KR20100006272A - High performance organic semiconductors based on anthracene backbone with vinyl group and the organic semiconductor thin film and organic thin film electronic devices using thereof - Google Patents

Abstract

PURPOSE: An organic semiconductor compound having high performance based on anthracene having vinyl group is provided to ensure high electrical characteristic and high thermal stability. CONSTITUTION: An organic semiconductor compound with vinyl group is synthesized by reacting phosphonate derivative of chemical formula 1 and aldehyde derivative of chemical formula 2. In chemical formulas 1 and 2, A is substituted or non-substituted cyclic alkyl group, substituted or non-substituted aryl group, substituted or non-substituted thiophenyl group, substituted or non-substituted pyridinyl group, substituted or non-substituted pyrrolyly group or substituted or non-substituted furanyl group. The organic semiconductor compound is denoted by one among chemical formula 3 to 6.

Description

High performance organic semiconductors based on anthracene backbone with vinyl group and the organic semiconductor thin film and organic thin film electronic devices using according to the anthracene skeleton having a vinyl group

The present invention relates to a high performance organic semiconductor compound based on an anthracene skeleton having a vinyl group, and an organic semiconductor thin film and an organic thin film electronic device using the same. Organic flexible electronics that exhibit good electrical properties, such as high field-effect mobilities, can be easily synthesized in large quantities and are also applicable at low substrate deposition temperatures. A high performance organic semiconductor compound that is promising for applications in flexible electronics.

In the past decades, asenes and thiophene oligomers have been described as FETs (MH Yoon, SA DiBenedetto, A. Facchetti, TJ Mark, J. Am. Chem . Soc ., 2006, 128 , 9598., K. Takimiya, Y. Kunugi, Y. Konda, H. Ebata, Y. Toyoshima, T. Otsubo, J. Am. Chem. Soc ., 2006, 128 , 3044., CD Dimitrakopoulos, RL Malenfant, Adv . Mater ., 2002, 14 , 99.), OLEDs (RH Friend, RW Gymer, AB Holmes, JH Burrouhes, RN Marks, C. Taliani, DDC Bardley, DA Dos Santos, JL Bredas, M, Logdlund, WR Salanek, Nature. , 1999, 397 , 121), photovoltaic cells (a) CJ Brabec, NS Sariciftci, JC Hummelen, Adv . Funct . Mater., 2001, 11 , 15; b) KM Coakley, MD McGhee, Chem . Mat., 2004, 16 , 4533.), sensor (a) B. Crone, A. Dodabalapur, Y.-Y. Lin, RW Filas, Z. Bao, A. La Duca, R. Sarpeshkar, HE Katz, W. Li, Nature., 2000, 403 , 521; b) Y, -Y. Lin, A. Dodabalapur, R. Sarpeshkar, Z. Bao, W. Li, K. Baldwin, VR Raju, HE Katz, Appl . Phys. Lett ., 1999, 74 , 2714.), and RF-ID tags (a) AT Brown, A. Pomp, CM Hart, DM Deleeuw, Science., 1995, 270 , 972; b) CJ Drury, CM Mutsaers, CM Hart, M. Matters, DM de Leeuw, Appl . Phys. Lett., 1998, 73 , 108.) has been extensively studied for use as organic semiconductors in devices. To date, pentacene has been characterized by very high field-effect mobility (0.3-0.7 cm ² / Vs on a Si / SiO ₂ substrate, 1.5 cm ² / Vs on chemically modified Si / SiO ₂ substrates, And 3.0 cm ² / Vs on modified alumina substrate) (DJ Gundlach, YY Lin, TN Jackson, SF Nelson, DG Schlom, IEEE Electron Device Lett., 1997, 18 , 87., YY Lin, DJ Gundlach, SF Nelson, TN Jackson, IEEE Electron Device Lett ., 1997, 18 , 606., TW Kelly, Y. Lin, DJ Gundlach, SF Nelson, TN Jackson, J. Phys. Chem . B., 2003, 107 , 5877. Remarkable properties as the best thin film material and rubrene as the best single-crystal material (15.4 cm ² / Vs) (a) VC Sundar, J. Zaumseil, V. Podzorov , E. Menard, RL Willett, T. Someya, ME Gershenson, JA Rogers, Science., 2004, 303 , 1644; b) V. Podzordov, S. E, Sysoev, E. Loginova, VM Pudalov, CE Gershenoon, Appl . Phys. Lett . B., 2003, 83107 , 3504.). However, pentacene-based devices show poor air stability and rapid deterioration of device performance (M. Yamada, I. Ikemoto, H. Kuroda, Bull. Chem . Soc. Jpn ., 1988, 61 , 1057.). Therefore, there is still a need for organic semiconductor materials that can be deposited at low substrate temperatures, are environmentally stable, and have high mobility and on / off current ratios.

Very recently, several research groups have developed semiconductors with high stability and conductivity by selecting conjugated vinylene-based oligomers (a) C. Videlot-Ackermann, J. Ackermann, H. Brisset, K. Kawamura, N. Yoshimoto, P. Raynal, A. EI Dassmi, F. Fages, J. Am. Chem . Soc ., 2005, 127 , 16346; b) N. Drolet, JF Morin, N. Leclerc, S. Wakim, Y. Tao, M. Leclerc, Adv . Funct . Mater., 2005, 15 , 1671; c) TC Gorjanc, I. Levesque. M. Dlori, Appl . Phys. Lett., 2004, 84 , 930.). In fact, the presence of double bonds of defined molecular composition firstly decreases the overall aromatic character of the planar structure to increase π-electron localization, and secondly, to reduce inherent rotational degrees of freedom (a) G. Distefano, M. Da Colle, D. Jones, M. Zambianchi, L. Favvafetto, A. Modelli, J. Phys. Chem ., 1993, 97 , 3504; b) E. Orti, PM Viruela, J. Sanchez-Marin, F. Tomas, J. Phys. Chem., 1995, 99 , 4955.) It increases the energy band gap. The introduction of vinylene units into the oligomer structure is a method of constructing coplanar molecules with extended π-conjugated length, which helps to maximize the composition of the molecules in the thin film. Devices derived from end-captured oligothiophenes with styryl units show relatively high field-effect mobility and on / off ratios, and are found to be stable under exceptionally long life and continuous operation under atmospheric conditions. lost. However, the research of these materials is still insufficient, and there is a continuous demand for continuous research on them and the discovery of materials with improved performance.

The present inventors seek to provide new organic semiconductor materials that are environmentally stable and meet the needs of organic semiconductor materials with high mobility and on / off current ratios.

In addition, it is possible to form a highly aligned organic semiconductor thin film including the above organic semiconductor materials, and to use this as an organic active layer to provide a high performance organic thin film transistor.

To this end, the present inventors synthesized organic semiconductor compounds based on anthracene skeletons having vinyl groups. As a more specific example, a new organic semiconductor compound having a 2,6-bis- (2-thienylvinyl) anthracene (2,6-bis (2-thienylvinyl) anthracene; TVAnt) skeleton was synthesized. Based on the above materials, alkyl-substituted TVAnts were synthesized and their electrical properties and the like were evaluated. As a more specific embodiment shows the technical spirit of the present invention by applying the TVAnt and hexyl-substituted HTVAnt to the organic semiconductor device, the technical spirit of the present invention is not limited by the embodiment.

The present invention provides an organic semiconductor compound synthesized by forming a vinyl group by a reaction between a phosphonate derivative represented by Formula 1 below and an aldehyde derivative represented by Formula 2.

<Formula 1>

<Formula 2>

Wherein A is a cyclic alkyl group, a phenyl group, a C1-C12 alkyl group, a substituted phenyl group, a thiophenyl group, a C1-C12 alkyl-substituted thiophenyl group, a naphthyl group, a C1-C12 alkyl-substituted naphthyl group, a biphenyl group, C1-C12 C12 alkyl substituted biphenyl group, anthracenyl group, C1 to C12 alkyl substituted anthracenyl group, phenanthrenyl group, C1 to C12 alkyl substituted phenanthrenyl group, fluorenyl group, C1 to C12 alkyl substituted flu Orenyl group, pyridinyl group, C1-C12 alkyl-substituted pyridinyl group, pyrrolyl group, C1-C12 alkyl-substituted pyrrolyl group, furanyl group, and C1-C12 alkyl-substituted furanyl group (The alkyl group of C1 is an expression referring to a methyl group having 1 carbon atom). More specifically, it may be an organic semiconductor compound represented by the following Chemical Formulas 3 to 6.

 <Formula 3>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12.

<Formula 4>

Wherein m is 1 to 5 and n is 0 to 11.

<Formula 5>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12.

<Formula 6>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12.

The present invention also provides an organic semiconductor thin film manufactured using the organic semiconductor compound described above, and an electronic device including the organic semiconductor thin film as a carrier transport layer.

In addition, the present invention also provides a method for producing an organic semiconductor compound, comprising the step of forming a vinyl group by a reaction between a phosphonate derivative represented by Formula 1 and an aldehyde derivative represented by Formula 2.

<Formula 1>

<Formula 2>

Wherein A is a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrrolyl group, and a substituted or unsubstituted group It is selected from the group consisting of a ring furanyl group.

An outline of the manufacturing process of the organic semiconductor compound of the present invention is as follows.

The synthesis of the organic semiconductor compound of the present invention starts with the preparation of 2,6-dimethylanthraquinone from the Diels-Alder reaction of isoprene and p- benzoquinone. Treatment of excessive amounts of sulfuryl chloride with 2,6-dimethylanthraquinone in the presence of catalytic amounts of 2,2'-azobis (2-methylpropionitrile) (AIBN) at reflux temperature will give 2,6-bis (chloromethyl) anthraquinone. And it is a key intermediate for the preparation of anthracene derivatives. Refluxing 2,6-bis (chloromethyl) anthraquinone in a mixture of water and Me ₂ SO yields an alcohol derivative, which is reduced using Zn and NH ₄ OH to yield a good yield of 2,6-bis (hydroxymethyl) anthracene To provide. Treatment of the resulting diol with PBr ₃ in DMF at room temperature yields 2,6-bis (bromomethyl) anthracene. One of the precursors of the Horner-Emmons olefination, 2,6-bis (diethylphosphorylmethyl) anthracene, is produced by the reaction of triethylphosphite with dibromide. Assembly of the oligomer to the thin film can be maximized by introducing vinylene units. Semiconductor materials were synthesized by the Horner-Emmons coupling reaction between phosphonates and aldehyde derivatives as shown in the figure above. Horner-Emmons coupling reactions are known as a means for forming all trans arrays. R in the last organic semiconductor compound is selected from the group consisting of H and C1 to C12 alkyl groups. The technical concept of the present invention will be described in more detail with reference to the case where R is hydrogen (TVAnt) and R is hexyl group (HTVAnt).

TVAnt and HTVAnt purified by sublimation were identified by high resolution mass spectrometry and elemental analysis, and their thermal stability was investigated by thermal gravimetric analysis (TGA) (FIG. 1). The thermal decomposition temperatures were 336 ° C. (TVAnt) and 376 ° C. (HTVAnt), while pentacene began to decompose at 260 ° C. (sublimation), confirming the high thermal stability of the (H) TVAnt compound.

Differential scanning calorimetry (DSC) measurements for the HTVAnt of FIG. 2 were obtained at 19 ° C. (10.1 kJ / mol), 100 ° C. (4.5 kJ / mol), 255 ° C. (30.5 kJ / mol, melting), 289 ° C., and 295 ° C. While showing phase transition, isotropic phase transition was observed beyond 295 ° C. Typical focal conical and fan-shaped structures were observed at 265 ° C., indicating that HTVAnt exhibits a well-aligned, liquid crystal structure like the smectic phase. The lower figure of FIG. 2 shows a polarized light micrograph of HTVAnt at 265 ° C. during the cooling process. Solid-solid phase transitions below 255 ° C. have not yet been identified.

3 and 4 show UV-vis spectra of (H) TVAnt on toluene and film (film), respectively. The UV-vis spectrum of the diluted solution of TVAnt in toluene showed absorption peaks at 426, 400, 345 and 328 nm, which is similar to the spectrum of HTVAnt. The long-wavelength absorption of the two compounds in the film (film) showed some red-shifts compared to those in solution.

Interestingly, in the PL spectrum, the maximum emission difference between the solution of the TVAnt and HTVAnt and the membrane (film) states was 100 and 70 nm, respectively, indicating that there is a very strong intermolecular attraction in the membrane state. This is shown in FIG. 5. When deposited on the film, the UV-vis spectra of TVAnt and HTVAnt showed long-wavelength absorption edges at 486 and 477 nm, respectively, corresponding to homo-lumo energy gaps of 2.55 and 2.59 eV, and that of pentacene It is significantly higher than that (2.2 eV).

Deeper insight into the electrical properties of these compounds was provided by cyclic voltammetry (CV). CV measurements of TVAnt and HTVAnt in 0.1 M Bu ₄ N ⁺ PF ₆ ⁻ / dichlorobenzene solution showed an irreversible oxidation peak. Onset potential of oxidation was located at 0.62 eV and 0.4 eV relative to ferrocene (FOC). Regarding the energy level of the FOC / ferrocenium reference (-4.8 eV), the homo energy levels of TVAnt and HTVAnt were -5.42 and -5.20 eV, respectively, which are lower than that of pentacene, and thus their high oxidative stability (FIG. 6).

Morphological characteristics were examined by X-ray diffraction (XRD) (FIG. 7). Thin film XRD patterns of TVAnt displayed the main (first) diffraction peaks at 2 θ = 4.34 ° ( d- spacing 20.34 μs), and the second, third and fourth order diffraction peaks were 2 θ = 8.56 °, 12.70 ° and 16.88, respectively. Showed at °. Strong intensity X-ray diffraction peaks indicate the formation of lamellar arrays and crystallization on the substrate. The d-spaced TVAnt obtained from the first reflection peak is 20.34 ms, comparable to the molecular length (21.28 ms) obtained from the MM2 calculation. This spacing is consistent with the single molecule layer thickness obtained by atomic force microscopy (AFM) shown in FIGS. 8 and 9, which indicates an almost perpendicular alignment of the molecules to the substrate surface. On the one hand, XRD results of the HTVAnt film (film) showed a weaker reflection peak than TVAnt with second order diffraction peak at 5.55 °. The film has a rather strong first-order diffraction peak of less than 3 °, which is difficult to solve because the temporary X-rays overlap with the diffracted beam. The d -spaced HTVAnt from the plane was 31.8 °, which is consistent with the first order diffraction of 2.78 °. The d- spacing was slightly smaller than the molecular length (36.38 mm 3) obtained from the MM2 calculation, indicating that the molecules are inclined from the normal to the layer by about 30 °. Weak intensity indicates that, at particularly high order peaks, the long range order of HTVAnt is not as good as that of TVAnt, suggesting a lower mobility for HTVAnt as compared to that of TVAnt. This is also consistent in the implementation of the devices. When used as a channel semiconductor in organic thin-film transistors (OTFTs), HTVAnt showed low FET mobility compared to TVAnt.

OTFTs of TVAnt and HTVAnt were prepared using a top contact structure with Au electrodes. A gold source and a drain contact (50 nm) were deposited on the organic layer through a shadow mask. Channel length L and width W are 50 and 500 μm, respectively. Thin films of two conjugated oligomers are formed by vacuum evaporation on (OTS) -coated Si / SiO ₂ substrates or untreated substrates at various temperatures ( T sub = 25, 50 and 75 ° C.). It became. All OTFTs showed typical p -channel TFT characteristics.

FIG. 10 shows drain currents I _DS to drain source voltages V _DS and the movement characteristics of TVAnt and HTVAnt TFTs grown at substrate temperature T _sub of 75 ° C. FIG. From the electrophoretic characteristics, we extracted the following parameters for each device and summarized it in Table 1: the carrier mobility, the on / off current ratio and the threshold voltage. voltage, and a subthreshold swing. TVAnt devices fabricated under various conditions showed FETs and flashing ratios> 10 ⁵ -10 ⁷ of greater than 0.1 cm ² / Vs under atmospheric conditions. In particular, excellent FET characteristics including FETs (measured at saturation) higher than 0.44 cm ² / Vs, and flashing ratio> 10 ⁵ were observed in TVAnt devices fabricated on OTS-treated substrates at T sub = 75 ° C. .

We found that TFT performance is critically dependent on the length of the side chain of the active material. Typically, the addition of alkyl chains (hexyl) is expected to increase the structural alignment of the membrane, thus activating charge transport. In our case, however, the mobility of TVAnt was three times higher than that of HTVAnt. When used as a channel semiconductor in OTFTs, HTVAnt showed lower FET mobility compared to TVAnt. This is not surprising because charge transport in organic semiconductors is governed by the crystal structure, and less-aligned HTVAnt is not expected to exhibit high mobility.

8 shows an AFM image of a film of a 30 nm thick oligomer deposited on an OTS-treated SiO ₂ / Si substrate at 75 ° C. FIG. At this temperature, the molecules were better aligned and a network of interlinked grains was observed for the TVAnt sample. The AFM step height for the lamellar structure of the TVAnt grain (obtained from the film deposited at 75 ° C.) was in good agreement with the d-spaced obtained from the XRD results and the calculated molecular length.

In the present invention, a novel organic semiconductor compound called TVAnt and alkyl-substituted TVAnt was synthesized, and the organic semiconductor compound exhibited high field-effect mobility and on / off current ratio when applied to organic electronic devices. In particular, under similar conditions, TVAnt has seven times higher mobility compared to dithiophen-2'-yl-2,6-anthracene (DTAnt), which does not contain vinyl groups. Furthermore, TVAnt and HTVAnt show high thermal stability when measured by TGA as compared to pentacene-based organic semiconductors. In addition, the organic semiconductor compound of the present invention can be used at a low substrate deposition temperature, there is an advantage that mass production is easy.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the present invention is not limited to the following examples and may be changed to other embodiments equivalent to substitutions and equivalents without departing from the technical spirit of the present invention. Will be apparent to those of ordinary skill in the art.

¹ H and ¹³ C NMR spectra were recorded using an Advance 300 MHz Bruker spectrometer in CDCl ₃ . ¹ H NMR chemical shifts in CDCl ₃ relative to CHCl ₃ (7.27 ppm) were measured and ¹³ C NMR chemical shifts in CDCl ₃ relative to CHCl ₃ (77.23 ppm).

<Physical measurement>

TGA analysis was performed on a TGA Q50 TA instrument at 10 ° C. min ⁻¹ under a nitrogen atmosphere. DSC analysis was performed on a DSC2910 TA instrument at 10 ° C. min ⁻¹ under nitrogen flow. UV-vis absorption spectra were recorded on a BECKMAN COULTER DU 800 spectrophotometer using 2.5 cm path-length quartz cells. For solid-state measurements, the oligomers were thermally evaporated in a vacuum chamber on quartz plates to form a film of 300 kPa thick at a deposition rate of 0.5 kS-1. XPD analysis was performed at room temperature with a Mac Science (M18XHF-22) diffraction meter using CuKα radiation as X-ray source at 50 kV and 100 mA. Data was collected from a conventional θ-2θ structure (2.5-30 °) from a thin film thermally evaporated in a vacuum chamber on a SiO2 / Si substrate at 0.5 kPa s-1 for 300 kPa. AFM images of the same vacuum-bonded thin film were obtained using a PSIA XE-100 Advanced Scanning Microscope. The voltammeter instrument used was a CH Instruments model 700C electrochemical workstation. Cyclic voltammograms (CVs) are the working electrode (Au) in dichlororobenzene (Au) and reference electrode (Ag) containing 0.1 M Bu4N + PF6- (tetrabutylammonium hexafluorophosphate) as a supporting electrolyte at a scan rate of 100 mV / s. / AgCl), and at room temperature in a three-electrode cell with a control electrode (Pt). All potentials were calibrated with standard ferrocene / ferrocenium redox couple (measured E = +0.41 V).

Fabrication of TFT devices

Field-effect measurements were performed using top-contact FETs. TFT devices having a channel length (L) of 50 μm and a channel width (W) of 1000 μm were fabricated from thermally oxidized, highly n-dop silicon substrates. The SiO 2 gate dielectric was 300 nm thick. The organic semiconductor 300 A was evaporated on a pretreatment free or OTS-pretreated oxide surface (0.1 μs s-1 at 1 × 10 −6 torr). Gold source and drain electrodes were evaporated on top of the film through a shadow mask. All measurements were performed at room temperature using a 4155C Agilent semiconductor parameter analyzer, with the mobility (μ) being plotted: μsat = (2 I _DS L ) / ( WC ( V _g- V _th ) ² ) was used in the saturation regime, where I _DS is the source-drain saturation current; C (1.18 x 10-8 F) is the oxide capacitance, V _g is the gate voltage, and V _th is the threshold voltage.

Synthesis of Organic Semiconductor Compound

All chemicals were purchased from Aldrich and Lancaster.

5- Hexyl 2-thiophenecarboxaldehyde (5- hexyl -2- thiophencarboxaldehyde )

To sterling THF (20 mL) solution containing 2-hexylthiophene (2.4 g, 13.26 mmol), slowly add 6.8 mL of n-BuLi (2.5 M in hexanes, 25 mmol) at 0 ° C. under nitrogen atmosphere. And stir the solution for 15 minutes. DMF (1.56 g, 21.39 mmol) is added and the mixture is warmed to room temperature. The mixture is poured into aqueous ammonium chloride (1N) solution and extracted with CH ₂ Cl ₂ . The organic layer is washed with water, dried over MgSO ₄ and evaporated. The residue is purified by column chromatography to give 2.7 g (97%) of yellow oil. 1 H NMR (300 MHz, CDCl 3): 9.82 (s, 1H), 7.55 (d, 1H, J = 4 Hz), 6.83 (d, 1H, J = 4 Hz), 2.85 (t, 1H, J = 7.5 Hz ), 1.0-1.28 (m, 8H), 0.87 (t, 3H, J = 6.5 Hz).

2,6- Bis (chloromethyl) anthraquinone (2,6- Bis ( cholormethyl ) anthraquinone)

2,6-dimethylanthraquinone (3.8 g, 16.09 mmol), SO ₂ Cl ₂ (50 mL), and 2,2'-azobis (2-methyl propionitrile (2,2 ') A mixture of -azobis (2-methyl propionitrile) (0.16 g, 0.96 mmol) was refluxed for 24 h Excess SO ₂ Cl ₂ was removed by distillation under vacuum The solid residue was filtered off Washed several times with petroleum ether and recrystallized with DMF to give 3.8 g (78%) of 2,6-bis (chloromethyl) anthraquinone ¹ H NMR (300 MHz, CDCl ₃ ): δ8.41 (m, 4H), 7.98 (s, 2H), 5.00 (s, 4H) .High-resolution mass spectrometry (HRMS): Calcd. for C ₁₆ H ₁₀ Cl ₂ O ₂ 304.0057. Found: 304.0034.

2,6- Bis (hydroxymethyl) anthraquinone (2,6-Bis ( hydroxymethyl ) anthraquinone)

A suspension of 2,6-bis (chloromethyl) anthraquinone (3.5 g, 11.47 mmol) in 300 mL of water and 400 mL of DMSO was refluxed with vigorous stirring. When heated for 4 hours, a clear solution is obtained. The reaction mixture is refluxed for 38 hours and then cooled to room temperature. The crystalline product was collected at leisure and recrystallized from DMF to yield 3.0 g (98%) of 2,6-bis (hydroxymethyl) anthraquinone. ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 8.17 (m, 4H), 7.85 (d, 2H, J = 10.7 Hz), 5.57 (s, 2H), 4.70 (s, 4H). High-resolution mass spectrometry (HRMS): Calcd. for C ₁₆ H ₁₂ O ₄ 268.0735. Found: 268.0749.

2,6- In bis (dihydroxymethyl) Thracene (2,6- Bis ( dihydroxymethyl anthracene)

Zinc powder (6.0 g) is added to a solution containing 2,6-bis (hydroxymethyl) anthraquinone (2.8 g 10.43 mmol) in concentrated ammonium hydroxide (70 mL). The reaction is refluxed overnight. Insoluble material is filtered off and washed with hot DMSO. The solution is precipitated in 200 mL of 1N HCl. The product collected by filtration is 1.86 g (75%) of 2,6-bis (dihydroxymethyl) anthracene. ¹ H NMR (300 MHz, DMSO-d ₆ ): δ 8.49 (s, 2H), 8.04 (d, 2H, J = 8.7 Hz), 7.94 (s, 2H), 7.46 (d, 2H, J = 8.7 Hz), 5.40 (t, 2H, J = 5.6 Hz), 4.69 (d, 4H, J = 5.6 Hz). High-resolution mass spectrometry (HRMS): Calcd. for C ₁₆ H ₁₄ O ₂ 238.0994. Found: 238.1003.

2,6- In bis (dibromomethyl) Thracene (2,6- Bis ( dibromomethyl anthracene)

PBr ₃ (4.4 g, 16.30 mmol) is added dropwise to a suspension with 2,6-bis (dihydroxymethyl) anthracene (1.5 g, 6.29 mmol) in DMF (30 mL) at 0 ° C. Once a yellow precipitate forms, heat the mixture to room temperature and stir for 4 hours. The solid was filtered off and washed with water and hexane to give 2,6-bis (dibromomethyl) anthracene as a yellow solid (2.2 g, 98%). The product is recrystallized from DMF to obtain a more pure substance. ¹ H NMR (400 MHz, DMSO): δ 8.56 (s, 2H), 8.15 (s, 2H), 8.12 (d, 2H, J = 11.5 Hz), 4.93 (s, 4H). High-resolution mass spectrometry (HRMS): Calcd. for C ₁₆ H ₁₂ Br ₂ 361.9306. Found: 361.9277.

2,5- Bis (diethylphosphorylmethyl) anthracene

(2,6- Bis ( diethylphosphorylmethyl anthracene)

2,6-bis (dibromomethyl) anthracene (2.2 g, 6.04 mmol) is added to triethylphosphite (50 mL) and the resulting solution is refluxed for 12 h. The solvent is removed in vacuo and the remainder is purified by column chromatography on silica gel using ethyl acetate / dichloromethane (2: 1) as eluent. The yield is 90%. ¹ H NMR (300 MHz, CDCl ₃ ): δ 8.49 (s, 2H), 8.04 (d, 2H, J = 8.7 Hz), 7.94 (s, 2H), 7.46 (d, 2H, J = 8.7 Hz) , 5.40 (t, 2H, J = 5.6 Hz), 4.69 (d, 4H, J = 5.6 Hz). ¹³ C NMR (300 MHz, CDCl ₃ ): 131.54, 130.83, 128.75, 128. 61, 128.39, 127. 84, 125. 67, (62.26, 62.16), (35.10, 33.27), (16.44, 16.30). MS (EI) m / z : (M ⁺ ) calcd for C ₂₄ H ₃₂ O ₆ P ₂ 478.16; found 478.

2,6- Bis (2-thienylvinyl) anthracene

(2,6- Bis (2- thienylvinyl ) anthracene) ( TVAnt )

LDA (1.5 M in cylohexane, 2.9 mL, 5.22 mmol) in a stirred solution with 2,6-bis (diethylphosphorylmethyl) anthracene (1.0 g, 2.09 mmol) in dry THF (50 mL) at -78 ° C under nitrogen atmosphere. Drop it and add it. Stir the mixture for 1 hour and add dropwise thiophene-2-carbaldehyde (0.58 g, 5.22 mmol) in THF (10 mL) every 10 minutes. After stirring the mixture at −78 ° C. for 2 hours and at room temperature for 12 hours, 5 mL of water is added and the solvent is evaporated. The residue is washed with water and methanol. The desired product is separated by sublimation. High resolution mass spectrometry (HRMS): Calcd. for C ₁₆ H ₁₀ Cl ₂ O ₂ 394.0850. Found: 394.0852, Anal. Calcd for CHS: C, 79.15; H, 4. 60; S, 16.25; Found: C, 79.24; H, 4.56; S, 16, 21.

2,6-bis [2- (5- Hexylthienyl ) Vinyl] anthracene

(2,6-Bis [2- (5- hexylthienyl ) vinyl] anthracene ) ( HTVAnt )

LDA (1.5 M in cylohexane, 3.2 mL, 5.75 mmol) in a stirred solution with 2,6-bis (diethylphosphorylmethyl) anthracene (1.2 g, 2.50 mmol) in dry THF (50 mL) at -78 ° C under nitrogen atmosphere. Drop it and add it. Stir the mixture for 1 hour and add dropwise 5-hexylthiophene-2-carbaldehyde (1.47 g, 7.50 mmol) in THF (20 mL) every 10 minutes. do. After stirring the mixture at −78 ° C. for 2 hours and at room temperature for 12 hours, 5 mL of water is added and the solvent is evaporated. The residue is washed with water and methanol. The desired product is separated by sublimation. High-resolution mass spectrometry (HRMS): Calcd. for C ₃₈ H ₄₂ S ₂ 562.2728. Found: 562.2728. Anal. Calcd .: C, 81.09; H, 7.52; S, 11.39; Found: C, 80.99; H, 7.03; S, 11.63.

2,6-bis [2- (5- Dodecylthienyl ) Vinyl] anthracene

(2,6-bis [2- (5- dodecylthienyl ) vinyl] anthracene ) ( DOTVAnT )

To a stirring solution with 2,6-bis (diethylphosphorylmethyl) anthracene (1.4 g, 2.92 mmol) in dry THF (50 mL) at -78 ° C under nitrogen atmosphere, add LDA (1.5 M in cylohexane, 3.2 mL, 5.75 mmol). Drop it and add it. Stir the mixture for 1 hour and drop 5-dodecylthiophene-2-carbaldehyde (2.30 g, 8.20 mmol) in THF (20 mL) in 10 minute cycles. Stir the mixture at -78 ° C for 2 hours, stir at room temperature for 12 hours, then add 5 mL of water and evaporate the solvent. The residue is washed with water and MeOH. The desired product is washed off. High-resolution mass spectrometry (HRMS): Calcd. for C50H66S2 730.4606. Found: 730.4604. Anal. Calcd .: C, 82.13; H, 9. 10; S, 8.77; Found: C, 82.11; H, 9.06; S, 8.83.

Through similar methods, alkyl-substituted compounds in the TVAnt skeleton can be synthesized, which are expected to show similar properties in general, although somewhat different. The method of alkyl substitution and the introduction of other substituents will be understood at the level of those skilled in the art, and the specific description is omitted for the sake of brevity of the specification but is also within the technical scope of the present invention.

1 is a graph of TGA analysis of (H) TVAnt.

2 shows the DSC (top) of the HTVAnt during the heating and cooling processes and the POM picture (bottom) during the cooling process.

3 and 4 show UV-vis spectra of (H) TVAnt on toluene solution and film (membrane), respectively.

5 shows the PL emission spectrum on toluene and film.

6 shows the cyclic voltammogram of (H) TVAnt.

FIG. 7 shows the XRD pattern of a (H) TVAnt thin film vacuum deposited on an OTS-treated SiO ₂ / Si substrate at T _sub = 75 ° C. FIG.

8 shows an AFM image of a non-contact mode of a) TVAnt b) HTVAnt.

9 shows AFM images of thin films on bare substrates of TVAnt.

FIG. 10 shows the source drain currents and source train voltages at various gate volts for top-contact field effect transistors using (H) TVAnt at 75 ° C. deposition temperature on an OTS-treated SiO ₂ substrate.

Claims (5)

An organic semiconductor compound synthesized by forming a vinyl group by a reaction between a phosphonate derivative represented by Formula 1 and an aldehyde derivative represented by Formula 2. <Formula 1>

<Formula 2>

Wherein A is a cyclic alkyl group, a phenyl group, a C1-C12 alkyl group, a substituted phenyl group, a thiophenyl group, a C1-C12 alkyl-substituted thiophenyl group, a naphthyl group, a C1-C12 alkyl-substituted naphthyl group, a biphenyl group, C1-C12 C12 alkyl substituted biphenyl group, anthracenyl group, C1 to C12 alkyl substituted anthracenyl group, phenanthrenyl group, C1 to C12 alkyl substituted phenanthrenyl group, fluorenyl group, C1 to C12 alkyl substituted flu Orenyl group, pyridinyl group, C1-C12 alkyl-substituted pyridinyl group, pyrrolyl group, C1-C12 alkyl-substituted pyrrolyl group, furanyl group, and C1-C12 alkyl-substituted furanyl group . An organic semiconductor compound represented by the following Chemical Formulas 3 to 6.  <Formula 3>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12. <Formula 4> Wherein m is 1 to 5 and n is 0 to 11. <Formula 5>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12. <Formula 6>

Wherein R is selected from the group consisting of H and alkyl groups of C1 to C12. An organic semiconductor thin film manufactured using the organic semiconductor compound of claim 1 or 2. An electronic device comprising the organic semiconductor thin film of claim 3 as a carrier transport layer. A method for producing an organic semiconductor compound, comprising the step of forming a vinyl group by a reaction between a phosphonate derivative represented by Formula 1 and an aldehyde derivative represented by Formula 2. <Formula 1>

<Formula 2>

Wherein A is a substituted or unsubstituted cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrrolyl group, and a substituted or unsubstituted group It is selected from the group consisting of a ring furanyl group.

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