KR101081509B1 - High soluble polyacene derivative and organic electronic device using the same - Google Patents

Abstract

Disclosed are a polyacene derivative having excellent solubility characteristics as an organic semiconductor material and an organic electronic device using the same. The present invention provides a polyacene derivative having a novel structure and an organic electronic device using the same, which have high thermal mobility, excellent thermal stability, excellent solubility and oxidation resistance in general solvents, and which can be manufactured in a solution process.

Polyacene, organic electronic device, solution, derivative

Description

High soluble polyacene derivative and organic electronic device using the same

The present invention relates to an organic semiconductor compound and an organic electronic device which is a polyacene derivative, and more particularly, to an organic electronic device having a substituent structure of benzylacetylene and thiophenylacetylene in a polyacene derivative including an anthracene structure. And it relates to an organic electronic device using the same.

Since it has been known since the late 1970s that proper doping of certain organics can bring the electrical conductivity close to copper, current organics are not only in terms of conductivity, but also from semiconductors, conductors (such as doped polyacetylene), from the best insulators (polystyrene, etc.). Not only that, but the superconductor (TMTSF) 2PF6, perchlorate, pentacene, etc., the best conductor, can be obtained in all parts of the material. Examples of semiconductors include p-type pentacene and n-type Alq ₃ , and dielectric materials include thermocrosslinkable polymer (PVP), ferroelectric PVDF and co-polymers based thereon, and inorganic nanoparticles and polymer composites. .

Through the development of organic materials with semiconductor properties for the past 10 years and various application researches using them, we have studied electromagnetic shielding films, capacitors, organic electroluminescence (EL) displays, organic thin film transistors, solar cells, and memory devices using multiphoton absorption. In addition, the expansion of applications based on this is in progress. 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. For example, an organic thin film transistor using an organic material is being studied for application to a next generation smart card, starting with an active driving element for an organic EL.

In addition, after the electrical oscillation characteristics using the organic semiconductor as an active layer were announced, research on the possibility of application as a laser diode and a research report on the high efficiency (2.4%) solar cell using the doped organic material (pentacene) were carried out. Active research is being conducted in the field of organic semiconductors, which are significantly lower in device fabrication cost.

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 needs 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. In this case, there is a useful aspect since it can be used, and in particular, a low-cost process is possible. Recently, researchers at Philips have published a programmable code generator consisting of 326 transistors using polymers on both substrates and electrodes, organic dielectrics and organic semiconductors.

The organic thin film transistor implemented on the plastic substrate can be applied to driving a bent liquid crystal display device, an electronic paper and an organic light emitting device. 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 a technology suitable for application to a large area that can be bent, and is highly applicable to an organic thin film transistor.

Research on organic thin film transistors began in the early 1980s, and recently, full-scale research is being 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. Organic thin film transistors are fabricated using organic compounds or polymers that represent semiconducting properties that can replace the conventional silicon-based inorganic materials in the channel layer, which is the key part of charge transfer and most affects device characteristics. As the organic semiconductor material, 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 classified into n-type materials that move electrons and p-type materials that transport holes, and low molecular organic semiconductor materials such as pentacene currently exhibit high charge mobility among p-type organic semiconductors.

Polyacene compounds such as anthracene and 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 properties. Recently, Lucent Technologies and 3M have reported high charge mobility of 3.2 to 5.0 cm ² / Vs using pentacene single crystals (Mater. Res. Soc. Symp. Proc. Vol. 771, L6). .5.1-L6.5.11 (2003). In addition, CNRS in France has reported relatively high charge mobility and current flashing ratio of 0.01 to 0.1 cm ² / Vs using oligothiophene derivatives. However, this conventional technology 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 are being developed to develop polyacene derivatives such as anthracene and pentacene, which can be solution-processed. An organic thin film transistor device having a charge mobility of 0.1 to 0.2 cm ² / Vs was reported as a method of implementing pentacene by treatment (PT Herwig and K. M, Adv. Mater . Vol. 11, p.480 (1999). )). Anthony (Anthony) researchers to impart solubility triisopropylsilyl ethynyl (triisopropylsilylethynyl) groups are pentamethyl to develop the derivative bonded to the sensor on both sides up to 1.5 cm ² / Vs enough charge movement in the solution process of the US University of Kentucky also An implementation of an organic thin film transistor device exhibiting 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). In order to impart solubility, researchers at the University of Wurzburg (W) in Germany have developed a pentacene derivative in which trimethoxyphenylethynyl groups are introduced as substituents on both sides of pentacene to implement organic thin film transistor devices. (F. W, 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 apply a polyacene-based organic semiconductor material such as pentacene to the solution process, it is generally necessary to increase the solubility by introducing a bulky or aliphatic alkyl substituent to pentacene, but at the same time, the thermal stability, oxidation stability, and high charge of the material Intermolecular affinity enhancement and crystallization techniques for mobility are also key requirements in the design and manufacture of organic semiconductor materials.

The present invention is to solve the problems of the prior art as described above, by introducing a substituent structure of benzylacetylene and thiophenylacetylene-based polyacene derivatives containing an anthracene structure to improve the solubility, crystallinity and stability of the compound The present invention provides an organic semiconductor material suitable for manufacturing an organic electronic device by a solution process because it exhibits high hole mobility and has excellent thermal stability and excellent solubility and oxidation resistance in general solvents, and an organic electronic device comprising the same. For the purpose of

The present invention relates to a polyacene derivative including an anthracene structure having excellent solubility characteristics, comprising a polyacene derivative having excellent hole mobility characteristics of an organic semiconductor material, and having a saturated hydrocarbon (C ₃ -C ₆₀ ) to increase solubility or It consists of functional groups of the triisopropyl silane family. It is designed to show the high hole mobility and the solution processing property in the same compound structure at the same time. Hexyl benzene and hexyl thiophene groups, including triple bonds and double bonds, are applied as a functional group of polyacene to increase the solubility to enable solution processing. This is an example of effectively increasing the solubility characteristics of the organic semiconductor material that has been a problem in the past.

The present invention provides a compound for an organic electronic device represented by the following formula (1) or (2) in order to achieve the above object:

[Formula 1]

[Formula 2]

Wherein Ar ₁ is selected from the group consisting of naphthalene, anthracene, tetracene and pentacene,

Ar ₂ and Ar ₃ are each independently a 5- or 6-membered heterocycloalkyl including one or more selected from (C ₆ -C ₆₀ ) arylene, (C ₃ -C ₆₀ ) heteroarylene, N, O and S Ethylene, (C ₃ -C ₆₀ ) cycloalkylene, adamantylene, (C ₇ -C ₆₀ ) bicycloalkylene, (C ₂ -C ₆₀ ) alkenylene, (C ₂ -C ₆₀ ) alkynylene, ( C ₆ -C ₆₀ ) ar (C ₁ -C ₆₀ ) alkylene, (C ₁ -C ₆₀ ) alkylenethio, (C ₁ -C ₆₀ ) alkyleneoxy, (C ₆ -C ₆₀ ) aryleneoxy or (C ₆ -C ₆₀ ) arylenethio, and

R ₁ and R ₂ each independently include one or more selected from hydrogen, deuterium, halogen, (C ₁ -C ₆₀ ) alkyl, (C ₆ -C ₆₀ ) aryl, N, O and S (C ₃ -C ₆₀₎ heteroaryl, morpholino, tea Omo poly furnace, N, O, and 5-ring or 6-ring heterocycloalkyl containing one or more selected from S, (C ₃ -C ₆₀₎ cycloalkyl, tri (C ₁ - C ₆₀ ) alkylsilyl, di (C ₁ -C ₆₀ ) alkyl (C ₆ -C ₆₀ ) arylsilyl, tri (C ₆ -C ₆₀ ) arylsilyl, adamantyl, (C ₇ -C ₆₀ ) bicycloalkyl , (C ₂ -C ₆₀ ) alkenyl, (C ₂ -C ₆₀ ) alkynyl, (C ₁ -C ₆₀ ) alkoxy, cyano, (C ₆ -C ₆₀ ) ar (C ₁ -C ₆₀ ) alkyl, (C ₁ -C ₆₀ ) alkyloxy, (C ₁ -C ₆₀ ) alkylthio, (C ₆ -C ₆₀ ) aryloxy, (C ₆ -C ₆₀ ) arylthio, (C ₁ -C ₆₀ ) alkoxycarbonyl , (C ₁ -C ₆₀ ) alkylcarbonyl, (C ₆ -C ₆₀ ) arylcarbonyl, (C ₆ -C ₆₀ ) aryloxycarbonyl, (C ₁ -C ₆₀ ) alkoxycarbonyloxy, (C ₁ -C ₆₀ ) alkylcarbonyloxy, (C ₆ -C ₆₀ ) arylcarbonyloxy, (C ₆ -C ₆₀ ) aryl Oxycarbonyloxy, (C ₁ -C ₆₀ ) alkylcarbonyloxy, (C ₆ -C ₆₀ ) arylcarbonyloxy, carboxyl, nitro or hydroxy, wherein adjacent substituents are bonded to each other Saturated or unsaturated fused rings can be formed.

Ar ₁ may be exemplified as a polyacene selected from the following structures, but is not limited thereto.

In addition, Ar ₂ and Ar ₃ may be each independently selected from the following structures, but are not limited thereto.

Wherein R ₃ to R ₁₁ are each independently selected from hydrogen, deuterium, (C ₁ -C ₆₀ ) alkyl, (C ₃ -C ₆₀ ) cycloalkyl, (C ₆ -C ₆₀ ) aryl or N, O and S It is selected from the group consisting of (C ₃ -C ₆₀ ) heteroaryl containing one or more.

R ₁ and R ₂ are each independently selected from the following structures, but are not limited thereto.

Wherein R ₂₁ to R ₃₁ are each independently selected from hydrogen, deuterium, (C ₁ -C ₆₀ ) alkyl, (C ₃ -C ₆₀ ) cycloalkyl, (C ₆ -C ₆₀ ) aryl or N, O and S It is selected from the group consisting of (C ₃ -C ₆₀ ) heteroaryl containing one or more.

The polyacene derivative including the anthracene structure of the present invention can be synthesized using conventional methods, and is not particularly limited. Synthesis process of the polyacene derivative, wherein Ar ₁ is an anthracene in Formula 1 is illustrated in Scheme 1 below, and the following preparation method does not limit the method of preparing the polyacene derivative of Formula 1 according to the present invention. Modifications of the following preparation methods will be apparent to those skilled in the art, and unless otherwise stated, the definitions of substituents in the following schemes are the same as defined in the above Formula 1.

[Scheme 1]

Intermediate Compound A was synthesized by reacting 1-bromo-4-hexylbenzene and trimethyl silyl acetylene at 50 ° C. to 70 ° C. for 12-24 hours, and reacting Compound A with potassium carbonate at room temperature for 3-10 hours to generate trimethyl silyl. Intermediate compound B can be synthesized. Intermediate C can be synthesized by reacting 2,6-diaminoanthracene-9,10-dione with tert-butyl nitrite and cooperbromide at 65 ° C. for 6-12 hours. Intermediate D may be synthesized by sequentially treating normal butyllithium, hydrochloric acid, and tin chromide to react the intermediate compound B with the intermediate compound C. The intermediate compound D and 2-ethynyl-5-hexylthiophene may be reacted at 90 ° C. for 12-24 hours to synthesize the final compound HB-ant-THT.

In order to increase the purity of the intermediate compound and the final compound for each synthesis step, the compound can be purified by recrystallization, reduced pressure distillation, column chromatography, and the like. Purity and structure confirmation of the compound can be performed using a nuclear magnetic resonance spectrometer, gas chromatography, melting point measurement.

Polyacene-based compound comprising an anthracene structure of the formula (1) according to the present invention is preferably for an organic electronic device, may be implemented as an organic thin film transistor interposed between the first electrode and the second electrode, in particular, substrate, source-drain In an organic thin film transistor including an electrode, an organic semiconductor thin film, an insulating film, and a gate electrode, the organic semiconductor thin film may be formed of at least one polyacene compound including an anthracene structure of Formula 1 according to the present invention. The organic electronic device according to the present invention may be manufactured according to a general device structure, and may adopt a bottom gate method in which a substrate / gate electrode / insulation film / derivative conductor thin film / source and a drain electrode are sequentially manufactured, or a substrate / source-drain electrode. It is possible to take the top gate method of the / based conductive thin film / insulating film / gate electrode.

In this case, the polyacene-based compound including an anthracene structure, which is an organic semiconductor material of the present invention, may be dissolved in an organic solvent to form a thin film by spin coating, drop casting, or inkjet coating, and applied to a device. The organic solvent may be dichlorobenzene, trichloroethane, N-methylpyrrolidone, toluene and the like, but is not limited thereto. In addition, the polyacene-based compound including the anthracene structure is mixed with at least one organic polymer compound selected from the group consisting of polyalphamethylstyrene, amorphous polycarbonate, and polycarbazole, dissolved in an organic solvent, and the coating method. A thin film can be formed.

As the gate insulating film of the organic electronic device of the present invention, SiO ₂ formed on a silicon substrate can be used, or a polymer insulating film such as Cytop (Japan Asahi Glass Co., Ltd.), polyvinylphenol, or the like can be used.

The polyacene derivative compound according to the present invention is excellent in thermal stability while implementing high hole mobility, and excellent in solubility and oxidation resistance in general solvents, thus enabling device fabrication by a solution process.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1 Synthesis of 2,6-Dibromo-9,10-bis (phenylethynyl) anthracene (3. B-ant-Br)

Ethinylbenzene ( 1 ) (0.394 g, 3.86 mmol) was dissolved in just distilled tetrahydrofuran (30 mL) in a 250 mL magnetic stirred round bottom flask dried in an oven. The solution was then cooled to −78 ° C. and n -butyllithium ( n- BuLi (1.57 mL, 3.92 mmol, 2.5 M solution in hexane)) was added dropwise over 15 minutes. The solution was stirred for 30 minutes and 2,6-dibromoanthracene-9,10-dione (2,6-dibromoanthracene-9,10-dione, 0.574 g, 1.57 mmol) was added at -78 ° C. The solution was stirred at room temperature for 3 hours and then water, tin chloride and hydrochloric acid were added. After completion of the reaction, the solution was poured into methanol to collect a precipitate. At this time, the yield was 0.820 g, the yield was 68%. ¹ H NMR and HRMS data of the obtained material are as follows. ¹ H-NMR (400 MHz, CDCl ₃ ): (ppm) 8.77 (s, 2H), 8.48 (d, J = 9.0 Hz, 2H), 7.75 (d, J = 7.4 Hz, 4H), 7.66 (d, J = 4.5 Hz, 2H), 7.42-7.48 (m, 6H). ¹³ C-NMR (400 MHz, CDCl ₃ ): (ppm) 133.04, 131.96, 131.02, 130.97, 129.46, 129.25, 129.20, 128.81, 123.11, 122.16, 118.22, 103.44, 85.57. HR-MS (EI) m / z (M ⁺ ): Calcd for C ₃₀ H ₁₆ Br ₂ , 533.96; found, 533.96. Anal. Calcd. for C ₃₀ H ₁₆ Br ₂ : C, 67.19 H, 3.01, found: C, 67.22; H, 3.01.

Example 2 Synthesis of 2,6-Dibromo-9,10-bis ((4-hexylphenyl) ethynyl) anthracene (4.HB-ant-Br)

The manufacturing method is the same as in Example 1. 1-ethynyl-4-hexylbenzene was used instead of the ethynylbenzene of Example 1. After completion of the reaction, the solution was poured into methanol to collect a precipitate. Yield 0.740 g, yield 67%. ¹ H NMR and HRMS data of the obtained material are as follows. ¹ H-NMR (400 MHz, CDCl ₃ ): (ppm) 8.77 (s, 2H), 8.49 (d, J = 9.4 Hz, 2H), 7.64-7.68 (m, 6H), 7.28 (d, J = 7.8 Hz, 4H), 2.68 (t, 4H), 1.62-1.70 (m, 4H), 1.30-1.39 (m, 12H), 0.90 (t, 6H). ¹³ C-NMR (400 MHz, CDCl ₃ ): (ppm) 144.55, 132.85, 131.88, 130.77, 130.72, 129.42, 129.16, 128.88, 121.96, 120.32, 118.14, 103.72, 85.10, 36.21, 31.86, 31.31, 29.10, 22.73 , 14.14. HR-MS (EI) m / z (M ⁺ ): Calcd for C ₄₂ H ₄₀ Br ₂ , 702.15; found, 702.14. Anal. Calcd. for C ₄₂ H ₄₀ Br ₂ : C, 71.60 H, 5.72, found: C, 71.62; H, 5.64.

Example 3 Synthesis of 5,5 '-(9,10-bis (phenylethynyl) anthracene-2,6-diyl) bis (ethyne-2,1-diyl) bis (2-hexylthiophene) 6.B-ant-THT)

In a 100 mL round bottomed flask for magnetic stirring, dried in an oven, the solution of [Example 1] (0.30 g, 0.056 mmol), bis (triphenylfospan) palladium ( II ) dichloride (0.020 g, 0.003 mmol), was just After filling with a mixture of distilled tetrahydrofuran (10 mL) and copper iodide (0.005 g, 0.003 mmol), triethylamine (15 ml) and diisopropylamine (5 ml), 2-ethynyl-5 Hexylthiophene (2-ethynyl-5-hexylthiophene) (5) (0.45 g, 0.224 mmol) was added followed by heating at 80 ° C. for 16 h. After completion of the reaction, the solution was poured into methanol to collect a precipitate. Crude extracts undergo B-ant-THT through recrystallization in acetone. 0.36 g of ( 6 ) was obtained as a crystal, and the yield was 71%. ¹ H NMR and HRMS data of the obtained material are as follows. ¹ H-NMR (400 MHz, CDCl ₃ ): (ppm) 8.72 (s, 2H), 8.56 (d, J = 9.0 Hz, 2H), 7.81 (d, J = 7.8 Hz, 4H), 7.64 (d, J = 9.0Hz, 2H), 7.49-7.44 (m, 6H), 7.22 (d, J = 3.5Hz, 2H), 6.73 (d, J = 3.5Hz, 2H), 2.85 (t, 4H), 1.72- 1.66 (m, 4H), 1.40-1.25 (m, 12H), 0.92-0.88 (m, 6H). ¹³ C-NMR (400 MHz, CDCl ₃ ): (ppm) 148.96, 132.53, 131.84, 131.75, 131.45, 130.22, 129.10, 128.85, 128.57, 127.39, 124.38, 123.10, 121.72, 120.30, 118.18, 102.97, 93.13, 85.81 , 85.52, 31.54, 30.28, 28.73, 22.58, 14.10. HR-MS (EI) m / z (M ⁺ ): Calcd for C ₅₄ H ₄₆ S ₂ , 758.30; found, 758.31. Anal. Calcd. for C ₅₄ H ₄₆ S ₂ : C, 85.44 H, 6.11; S, 8.45 found: C, 85.23 H, 6.02; S, 8.58.

Example 4 5,5 '-(9,10-bis ((4-hexylphenyl) ethynyl) anthracene-2,6-diyl) bis (ethyne-2,1-diyl) bis (2-hexylcysyl Offen)) (7.HB-ant-THT)

The synthesis method is the same as in [Example 3] . 2,6-dibromo-9,10-bis ((4-hexylphenyl) of [Example 2] instead of 2,6-dibromo-9,10-bis (phenylethynyl) anthracene of [Example 1] Ethynyl) anthracene was used. After completion of the reaction, the solution was poured into methanol to collect a precipitate. The crude extract obtained 0.65 g of HB-ant-THT (7) as a crystal by recrystallization in acetone. The yield was 87%. ¹ H NMR and HRMS data of the obtained material are as follows. ¹ H-NMR (400 MHz, CDCl ₃ ): (ppm) 8.73 (s, 2H), 8.57 (d, J = 8.6 Hz, 2H), 7.72 (d, J = 8.2 Hz, 4H), 7.63 (d, J = 9.0Hz, 2H), 7.29 (d, J = 8.2Hz, 4H), 7.21 (d, J = 3.5Hz, 2H), 6.72 (d, J = 3.5, 2H), 2.85 (t, 4H), 2.70 (t, 4H), 1.72-1.63 (m, 8H), 1.39-1.25 (m, 24H), 0.92 (t, 12H). ¹³ C-NMR (400 MHz, CDCl ₃ ): (ppm) 148.90, 144.16, 132.48, 131.74, 131.45, 130.31, 128.99, 128.69, 127.46, 124.35, 121.60, 120.35, 120.23, 118.26, 103.26, 93.19, 85.39, 85.28 , 36.04, 31.73, 31.54, 31.31, 30.29, 28.97, 28.73, 22.63, 22.58, 14.14, 14.10. HR-MS (EI) m / z (M ⁺ ): Calcd for C ₆₆ H ₇₀ S ₂ , 926.49 found, 926.49. Anal. Calcd. for C ₆₆ H ₇₀ S ₂ : C, 85.48 H, 7.61; S, 6.92 found: C, 85.50; H, 7. 74; S, 6.87.

[Example 5] Ultraviolet-Visible Light Absorption Irradiation Before and After Annealing of HB-ant-THT (7)

Ultraviolet-visible spectrum (range of 190nm-1100nm) for spin-coated film (dashed line) and thin film (dashed line) after annealing it as measured by ultraviolet-visible absorption spectrometer (HP8453, Photodiode array type) It is shown in 2. Annealing was carried out at 120 to 10 minutes. The as-coated thin film before heat treatment of FIG. 2 exhibits a spectrum almost similar to that after heat treatment. This means that even if the compound according to the present invention is formed into a thin film and further subjected to heat treatment, the order is already fully developed in the molecular arrangement and there is no further significant change.

Example 6 Investigation of XRD Pattern of HB-ant-THT (7)

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 HB-ant-THT 7 shows during the heating and cooling cycles is shown in FIG. 3. 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. In FIG. 3, the thin film coated on Si / SiO ₂ shows first-order reflection at 3.85 ^° . Optimized molecular alignment analysis was performed by measuring the length of molecules via the DFT method (Spartan'06), which is shown in the diagram on the right side of the graph. This is because the molecules are arranged in two dimensions via four terminal hexyl groups, thereby allowing the organic thin film according to the present invention to have high field-effect mobility in TFT equipment as described below (Example 8, Fig. 5). The reason for the molecular arrangement is given.

Example 7 AFM Image Investigation of Thin Film of HB-ant-THT (7)

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) and then dried in vacuo at 40 ° C. (solvent: chloroform, concentration: 10 mg / ml). 4 shows that the thin film structure of the present invention prepared at room temperature already exists in a form of organic packing between molecules before heat treatment.

Example 8 Fabrication of Organic Thin Film Transistor (OTFT)

To verify its function as a thin film transistor, HB-ant-THT (7) was spin-coated to 40-50 nm thick with 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 (115 nm) through shadow masks with channels of width and length of 1500 μm and 150 μm, respectively. All field effect mobility was calculated by μ _sat = (2I _DS L) / (WC (V _g -V _th ) ² ) , where I _DS saturation drain current, C is oxide insulator (SiO ₂ : capacitance of oxide 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 237 high voltage source meter at room temperature. 5 shows the characteristics of the organic thin film formed by B-ant-THT and HB-ant-THT prepared according to the present invention. Figure 5 is a left side graph of drain current (I _DS) against (versus) the drain-source voltage represents a (V _DS) of, and the right compared to I _DS and I _DS ^1/2 (versus) gate voltage (Vg), V _DS Is 60V. Here, after the thin film was applied, annealing was not performed through heat treatment. B-ant-THT and HB-ant-THT were respectively 0.04 cm ² / Vs (I _on / I _off = 2.8 x 10 ⁵ ) and 0.24 cm ² / It can be seen that it exhibits high field-effect mobility of Vs (I _on / I _off = 5.4 × 10 ⁶ ).

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims. It will be understood that the invention may be varied and varied without departing from the scope of the invention. Many embodiments other than the above-described embodiments are within the scope of the claims of the present invention.

1 is a cross-sectional view of a transistor device including an organic semiconductor layer (active layer) made of a polyacene derivative compound including an anthracene structure according to an embodiment of the present invention.

Figure 2 shows the ultraviolet-visible light absorption spectrum in the solution state and the film state of the compound according to Example 4 of the present invention.

Figure 3 shows the XRD spectrum which can confirm the crystallinity and strength in the film state of the compound according to Example 4 of the present invention.

Figure 4 shows the AFM image which can confirm the crystallinity of the compound according to Example 4 of the present invention in the film state.

Figure 5 shows the current density according to each hole movement prepared with a polyacene derivative compound including an anthracene structure according to Examples 3 and 4 of the present invention.

Claims (8)

Anthracene-based derivatives represented by Formula 1 below: [Formula 1]

Wherein Ar ₁ is an anthracene; Ar ₂ and Ar ₃ are each independently (C ₆ -C ₆₀ ) arylene or (C ₃ -C ₆₀ ) heteroarylene; R ₁ and R ₂ are each independently hydrogen or (C ₁ -C ₆₀ ) alkyl, and adjacent substituents may be bonded to each other to form a saturated or unsaturated fused ring. In the above formula, the substitution sites of Ar ₂ and Ar ₃ represent symmetry in the up, down, left, and right directions based on the anthracene molecules, and are selected from one of 1 or 2 of Table 1 below.

Serial Number Ar ₂ Ar ₃ One (2,6) (9,10) 2 (2,6) (1,4) delete delete delete An organic electronic device comprising an organic semiconductor thin film formed using one or more of the compounds according to claim 1. The organic electronic device of claim 5, further comprising an organic semiconductor thin film formed by dissolving the compound in an organic solvent using spin coating, drop casting, or inkjet coating. The organic electronic device of claim 5, wherein the organic semiconductor thin film further comprises one or more organic polymer compounds selected from polyalphamethylstyrene, amorphous polycarbonate, or polycarbazole. The organic electronic device of claim 6, wherein the organic solvent is selected from the group consisting of dichlorobenzene, trichloroethane, N-methylpyrrolidone, and toluene.

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