, and an organic semiconductor polymer pattern may not be formed in other regions of the substrate except for the first region. The unit coating process is different from the first region. The organic semiconductor polymer pattern may be continuously formed by additionally forming an organic semiconductor polymer pattern in the second region, which is a region different from the first region. The organic semiconductor polymer pattern formed in the second region may be the same or different from the organic semiconductor polymer pattern formed in the first region, and the thickness of the pattern formed in the second region may be the same or different from the thickness of the pattern formed in the first region. Can be. For example, when a polymer pattern of different thickness is to be formed in different regions, a unit coating process is performed by forming the first region, and then a unit coating process including an organic semiconductor polymer emulsion having different emulsion concentrations is formed in the second region. It can be formed on to form a polymer pattern of different thickness in different regions.

In the method of manufacturing an organic semiconductor polymer pattern according to an example of the present invention, the thickness of the organic semiconductor polymer pattern produced through a unit coating process may be 1 to 1000 nm, specifically 2 to 500 nm, more specifically 5 To 200 nm, preferably 10 to 100 nm. However, this is only an example, and is not limited to the above numerical range, and can be arbitrarily set and adjusted to a thickness that can be preferably used for photoelectric devices. The surface roughness (R _rms , root mean squared surface roughness) of the organic semiconductor polymer pattern may be 20 nm or less and 0.5 nm or more, specifically 10 nm or less, more specifically 8 nm or less, and preferably 5 nm or less. In the method of manufacturing an organic semiconductor polymer pattern according to the present invention, formation of a cluster in which some particles are aggregated is suppressed as the cohesion between particles occurs very homogeneously in the first region after the emulsion particles are coated on the substrate. And have a film characteristic having a continuous surface morphology.

In the method of manufacturing an organic semiconductor polymer pattern according to an example of the present invention, the first region of the substrate having the first surface property may be a self-assembled monolayer or a hydrophobic polymer layer formed on the substrate. Specifically, in order to modify the surface properties of the substrate, the surface properties of the substrate can be hydrophobically modified by coating with a hydrophobic polymer on the substrate, and the hydrophobic polymer can be coated through known means such as spin coating, which is a sugar. Since it is known in the industry, detailed description is omitted. In addition, in order to modify the surface properties of the substrate, a thin film may be formed of a self-assembled monolayer to modify the surface properties of the substrate to hydrophobicity. The substrate may include a functional group capable of reacting with a reactive functional group of a self-assembled compound capable of forming a self-assembled monolayer, and a reactive functional group of a self-assembled compound and a functional group of a substrate may react with each other to form a bond. Through the reaction, the surface of the substrate may include a self-assembled monolayer having a crystal structure that is spontaneously aligned with a self-assembled compound, and the surface properties of the substrate may be modified with the surface properties of the self-assembled monolayer. As a method of modifying the surface of the substrate with a self-assembled compound, a method of dissolving the self-assembled compound in a solvent and immersing or spraying the surface of the substrate in the prepared solution may be used. What is known in the art can be used without limitation.

The self-assembled compound may include a reactive functional group and a hydrophobic group, and a non-limiting example of the reactive functional group may be any one or more selected from the group consisting of alcohol, amine, carboxylic acid and thiol, and hydrophobic groups include alkyl, aryl and It may be any one or more selected from the group consisting of alkyl and aryl substituted with other substituents or hetero elements. As a specific example, when the substrate is glass, the surface of the glass is hydrophilic, and an alkylsilane-based compound such as alkyltrichlorosilane may be preferably selected as a self-assembled compound to react with a silanol group present on the surface, and the substrate is a metal. In one case, an alkylthiol-based compound may be preferably selected.

In the method of manufacturing an organic semiconductor polymer pattern according to an example of the present invention, the first step includes applying a self-assembled compound to a first region of a substrate having a first surface property, wherein the self-assembled compound is alcohol , It may be a compound containing any one or more functional groups selected from the group consisting of amines, carboxylic acids and thiols. The step of applying the self-assembled compound to the substrate is to selectively apply only to the first region, and the other regions of the substrate except the first region and the first region to which the self-assembled compound is applied are different from each other and have different surface properties. it means. Since the application of the self-assembled compound is applied to a specific first region, it is applied through a printing process such as microcontact printing or dip-pen nanolithography rather than a conventional immersion or spraying method. May be As described above, by selectively applying the self-assembled compound to the first region, a pattern having different surface properties can be produced in one process, and the organic semiconductor polymer precisely formed in a specific region despite simply coating the emulsion on the substrate. A pattern can be produced, and it can be advantageous to manufacture a fine pattern with a smaller line width.

In a method of manufacturing an organic semiconductor polymer pattern according to an embodiment of the present invention, a first step of surface-treating a first area of a substrate having a first surface property with a second surface property; A second step of including an organic semiconductor polymer on the inner phase and coating an emulsion containing a surfactant on the substrate; And a third step of drying the coated substrate and washing with alcohol. The organic semiconductor polymer included in each unit coating process may be the same or different.

The unit coating process and the organic semiconductor polymer pattern prepared therefrom are respectively referred to as a first unit coating process and a first pattern, and the first pattern is not treated with an organic solvent as it has low surface energy as described above. The pattern is not damaged or affected by the packing or crystallinity of the polymer. Therefore, even if the second unit coating process is performed, the physicochemical properties of the first pattern are maintained, and the second pattern manufactured through the second unit coating process also has high uniformity, excellent flatness and continuous surface mole like the first pattern. You can have a pologe.

In particular, in the case where the RGB must be independently emitted from each pixel in the independent pixel method of the RGB method of the organic light emitting diode (OLED), it is necessary to form the patterns for light emission independently. In the case of manufacturing an RGB pattern in the existing inkjet process, the pattern has a very low uniformity, high defect rate and low performance, and also has a disadvantage in that the process productivity is very low due to the characteristics of the inkjet process. To solve this, a solution process may be employed, but there is a problem in that a pattern is damaged in a process of manufacturing a pattern by a solution process in which a previously manufactured pattern is subsequently performed, and thus there is a limit in manufacturing a continuous pattern with a solution process Have However, even if the unit coating process is continuously performed according to an embodiment of the present invention, the first pattern produced has low surface energy and has hydrophobic properties, so that the pattern or the pattern swelled by the emulsion or water included in the second unit coating process. Since the damage problem is fundamentally blocked, the uniformity, flatness and continuous surface morphology of the pattern can be maintained. Therefore, in the continuous production of the RGB pattern, the first unit coating process, the second unit coating process, and the third unit coating process can be continuously performed to independently fabricate each RGB pattern without damaging the pattern. The first regions, which are surface-treated in the first step of each unit coating process and modified with the second surface properties, may be different from each other in the plane direction, and each of the RGB patterns in each of the different first regions is manufactured to produce an independent pixel method. An organic light emitting diode device can be fabricated.

According to a modified example of the present invention, the first unit coating process, the second unit coating process, and the third unit coating process may be performed in the same first region, where the position of the surface direction in which the organic semiconductor polymer pattern is formed Is all the same, and may be a tandem structure stacked in a vertical direction. Since the first area of each unit coating process is the same, the step of surface treating the first area with the second surface property may be performed only in the first unit coating process and may be omitted in the remaining unit coating process. At this time, since the surface of the organic semiconductor polymer pattern prepared through the first unit coating process has a hydrophobic surface property, it may not spontaneously be coated on the surface due to weak interaction when the emulsion is coated on the substrate. Therefore, the first surface property of the substrate needs to have more hydrophobicity than the hydrophobic surface property of the organic semiconductor polymer pattern, for example, a superhydrophobic surface. By modifying the first surface property of the substrate to be superhydrophobic, even if the surface of the organic semiconductor polymer pattern produced through the first unit coating process has hydrophobicity, the emulsion is selectively positioned on the organic semiconductor polymer pattern during subsequent emulsion coating to vertically The second pattern and the third pattern may be formed in the direction.

The present invention provides an organic semiconductor polymer pattern manufactured by the method for manufacturing an organic semiconductor polymer pattern as described above. The organic semiconductor polymer pattern according to an example of the present invention may be a pattern having a uniform, flat and continuous surface morphology even though it is environmentally friendly and does not use a vacuum process and uses a simple and economical process in an atmospheric environment. . The thickness of the pattern can be adjusted according to the concentration of the organic semiconductor polymer emulsion included in the unit coating process, the amount of coating, and the number of coatings, so that the thickness of the film can be freely controlled from a thin film to a thick thick film.

When sequentially patterning a plurality of different organic semiconductor polymers into a solution process, a negative influence may inevitably occur on the organic semiconductor polymer pattern already formed by a subsequent patterning process. However, the organic semiconductor polymer pattern produced by the manufacturing method according to the present invention is capable of forming a uniform high-quality thin film in all of a plurality of different organic semiconductor polymer patterns even though a plurality of different organic semiconductor polymers are sequentially patterned. It has excellent properties.

The organic semiconductor polymer pattern according to an example of the present invention may be included in a photoelectric device, and for example, it may be any one selected from OLED devices, surface lighting, e-paper, e-books, touch panels, and solar cells. The photovoltaic device according to an example of the present invention is eco-friendly and economical, but one or two or more different organic semiconductor polymer patterns have uniform high-quality thin film properties, and thus may have particularly excellent usefulness in the photoelectric device as described above. For example, the photoelectric device according to the present invention may have a charge mobility of 0.01 cm ² / V · s or more, preferably 0.03 cm ² / V · s or more, and more preferably 0.06 cm ² / V · s or more. Can be.

The method of manufacturing the organic polymer pattern according to the present invention, the organic polymer pattern and the photoelectric device produced therefrom can exhibit excellent charge mobility in a simple and eco-friendly solution process, and each organic polymer is produced even if the organic polymer pattern is continuously produced. Since there is no negative effect on the pattern, it can be widely used in the semiconductor industry, electronic devices, and photoelectric devices industry.

Hereinafter, the present invention will be described in detail through examples, but these are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples.

[Production Example 1]

Preparation of self-assembled monolayer coated ITO substrate

As a self-assembled compound, a solution was prepared by dissolving octyl trichlorosilane (OTS) in toluene so that the concentration of OTS was 5% by volume, and then immersing the ITO substrate in the solution for 10 minutes at room temperature to be coated with a self-assembled monolayer. An ITO substrate was prepared.

Using a patterned mask on an ITO substrate coated with a self-assembled monolayer, a pattern was prepared so that the surface of the ITO substrate was exposed only to the first region by treating with oxygen plasma at a pressure of 0.35 mbar only locally in the first region.

[Production Example 2]

Preparation of ITO substrate coated with hydrophobic polymer

Dissolve poly [perfluoro (4-vinyloxy-1-butene)] (Cytop) in a fluorine-based solvent (CTL-809M, Asahi Glass Co., Ltd., Japan), and a hydrophobic polymer solution having a concentration of 7.5% by volume at normal temperature and pressure After preparing, the hydrophobic polymer solution on an ITO substrate was spin-coated at 1000 rpm for 60 seconds at room temperature. The ITO substrate coated with the hydrophobic polymer was annealed at 180 ° C for 30 minutes.

Using a patterned mask on the annealed ITO substrate, a pattern was prepared so that the surface of the ITO substrate was exposed only in the first region by treatment with oxygen plasma locally in only the first region.

[Experimental Example 1]

Analysis of materials

The surface and cut surface of the organic semiconductor polymer pattern were measured by a high resolution field emission scanning electron microscope (SU8020 / Hitachi) and focus ion beam technology. The size of the emulsion particles was measured by a dynamic light scattering method (Zetasizer, Nano-ZS90 / Malvern), and the FT-IR absorption spectrum was measured by an FT-IR spectrometer (FT / IR 4700 / JASCO).

Grazing-Incidence X-ray Diffraction (GIXD) was measured by PLS-II 3C and 9AU-SAXS beamlines, and the X-rays incident from the in-vacuum undulator (IVU) were monochromated using a Si (111) double crystal. , KB focusing mirror system was used to inspect the detector. The horizontal and vertical beam sizes were 300 μm and 30 μm, respectively, and the incident angle was set to 0.12 ° above the critical angle. The GIXD pattern was recorded with a 2D CCD detector (Rayonix, SX-165), the scattering angle was normalized using a pre-standardized sucrose (Monoclinic, P21), and the distance between the sample and the detector was about 229 mm.

[Experimental Example 2]

Analysis of electrical properties

Polymer field effect transistors (PFETs) and complementary inverters were measured using a semiconductor parameter analyzer (Keithley 4200A-SCS / Keithley), and the electrical properties of the photodiode were 150W 1/8 m monochromatic light spectrometer, Stanford Research SR830 It was irradiated with a xenon arc lamp equipped with a lock-in amplifier, AFG310 arbitrary function generator (Tektronix) and an OEM infrared green laser source (LSR532NL-300), and measured with a Keithley 2400 Source Meter.

Preparation of PNDI-TVT polymer pattern

poly ((E) -2,7-bis (2-decyltetradecyl) -4-methyl-9- (5- (2- (5-methylthiophen-2-yl) vinyl) thiophen-2-, an n-type organic semiconductor polymer yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2H, 7H) -tetraone] (PNDI-TVT) 5 mg dissolved in 2 ml of chloroform solvent at a concentration of 2.5 mg / ml An organic phase solution in which an organic semiconductor polymer was dissolved was prepared.

For the preparation of the aqueous solution, 30 mg of cetyl trimethylammonium bromide (C ₁₆ TAB) was dissolved in 6 ml of distilled water to prepare an aqueous solution.

The two solutions were mixed to prepare a mixed solution, and the organic phase solution was mixed in a ratio of 20 ml and the aqueous solution in a ratio of 6 ml, followed by stirring for 1 minute and sonication (Branson Model 8510 Ultrasonic Cleaner). After stirring and sonication were repeated until the color of the solution no longer changed, a mini-emulsion was prepared, followed by further stirring for 1 hour. Subsequently, the PNDI-TVT emulsion was prepared by completely evaporating and removing chloroform while stirring the mini-emulsion to 65 ° C.

A film was prepared by spray coating the prepared PNDI-TVT emulsion on the substrate prepared in Preparation Example 1 and evaporating water. The film was immersed in ethanol at room temperature for 3 minutes to remove C16TAB, and annealing was performed at a temperature of 200 ° C for 10 minutes to prepare a PNDI-TVT polymer pattern.

Preparation of PNDI-TVT polymer pattern

A polymer pattern was prepared in the same manner as in Example 1, except that the substrate prepared in Example 1 was used instead of the substrate prepared in Preparation Example 1.

[Examples 3 to 8]

Preparation of PNDI-TVT polymer pattern

The surfactant in Example 1 was sodium dodecyl sulfate (SDS, Example 3), sodium dodecyl benzene sulfonate (SDBS, Example 4), benzyl dodecyl ammonium bromide (BDAB, Example 5), decyl trimethyl ammonium bromide (C ₁₀ TAB , Example 6), and was prepared in the same manner as in Example 1, except that dodecyl trimethyl ammonium bromide (C ₁₂ TAB, Example 7) and hexadecyltrimethyl ammonium bromide (C ₁₄ TAB, Example 8) were used.

[Example 9]

Preparation of PPDT2FBT polymer pattern

A PPDT2FBT polymer pattern was prepared in the same manner as in Example 1, except that PPDT2FBT was used instead of PNDI-TVT in Example 1.

[Example 10]

Preparation of PPDT2FBT / F8T2 polymer pattern

On the substrate on which the PPDT2FBT polymer pattern prepared in Example 9 was formed, a second pattern different from the polymer pattern prepared in Example 1 was used locally in the second region by using a different patterned mask. A pattern was prepared so that the surface of the ITO substrate was exposed.

Specifically, 5 mg of poly (9,9-dioctylfluorene-alt-bithiophene), (F8T2), an organic semiconductor polymer, was dissolved in a 2 ml chloroform solvent at a concentration of 2.5 mg / ml to prepare an organic phase solution in which the organic semiconductor polymer was dissolved. A film was prepared by spray coating an F8T2 emulsion prepared in the same manner as in the method for preparing an organic semiconductor polymer emulsion of Example 9 on an ITO substrate on which the pattern was formed and evaporating water, except for one. The film was immersed in ethanol at room temperature for 3 minutes to remove C ₁₆ TAB, and annealing was performed at a temperature of 170 ° C. for 10 minutes to prepare a polymer pattern in which PPDT2FBT and PBTTT were patterned, respectively.

[Example 11 and Example 12]

Preparation of PDPP-SVS and PIID-SVS polymer patterns

The organic semiconductor polymer in Example 1 was prepared in the same manner as in Example 1, except that PDPP-SVS (Example 11) and PIID-SVS (Example 12) were used instead of PNDI-TVT.

[Comparative Example 1]

Preparation of PNDI-TVT polymer pattern without alcohol extraction step

A PNDI-TVT polymer pattern was prepared in the same manner as in Example 1, except that the step of removing C ₁₆ TAB by immersion in ethanol in Example 1 was not performed.

[Comparative Example 2]

Preparation of PNDI-TVT polymer pattern using dialysis method

The method of preparing the PNDI-TVT emulsion was performed in the same manner as in Example 1, but C ₁₆ TAB was removed while continuously replacing distilled water for 6 hours using a semi-permeable membrane tube to remove the surfactant from the prepared PNDI-TVT emulsion. . Subsequently, it was put into a tube with a filter, centrifuged at 8000 rpm, and PNDI-TVT was concentrated to nanoparticles, and then PNDI-TVT was separated. At this time, the mass ratio of C ₁₆ TAB compared to PNDI-TVT was 1: 2.2 as a result of analysis by FT-IR.

The PNDI-TVT nanoparticle dispersion obtained by redispersing the separated PNDI-TVT in distilled water was spray-coated on the substrate prepared in Preparation Example 1 and water was evaporated to prepare a film. The film was prepared by performing annealing at a temperature of 200 ° C for 10 minutes to prepare a PNDI-TVT polymer pattern.

(A), (b), (c), and (d) of FIG. 1 show the size distribution of emulsion particles according to Examples 3 to 5 and 7, respectively, measured by dynamic light scattering, and for all surfactants. It shows that the average particle diameter is distributed in 50 to 200 nm.

2 (e), (f), (g), and (h) show scanning electron micrographs of the surfaces of the PNDI-TVT polymer patterns prepared according to Examples 3 to 5 and 7, respectively. As can be seen from FIG. 2, in the case of Example 3 using an anionic aliphatic surfactant, a very rough pattern was obtained while Examples 5 to 7 had flat surfaces. Particularly, in the case of an aliphatic cationic surfactant, it can be seen that a very flat surface is obtained, because the cationic surfactant is substantially all removed by alcohol, and the phenomenon of uniform mixing occurs across the film of PNDI-TVT particles. .

3 (a), (b), and (c) show the FT-IR results of the patterns before and after washing the organic semiconductor polymer patterns prepared from Examples 6, 8, and 1 with ethanol, respectively. Did. Before washing with ethanol, the specific absorption peak of the surfactant (1320 ~ 1500cm-1) appeared strongly, but after washing, the surfactant was absorbed through ethanol washing of the organic semiconductor polymer pattern when it was seen that the absorption peak was significantly reduced and appeared as a noise level. It suggests that can be effectively removed.

FIG. 4 shows the GIXD image of the PNDI-TVT polymer pattern prepared from Examples 1 and 6 to 8, and the crystallinity of the PNDI-TVT polymer pattern is improved as the carbon number of the cationic surfactant increases. Is showing. Since the number of carbon atoms in the side chain of the PNDI-TVT polymer is 24, and the number of carbon atoms in the straight-chain alkyl group of the double side chain is 14, the packing of the organic semiconductor polymer is effectively induced when the carbon number of the cationic surfactant is the same or similar. This means that the crystallinity of the polymer is further improved.

Figure 5 shows the n-type transfer properties of the PFETs containing the polymer patterns of Examples 6 to 8 and 1 (b) is PNDI-TVT dissolved in dichlorobenzene and coated on a substrate n-type PFET It shows the type transfer characteristics. The transfer curve was measured at saturation condition of V _DS = 30V. As a result of measuring the charge mobility of the Examples and Comparative Examples, it was shown as in the following table, and Examples 3 and 4 using anionic surfactants showed low charge mobility while Example 1 using a cationic surfactant. And 5 to 8, the average value of charge mobility was all 0.01 cm ² / V · s or more, and the tendency to increase as the number of carbon atoms in the alkyl group increased, and in Example 1, the average value was 0.71 cm ² / V · s. The highest value was 0.1 cm ² / V · s. In contrast, Comparative Examples 1 and 2 exhibited very low charge mobility due to the high surfactant content.

In the case of the PDPP-SVS polymer pattern prepared in Example 11 and the PIID-SVS polymer pattern prepared in Example 12, charge mobility of 2.4 cm ² / V · s and 0.90 cm ² / V · s was shown, respectively. The charge mobility is close to the charge mobility of the polymer pattern prepared by dissolving PDPP-SVS and PIID-SVS in chlorform, respectively, 3.7 cm ² / V · s and 1.3 cm ² / V · s, the theoretical value It corresponds to a high value corresponding to 64% and 69% of. Therefore, the method of manufacturing the organic semiconductor polymer pattern according to the present invention is a uniform high-quality organic semiconductor polymer having a value of 60%, preferably 65% or more of the theoretical charge mobility, despite using a simple and economical patterning process in an atmospheric environment. It suggests that a thin film can be formed.

As described above, in the present invention, it has been described by specific matters and limited embodiments and drawings, which are provided to help the overall understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention Various modifications and variations can be made by those skilled in the art.

Therefore, the spirit of the present invention is not limited to the described embodiments, and should not be determined. It will be said that not only the claims described below, but also all those with equivalent or equivalent modifications to the claims are within the scope of the spirit of the present invention.

Claims (14)

A first step of surface-treating the first area of the substrate having the first surface property with the second surface property;
A second step of including an organic semiconductor polymer in the inner phase and coating an emulsion containing a surfactant on the substrate; And
A third step of removing the surfactant by drying the coated substrate and washing with alcohol; includes a unit coating process,
The first surface property and the second surface property are hydrophilic or hydrophobic, respectively, and the manufacturing method of the organic semiconductor polymer pattern, characterized in that different from each other. According to claim 1,
The method of manufacturing an organic semiconductor polymer pattern in which the emulsion in the second step is an oil-in-water emulsion. According to claim 1,
Method for producing an organic semiconductor polymer pattern of the side chain of the organic semiconductor polymer and a hydrophobic group of a surfactant. According to claim 1,
A method for producing an organic semiconductor polymer pattern in which the straight chain carbon number C _P of the side chain of the organic semiconductor polymer and the linear carbon number C _S of the hydrophobic group of the surfactant satisfy the following relationship.
[Relationship 1]
0.8 <C _P / C _S <1.2 According to claim 1,
The surfactant is (C10-C16) a method for producing an organic semiconductor polymer pattern that is an aliphatic cationic surfactant. According to claim 1,
A method of manufacturing an organic semiconductor polymer pattern further comprising performing the unit coating process in a region different from the first region of the hydrophilic substrate. According to claim 1,
The alcohol is a method for producing an organic semiconductor polymer pattern containing (C2-C4) alcohol. According to claim 1,
The method of manufacturing an organic semiconductor polymer pattern having a thickness of the polymer pattern is 10 to 100 nm. According to claim 1,
Method of manufacturing an organic semiconductor polymer pattern having a surface roughness (R _rms ) of the pattern is 10 nm or less. According to claim 1,
A method of manufacturing an organic semiconductor polymer pattern in which a first self-assembled monolayer or hydrophobic polymer layer is formed on a substrate in the first region of the substrate having the first surface property. According to claim 1,
The first step includes applying a self-assembled compound to a first region of a substrate having a first surface property, wherein the self-assembled compound is selected from the group consisting of alcohol, amine, carboxylic acid, and thiol. Method for producing an organic semiconductor polymer pattern that is a compound containing any one or more functional groups. According to claim 1,
A method of manufacturing an organic semiconductor polymer pattern including the unit coating process at least twice, but the organic semiconductor polymer included in each unit coating process may be the same or different. An organic semiconductor polymer pattern produced by the manufacturing method according to any one of claims 1 to 12. An optoelectronic device comprising the organic semiconductor polymer pattern of claim 13.

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