KR20130136306A - Diketopyrrolopyrrole polymer derivative containing 1,2-di(selenophen-2-yl)ethene and organic thin film transistor including the derivative - Google Patents

Abstract

The present invention provides a diketopyrrolopyrrole polymer derivative containing 1,2-di(selenophen-2-yl)ethene, and an organic thin film transistor including the derivative. The organic thin film transistor including the diketopyrrolopyrrole polymer derivative containing 1,2-di(selenophen-2-yl)ethane has high hole mobility and excellent thermal stability. [Reference numerals] (AA) Source electrode;(BB) Organic semiconductor thin film;(CC) Drain electrode;(DD) Insulating (film SiO_2);(EE) Gate electrode;(FF) Substrate

Description

Diketopyrrolopyrrole polymer derivative containing 1,2-di (selenophen-2-yl) ethene and organic including a diketopyrrolopyrrole polymer derivative comprising 1,2-diselenophen-2-ylethyne thin film transistor including the derivative}

The present invention relates to a diketopyrrolopyrrole-based polymer derivative including 1,2-diselenophen-2-ylethyne and an organic thin film transistor comprising the same.

Since it is known from the late 1970s that electrical conductivity can be reached almost close to copper through proper doping of certain organics, organics are now in terms of conductivity, from the best insulators (polystyrene, etc.) to semiconductors, conductors (doped polyacetylenes, etc.) In addition, all kinds of electronic materials can be obtained, including superconductors (TMTSF) ₂ PF ₆ , perchlorate, pentacene, etc.). Examples of the semiconductor include p-type pentacene, n-type C ₆₀ , Alq _3, and the like, and dielectrics include polyvinylidene fluoride (PVDF), which is a ferroelectric, and co-polymers based thereon.

In recent decades, the development of organic materials with semiconductor properties and various application studies using them have been actively conducted. The scope of application research using organic semiconductors such as electromagnetic shielding films, capacitors, organic electroluminescence (EL) displays, organic thin film transistors, solar cells, and memory devices using multiphoton absorption phenomena continues to expand. In particular, the organic EL field is partly commercialized and serves as a catalyst for activating applied research using organic materials in the electronic field.

Organic thin film transistors using organic materials are being studied in next generation smart cards, using active driving devices for organic EL. In addition, after the results of the research on the electric oscillation characteristics using the organic semiconductor as an active layer, it has been attracting much attention about the application as a laser diode. In addition, the solar cell made of doped pentacene is showing a rapid development, such as 2.4% efficiency, the device manufacturing cost is significantly lower than the inorganic.

In addition, since flexible electronic circuit boards are expected to be an important element technology for future industries, the development of organic thin film transistors capable of meeting these requirements is emerging as an important research field. Organic thin film transistors cannot be used in high-speed devices that use silicon (Si) or germanium (Ge) due to their low charge mobility due to the characteristics of organic semiconductors, but they are used when devices are fabricated over a large area, low temperature processes are required, or bending is required. Organic thin film transistors can be useful because they are possible, and particularly low cost processes are possible. Recently, researchers at Philips have produced a programmable code generator, which consists of 326 transistors, using substrates, electrodes, organic dielectrics (insulators), and organic semiconductors all using polymers.

Organic thin film transistors implemented on plastic substrates can also be applied to bendable liquid crystal display devices, or to drive electronic paper and organic light emitting devices, which have recently attracted great interest. In particular, recently developed electronic paper is a display device that does not require high charge mobility and fast switching speed by voltage driving, and is an advantageous technology to be applied to a large area that can be bent, and thus the application of the organic thin film transistor is very high.

Research on organic thin film transistors began in the early 1980s, and recently, full-scale research has been conducted worldwide. The transistor device includes a substrate, a gate electrode, an insulating film, a channel layer, a source / drain electrode, and a protective layer to prevent external moisture and oxygen transmission. The organic thin film transistor is fabricated by replacing the existing silicon based inorganic material with the organic compound or the polymer material which exhibits the semiconductor characteristic, which is the key part of the charge transfer which has the greatest influence on the device characteristics. As organic semiconductor materials, polyacene compounds such as anthracene, tetracene, pentacene, and the like have been studied along with polyphenylenevinylene, polypyrrole, polythiophene, and oligothiophene. Since it is strong, it has high crystallinity and thereby has high carrier mobility. Organic semiconductor materials are divided into n-type materials that move electrons and p-type materials that transport holes. Among the p-type organic semiconductors, high charge mobility is present in low molecular organic semiconductor materials such as pentacene.

Polyacene compounds such as pentacene have high crystallinity due to strong π-π affinity resulting from aromatic molecules between neighboring molecules, and have been reported to exhibit excellent charge mobility characteristics. Recent publications have reported high charge mobilities of 3.2 to 5.0 cm ² / Vs using pentacene single crystals in Lucent Technologies or 3M (Mater. Res. Soc. Symp. Proc. Vol. 771, L6.5.1). L 6.5.11 (2003). French CNRS has also reported relatively high charge mobility and current flashing ratios of 0.01 to 0.1 cm ² / Vs using oligothiophene derivatives. However, the prior art has a disadvantage in that expensive vacuum equipment is required in order to manufacture a thin film required for device fabrication, and expensive process equipment is required and the process cost is high.

In order to solve this problem, researches for developing polyacene derivatives such as pentacene, which are capable of solution processing, have been developed in various research groups worldwide. Mullen Research Group in Germany synthesized soluble pentacene precursor, coated organic substrate with solution process, and then heat treated it to realize pentacene, and thus, organic thin film transistor device showing charge mobility of 0.1 ~ 0.2 cm ² / Vs. (PT Herwig and K. Mlen, Adv. Mater . Vol. 11, p. 480 (1999)). In Anthony (J. Anthony) working group of the University of Kentucky, USA in order to impart solubility triisopropylsilyl ethynyl (triisopropylsilylethynyl) groups are pentamethyl to develop the derivative bonded to both sides of the metallocene up to 1.5 cm ² / Vs to about the solution process An implementation of an organic thin film transistor device exhibiting charge mobility characteristics has been reported (JE Anthony, et.al., J. Am . Chem . Soc ., Vol . 123, p . 9482 (2001); JE Anthony, et.al. ., Tech. Dig .- Int. Electron Devices Meet . , p. 113 (2006)). The Wurthner research group at the University of Wurzburg, Germany, developed pentacene derivatives in which trimethoxyphenylethynyl groups were introduced as substituents on both sides of pentacene to provide solubility. (F. Wurthner, et.al., J. Mater . Chem . , Vol . 16, p . 3708 (2006)). However, these derivatives exhibited very low thermal and oxidative stability and low charge mobility.

In order to make polyacene-based organic semiconductor materials such as pentacene suitable for the solution process, it is generally important to increase the solubility by introducing a bulky or aliphatic alkyl substituent to pentacene, but in addition to solubility, such as thermal stability, oxidation stability, etc. In order to increase the stability and charge mobility, the intermolecular affinity to induce crystallization should be considered very important when designing substituents.

Accordingly, the present inventors have completed the present invention to solve the above-mentioned problems in the prior art. SUMMARY OF THE INVENTION An object of the present invention is to provide a diketopyrrolopyrrole-based polymer derivative including 1,2-diselenophen-2-ylethyne to improve solubility, electron donating ability and crystallinity.

In addition, an object of the present invention is to provide an organic semiconductor thin film comprising a diketopyrrolopyrrole polymer derivative including the 1,2- disselenophen-2-ylethyne.

Another object of the present invention is to provide an organic thin film transistor having high hole mobility and excellent thermal stability by including a diketopyrrolopyrrole polymer derivative including the 1,2-diselenophen-2-ylethyne. have.

According to an aspect of the present invention may be provided with a diketopyrrolopyrrole polymer derivative comprising 1,2- disselenophen-2-ylethyne represented by the formula (1).

[Formula 1]

In Formula 1, R ₁ is C3 to C60 hetero, including at least one selected from hydrogen, deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C6 to C60 aryl group, N, O and S It may be selected from the group consisting of an aryl group, a heteroalkynyl group of C1 to C60, an alkynyl group of C1 to C60 and a heteroalkyl group of C1 to C60.

According to one embodiment of the diketopyrrolopyrrole polymer derivatives containing 1,2-diselenenophen-2-ylethyne according to the present invention, R ₁ may be selected from the following structures.

In the above structure, R ₂₁ to R ₃₁ are hydrogen, deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C3 to C60 heteroaryl group including at least one selected from N, O and S and C6 to C60 It may be selected from the group consisting of an aryl group.

According to another aspect of the present invention, an organic semiconductor thin film for an organic thin film transistor including a diketopyrrolopyrrole-based polymer derivative including the 1,2-diselenophen-2-ylethyne may be provided.

According to an embodiment of the organic semiconductor thin film according to the present invention, the organic semiconductor thin film is at least one selected from the group consisting of polyalphamethylstyrene, amorphous polycarbonate, polyarylamine, polycarbazole, polythiophene and mixtures thereof It may further comprise an organic polymer compound.

According to another aspect of the present invention, in an organic thin film transistor including a substrate, a source-drain electrode, a channel layer, an insulating film, and a gate electrode, the channel layer is the 1,2-diselenophen-2-ylethene. An organic semiconductor thin film transistor comprising a diketopyrrolopyrrole-based polymer derivative comprising a may be provided.

According to another aspect of the invention, there can be provided an optoelectronic device comprising a diketopyrrolopyrrole polymer derivative containing the 1,2- disselenophen-2-ylethyne.

The diketopyrrolopyrrole polymer derivatives containing 1,2-diselenophen-2-ylethyne according to the present invention have excellent solubility and oxidation resistance in common solvents, and 1,2-diselenophen-2- The organic thin film transistor including a diketopyrrolopyrrole-based polymer derivative containing ilethene shows high hole mobility and excellent thermal stability.

1 is an NMR spectrum of the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.
FIG. 2 is a cross-sectional view of an organic thin film transistor including an organic semiconductor layer prepared using the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.
Figure 3 shows the ultraviolet-visible absorption spectrum in the solution state and thin film state of the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.
Figure 4 shows the XRD spectrum which can confirm the high crystallinity in the thin film state of the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.
Figure 5 shows the AFM image which can confirm the crystallinity in the thin film state of the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.
Figure 6 shows the current density according to each hole movement that can be observed in the organic thin film transistor prepared with the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 of the present invention.

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

According to one aspect of the present invention, a diketopyrrolopyrrole derivative may be provided comprising 1,2- disselenophen-2-ylethyne represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ is C3 to C60 hetero, including at least one selected from hydrogen, deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C6 to C60 aryl group, N, O and S It may be selected from the group consisting of an aryl group, a heteroalkynyl group of C1 to C60, an alkynyl group of C1 to C60 and a heteroalkyl group of C1 to C60.

The biggest characteristic of the derivative of Formula 1 is that the diketopyrrolopyrrole includes 1,2- disselenophen-2-ylethyne structure. In general, in order to make a polyacene organic semiconductor material such as pentacene suitable for a solution process, it is generally important to increase solubility by introducing a bulky substituent or an aliphatic alkyl group substituent to pentacene, but in addition to solubility, thermal stability and oxidation stability of the material In order to increase the stability and charge mobility, such as to improve the intermolecular affinity to induce crystallization is also a very important consideration in the design of the substituent, in the present invention as described above in the diketopyrrolopyrrole 1,2- disselenophene This was achieved by including a 2-ylethyne structure.

According to an embodiment, the R ₁ may be selected from the following structures independently of each other.

In the above structure, R ₂₁ to R ₃₁ are hydrogen, deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C3 to C60 heteroaryl group including at least one selected from N, O and S and C6 to C60 It may be selected from the group consisting of an aryl group.

The diketopyrrolopyrrole polymer derivatives including 1,2-diselenophen-2-ylethyne according to the present invention can be synthesized using conventional methods, and are not particularly limited. The synthesis process of the diketopyrrolopyrrole polymer derivatives in which the double bond and biselenophene structures represented by Chemical Formula 1 are introduced is shown in Scheme 1 below. The following preparation method is not intended to limit the method for producing a diketopyrrolopyrrole derivatives containing 1,2- disselenophen-2-ylethyne of the formula (1) according to the present invention.

[Reaction Scheme 1]

Phosphoryl chloride is slowly added to dimethylformaldehyde at 0 ° C. and then stirred for 20 minutes. Thereafter, selenophene dissolved in dichloroethane was slowly added at 0 ° C., stirred at room temperature for 20 minutes, and reacted at 100 ° C. for 12 hours to synthesize Intermediate A, and then put Compound A into tetrahydrofuran and zinc powder. TiCl ₄ was added slowly at −10 ° C. and stirred for 1 hour. Then Compound A was slowly added at 20 ° C. and then reacted at 65 ° C. for 4 hours to produce Intermediate B. After dissolving Compound B in tetrahydrofuran, butyllithium was slowly added at -78 ° C for 20 minutes and stirred for 30 minutes. Thereafter, 1M trimethyltin chloride was added at -78 ° C for 30 minutes, followed by reaction for 10 hours, thereby preparing Compound C. The intermediates D and C were reacted at 90 ° C. for 24 hours under a (Pd (PPh ₃ ) ₄ ) catalyst to synthesize final compound E (poly (DPP-alt-DTEBSe)).

According to the present invention, a diketopyrrolopyrrole-based polymer derivative including 1,2-diselenophen-2-ylethyne represented by Chemical Formula 1 may be employed in an organic semiconductor thin film for an organic thin film transistor. The organic semiconductor thin film includes a diketopyrrolopyrrole polymer derivative including 1,2- disselenophen-2-ylethyne represented by Chemical Formula 1, polyalphamethylstyrene, amorphous polycarbonate, polyarylamine, It may further comprise at least one organic polymer selected from the group consisting of polycarbazole and polythiophene.

In the present invention, the organic thin film transistor includes a substrate, a source-drain electrode, a channel layer, an insulating film, and a gate electrode. Here, the channel layer is an organic semiconductor thin film including a diketopyrrolopyrrole polymer derivative containing 1,2- disselenophen-2-ylethyne represented by the formula (1).

The organic semiconductor thin film may be formed by dissolving a diketopyrrolopyrrole polymer derivative including 1,2-diselenophen-2-ylethyne represented by Chemical Formula 1 in an organic solvent and then coating it on a substrate. In this case, at least one organic polymer selected from the group consisting of polyalphamethylstyrene, amorphous polycarbonate, polyarylamine, polycarbazole, and polythiophene may be dissolved and coated together in an organic solvent. The coating is one of spin coating, drop casting or inkjet coating. Here, the organic solvent may be one selected from the group consisting of dichlorobenzene, trichloroethane, N-methylpyrrolidone and toluene, but is not limited thereto.

The organic thin film transistor according to the present invention may be manufactured according to a general device structure, and may include a bottom gate method or a substrate / source-drain electrode / derivative conductor in which a substrate / gate electrode / insulation film / derivative thin film / source-drain electrode are sequentially formed. A top gate method in which thin film / insulation film / gate electrodes are formed in this order may be taken. 2 is a cross-sectional view of a bottom gate organic thin film transistor element.

SiO ₂ may be used as the insulating film, and polymer insulating films such as Cytop (Japan Asahi Glass Co., Ltd.), polyvinylphenol, and polymethyl methacrylate may also be used.

In one embodiment, the diketopyrrolopyrrole polymer derivatives containing 1,2- disselenophen-2-ylethyne represented by the formula (1) may be employed in the optoelectronic device, the organic electroluminescent device, organic The solar cell, an organic transistor or a memory device, and the like.

Hereinafter, a method for synthesizing a diketopyrrolopyrrole-based polymer derivative including 1,2-diselenophen-2-ylethyne represented by Chemical Formula 1, an organic thin film transistor including the same, and a method of manufacturing the same Explain.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

In order to increase the purity of the intermediate compound and final compound in each synthesis step, the compound was purified by recrystallization, pressure distillation, column chromatography, and the like. The purity and structure of the compounds were determined using nuclear magnetic resonance spectroscopy, gas chromatography, and melting point measurement.

Example  1: polymer derivative poly ( TDPP - Bise Synthesis of (F)

Intermediate (E) -1,2-bis (5- ( Trimethylstannyl ) Selenophen Synthesis of 2-yl) ethane (C)

Phosphoryl chloride (8.54 mL, 91.6 mmol) was slowly added to dimethylformaldehyde (7.71 mL, 99.2 mmol) at 0 ° C. and stirred for 20 minutes. Thereafter, selenophene (10 g, 76.3 mmol) dissolved in dichloroethane (8 ml) was slowly added at 0 ° C., stirred at room temperature for 20 minutes, and then stirred at 100 ° C. for 12 hours. After the reaction, water was added, extraction was performed with methylene chloride and water, and the residue was purified by column chromatography (only methylene chloride) to obtain 10 g (yield 82%) of Compound A. Add zinc powder to tetrahydrofuran (400 mL). TiCl ₄ was added slowly at −10 ° C. and stirred for 1 hour. Then Compound A (10 g, 62.9 mmol) was slowly added at 20 ° C, followed by stirring at 65 ° C for 4 hours. After the reaction, 10% aqueous potassium carbonate solution was added, extracted with ether and water, and purified by column chromatography (methylene chloride: hexane = 1: 1) to obtain 4 g (yield 44%) of compound B. The compound B (2 g, 6.99 mmol) was dissolved in tetrahydrofuran (120 mL), and butyl lithium (7.0 mL, 17.4 mmol) was slowly added at -78 ° C. for 20 minutes, followed by stirring for 30 minutes. Then 1M trimethyltin chloride (4.18mL, 20.9mmol) was added at -78 ° C for 30 minutes and reacted for 10 hours. After the reaction, water was added, extraction was performed with methylene chloride and water, and precipitated several times, followed by filtration through a filter to obtain 1.9 g (yield 44%) of compound C.

Polymer derivatives poly ( DPP - bottom - DTEBSe Synthesis of (E)

The compound D (0.83 g, 0.817 mmol) was dissolved in toluene (30 mL), the compound C (500 mg, 0.817 mmol) and the catalyst (Pd (PPh3) 4) (47 mg, 0.0409 mmol) were added at 90 ° C. The reaction was for 48 hours. After cooling to room temperature (25 ° C.), diluted with chloroform (100 mL), and the solution precipitated with methanol (800 mL) / 1 N hydrochloric acid (100 mL) solution was filtered through a filter to obtain a precipitate. This procedure was repeated twice. The precipitate obtained was dried and then dissolved in methanol, acetone, and hexane in soxhlet, and then dissolved in chloroform. alt-DTEBSe) (E) was obtained. 1 shows an NMR spectrum of the obtained polymer derivative poly (TDPP-BiSe). 3,6-bis- (5-bromo-2-thiophenyl) -N, N'-bis ((octyldodecyl) -1,4-dioxo-pyrrolo at 8.8 ppm as shown in FIG. Broad portions of hydrogen in [3,4-c] pyrrole and broad portions of hydrogen in selenophene were observed at 6.9 ppm.

Example  2: poly ( DPP - bottom - DTEBSe UV-Vis absorbance in solution and film

The ultraviolet-visible absorption spectrum of the solution state (blue line) and the thin film state after annealing (red line) measured by an ultraviolet-visible spectrometer (HP8453, Photodiode array type) are shown in FIG. 3. Table 1 below shows the maximum absorption wavelength (λ _max ) and absorption disconnection wavelength (λ _cut ) of the solution state and the thin film state. _off ) and E _g opt values.

At this time, the maximum absorption wavelength (λ _max ) means the wavelength of the maximum absorption intensity in the ultraviolet absorption spectroscopy. Here, the wavelength at the point where absorption is extinguished is the absorption disconnected wavelength (λ _{cut off} ), and the difference between the electron ground state and the excited state, which can be determined by absorption absorption wavelength using ultraviolet absorption spectroscopy, is the optical band gap (E _g opt).

 The maximum absorption wavelength, absorption break wavelength and optical bandgap in solution state have weaker interaction because the distance between each polymer is relatively far compared to the film state, and the interaction increases as the distance between polymers gets closer in the film state. . Generally, since a semiconductor layer is comprised in a film state (thin film state), the optical characteristic in a film state (thin film state) represents the semiconductor characteristic of the synthesized polymeric material as it is.

It can be seen that the optical properties of the polymer shown in Table 1 shows the formation of a small bandgap, this property is a property that can induce the excitation of electrons with a small energy, can induce a high density of holes and electrons .

Poly (DPP-alt-DTEBSe) in solution Thin film poly (DPP-alt-DTEBSe) Absorption wavelength 731 nm 745 nm, 843 nm Absorption Disconnection Wavelength 911 nm 934 nm Optical bandgap 1.36 eV 1.33 eV

Example  3: poly ( DPP - bottom - DTEBSe )of XRD  Pattern investigation

XRD experiments were performed under temperature conditions using Synchrotron Radiation (1.542 Å Pohang Synchrotron Laboratory). The pattern that the thin film of spin coated poly (DPP-alt-DTEBSe) shows during the heating and cooling cycles is shown in FIG. 4. The thin film was formed through drop-casting on a silicon wafer and dried at 70 ° C. in a vacuum (solvent: chloroform, concentration: 10 mg / ml). The diffraction pattern at each temperature is the result of the thin film produced for 5 minutes at each temperature. Optimized molecular alignment analysis was performed by measuring the length of the molecules via the DFT method (Spartan'06). Referring to FIG. 4, the high crystallinity of the polymer derivative poly (DPP-alt-DTEBSe) prepared in Example 1 may be confirmed in the thin film state through the XRD spectrum.

Example  4: poly ( DPP - bottom - DTEBSe )of AFM  Image investigation

AFM (Digital Instrument Multimode, including nanoscope IIIa controller) observed the surface of the sample using a silicon cantilever in tapping mode. Thin film samples were applied onto silicon wafers by spin coating (1500 rpm) before annealing and dried in vacuo at 170 ° C. (after annealing) (solvent: chloroform, concentration: 10 mg / ml). 5 shows that the thin film structure of the present invention prepared at room temperature already exists in the form of organic packing between molecules before heat treatment, and the organic packing between molecules is further after heat treatment. It is showing an increase.

Example  5: organic thin film transistor manufacturing

In order to verify its function as a thin film transistor, poly (DPP-alt-DTESe) was spin coated to a thickness of 40 to 50 nm using chloroform as a solvent on a strongly n-doped Si / SiO ₂ substrate. The surface was treated with octyltrichlorosilane (OTS) to make a hydrophobic dielectric surface. The source and drain electrodes were deposited (100 nm) through a shadow mask with channels of width and length of 1500 μm and 150 μm, respectively. All field effect mobility is calculated by μ _sat = (2 I _DS L ) / ( WC ( V _G - V _TH ) ² ) where I _DS is the saturation drain current and C is the capacitance of oxide insulator dielectric, V _G is the gate bias, and V _TH is the threshold voltage. The performance of the manufactured equipment was measured with a Keithley 4200 high voltage source meter at room temperature.

6 is a view showing the electrical characteristics of the organic thin film transistor using the organic polymer thin film developed in the present invention showed a high hole mobility of 1.0 ~ 1.2 cm ² / Vs for the thin film device before heat treatment. In addition, the remarkable characteristics of the organic thin film transistor using a thin film heat-treated for 10 minutes at 250 degrees Celsius showed a high hole mobility of 4.0 ~ 4.5 cm ² / Vs. This is much higher than the level of charge mobility of a typical organic polymer thin film transistor, and in particular, the highest charge mobility ever published in organic polymer thin film transistor far exceeds 3.3 cm ² / Vs ( J. Am . . Soc. 2011, 133, 2605-2612 Note).

In conclusion, the diketopyrrolopyrrole polymer derivatives containing 1,2-diselenophen-2-ylethyne according to the present invention is excellent in solubility and oxidation resistance in common solvents, 1,2-diselenophene It can be seen that the organic thin film transistor including the diketopyrrolopyrrole-based polymer derivative containing 2-ylethyne exhibits high hole mobility and excellent thermal stability.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (6)

A diketopyrrolopyrrole polymer derivative comprising 1,2-diselenophen-2-ylethyne represented by the following Chemical Formula 1.
[Chemical Formula 1]

[In the above formula (1)
R ₁ is hydrogen, deuterium, C 1 to C 60 alkyl group, C 3 to C 60 cycloalkyl group, C 6 to C 60 aryl group, C 3 to C 60 heteroaryl group including one or more selected from N, O and S, C 1 to C60 heteroalkynyl group, C1 to C60 alkynyl group and C1 to C60 heteroalkyl group.] The method of claim 1,
R ₁ is a diketopyrrolopyrrole polymer derivative comprising 1,2- disselenophen-2-ylethyne, characterized in that selected from the following structure.

[In the above structure, R ₂₁ to R ₃₁ are hydrogen, deuterium, C1 to C60 alkyl group, C3 to C60 cycloalkyl group, C3 to C60 heteroaryl group containing at least one selected from N, O and S and C6 to C60 Is selected from the group consisting of aryl groups.] An organic semiconductor thin film for an organic thin film transistor comprising a diketopyrrolopyrrole-based polymer derivative comprising 1, 2-diselenophen-2-ylethyne according to claim 1. The method of claim 3, wherein
The organic semiconductor thin film further comprises at least one organic polymer compound selected from the group consisting of polyalphamethylstyrene, amorphous polycarbonate, polyarylamine, polycarbazole, polythiophene, and mixtures thereof. . An organic thin film transistor comprising a substrate, a source-drain electrode, a channel layer, an insulating film, and a gate electrode, wherein the channel layer comprises 1,2-diselenophen-2-ylethyne according to claim 1 or 2. An organic semiconductor thin film transistor comprising a diketopyrrolopyrrole polymer derivative. An optoelectronic device comprising a diketopyrrolopyrrole-based polymer derivative comprising the 1,2-diselenenophen-2-ylethyne of claim 1.

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