KR101005808B1 - A method for preparing photo-crosslinkable organic gate insulator and organic thin film transistor device using the same - Google Patents

Abstract

The present invention relates to a novel synthesis of organic insulators, which is a key component of an organic thin film transistor (OTFT), which can be applied as a driving switching device of a next-generation flexible display, and to manufacturing an organic thin film transistor using the same. In more detail, a novel organic insulator manufactured by chemical reaction between a hydroxyl group of polyvinylphenol (PVP) or polyvinyl alcohol (PVA), which is widely used as an organic insulator, and a functional group having photoreactive properties, and the same It relates to the manufacture of the organic thin film transistor used.

In the organic insulator according to the present invention, the hydroxy group is removed in the thin film, thereby reducing the hysteresis and improving the insulation characteristics. The organic insulator has an effect of lowering the process temperature of the organic insulator thin film manufacturing process through curing through UV.

Organic Insulator, Polyvinylphenol, Polyvinyl Alcohol, Photoreaction, Curing, Organic Thin Film Transistor

Description

A method for preparing photo-crosslinkable organic gate insulator and organic thin film transistor device using the same}

The present invention provides a method for preparing a new organic insulator that can be photocured by a low temperature process and a photopolymerization method that can be used as an organic thin film transistor (OTFT) that can be applied as a driving switching device in a next-generation flexible display, and an organic insulator prepared therefrom. It relates to a thin film transistor.

Since the 1980s, research on organic thin film transistors (OTFTs) using organic materials as active layers has been actively conducted worldwide. The organic thin film transistor is almost similar in structure to a conventional silicon transistor (Si-TFT), but there is a difference in using an organic material instead of silicon in the semiconductor region. The organic thin film transistor can simplify the manufacturing process by using spin coating or printing method of atmospheric pressure instead of the physical / chemical deposition method using the inorganic thin film of the conventional silicon transistor, and has the advantage of low temperature process.

In general, as an insulator of an organic thin film transistor, inorganic silicon dioxide (SiO ₂ ) is used, and as organic materials, polyvinyl alcohol (PVA), polyvinylphenol (PVP), polymethylmethacrylate (PMMA), and polyimide ( Substances such as PI) are used. Since the insulator forms an interface with the organic semiconductor, the crystallinity and shape of the organic semiconductor depend on the interface characteristics of the insulator, which is an essential part of the device characteristics of the final thin film transistor.

In the case of polyvinyl alcohol (PVA) -based or polyvinyl phenol (PVP) -based organic insulators in the prior art, the application of a curing agent is used to thermally cure the polymer at high temperature, thereby limiting its application to flexible substrates. Since the hydroxy group is included in the structure afterwards, when the organic insulating film made of such a material is applied to the organic thin film transistor, there are problems such as leakage current and hysteresis expression by the hydroxy group.

In order to obtain the excellent characteristics of the organic thin film transistor, it is necessary to develop an organic insulator having excellent insulating properties. In order to implement the organic thin film transistor on a flexible substrate, the process temperature of forming the organic insulator thin film must be low temperature process. In addition, the organic insulator needs to be patterned in order to manufacture an actual array device using an organic thin film transistor. Therefore, it is necessary to develop an organic insulator having excellent solubility in the solvent used in the solution process and excellent chemical resistance to the solvent used in the subsequent solution process so that the organic insulating film can be easily patterned through a printing process.

In the present invention, polyvinyl alcohol or polyvinylphenol, which is widely used as an organic insulator, which is a key component of an organic thin film transistor (OTFT), which can be applied as a driving switching device in a next-generation flexible display, is reacted with a functional group capable of photocuring. It is intended to reduce the curing temperature of the insulator and to improve the insulating properties.

In the present invention, in order to enable the curing reaction of polyvinyl alcohol or polyvinyl phenol organic insulator polymer containing a hydroxyl group by photoisomerization reaction, acryl having various structures capable of photoreaction in a lower energy region than cinnamoyl group A novel organic insulator was prepared by reacting with an acrylloyl group and applied as an organic insulator of an organic thin film transistor device to solve the problem of causing leakage current or hysteresis in the device. Through the photocuring method, it is possible to obtain an effect of lowering the process temperature of the organic insulator thin film manufacturing.

In the case of polyvinylphenol, which is most commonly used as an organic insulator, it is difficult to apply it to a flexible plastic substrate because a high temperature process of 200 ° C. or higher must be applied for thermal curing, and since hydroxy groups exist in the insulator thin film even after curing. There was a serious problem such as hysteresis in the device characteristics.

The present invention is an organic insulator of an organic thin film transistor, and has various structures such as acryloyl, which is capable of photoreaction in a lower energy region than conventional hydroxyl groups of polyvinyl alcohol or polyvinylphenol and cinnamoyl groups. The present invention provides a polyvinyl-based organic polymer capable of photocuring by reaction with a group, and a method of manufacturing the same, and provides an organic thin film transistor including an organic insulating layer formed by applying and curing the polyvinyl-based organic polymer.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a polyvinyl organic polymer for a gate insulating film of an organic thin film transistor represented by the following formula (1) or (2).

[Formula 1]

[Formula 2]

In Formulas 1 to 2, A ¹ and A ² are independently a chemical bond or phenylene, a and b are independently an integer of 1 to 10, n and m are independently a natural number of 10 to 2000, R ¹¹ To R ¹⁹ and R ²¹ to R ²⁷ are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen.

More preferably, the polyvinyl organic polymer of Formula 1 or Formula 2 has a mass average molecular weight in the range of 5000 to 1,000,000 g / mol, and when the molecular weight is less than 5,000, leakage current due to low molecular weight of the organic insulating film itself This is because the problem may occur, and when the molecular weight exceeds 1,000,000, it may be disadvantageous in that the workability due to the high molecular weight is considerably inferior in the organic insulating film forming process.

In Formula 1 or Formula 2, the polyvinyl-based organic polymer specifically includes a compound having the following structure, and n and m in the following structure are as defined above.

The present invention is a method for producing a polyvinyl organic polymer represented by Formula 1 or Formula 2, by reacting acryloyl halide of Formula 4 or Formula 5 from a polymer having a hydroxyl group of Formula 3 It provides a method of manufacturing.

(3)

[Formula 4]

[Chemical Formula 5]

[In Formula 3, A is a chemical bond or phenylene, k is a natural number of 10 to 2000, X is a halogen element in Formulas 4 to 5, a and b are independently an integer of 1 to 10, R ¹¹ To R ¹⁹ and R ²¹ to R ²⁷ are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen.]

Polyvinyl-based organic polymer of Chemical Formula 1 is prepared by reacting the compound of Chemical Formula 3 with the compound of Chemical Formula 4, and the polyvinyl organic compound of Chemical Formula 2 is reacted with the compound of Chemical Formula 3 Polymers are prepared.

The compound of Chemical Formula 3 is a polymer such as polyvinylphenol and polyvinyl alcohol, which are frequently reported as existing organic insulators, and a polymer having a number average molecular weight of 5k to 1000k may be used. The compound of Formula 4 or Formula 5, which reacts with the compound of Formula 3, has a photocuring group and an aromatic group conjugated with the photocuring group so that an intermolecular reaction may be caused by light, and a lower energy may be easily irradiated. Photocuring may occur. In the compound of Formula 4 or Formula 5, as the photocuring group and the conjugated aromatic group increase, there is an advantage that the energy of the wavelength required for the photoreaction may be lowered. This can minimize the destruction of the organic insulator polymer and the degradation of properties due to UV used in photocuring. As the compound of Formula 4, 3-biphenyl-4-yl-acryloyl chloride is typically represented, and as the compound of Formula 5, 3- 3-naphthalen-1-yl-acyloyl chloride is mentioned. 3-biphenyl-4-yl-acryloyl chloride and 3-naphthalen-1-yl-acryloyl chloride (3-naphthalen-1-yl-acyloyl chloride ) Increases the length of conjugated bonds than cinnamoyl chloride, allowing photoreaction at lower energy.

In another aspect, the present invention provides a method for producing an organic insulating film through a solution process using the polyvinyl-based organic polymer of Formula 1 or Formula 2 and an organic thin film transistor comprising the organic insulating film.

The organic thin film transistor according to the present invention includes an organic insulating film formed by applying a coating liquid containing a polyvinyl-based organic polymer into which the photoreactor of Formula 1 or Formula 2 is introduced onto a substrate on which a gate electrode is formed and then photocuring the same.

3 illustrates a structure of a bottom gate top-contact organic thin film transistor according to one embodiment of the present invention. Referring to FIG. 3, a gate electrode 2, an organic insulating film 3, an organic semiconductor layer 4, a source electrode 5, and a drain electrode 6 are formed on a substrate 1 made of glass or plastic. Although not shown, a protective layer may be further formed on the source electrode and the drain electrode.

The coating liquid for forming the organic insulating film may include a solvent that facilitates viscosity control and has excellent solubility in polyvinyl organic polymers. Examples of suitable solvents include chloroform, toluene, cyclohexane, dichlorobenzene, and the like. . The application can be performed by one or more methods selected from spin coating, ink jet printing, roll coating, screen printing, and dipping.

1 illustrates a curing mechanism by photopolymerization of a polyvinyl organic polymer according to the present invention and is cured by a reaction between acryloyl groups, which are photocuring functional groups of a polyvinyl organic polymer represented by Formula 1 or Formula 2 Indicates.

Photocuring in the present invention is carried out through a heat treatment of 120 ℃ to 150 ℃ after UV irradiation. If there is no photocuring process, the process can be performed at a significantly lower temperature than heat treatment of 200 ° C or more is required. The UV irradiation energy is more preferably performed in the range of 500mJ to 2000mJ in terms of curing properties and physical properties.

In the present invention, the thickness of the organic insulating film can be adjusted in the range of 30 nm to 1000 nm, it is more advantageous to control within the above range in terms of insulation of the organic insulating film and low voltage driving of the final organic thin film transistor.

In the present invention, the organic semiconductor layer is pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C ₆₀ , phenylenetetracarboxylic dianydride, naphthalenetetracarboxylic dianydride, and naphthalenetetracarboxylic dianydride. , At least one selected from fluorinated phthalocyanine and derivatives thereof.

The organic thin film transistor according to the present invention has a field mobility of 0.01 to 10 cm ² / Vs, which means that the organic thin film transistor has suitable performance as an organic thin film transistor as a range of field mobility values of a conventional organic thin film transistor. .

In addition, the present invention provides a display device using the organic thin film transistor according to the present invention, the display device may be an organic light emitting display, an electronic paper or a liquid crystal display.

The polyvinyl-based organic polymer incorporating the photocuring agent according to the present invention has no problem in implementing a device on a flexible plastic substrate since the thin film manufacturing process is possible at a low temperature of about 120 to 150 ° C. when the organic curing film is used. In addition, by removing the hydroxy group present in the polyvinyl alcohol or polyvinylphenol by introducing a photoreactor, it can be expected to solve the problems such as hysteresis and finally improve the device reliability when applied to the device. In addition, the organic semiconductor layer through the solution process on the organic insulating film and other chemicals that are not damaged by the organic solvent at the time of the other process achieved by photocuring can solve the problem in the application in the actual array device fabrication.

Therefore, the novel photocurable organic insulator of the present invention can be used in organic thin film transistors that can be applied as driving switches to flexible next generation flexible displays and sensors, and can be used in process temperature, chemical resistance, and electrical characteristics compared to conventional organic insulators. And excellent properties.

The present invention will be described in more detail with reference to the following Examples. However, the following examples are merely examples of the present invention, and the claims of the present invention are not limited thereto.

Preparation Example 1 Preparation of 3-naphthalen-1-yl-acryloyl chloride (3-naphthalen-1-yl-acyloyl chloride)

2 g of 3-naphthalen-1-yl-acrylic acid was added to a 500 mL round bottom flask, dissolved in 200 mL MC, and 2 mL of oxalyl dichloride was added thereto. Next, the catalytic amount of DMF (N, N-dimethylformamide) was added, followed by stirring at room temperature for 2 hours. Finally, the reaction mixture was concentrated under reduced pressure to remove volatiles, thereby obtaining a yellow solid compound.

Preparation Example 2 Preparation of 3-biphenyl-4-yl-acryloyl chloride

2 g of 3-biphenyl-4-yl-acrylic acid was added to a 500 mL round bottom flask, dissolved in 200 mL MC, and 2 mL of oxalyl dichloride was added and stirred. Subsequently, DMF (N, N-dimethylformamide) was added in a catalytic amount and stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and finally to a yellow final compound.

Example 1 Preparation of Polyvinylphenol (NAP-PVP) Substituted with 3-Naphthalen-1-yl-acryloyl Chloride

To a 250 mL round bottom flask, 5.0 g (40 mmol) of polyvinylphenol (number average molecular weight 20K) and 10.40 g (48 mmol) of 3-naphthalen-1-yl-acryloyl chloride of Preparation Example 1 were added, followed by ethyl acetate solvent. 100 mL was injected. 6.56 mL (40 mmol) of triethylamine was added as a base, and 0.4 mg (0.04 mmol) of hydroquinone was added as a photoreaction inhibiting catalyst, followed by reaction at room temperature for 12 hours. After completion of the reaction, the solvent was distilled under reduced pressure to minimize the reaction mixture. The reaction mixture was slowly added dropwise to methanol to precipitate the final compound as a white solid, followed by drying.

¹ H-NMR (δ, DMSO- d ₆ ) 7.86-6.99 ppm (broad m, Aromatic 11H, vinyl 1H), 6.42 ppm (broad d, vinyl 1H, 3.22 1.39 (broad m, -CH ₂ and -CH).

Example 2 Preparation of Polyvinylphenol (BIP-PVP) Substituted with 3-Biphenyl-4-yl-Acryloyl Chloride

Instead of 10.40 g (48 mmol) of 3-naphthalen-1-yl-acryloyl chloride of Preparation Example 1, using 11.65 g (48 mmol) of 3-biphenyl-4-yl-acryloyl chloride of Preparation Example 2 A polyvinylphenol (BIP-PVP) substituted with 3-biphenyl-4-yl-acryloyl chloride was prepared in the same manner as in Example 1 except that.

¹ H-NMR (δ, DMSO- d ₆ ) 7.75-6.99 ppm (broad m, Aromatic 13H, vinyl 1H), 6.39 ppm (broad d, vinyl 1H, 3.12 1.29 (broad m, -CH ₂ and -CH).

Manufacture of organic insulating film

The polyvinylphenol polymer having the photocuring group prepared in Examples 1 and 2 was dissolved in an organic solvent such as chloroform to form a thin film by spin coating, and the photolysis reaction was performed by blocking UV of 254 nm or less to 2.5% or less. UV curing was performed using Melles Griot's UG11 filter to minimize photocuring reaction by photopolymerization. Examples 3 and 4 show the photocuring process of the respective polymers.

Example 3 Preparation and Photocuring of Polyvinylphenol (NAP-PVP) Thin Film Substituted with 3-Naphthalen-1-yl-acryloyl Chloride

The organic insulator thin film was prepared by spin coating at a speed of about 3000 rpm using a solution obtained by dissolving the polymer (NAP-PVP) prepared in Example 1 in a chloroform solvent at a concentration of 6 wt%. The prepared thin film was adjusted to 300 nm in thickness and the prepared thin film was subjected to soft baking (90 ° C., 10 minutes) to remove excess solvent. UV light of 500 mJ ~ 1000mJ (average 750mJ) was irradiated for photocuring the thin film, and finally, the organic insulator thin film was finally prepared by hard baking at 120 ° C. for 30 minutes.

Example 4 Preparation and Photocuring of Polyvinylphenol (BIP-PVP) Thin Film Substituted with 3-Biphenyl-4-yl-Acryloyl Chloride

An organic insulator thin film was manufactured in the same manner as in Example 3, except that the polymer (BIP-PVP) prepared in Example 2 was used instead of the polymer (NAP-PVP) prepared in Example 1.

Comparative Example 1 Preparation of Polyvinylphenol (PVP) Thin Film

An organic insulator thin film was fabricated using polyvinylphenol, which is widely used as an organic insulator. Polyvinylphenol having a number average molecular weight of about 20,000 was dissolved in PGMEA (propylene glycol monomethyl ether acetate) solvent at 10wt% and a cross-linking agent, poly (melamine-co-formaldehyde) methylated ((poly (melamine -co-formaldehyde) methylated) was added in a ratio of 5 to 1 by weight of polyvinylphenol (weight ratio) to prepare a solution A thin film was prepared to a thickness of 300 nm by spin coating at 3000 rpm. In order to compare the thin film cured at 200 ° C. with the polymer thin film to which the photocuring machine proposed in the present invention was introduced, the thin film cured at 120 ° C. was compared and analyzed with the thin films of Examples 3 and 4. It was.

Characterization of Fabricated Organic Insulator Thin Films

Polyvinylphenol (NAP) substituted with 3-naphthalene-1-yl-acryloyl chloride (NAP) prepared in Example 3 among polyvinylphenol polymers having photocuring groups introduced therein The surface characteristics of the organic insulator thin film before and after photocuring were investigated. First, the surface energy, an important characteristic of organic insulator thin film used as organic thin film transistor, was analyzed by the water contact angle measurement method. As shown in FIG. 2, the water contact angles before and after the photocuring reaction through UV irradiation after forming the organic insulator thin film were 78.4 ^° and 75.0 ^° , and there was no significant difference. The surface energy of the thin film calculated with the water contact angle and the contact angle of diodomethane was 48.7 mN / m and 49.7 mN / m, respectively, before and after photocuring. The surface energy of the organic insulator thin film through UV irradiation showed similar values. It was. This indicates that the hydroxyl group of the polyvinylphenol does not exist in the polymer by reacting with 3-naphthalen-1-yl-acryloyl chloride (NAP) even before the photocuring reaction, which indicates leakage current and hysteresis in the final organic thin film transistor characteristics. The improvement effect can be expected.

Chemical resistance of the organic insulator thin film, which is important in the manufacture of organic thin film transistor through solution process, was evaluated by dipping the thin film in general organic solvents (cyclohexanone, chloroform and N, N-dimethylformamide: NMP) and measuring the surface roughness of the thin film. In the case of cyclohexanone, chloroform and NMP solvent, polyvinylphenol (NAP-PVP) in which 3-naphthalen-1-yl-acryloyl chloride (NAP) was introduced before curing was completely removed. In the case of the thin film which was dissolved in the solvent again and photocured by UV irradiation, the three organic solvents were not damaged at all. Atomic force microscopy (AFM) analysis showed that the RMS value, which is the surface roughness, was excellent even after treatment with organic solvent. In addition, in the case of the organic insulator thin film using the polyvinylphenol (PVP) polymer which does not have the conventional photocuring group prepared in Comparative Example 1, when the curing temperature is 120 ℃, all three solvents were damaged. In the case of the polyvinyl alcohol thin film cured at 200 ℃, after the treatment in the NMP solvent it was confirmed that the surface damage of the thin film occurs with an RMS value of 10 nm or more. In the present invention, the polyvinyl phenylene (NAP-PVP) in which the photocuring group is introduced is used in a general organic solvent than polyvinyl phenol, which has been widely used as an organic insulator, through a curing reaction through photopolymerization at a low process temperature of 120 ° C. It showed the advantage of having excellent chemical resistance.

Fabrication and Characterization of Organic Thin Film Transistors

The organic thin film transistor was fabricated using the polyvinyl alcohol organic insulator thin film into which the photocuring machine of the present invention was introduced and its characteristics were measured. As an organic semiconductor, pentacene, which is widely used in organic thin film transistors and has a relatively good performance, was used. Since the substrate has a process temperature of 120 ° C. in the case of the organic insulator developed in the present invention, plastic substrates such as glass and polyether sulfone were used. The device structure of the organic thin film transistor is a top-contact type (device) manufacturing method is as follows. Substrate cleanliness is one of the most important factors in the manufacture of electronic devices, so ultrasonic cleaning with detergent, distilled water, acetone, and isopropyl alcohol was used, followed by drying sufficiently in an oven. Only the protective film was detached and used as it is.

On the well cleaned substrate, gold was first thermally vacuum-deposited in a vacuum of ¹ × 10 ⁻⁶ torr using a shadow mask to form a 2 mm wide gate electrode having a thickness of 40 nm. The photocurable polyvinylphenol (NAP-PVP) organic insulator of the present invention is spin coated to a thickness of 300 nm, dried at 90 ° C. for 10 minutes, and then photocured through UV irradiation (1000 mJ). The final drying for 30 minutes at a temperature of 120 ℃ to obtain a photo-cured polyvinyl alcohol organic insulator thin film.

As a comparative example, the thin film was spin-coated at 90 ° C. for 10 minutes after the conventional polyvinylphenol (PVP) having no photocuring group was introduced in the present invention in the same manner as the polyvinylphenol (NAP-PVP) process temperature at which the photocuring group was introduced. 30 minutes of treatment at a temperature of 120 ℃ to produce an organic insulator thin film.

Pentacene, an organic semiconductor, was deposited to a thickness of 50 nm on the organic insulator thin films prepared as described above using thermal vacuum deposition in a vacuum of 1 × 10 ⁻⁶ torr. At this time, the temperature of the substrate having a great influence on the crystallization of pentacene was kept constant at 90 ℃. Finally, gold was deposited to a thickness of 50 nm in the same manner as gate deposition to form a source and a drain electrode. Bottom-contact devices were fabricated by changing the order of formation of pentacene, source, and drain electrodes. The characteristics of the device fabricated as described above were measured in the saturation region by measuring the drain voltage-drain current according to the gate voltage and the gate voltage-drain current curve according to the drain voltage by using the E5272 device of Agilent Technology. Various characteristics were evaluated using the current and voltage equations.

와 V_gs 의 그래프로부터 I_ds 가 0인 게이트 전압으로 결정되고 전계효과 전하이동도는

와 V_gs의 그래프의 기울기로부터 산출하였다.Where V _T is the threshold voltage, V _gs is the applied gate voltage, μ is the field effect charge mobility, W and L are the width and length of the channel, and C is the capacitance of the insulating film. Threshold voltage

From the graphs of V _gs and V _gs , we determine the gate voltage with I _ds 0 and the field effect charge mobility

It was computed from the slope of the graph of and V _gs .

In FIG. 4, polyvinyl alcohol having a current-voltage characteristic and a photocuring group introduced with an organic thin film transistor prepared by curing an existing polyvinylphenol (PVP) organic insulator at 120 ° C. was treated using an organic insulator treated at 120 ° C. after photocuring. The current-voltage characteristics of the organic thin film transistor are shown and FIG. 5 shows the current-voltage characteristics of the organic thin film transistor using the polyvinyl phenol (NAP-PVP) organic insulator thin film in which the photocuring group proposed in the present invention is introduced. The existing polyvinyl alcohol showed a high leakage current (10 ^-7 ~ 10 ^-8 A) as shown in Figure 4 and confirmed that almost no operation with a thin film transistor. In the case of the organic thin film transistor using polyvinylphenol (NAP-PVP) to which the photocuring group introduced in the present invention is applied, the leakage current value was very low as 4.8X10 ^-12 A as shown in FIG. In case of the lighting current ratio (I _on / I _off ), the characteristics were 2X10 ^-5 , which is superior to the device using the polyvinylphenol organic insulator. For other driving voltages, -14V and subthreshold slope (SS) values were 1.37 V / dec, which was better than -27V and 7.87 V / dec of the device using the polyvinylphenol organic insulator thin film. . Table 1 summarizes the important characteristics of the organic thin film transistor using the conventional polyvinylphenol (PVP) and the polyvinylphenol (NAP-PVP) organic insulator thin film in which the photocuring group of the present invention is introduced.

TABLE 1

1 shows a curing mechanism by photopolymerization of a polyvinyl organic polymer according to the present invention,

2 is a water contact angle measurement before and after photocuring of the polyvinyl-based organic polymer according to the present invention,

3 is a cross-sectional view illustrating a structure of a bottom-gate top-contact organic thin film transistor according to one embodiment of the present invention;

4 is a current-voltage (I-V) curve of an organic thin film transistor element after a 120 ° C. process of a conventional polyvinyl alcohol organic insulator.

5 is a current-voltage (I-V) curve of the organic thin film transistor device after the photocuring and 120 ℃ process of the novel organic insulator according to the present invention.

<Description of the symbols for the main parts of the drawings>

1: substrate 2: gate electrode 3: organic insulating film

4: organic semiconductor layer 5: source electrode 6: drain electrode

Claims (12)

Polyvinyl organic polymer for organic insulating film of the organic thin film transistor represented by the following formula (1) or (2). [Formula 1]

[Formula 2]

[In Formula 1 to Formula 2, A ¹ and A ² are independently a chemical bond or phenylene, a and b are independently an integer of 1 to 10, n and m are independently a natural number of 10 to 2000, R ¹¹ to R ¹⁹ and R ²¹ to R ²⁷ are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen.] The method of claim 1, The polyvinyl-based organic polymer represented by Formula 1 and Formula 2 has a polyvinyl-based organic polymer having a mass average molecular weight in the range of 5000 to 1,000,000 g / mol. A method of preparing a polyvinyl-based organic polymer of Formula 1 or 2 according to claim 1 by reacting acryloyl halide of Formula 4 or Formula 5 from a polymer having a hydroxyl group of Formula 3 below. (3)

[Formula 4]

[Chemical Formula 5]

[In Formula 3, A is a chemical bond or phenylene, k is a natural number of 10 to 2000, X is a halogen element in Formulas 4 to 5, a and b are independently an integer of 1 to 10, R ¹¹ To R ¹⁹ and R ²¹ to R ²⁷ are independently selected from hydrogen (H), (C 1 -C 10) alkyl, cyano or halogen.] An organic thin film transistor comprising a gate electrode, an organic insulating film, an organic semiconductor layer, a source electrode, and a drain electrode on a glass and plastic substrate, wherein the organic insulating film contains a coating liquid containing the polyvinyl organic polymer according to claim 1. An organic thin film transistor formed by coating on the formed substrate and photocuring. The method of claim 4, wherein The photocuring is an organic thin film transistor made through a heat treatment of 120 ℃ to 150 ℃ after UV irradiation. The method of claim 5, The UV irradiation is an organic thin film transistor is performed in the range of 500mJ to 2000mJ. The method of claim 4, wherein Wherein said coating is performed by one or more methods selected from spin coating, ink jet printing, roll coating, screen printing, and dipping. The method of claim 4, wherein The organic insulating film is an organic thin film transistor having a thickness of 30 nm to 1000 nm range. The method of claim 4, wherein The organic semiconductor layer is pentacene, metal phthalocyanine, polythiophene or phenylenevinylene, C ₆₀ , phenylenetetracarboxylic dianydride, naphthalenetetracarboxylic dianydride, fluorine An organic thin film transistor comprising at least one member selected from fluorophthalocyanine and derivatives thereof. The method of claim 9, The organic thin film transistor is an organic thin film transistor, characterized in that the field mobility is in the range of 0.01 ~ 10cm ² / Vs. A display device comprising the organic thin film transistor of any one of claims 4 to 10. The method of claim 11, The display device is selected from an organic light emitting display, an electronic paper or a liquid crystal display.

Images