WO2008120839A1 - Novel organic semiconductor compound, and organic thin film transistor using the same - Google Patents

Abstract

The present invention relates to novel mono- molecular organic semiconductor compounds and organic thin film transistors comprising the same. The organic semiconductor compounds according to the present invention are characterized by a structure of an acene derivative substituted with acetylene groups at both ends, a structure of anthracene derivative substituted with acetylene groups, or a structure of a multi-nuclear aromatic derivative functionalized by naphthalene having an electron-donor substituent at both ends.

Description

[DESCRIPTION]

[invention Title]

NOVEL ORGANIC SEMICONDUCTOR, AND ORGANIC THIN FILM TRANSISTOR USING THE SAME

[Technical Field]

The present invention relates to organic thin film transistors (OTFT) . More specifically, it relates to novel organic semiconductor compounds having high π-electron overlap, and organic thin film transistors which employ the compounds as a semiconductor layer, having improved charge mobility and on/off ratio.

[Background Art]

The desire for developments in data communication in this century and communication devices for individual pocket use requires high performance electric materials, as novel substances for data communication to provide display of novel concept, which can afford ultra-micro processing and ultrahigh integrated circuits, enabling small, light, slim and convenient data communication devices. Among them, organic thin film transistors (OTFT) have been widely researched due to their usability for significant constituents of plastic circuit parts in display drivers of portable computers, organic EL devices, smart cards, electric tags, pagers, mobile phones, or the like, and memory devices such as asynchronous transfer mode (ATM) and identification tags.

By virtue of discoveries of organic conductor compounds and semiconductor compounds, there has been rapid development in the field of molecular electronics for recent 20 years. During the period, a variety of compounds showing semiconductor or electro-optical properties have been discovered. It had been generally understood that molecular electronics could not replace common silicon-based semiconductor devices. Instead, it was anticipated that molecular electronic components would open up a new realm in coating an extensive area, requiring compatibility, structural flexibility, processibility at low temperature and low cost. Organic semiconductor compounds are currently developed in the field of organic thin film transistors (OTFT) , organic light emitting diodes (OLED), sensors and photoelectric cell devices.

An OTFT employing an organic semiconductor can be simply produced as compared to a conventional OTFT employing amorphous silicon and polysilicon, with low cost. Further, the OTFT' s have been currently researched since they have advantages in excellent compatibility with plastic substrates for embodiment of flexible displays.

Since a low-molecular system using Cu-phthalocyanine and a high-molecular field effect transistor using polyacetylene have been discovered by G. H. Heilmeier et al . (1964) and F. Ebisawa et al . (1983), respectively, a number of researches have been performed. Among various performances of an OTFT, the most important are charge mobility and on/off ratio, with the most valuable measure of evaluation being charge mobility. The charge mobility varies depending on the type of semiconductor material, process for forming a thin film (structure and morphology), operation voltage, and the like.

An organic thin film transistor (OTFT) generally consists of a substrate, a gate electrode, an insulator, source/drain electrodes and a channel layer. OTFT' s are classified as OTFT' s of bottom contact type (BC type) wherein a channel layer is formed on source and drain electrodes, and those of top contact type (TC type) wherein a metal electrode is formed on a channel layer.

Simplification of structure and integration of OTFT in an organic semiconductor circuit afforded a method for producing smart cards or price tags with low cost, which could not be achieved by using the silicon techniques because of insufficient flexibility of silicon component and high cost. Further, OTFT can be employed as a circuit device in a flexible matrix display having a large area.

Fig. 1 is a cross-sectional view showing a general structure of an OTFT comprising a substrate (H)/ a gate electrode (16)/ a gate insulator layer (12) / electrode layers (source, drain) (14 and 15)/ channel material layer (13). As shown in Fig. 1, a gate electrode is formed on the upper side of the substrate. On the upper side of the gate electrode, an insulator is formed, on which channel material layer and source/drain electrodes are formed. The principle of operation of an OTFT having such a structure is described below, by means of an example of p-type semiconductor: First, voltage is applied between the source and the drain to flow the current. Under a low voltage, a current proportional to the voltage flows. When a positive voltage is applied to the gate, all the holes (positive charges) are forced to the upper side of the channel material layer due to the electric field produced by the applied voltage. Thus, a depletion layer wherein no conductive charge exists is formed in a region near the insulator layer. Under the circumstances, only low current flows even with applying a voltage between the source and the drain, because conductible charge carrier has been decreased. On the other hand, when a negative voltage is applied to the gate, an accumulation layer is formed in a region near the insulator layer, due to the effect of the electric field produced by the applied voltage, wherein positive charge has been induced. At this time, more current can flow since a number of conductible charge carriers exist between the source and the drain. Therefore, the current flowing between the source and the drain can be controlled by alternately applying positive voltage and negative voltage while the voltage to the gate, being applied between the source and the drain.

The materials employed for an OTFT which is constituted according to the above-described principle include electrodes (source, drain), a substrate and a gate electrode requiring high thermal stability, an insulator having high insulating property and dielectric constant, and a semiconductor material that provides sufficient delivery of the charge. Among them, an essential material having various problems to be solved is the organic semiconductor.

Recently, a variety of organic semiconductor materials for a channel layer of an OTFT have been researched, and the transistor properties have been reported. Organic semiconductors are classified into low molecular, oligomeric and high molecular semiconductors depending on the molecular weight, and into n-type and p-type semiconductors depending on the function of delivery of electrons or holes. In general, a low molecular semiconductor, when being used for forming channel material, exhibits excellent charge mobility due to easy purification to remove most of the impurities. Though the purification to high purity is difficult, a high molecular semiconductor shows excellent heat resistance and advantages in preparation, cost and mass production, since it can be spincoated or printed. It is commonly known that the charge mobility of high molecular semiconductor is lower than that of low molecular semiconductor, but the former is a substance that can sufficiently overcome the problem from the aspect of the manufacturing process or cost. For the embodiment of flexible displays, the high molecular materials should be firstly developed.

The low molecular or oligomeric organic semiconductor materials that have been extensively researched include melocyanine, phthalocyanine, perylene, pentacene, anthracene, C60, thiophene oligomer, and the like. Lucent Technologies and 3M reported high charge mobility of 3.2-5.0 cm²/Vs or more by using pentacene monocrystals (Mat. Res. Soc . Symp . Proc . 2003, Vol. 771, L6.5.1-L66.5.11) . Those values are comparable with or superior to that of amorphous silicon. CNRS (France) also reported relatively high charge mobility and on/off ratio of 0.01-0.1 cm²/Vs by using an oligothiophene derivative. However, in the conventional techniques, formation of thin film essentially depends on a vacuum process, so that the production cost is high.

With respect to pentacene, oxidative or thermal stability during long term has not been known, thereby the lifetime for use of the pentacene semiconductor device cannot be known. Another factor to be considered with respect to the utility of an organic semiconductor is easiness of synthesis and purification. Finally, various organic semiconductor materials may be required having a certain range of physical and chemical properties depending on a particular application.

As a high molecular material, it is reported that a high molecular OTFT device was experimentally manufactured by employing F8T2 (a polythiophene substance), having 0.01-0.02 cm²/Vs of charge mobility (International Laid-Open No. WO 00/7961, Science, 2000, vol. 290, pp. 2132-2126). In addition, USP 6,107,117 discloses a process for manufacturing an OTFT device having 0.01-0.04 cm²/Vs of charge mobility by using a regioregular polythiophene, P3HT.

Though the technique described above is advantageous in manufacturing process, cost and mass production via wet process at ambient temperature, purification with high purity is difficult to cause the problems of showing low charge mobility and high interrupting leakage current.

[Disclosure]

[Technical Problem]

The first object of the present invention is to provide novel organic semiconductor compounds of acene derivatives having a substituent comprising arylacetylene groups. The second object of the present invention is to provide organic semiconductor compounds having excellent charge mobility and high on/off ratio by introducing acetylene derivatives to anthracene having p-type semiconductor property in order to ensure solubility, and an aryl derivative to increase overlap of π-electrons and intermolecular crystallinity . The third object of the present invention is to provide novel organic semiconductor compounds having high thermal stability, π- electron overlap and intermolecular crystallinity, and thereby enhanced charge mobility and on/off ratio, by introducing naphthalenes having electron-donor substituents at both terminals .

The fourth object of the present invention is to provide an organic thin film transistor having excellent charge mobility and high on/off ratio, by using said organic semiconductor compound having high π-electron density and π- electron overlap and intermolecular crystallinity.

[Technical Solution]

The present invention relates novel monomolecular organic semiconductor compounds represented by one of Chemical Formulas (1) to (3), and OTFT' s employing the same. The organic semiconductor compounds according to the present invention are characterized by having an anthracene structure substituted with acetylene groups as is represented by Chemical Formula (2) , or characterized by a multi-nuclear aromatic structure which is multi- functionalized at both terminals, comprising naphthalenes having electron-donor substituent (s) , as is represented by Chemical Formula (3).

[Chemical Formula 1]

(ATi)_n-S-A-SS- (Ar₂) a

In Chemical Formula (1), A represents (C₆-C₃₀) arylene or (C₆-C₃₀) heteroarylene,- Ari and Ar₂ independently represent (C₆- C₃₀) aryl or (C₄-C₃₀) heteroaryl; m and n independently represent an integer of 1 to 4 ;

A, Ar₁ or Ar₂ may be independently substituted by at least one substituent (s) selected from the group consisting of hydroxyl group, linear, branched or cyclic (Ci-C₃₀) alky1 group, linear, branched or cyclic (Ci-C₃₀) alkoxy group, (C₁- C₃₀) alkoxy (C₁-C₃₀) alkyl group, (C₅-C₃₀) ar (C₁-C₃₀) alkyl group, (C₅- C₃₀) aryl group, amino group, mono- or di (C₆-C₃₀) alkylamino group, mono- or di (C₆-C₃₀) arylamino group, (C₁-C₃₀) alkoxycarbonyl group, cyano group or halogen.

[Chemical Formula 2]

In Chemical Formula (2) , A₁ and A₂ are independently selected from the group consisting of C, Si and Ge; Ri₁, R₁₂, R₁₃ and R₁₄ are independently selected from the group consisting of hydrogen; linear, branched or cyclic (Ci-C₃₀) alkyl group; linear, branched or cyclic (C₂-C₄₀) alkenyl group; linear, branched or cyclic (C₃-C₄₀) alkynyl group; linear, branched or cyclic (C₁-C₃₀JaIkOXy group; (C₆-C₄₀) aryl group,- (C₄- C₃₀) heteroaryl group, (C₆-C₃₀) ar (C₁-C₃₀) alkyl group; (C₁- C₃₀) alkoxy (C₁-C₃₀) alkyl group; (C₁-C₃₀) alkoxy (C₂-C₃₀) alkenyl group; (C₆-C₅₀) heteroaryl (C₁-C₃₀) alkyl group; (C₁-C₄₀) carbyl ; hydro (C₁-C₄₀) carbyl group; (C₆-C₄₀) aryloxy group; (C_x- C₄₀) alkoxycarbonyl group; (C₆-C₄₀) aryloxycarbonyl group; cyano group; carbamoyl group (-C(=O)NH₂); haloformyl group (-C(=O)-X, wherein X represents a halogen atom); formyl group (-C(=O)-H); isocyano group; isocyanate group; thiocyanate group; thioisocyanate group; mono- or di (C₁-C₃₀) alkylamino group; mono- or di (C₆-C₃₀) arylamino group; hydroxyl group,- halogen group,- nitro group and silyl group; or R₁₁, R₁₂, R₁₃ and R₁₄ are independently cross-linked with carbon of adjacent anthracene group via alkylene or alkenylene to form saturated or unsaturated (C₄-C₃₀) ring, wherein the carbon atom in the saturated or unsaturated ring may be substituted by oxygen atom, sulfur atom or chemical formula -N(R₃)- [R_a represents a hydrogen atom or (C₁-C₃₀) alkyl group] ; and the alkyl, alkenyl, alkynyl, alkoxy, aryl or heteroaryl group of R₁₁, R₁₂, R₁₃ or R_X4 may be further substituted by at least one substituent (s) selected from the group consisting of (C₁-C₃₀) alky1; (C₂- C₃₀)alkenyl; (C₃-C₃₀) alkynyl ; (Ci-C₃₀) alkoxy; (C₆-C₄₀) aryloxy group; (C₆-C₃₀) aryl; (C₄-C₃₀) heteroaryl; formyl group; amino group,- hydroxyl group; nitro group; halogen and silyl group,-

Ri5, Ri₆, RI7A Ri8, RI9 and R₂O are independently selected from the group consisting of hydrogen; linear, branched or cyclic (Ci-C₃₀) alkyl group; linear, branched or cyclic (C₂- C₄₀)alkenyl group; linear, branched or cyclic (C₃-C₄₀) alkynyl group; linear, branched or cyclic (Ci-C₃₀) alkoxy group; (C₆- C₄₀) aryl group; (C₄-C₃₀) heteroaryl group, (C₅-C₃₀) ar (Ci-C₃₀) alkyl group; (Ci-C₃₀) alkoxy (C₁-C₃₀) alkyl group; (Ci-C₃₀) alkoxy (C₂- C₃₀)alkenyl group; (C₆-C₅₀) heteroaryl (Ci-C₃₀) alkyl group; (Ci- C₄₀) carbyl; hydro (Ci-C₄₀) carbyl group; (C₆-C₄₀) aryloxy group; (Ci-C₄₀) alkoxycarbonyl group,- (C₆-C₄₀) aryloxycarbonyl group,- cyano group; carbamoyl group (-C (=0) NH₂) ; haloformyl group (- Ci=O)-X₁ wherein X represents a halogen atom); formyl group (- Ci=O)-H); isocyano group,- isocyanate group; thiocyanate group; thioisocyanate group; mono- or di (Ci-C₃₀) alkylamino group; mono- or di (C₆-C₃₀) arylamino group; hydroxyl group; halogen group,- nitro group and silyl group,- and the alkyl, alkenyl, alkynyl, alkoxy, aryl or heteroaryl group of Ri₅, R_i6, R_i7, Ri₈, Ri₉ or R₂O may be further substituted by at least one substituent (s) selected from the group consisting of (Ci- C₃₀)alkyl; (C₂-C₃₀) alkenyl ; (C₃-C₃₀) alkynyl ; (Ci-C₃₀) alkoxy; (C₆- C₄₀)aryloxy group; (Cg-C₃₀) aryl ; (C₄-C₃₀) heteroaryl; formyl group; amino group; hydroxyl group; nitro group; halogen and silyl group.

[Chemical Formula 3]

In Chemical Formula (3), Ar₃ represents (C₆-C₃₀) arylene or (C₆-C₃₀) heteroarylene; R₃1 and R₃₂ independently represent hydrogen, linear, branched or cyclic (C₁-C₂₅) alkyl, (C₅-C₂₅) aryl, (C₄-C₂₅) heteroaryl, (C₁-C₂₅) alkoxy (Ci-C₂₅) alkyl , (C₅-C₂₅) ar (C₁- C₂₅) alkyl, (C₄-C₂₅) heteroaryl (C₁-C₂₅) alkyl, linear, branched or cyclic (C₂-C₂₅) alkenyl, linear, branched or cyclic (C₂- C₂₅) alkynyl, mono-, di- or tri (C₁-C₂₅) alkylsilyl, mono-, di- or tri (C₅-C₂₅) arylsilyl, saturated or unsaturated 3- to 7-membered heterocycloalkyl comprising oxygen, nitrogen or sulfur atom in the heterocycle, or saturated or unsaturated 3- to 7-membered heterocycloalkyl (C₁-C₂₅) alkyl comprising oxygen, nitrogen or sulfur atom in the heterocycle; provided that if both R₃₁ and R₃₂ are hexyl , Ar₃ is not anthracene or thienothiophene,-

X₁ and X₂ are independently selected from the group consisting of 0, N, S and (Ci-C₂₅) alkylene; x and y independently represent an integer of 1 or 2; p and r independently represent an integer of 0, 1 or 2 ; q is an integer from 1 to 4 ;

Ar₃ may be further substituted by at least one substituent (s) selected from the group consisting of hydroxyl, linear, branched or cyclic (Ci-C₂s) alkyl, linear, branched or cyclic (C₁-C₂₅) alkoxy, (Ci-C₂₅) alkoxy (Ci-C₂₅) alkyl, (C₅-C₂₅) ar (Ci- C₂₅) alkyl, (C₅-C₂₅) aryl, amino, mono- or di (C₆-C₂₅) alkylamino, mono- or di (C₆-C₂₅) arylamino, cyano and halogen; and the alkyl, aryl, heteroaryl, alkoxyalkyl, aralkyl, heteroarylalkyl, alkenyl, alkynyl, alkylsilyl, arylsilyl, heterocycloalkyl or heterocycloalkylalkyl group of R₃i or R₃₂ may be further substituted by at least one substituent (s) selected from the group consisting of (Ci-C₂₅) alkyl, (C₂- C₂₅) alkenyl, (C₃-C₂₅) alkynylamino group, hydroxyl group, (Ci- C₂₅) alkoxy, (C₆-C₂₅) aryloxy group, (C₆-C₂₅) aryl, (C₄- C₂₅) heteroaryl, halogen or silyl group.

In addition, the present invention provides an OTFT comprising a first electrode; a second electrode; and an organic semiconductor compound selected from the compounds represented by one of Chemical Formulas (1) to (3) between the first electrode and the second electrode. Further, the present invention provides an OTFT comprising a substrate, a gate electrode, a gate insulator layer, channel material layer and source/drain electrodes, wherein the channel material layer is formed of an organic semiconductor compound selected from the compounds represented by one of Chemical Formulas (1) to (3) .

[Description of Drawings]

Fig. 1 is a cross-sectional view showing the structure of common OTFT which comprises a substrate/a gate electrode/ a gate insulator layer/ electrode layers (source, drain)/ channel material layer.

Fig. 2 illustrates properties of an OTFT employing an organic semiconductor compound (Compound 101) according to the present invention as channel material; (a) transfer curve

(source-drain voltage & square root current-drain voltage) ,

(b) output curve (current-voltage) .

Fig. 3 illustrates thermal gravity analysis (TGA) curves of the organic semiconductor compounds (Compounds 101, 102, 103 and 104) according to the present invention; (a) Compound (101), (b) Compound (102), (c) Compound (103), (d) Compound (104) .

Fig. 4 illustrates differential scanning calorimeter (DSC) curves of the organic semiconductor compounds (Compounds 101 and 102) according to the present invention; (a) Compound (101), (b) Compound (102).

Fig. 5 illustrates DSC curves of the organic semiconductor compounds (Compounds 105, 106, 107 and 108) according to the present invention.

Fig. 6 illustrates TGA curves of the organic semiconductor compounds (Compounds 105, 106, 107 and 108) according to the present invention.

Fig. 7 illustrates a transfer curve of an OTFT employing Compound (105) as channel material; (a) source-drain voltage; (b) square root current-drain voltage.

Fig. 8 illustrates an output curve (current-voltage) of an OTFT employing Compound (105) as channel material.

Fig. 9 illustrates TGA curves of the organic semiconductor compounds according to the present invention; (a) Compound (112) , (b) Compound (113) , (c) Compound (114) , (d) Compound (116) , (e) Compound (117) and (f) Compound (118) .

Fig. 10 illustrates DSC curves of the organic semiconductor compounds according to the present invention; (a) Compound (112) , (b) Compound (113) , (c) Compound (114) , (d) Compound (116) , (e) Compound (117) and (f) Compound (118) .

Fig. 11 illustrates properties of an OTFT employing Compound 113 as channel material; (a) transfer curve of the OTFT, (b) output curve (current-voltage) of the OTFT.

* Description of the reference numbers of significant parts of the drawings

11: substrate

12 : insulator layer 13 : channel material layer

14 : source electrode

15 : drain electrode

16: gate electrode

[Best Model

Other and further objects, features and advantages of the invention will appear more fully from the following description.

In an organic semiconductor compound represented by Chemical Formula (1) , A can be selected from the group consisting of phenylene, naphthylene, anthrylene, phenanthrylene, tetracenylene, pentacenylene, pyrenylene, chrysenylene and fluorenylene. In particular, the compound can be exemplified by following arylenes :

In Chemical Formula (1) , Ar₁ and Ar₂ are independently- selected from aryl or heteroaryl represented by one of the following chemical formulas (the position of linkage with acetylene group is selected from the aromatic ring carbons of the substituent having one of the structures represented by following formulas) :

In the aryl or heteroaryl having the structure represented as above, Ri is independently selected from the group consisting of hydrogen, hydroxyl group, linear, branched or cyclic (Ci-C₃₀) alkyl group, linear, branched or cyclic (Ci- C₃₀)alkoxy group, (Ci-C₃₀) alkoxy (Ci-C₃₀) alkyl group, (C₅- C₃₀) ar (Ci-C₃₀) alkyl group, (C₅-C₃₀) aryl group, amino group, mono- or di (C₆-C₃₀) alkylamino group, mono- or di (C₆-C₃₀) arylamino group, (Ci-C₃₀) alkoxycarbonyl group and cyano group.

In the organic semiconductor compound represented by Chemical Formula (2) , Ri₅, Ri₆, Ri₇, Ris, R₁₉ and R₂₀ are independently selected from the group consisting of (Ci- C₁₀) alkyl group, tri (Ci-Ci₀) alkylsilyl group; tri (Ci- C₁₀) alkoxysilyl group and tri (C₆-Ci₀) arylsilyl group. The silyl groups are exemplified by trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylpropylsilyl , dimethylisopropylsilyl , dipropylmethylsilyl , diisopropylmethylsilyl , dipropylethylsilyl , diisopropylethylsilyl , diethylisopropylsilyl, triisopropylsilyl, trimethoxysilyl, triethoxysilyl and triphenylsilyl .

Aryl and heteroaryl selected for Rn to R₁₄ are exemplified by the substituents represented by one of the following chemical formulas:

fli^

wherein, R_2i, R22, R23 , R24, R25 and R₂₆ are independently- selected from the group consisting of hydrogen, (Ci-C₃₀) alkyl group, (C₆-C₃₀) aryl group and (Ci-C₃₀) alkoxy (C₆-C₃₀) aryl group; and alkyl or aryl of R₂₁, R₂₂, R23, R24, R25 or R₂₆ may be substituted by at least one substituent (s) selected from the group consisting of (Ci-C₃₀) alkoxy and halogen; and the position of linkage where the substituent is bonded is selected from the carbons in the substituent ring.

In the organic semiconductor compound represented by Chemical Formula (3), Ar₃ is exemplified by arylene or heteroarylene having the structure represented by one of the following chemical formulas:

R, 41 V

wherein, R_4x to R₄₇ are independently selected from the group consisting of hydrogen, (C₁-C₂₅) alkyl, (C₅-C_2S) aryl and (C₅-C₂₅) ar(Ci-C₂5) alkyl, and the alkyl and aryl of said R₄₁ to R₄₇ may be further substituted by at least one substituent (s) selected from the group consisting of (Ci-C₂₅) alkoxy and halogen.

The aryl or heteroaryl selected for the substituent R₃₁ or R₃₂ is exemplified by the substituents represented by one of the following chemical formulas:

wherein, R₅₁, R₅₂, R₅₃, R₅₄, R₅₅ and R₅₆ are independently selected from the group consisting of hydrogen, amino, linear, branched or cyclic (C₁-C₂₅) alkyl, linear, branched or cyclic (C₁-C₂₅) alkoxy, (C₁-C₂₅) alkoxy (C₁-C₂₅) alkyl, (C₅-C₂₅) ar (C₁- C₂₅)alkyl, (C₅-C₂₅) aryl, mono- or di (C₆-C₂₅) alkylamino, mono- or di (C₆-C₂₅) arylamino group; and the position of linkage where the substituent is bonded is selected from the carbons in the substituent ring.

The organic semiconductor compounds represented by Chemical Formula (1) according to the present invention are organic semiconductor compounds of acene derivative type, which have arylacetylene substituents at both terminal, with high π-electron density and π-electron overlap and intermolecular crystallinity .

The organic semiconductor compounds according to the present invention represented by Chemical Formula (2) are organic semiconductor compounds modified by acetyl group at 9- and/or 10 -position of anthracene. Those compounds facilitate formation of intermolecular packing and π-stacking, and provide excellent crystallinity. Further, aliphatic groups enhance solubility and flowability of these molecules, helping to give crystallinity to the molecules.

The organic semiconductor compounds according to the present invention represented by Chemical Formula (3) are multi-nuclear aromatic derivatives functionalized by naphthalenes having electron-donor substituent (s) . These compounds are very linear, having naphthalenes as electron- rich multi-nuclear aromatics at both terminals, thereby facilitating intermolecular packing and π-stacking and providing excellent crystallinity. Aliphatic groups are also helpful to provide the molecules with crystallinity by increasing the solubility and flowability of these molecules. As can be seen from the differential scanning calorimeter (DSC) curves, these compounds have different phase transition temperatures; which indirectly shows that the organic semiconductor compounds according to the present invention represented by Chemical Formula (3) have liquid crystallinity . The liquid crystallinity is a major cause of excellent crystallinity of these molecules.

The organic semiconductor compounds represented by one of Chemical Formulas (1) to (3) according to the present invention can be exemplified by following compounds, but they are not restricted thereto.

C₁₀H₂i

The organic semiconductor compound having arylacetylene structure represented by Chemical Formula (1) , wherein Ari and Ar₂ are identical so that the compound has symmetrical structure, can be prepared by coupling 2 equivalents of arylacetylene compound with dihaloaryl compound, as shown in Reaction Formula (1) . The coupling reaction is proceeded by using Cul/Pd (PPh₃) ₂Cl₂ as a coupling agent in the presence of triethylamine and organic solvent.

[Reaction Formula 1]

2 Ar₁ = X-A-X Ar₁ -A- -Ar₁

The asymmetric compounds can be prepared by separately reacting arylacetylene compound and dihaloaryl compound in discrete steps :

[Reaction Formula 2]

Ar₁-= + X-A-X ► Ar₁ zzz A-X

Ar,

The process for preparing the organic semiconductor compounds having arylacetylene structure represented by Chemical Formula (1) according to the present invention is not restricted by above-described process for preparation. The compounds may be prepared according to conventional organic chemical reactions other than the processes described above. The arylacetylene compound and halodiaryl compound, employed as intermediates can be easily prepared via conventional organic chemical reactions by a person having ordinary skill in the art .

The final organic semiconductor compounds represented by Chemical Formula (3) according to the present invention can be prepared via alkylation, Grignard coupling reaction, Suzuki coupling reaction, or the like.

The process for preparing the organic semiconductor compounds represented by one of Chemical Formulas (1) to (3) according to the present invention is not restricted by above- described processes for preparation. The compounds may be prepared according to conventional organic chemical reactions other than the processes described above.

The organic semiconductor compounds according to the present invention can be employed as channel material in an OTFT. The OTFT according to the present invention comprises a first electrode; a second electrode; and an organic semiconductor compound represented by one of Chemical Formulas (1) to (3) between the first electrode and the second electrode. More specifically, the present invention provides an OTFT comprising a substrate (11) , a gate electrode (16) , a gate insulator (12) , channel material (13) and source/drain electrodes (14 and 15) , wherein the channel material is made of an organic semiconductor compound selected from the compounds represented by one of Chemical Formulas (1) to (3) . The constitution of the OTFT of the present invention includes a top-contact type which comprises a substrate/a gate electrode/ a gate insulator layer/ channel material layer/ source / drain electrode in the order (not shown) , as well as a bottom-contact type which comprises a substrate (H)/ a gate electrode (16)/ a gate insulator layer (12)/ source and drain electrodes (14 and 15)/ channel material layer (13) in the order as shown in Fig. 1.

The organic semiconductor compounds according to the present invention are low-molecular semiconductor compounds having typical properties of p-type semiconductors. The acene derivatives comprising arylacetylene group, represented by Chemical Formula (1) contain acetylene groups to increase intermolecular linearity. When these compounds are applied to an OTFT, excellent charge mobility and high on/off ratio can be effected due to high π-electron overlap of the compounds. The compounds having anthracene structure substituted with acetylenes, represented by Chemical Formula (2) have enhanced π-electron overlap and intermolecular crystallinity, so that an OTFT having excellent charge mobility and high on/off ratio can be obtained therefrom.

The multi-nuclear aromatic derivatives functionalized with naphthalenes having electron-donor substituents at both terminals, as represented by Chemical Formula (3) are very linear. By virtue of having naphthalenes as electron-rich multi -nuclear aromatics at both terminals, the compounds are thermally stable, facilitate intermolecular packing and π- stacking, and provide excellent crystallinity. When applied to an OTFT, the effects of excellent hole and electron mobility, low threshold voltage, large current change per unit voltage and high on/off ratio can be obtained.

Specific example of the process for preparing an OTFT wherein the low-molecular organic semiconductor compound represented by one of Chemical Formulas (1) to (3) is employed as the channel material is described below:

As the substrate (11) , n-type silicon used for conventional OTFT is preferably used. The substrate comprises the function of a gate electrode. Otherwise, a glass substrate or a clear plastic substrate having excellent surface smoothness, easiness in handling and water resistance may be also used. In this case, a gate electrode should be added on the substrate. The material usable as a substrate is exemplified by glass, polyethylenenaphthalate (PEN) , polyethyleneterephthalate (PET) , polycarbonate (PC) , polyvinylalcohol (PVP) , polyacrylate, polyimide, polynorbornene and polyethersulfone (PES) , but not limited thereto.

As the gate insulator (12), any conventionally used insulator having high dielectric constant may be employed. Specifically, the insulator may be a strongly dielectric insulator selected from the group consisting of Ba_0.33Sr_0.66 ¹TiO₃ (BST) , Al₂O₃, Ta₂O₅, La₂O₅, Y₂O₃ and TiO₂; an inorganic insulator selected from the group consisting of PdZr₀.₃₃Ti₀^O₃ (PZT) , Bi₄Ti₃Oi₂, BaMgF₄, SrBi₂(TaNb)₂O₉, Ba(ZrTi)O₃ (BZT), BaTiO₃, SrTiO₃, Bi₄Ti₃Oi₂, SiO₂, SiN_x and AlON; or an organic insulator selected from the group consisting of polyimide, benzocyclobutene (BCB) , parylene, polyacrylate, polyvinylalcohol and polyvinylphenol . Silicon dioxide (SiO₂) is preferably used because it has high dielectric constant, and can be easily formed on a gate electrode.

Though the gate electrode (16) and the source/drain electrodes (14 and 15) can be made of any conductive substance, the substance can be preferably selected from the group consisting of gold (Au) , silver (Ag) , aluminum (Al) , nickel (Ni) , chromium (Cr) and indium tin oxide (ITO) .

Between the source and drain electrodes (14 and 15) and the channel material layer (13) , the surface may be treated by coating with HMDS (1, 1, 1, 3 , 3 , 3-hexamethyldisilazane) , OTS

(octyltrichlorosilane) or OTDS (octadecyltrichlorosilane) , or untreated.

The channel material layer employing the organic semiconductor compound according to the present invention may be coated via a coating process conventionally known in the art, including vacuum vapor-deposition, screen printing, printing process, spin casting process, spin coating process, dipping process or ink-jet process, to form a thin film. Vapor-deposition of the channel material layer can be carried out by using a hot solution at a temperature of 40^°C or higher, to make the thickness of about 500 A.

Examples Now the present invention is illustrated in more detail by referring to specific examples. However, the present invention is not restricted by those examples, and it is apparent to a person having ordinary skill in the art that various alterations and modifications can be made within the spirit and scope of the present invention.

[Preparation Example 1] Preparation of 4- bromoalkylbenzene (Compound 2)

R= -C₅H₁₁ 1a(48%) R'= -C₆H₁₃ 2a(45%)

-C₉H₁₉ 1 b(65%) -C₁₀H₂₁ 2b(59%)

Preparation of Compound (1) [4-bromoalkanoylbenzene] To a mixture of bromobenzene (77 g, 0.49 mol) and AlCl₃ (39.7 g, 0.294 mol), alkanoyl chloride (46.7 g, 0.245 mol) was slowly added dropwise, and the resultant mixture was stirred at 50 ^°C for 1 hour. The reaction temperature was then lowered to room temperature, and cold water was added to the reaction mixture. After extraction with CH₂Cl₂, the organic layer was washed with 2M HCl and water, and dried over anhydrous MgSO₄. After filtering MgSO₄ off by using a filter paper. The filtrate was evaporated by using a rotary evaporator to remove the solvent. Recrystallization from EtOH gave white solid.

4-Bromohexanoylbenzene (Ia) : ¹H NMR (CDCl₃, 300 MHz) : δ 7.81-7.86 ppm (d, 2H, J=8.61 Hz), 7.58-7.55 ppm (d, 2H, J^"=8.80 Hz), 2.93-2.88 ppm (t, 2H, J^"=7.36 Hz), 1.76-1.66 ppm (m, 2H), 1.36-1.34 ppm (m, 4H), 0.92-0.88 ppm (t, 3H, J=6.81 Hz)

4-Bromodecanoylbenzene (Ib) : ¹H NMR (CDCl₃, 300 MHz) : δ 7.84-7.81 ppm (d, 2H, J-=8.42 Hz), 7.61-7.58 ppm (d, 2H, J=8.37 Hz), 2.95-2.90 ppm (t, 2H, J=7.38 Hz), 1.77-1.68 ppm (m, 2H), 1.28 ppm (m, 12H), 0.91-0.86 ppm (t, 3H, J^"=6.55 Hz)

Preparation of Compound (2) [4-bromoalkylbenzene]

Compound (1) (159 g, 0.51 mol) , hydrazine hydrate (70 mL) and KOH (114.46 g, 2.04 mol) were dissolved in triethylene glycol (700 mL) , and the solution was heated under reflux for 2 hours . The reaction temperature was lowered to room temperature, and water and HCl were added to the reaction mixture. After extraction with CH₂Cl₂, the organic layer was washed with water and dried over anhydrous MgSO₄. After filtering off MgSO₄ by using a filter paper, the filtrate was evaporated by using a rotary evaporator to remove the solvent. Purification by column chromatography (eluent: n-hexane) gave colorless liquid.

4-Bromohexylbenzene (2a): ¹H NMR (CDCl₃, 300 MHz): δ 7.45- 7.42 (d, 2H, J=8.33 Hz), 7.11-7.08 ppm (d, 2H, J=8.32 Hz), 2.63-2.58 ppm (t, 2H, J=I.69 Hz), 1.67-1.62 ppm (m, 2H), 1.40- 1.35 ppm (m, 6H), 0.97-0.93 ppm (t, 3H, <J=6.60 Hz)

4-Bromodecylbenzene (2b): ¹H NMR (CDCl₃, 300 MHz): δ 7.43- 7.40 ppm (d, 2H, J=8.18 Hz), 7.09-7.06 ppm (d, 2H, J=8.21 Hz), 2.61-2.56 ppm (t, 2H, J=6.8 Hz), 1.64-1.58 ppm (m, 2H), 1.3 ppm (m, 21H), 0.94-0.90 ppm (t, 3H, J=6.57 Hz)

[Preparation Example 2] Preparation of 1- bromodecyloxybenzene (Compound 3)

3

To a solution of 4-bromophenol (5 g, 28.9 mmol) in ethanol, added were bromodecane (7.06 g, 6.6 mL, 31.79 mmol), NaI (0.3 g, 2.02 mmol) and KOH (1.78 g, 31.79 mmol). The resultant mixture was heated under reflux for 22 hours. The reaction temperature was lowered to room temperature, and the solvent was completely removed by using a rotary evaporator. Water was added to the reaction mixture, and the mixture was extracted with EtOAc. The organic layer was washed with water and dried over anhydrous MgSO₄. After filtering off MgSO₄ by using a filter paper, the filtrate was evaporated by means of a rotary evaporator to remove the solvent. Purification by column chromatography (eluent: n-hexane) gave colorless liquid.

¹H NMR (CDCl₃, 300 MHz): δ 7.4-7.37 ppm (d, 2H, J=8.81 Hz), 6.81-6.78 ppm (d, 2H, J=8.84 Hz), 3.95-3.91 ppm (t, 2H, J=6.55 Hz) , 1.82-1.77 ppm (m, 2H) , 1.31 ppm (m, 14H) , 0.94-0.90 ppm (t, 3H, J=6.52 Hz)

[Preparation Example 3] Preparation of l-ethynyl-4- alkylbenzene (Compound 5)

R= -C₆H₁₃ 4a(78%) R= -C₆H₁₃ 5a(42%)

-C₁₀H₂₁ 4b(88%) -C₁₀H₂₁ 5b(70%)

-OC₁₀H₂₁ 4c(50%) -OC₁₀H₂₁ 5c(67%)

Preparation of Compound A [ (2- (4- alkylphenyl) ethynyl) trimethylsilane

Compound (2) or (3) (10 g, 33.41 mmol) obtained from Preparation Example 2 or Preparation Example 3 was added to dry triethylamine (50 mL) , and trimethylsilyl-acetylene (4.6 mL, 33.41 mmol), Pd(dppf)Cl₂ (0.54 g, 0.66 mmol) and CuI (0.38 g, 2.00 mmol) were added thereto. After heating the mixture under reflux for 16 hours, the reaction temperature was lowered to room temperature, and volatile substances were removed by using a rotary evaporator. Purification by column chromatography (eluent: n-hexane) gave colorless liquid.

2- (4-Hexylphenyl) ethynyl) trimethylsilane (4a) ¹H NMR

(CDCl₃, 300 MHz): δ 7.51-7.48 ppm (d, 2H, J=8.18 Hz), 7.20-7.18 ppm (d, 2H, J=8.14 Hz), 2.70-2.65 ppm (t, 2H, J=7.69 Hz),

1.69-1.66 ppm (m, 2H), 1.14 ppm (m, 6H), 1.01-0.99 ppm (t, 3H,

J=6.77 Hz), 0.38 ppm (s, 9H) (2- (4-Decylphenyl) ethynyl) trimethylsilane (4b) ¹H NMR

(CDCl₃, 300 MHz): δ 7.52-7.47 ppm (dd, 2H, J=8.17 Hz, J=8.53

Hz), 7.21-7.12 ppm (dd, 2H, J=7.98 Hz, J=8.20 Hz), 2.72-2.62 ppm (m, 2H), 1.69 ppm (m, 2H), 1.9 ppm (s, 9H), 1.27-1.22 ppm

(m, 14H), 1.04-0.99 ppm (t, 3H, J=6.53)

2- (4 -Decyloxyphenyl) ethynyl) trimethylsilane (4c) ¹H NMR (CDCl₃, 300 MHz): δ 7.43-7.40 ppm (d, 2H, J=8.84 Hz), 6.84-6.81 ppm (d, 2H, J=8.86 Hz), 3.98-3.94 ppm (t, 2H, J=6.58 Hz), 1.81-1.74 ppm (m, 2H), 1.30 ppm (m, 14H), 0.93-0.89 ppm (t, 3H, J=6.70 Hz), 0.26 ppm (s, 9H)

Preparation of Compound (5) [l-ethynyl-4-alkylbenzene]

Compound (4) (9.3 g, 29.56 mmol) obtained as above was added to THF (70 mL) , and IM t-Bu₄NF solution in THF (10 mL, 10.05 mmol) was slowly added thereto at ambient temperature. After stirring for 2 hours, the solvent was removed by using a rotary evaporator. Purification by column chromatography (eluent: n-hexane) gave colorless liquid.

1-Ethynyl-4 -hexylbenzene (5a) ¹H NMR (CDCl₃, 300 MHz) : δ 7.47-7.44 ppm (d, 2H, J=8.11 Hz), 7.19-7.16 ppm (d, 2H, J=8.02 Hz), 3.07 ppm (s, IH), 2.67-2.62 ppm (t, 2H, J=7.68 Hz), 1.66- 1.57 ppm (m, 2H), 1.34 ppm (m, 6H), 0.96-0.91 ppm (t, 3H, J=6.34 Hz) l-Decyl-4-ethynylbenzene (5b) ¹H NMR (CDCl₃, 300 MHz) : δ 7.47-7.45 ppm (d, 2H, J=7.89 Hz), 7.19-7.17 ppm (d, 2H, J=7.91 Hz), 3.08 ppm (s, IH), 2.68-2.63 ppra (t, 2H, J=7.70 Hz), 1.69- 1.63 ppm (m, 2H), 1.35 ppm (m, 14H), 0.97-0.93 ppm (t, 3H, J=6.47 Hz)

1- (Decyloxy) -4-ethynylbenzene (5c) ¹H NMR (CDCl₃, 300 MHz): δ 7.47-7.44 ppm (d, 2H, J=8.79 Hz), 6.87-6.84 ppm (d, 2H, J=8.81 Hz), 3.99-3.95 ppm (t, 2H, J=6.55 Hz), 1.81 ppm (m, 2H), 1.32 ppm (m, 14H), 0.94-0.91 ppm (t, 3H, J=6.95 Hz)

[Preparation Example 4] Preparation of 2,6- dibromoanthracene (Compound 7)

t-Butylπitrite CuBr₂, acetonitrile

Preparation of Compound (6) [2 , 6-dibromoanthraquinone] In acetonitrile (150 ml) , dissolved were t-butylnitrite (30.3 g, 0.294 mol) and CuBr₂ (50.25 g, 0.225 mol) , and the solution was heated to 65^°C. 2 , 6-diaminoanthraquinone (20 g, 0.084 mol) was slowly added, and the reaction was continued for 1 hour. The reaction solution was poured into 6N HCl, and the resultant mixture was stirred for 1 hour. The solid was filtered, and washed with HCl, water and EtOH. The filtered compound was recrystallized from 1,4-dioxane to obtain 13.09 g (42.6%) of brown solid.

¹H NMR (300 MHz, CDCl₃, ppm): 8.45 (s, 2H), 8.20 (d, 2H), 7 . 98 ( d, 2H)

Preparation of Compound (7) [2, 6-dibromoanthracene] Compound (6) (2 , 6-dibromoanthraquinone) (15 g, 40.98 mmol) obtained as above, 600 ml of glacial acetic acid, 105 ml of HI and 60 ml of H₃PO₂ were charged in a reactor, and the mixture was heated under reflux at 150^°C for 4 days. After washing with water and ethanol, the mixture was extracted with toluene by means of a Soxhlet device to obtain yellowish green solid (6.9 g, 50%) .

¹H NMR (300 MHz, CDCl₃, ppm) : 8.31 (s, 2H), 8.18 (s, 2H), 7.90 (d, 2H) , 7.56 (d, 2H)

[Preparation Example 5] Preparation of 2,6- dibromoanthraquinone (Compound 8)

To a 100 mL 2 -necked flask, charged were t-BuONO (1.95 g, 18.88 mmol), CH₃CN (300 mL) and CuBr₂ (4.22 g, 18.88 mmol), and the mixture was heated to 65 ^°C . To the mixture, 2,6- diaminoanthraquinone (20 g, 83.9 mmol) was added dropwise in 4 portions. After 6 hours, the reaction was quenched by adding 20% HCl solution, and the solid produced was filtered, and recrystallized from 1,4-dioxane. Yield: 24 g (80%) m.p. : 194 ^°C

¹H-NMR ( 300 MHz , CDCl₃ , ppm) : 8.46 (d, IH), 8.20 (d, IH), 7 . 97 (m , 2H)

[Preparation Example 6] Preparation of 2 , 6-dibromo-9 , 10- bis (triisopropylsilyl) acetyl anthracene (Compound 9)

In a 100 mL 3-necked flask, triisopropyl acetylene (1.8 g, 9.87 mmol) was dissolved in dry THF (10 mL) . Isopropyl magnesium chloride (4.9 mL, 19.74 mmol) was added thereto, and the mixture was stirred at 60 ^°C for 15 minutes. After cooling to ambient temperature, a solution of 2 , 6-dibromoanthraquinone (8) (0.59 g, 1.62 mmol) obtained from Preparation Example 5 dissolved in dry THF (10 mL) was slowly added dropwise. The resultant mixture was stirred at 60^°C for 30 minutes, and cooled to ambient temperature. A saturated solution of SnCl₂ in 10% HCl (200 mL) was added, and the mixture was stirred at

60^°C for 15 minutes. After extraction with MC, the organic layer was dried over MgSO₄, and the solvent was removed by using a rotary evaporator. The product was isolated by means of column chromatography (eluent: hexane) . Yield: 0.46 g (41%) m.p. : 168 ^°C

¹H NMR (300 MHz, CDCl₃, ppm) : 8.94 (d, IH), 8.82 (d, IH), 7.69 (m, IH), 1.38-1.23 (m, 21H)

[Preparation Example 7] Preparation of 2 , 2 ' -bithiophene (Compound 10)

To a 500 mL 3 -necked round bottomed flask, charged was 9.7 g of magnesium, and the flask was dried. Ether (5 mL) was added thereto, and the flask was slightly heated. To the flask, 2-bromothiophene (60 g) and ether (300 mL) were slowly added dropwise. The Grignard reagent was slowly added dropwise to a mixed solution of 2-bromothiophene, Ni(dppp)Cl₂ and ether (50 mL) . After 20 hours, the mixture was stirred with 2N-HC1 for 2 hours. The mixture was extracted with ether, dried over MgSO₄, and evaporated by using a rotary evaporator to remove the solvent. The product was isolated from vacuum distillation.

Yield: 44 g (88%) m.p. : 32-33^°C

¹H NMR (300 MHz, CDCl₃, ppm) : 7.12-7.24 (dd, 4H), 7.04 (t, 2H)

[Preparation Example 8] Preparation of 2- ( [2,2' ]bithiophenyl-5-yl) -4,4,5, 5-tetramethyl-l, 3 , 2- dioxaborolane (Compound 11)

To a 500 mL 3 -necked round bottomed flask, charged were

THF (300 mL) and 2-bromo-5- ( thiophen-2-yl) thiophene (30 g, 0.12 mol) , and the mixture was chilled to -78^°C by using liquefied nitrogen. Then, n-BuLi (36.03 g, 0.13 mol) was slowly added dropwise thereto. After stirring at ambient temperature for 1 hour, 2-isopropoxy-4 , 4 , 5, 5-tetramethyl- [1, 3 , 2] -dioxaborolane (22.3 g) was slowly added dropwise at -

78^°C to the mixture. After 12 hours, water was poured thereto, to quench the reaction. The reaction mixture was extracted with ether, dried over MgSO₄ and evaporated by using a rotary evaporator to remove the solvent. The product was isolated via column chromatography (eluent: hexane/EA = 10/1) . Yield: 18 g (52%)

¹H NMR (300 MHz, CDCl₃, ppm) : 7.18 (d, IH), 7.02 (m, 4H), 1.31 (m, 12H)

[Preparation Example 9] Preparation of 2-anthracene-2-yl- 4, 4, 5, 5-tetramethyl-l, 3, 2-dioxaborolane (Compound 12)

To a 500 mL 3 -necked round bottomed flask, charged were THF (300 mL) and 2-bromoanthracene (10 g, 38.9 mmol) , and the mixture was chilled to -78^°C by using liquefied nitrogen. Then, n-BuLi (11.86 g, 42.8 mmol) was slowly added dropwise thereto. After stirring at ambient temperature for 1 hour, 2- isopropoxy-4 , 4 , 5, 5-tetramethyl- [1, 3 , 2] -dioxaborolane (7.96 g) was slowly added dropwise at -78^°C to the mixture. After 12 hours, water is poured thereto, to quench the reaction. The reaction mixture was extracted with ether, dried over MgSO₄ and evaporated by using a rotary evaporator to remove the solvent. The product was isolated via column chromatography (eluent: hexane/EA = 5/1) .

Yield: 3.42 g (29%) m.p. : 71^°C ¹H NMR ( 300 MHz , CDCl₃ , ppm) : 8 . 32 ( s , 2H) , 7 . 91 ( d , 4H) , 7 . 32 (m , 3H ) , 1 . 29 (m , 12H)

[Preparation Example 10] Preparation of 2-naphthalene-2- yl-4 , 4 , 5 , 5-tetramethyl-l, 3 , 2-dioxaborolane (Compound 13)

To a 500 mL 3 -necked round bottomed flask, charged were THF (300 mL) and 2-bromonaphthalene (10 g, 48.3 mmol) , and the mixture was chilled to -78^°C by using liquefied nitrogen. Then, n-BuLi (14.73 g, 53.1 mmol) was slowly added dropwise thereto. After stirring at ambient temperature for 1 hour, 2- isopropoxy-4, 4, 5, 5-tetramethyl- [1, 3, 2] -dioxaborolane (9.87 g) was slowly added dropwise at -78^°C to the mixture. After 12 hours, water is poured thereto, to quench the reaction. The reaction mixture was extracted with ether, dried over MgSO₄ and evaporated by using a rotary evaporator to remove the solvent. The product was isolated via column chromatography (eluent: hexane/EA = 5/1) .

Yield: 4.05 g (41%) m.p. : 93 ^°C

¹H NMR (300 MHz, CDCl₃, ppm): 7.81 (d, 4H), 7.29 (t, 3H), 1 . 26 (m , 12H)

[Preparation Example 11] Preparation of 2 , 6 - dibromo- 9 , 10 - dihydroanthracene ( Compound 15 )

Preparation of 2 , 6-dibromoanthracene-9 , 10-dione (Compound ill

In acetonitrile (150 ml) , dissolved were t-butylnitrite (30.3 g, 0.294 mol) and CuBr₂ (50.25 g, 0.225 mol) , and the solution was heated to 65^°C . To the solution, added was 2,6- diaminoanthracene- 9, 10-dione (20 g, 0.084 mol), and the resultant mixture was reacted for 1 hour. The reaction solution was then poured to 6N HCl, and the mixture was stirred for 1 hour. The solid was filtered, and washed with HCl, water and EtOH. The filtered compound was recrystallized from 1,4-dioxane to obtain the desired compound, 2,6- dibromoanthracene- 9 , 10-dione (Compound 14) (13.09 g, yield: 42.6%) .

Preparation of 2 , 6-dibromo-9 , 10-dihydroanthracene

(Compound 15)

Compound (14) (2 , 6-dibromoanthracene-9 , 10-dione) (15 g, 40.98 mmol) , 600 ml of glacial acetic acid, 105 ml of HI and 60 ml of H₃PO₂ were charged in a reactor, and the mixture was

heated under reflux at 150 ^°C for 4 days. After washing with water and ethanol, the mixture was extracted with toluene by means of a Soxhlet device to obtain the desired compound, 2,6- dibromo-9, 10-dihydroanthracene (Compound 15) (6.9 g, yield: 50%) .

[Preparation Example 12] Preparation of 2-bromo-5- (5- bromothiophen-2-yl) thiophene (Compound 16)

16 In dimethyl formamide, dissolved was 2- (thiophen-2- yl) thiophene (30 g, 0.18 mol) . Then, with the light shielded, N-bromosuccinimide (70.7 g, 0.4 mol) was diluted with dimethyl formamide, and the dilution was slowly added dropwise to the solution at 0 ^°C After 12 hours, the reaction was quenched, extracted with methylene chloride, and dried over magnesium sulfate. The solvent was removed, and the residue was purified via chromatography to obtain the desired compound, 2-bromo-5- (5-bromothiophen-2 -yl) thiophene (Compound 16) (29.8 g, yield: 51%) .

[Preparation Example 13] Preparation of 6- methoxynaphthalen-2-yl-2-boronic acid (Compound 18)

17 18

Preparation of 2-bromo-6-methoxynaphthalene (Compound 17) In ethanol (300 mL) , dissolved were 6-bromonaphthalen-2- ol (30 g, 0.135 mol) , iodomethane (20.58 g, 0.145 mol) , KOH

(8.25 g, 0.147 mol) and NaI (1.35 g, 0.009 mol), and the mixture was heated under reflux for 24 hours. After removing ethanol by using a rotary evaporator, water was poured to the residue to quench the reaction. Extraction with ethyl acetate and purification via column chromatography (eluent: hexane) gave the desired compound, 2-bromo-6-methoxynaphthalene

(Compound 17) (3O g, yield: 94%) .

Preparation of 6-methoxynaphthalen-2-yl-2-boronic acid

(Compound 18)

In THF (250 mL) , dissolved were 2-bromo-6- methoxynaphthalene (Compound 17) (15.41 g, 0.065 mol) and Mg

(1.74 g, 0.072 mol), and the Grignard reagent was reacted for 1 hour. The temperature was lowered to -78 ^°C by adding liquefied nitrogen to the surroundings. Triethyl borate was then injected to the mixture by using a syringe, and the reaction was continued for about 10 hours. After quenching the reaction by adding 2N HCl, the precipitate was filtered, recrystallized from THF, to obtain the desired compound, 6- methoxynaphthalen-2-yl-2-boronic acid (Compound 18) (8 g, yield : 31% ) .

[Preparation Example 14] Preparation of 6- (hexyloxy)naphthalen-2-yl-2-boronic acid (Compound 20)

19 20

Preparation of 2 -bromo- 6 - (hexyloxy) naphthalene (Compound

In ethanol (300 mL) , dissolved were 6-bromonaphthalen-2- ol (30 g, 0.135 mol) , bromohexane (24 g, 0.145 mol) , KOH (8.25 g, 0.147 mol) and NaI (1.35 g, 0.009 mol), and the mixture was heated under reflux for 24 hours. After removing ethanol by using a rotary evaporator, water was poured to the reaction mixture to quench the reaction. Extraction with ethyl acetate and purification via column chromatography (eluent: hexane) gave the desired compound, 2-bromo- 6- (hexyloxy) naphthalene (Compound 19) (32.98 g, yield: 79.8%).

Preparation of 6- (hexyloxy) naphthalen-2-yl-2-boronic acid (Compound 20)

In THF (250 mL) , dissolved were 2 -bromo- 6- (hexyloxy) naphthalene (Compound 19) (20 g, 0.065 mol) and Mg (1.74 g, 0.072 mol), and the Grignard reagent was reacted for 1 hour. The temperature was lowered to -78 °C by adding liquefied nitrogen to the surroundings. Triethyl borate was then injected to the mixture by using a syringe, and the reaction was continued for about 10 hours. After quenching the reaction by adding 2N HCl, the precipitate was filtered and recrystallized from THF to obtain the desired compound, 6- (hexyloxy) naphthalen-2-yl-2-boronic acid (Compound 20) (9 g, yield: 50.8%) .

[Preparation Example 15] Preparation of 6- (decyloxy) naphthalen-2-yl-2-boronic acid (Compound 22)

21 22

Preparation of 2 -bromo- 6 - (decyloxy) naphthalene (Compound 21)

In ethanol (300 mL) , dissolved were 6-bromonaphthalen-2- ol (30 g, 0.135 mol) , 1-bromodecane (32.07 g, 0.145 mol) , KOH

(8.25 g, 0.147 mol) and NaI (1.35 g, 0.009 mol), and the mixture was heated under reflux for 24 hours . After removing ethanol by using a rotary evaporator, water was poured to the reaction mixture to quench the reaction. Extraction with ethyl acetate and purification via column chromatography (eluent: hexane) gave the desired compound, 2-bromo-6-

(decyloxy) naphthalene (Compound 21) (32 g, yield: 65%).

Preparation of 6- (decyloxy) naphthalen-2-yl-2-boronic acid (Compound 22) In THF (250 mL) , dissolved were 2-bromo-6- (decyloxy) naphthalene (Compound 21) (23.61 g, 0.065 mol) and Mg (1.74 g, 0.072 mol), and the Grignard reagent was reacted for 1 hour. The temperature was lowered to -78 ^°C by adding liquefied nitrogen to the surroundings. Triethyl borate was then injected to the mixture by using a syringe, and the reaction was continued for about 10 hours. After quenching the reaction by adding 2N HCl, the precipitate was filtered and recrystallized from THF to obtain the desired compound, 6- (hexyloxy) naphthalen-2-yl-2-boronic acid (Compound 22) (7.5 g, yield: 36%) .

[Example 1] Preparation of Compound (101)

Compound (7) (3 g, 9 mmol) obtained from Preparation Example 4, phenylacetylene (0.312 g, 2 mmol), CuI(I) (1.151 g, 2 mmol) and Pd(pph₃)₂Cl₂ (6 mol%) were added to dry toluene (30 mL) and dry triethylamine (30 mL) , and the mixture was heated under reflux for 18 hours. The reaction temperature was lowered to room temperature, and the volatile substances were removed by using a rotary evaporator. After washing with dichloromethane, the solid was extracted with toluene by using a Soxhlet device to obtain yellowish green solid (2.41 g, 71.3%) .

MS m/z (%) : 378 (M+)

[Examples 2 to 4] Preparation of Compounds (102, 103 and

104)

Compound (7) (1 g, 2.98 mmol) obtained from Example 4 was added to dry i-Pr₂NH (15 mL) and dry toluene (15 mL) . To the mixture, added were Compound (5) (5.96 mmol) obtained from Preparation Example 3, Pd(dppf)Cl₂ (6 mol%) and CuI (34 mg, 0.18 mmol), and the resultant mixture was heated under reflux for 16 hours. The reaction temperature was lowered to room temperature, and the precipitate was filtered. The precipitate was washed with toluene, and purified with toluene by using a Soxhlet device .

Compound (102) : Light yellow solid, ¹H NMR (CDCl₃, 300 MHz): δ 8.37 ppm (s, 2H), 8.21 ppm (s, 2H), 7.99-7.97 ppm (d, 2H, J=8.64 Hz), 7.57-7.52 ppm (m, 6H), 7.28-7.20 ppm (d, 4H, J=7.44 Hz), 2.68-2.63 ppm (t, 4H, J=7.13 Hz), 1.65 ppm (m, 4H), 1.34 ppm (m, 12H), 0.91 ppm (m, 6H)

Compound (103) : Light yellowish green, ¹H NMR (CDCl₃, 300 MHz): δ 8.36 ppm (s, 2H), 8.21 ppm (s, 2H), 7.99-7.96 ppm (d, 2H, J=8.81 Hz), 7.58-7.52 ppm (m, 6H), 7.23-7.20 ppm (d, 4H, J=8.16 Hz), 2.68-2.63 ppm (t, 4H, J=7.68 Hz), 1.68-1.61 ppm (m, 4H), 1.34-1.30 ppm (m, 28H), 0.93-0.89 ppm (t, 6H, J=6.71 Hz)

Compound (104) : Light yellowish green, EI, MS m/z (%) : 691 (M+)

[Example 5] Preparation of 2 , 6-di (bithiophenyl) -9, 10- bis ( triisopropyl silyl) acetyl anthracene (Compound 105)

Pd(pph₃)₄, 2M-K₂CO₃ .

9 ¹⁰⁵

To a 100 mL 2-necked round bottomed flask, charged were 2 , 6-dibromo-9 , 10-bis (triisopropyl silyl) acetyl anthracene (Compound 9) (1 g, 1.43 mmol) obtained from Preparation Example 6, and 2- ( [2 , 2 ' ] bithiophenyl-5 -yl) -4 , 4 , 5 , 5- tetramethyl-1, 3, 2-dioxaborolane (Compound 11) (1.04 g, 3.57 mmol) obtained from Preparation Example 8, THF (5 mL) , toluene (30 mL) and 2M-K₂CO₃ (50 mL) , and the mixture was bubbled with nitrogen. Under nitrogen atmosphere, added was Pd(PPh₃)₄ (0.1 g) as a catalyst, and the reaction was continued at 90^°Cfor 24 hours. Then the reaction was quenched by pouring 2N-HC1, and the solid produced was filtered, extracted with methanol and toluene by using a soxlet device, and recrystallized from CHCl₃.

Yield: 1.23 g (83%) mp : 289 ^°C

¹H NMR (300 MHz, CDCl₃, ppm) : 8.85 (s, IH), 8.63 (d, IH), 7.92 (d, IH), 7.47 (d, IH), 7.29-7.26 (m, 2H), 7.10 (m, IH), 1.41-1.28 (m, 21H)

[Example 6] Preparation of 2 , 6-di (2-naphthyl) -9, 10- bis (triisopropyl silyl) acetyl anthracene (Compound 106)

9 106

To a 100 mL 2-necked round bottomed flask, charged were 2 , 6-dibromo-9, 10-bis (triisopropyl silyl) acetyl anthracene (Compound 9) (1 g, 1.43 mmol) obtained from Preparation Example 6, and 2 -naphthalene-2 -yl-4 , 4 , 5 , 5-tetramethyl-l, 3 , 2- dioxaborolane (Compound 13) (0.90 g, 3.57 tnmol) obtained from Preparation Example 10, THF (5 mL) , toluene (30 mL) and 2M- K₂CO₃ (50 mL) , and the mixture was bubbled with nitrogen. Under nitrogen atmosphere, added was Pd(PPh₃)₄ (0.1 g) as a catalyst, and the reaction was continued at 90^°Cfor 24 hours. Then the reaction mixture was poured to 2N-HC1 to quench the reaction, and the solid produced was filtered, extracted with methanol and toluene by using a soxlet device, and recrystallized from CHCl₃.

Yield: 0.97 g (86%)

¹H NMR (300 MHz, CDCl₃, ppm) : 8.93 (s, IH), 8.67 (d, IH), 8.21 (d, IH), 7.81-7.98 (m, 5H), 7.41-7.50 (m, 2H), 1.38-1.10 (m, 21H)

[Example 7] Preparation of 2, 6-di (2-anthracenyl) -9, 10- bis ( triisopropyl silyl) acetyl anthracene (Compound 107)

9 ¹⁰⁷

To a 100 mL 2 -necked round bottomed flask, charged were 2 , 6-dibromo-9 , 10-bis (triisopropyl silyl) acetyl anthracene (Compound 9) (1 g, 1.43 tnmol) obtained from Preparation Example 6, and 2 -naphthalene-2 -yl-4 , 4 , 5 , 5-tetramethyl-l, 3 , 2- dioxaborolane (Compound 12) (1.08 g, 3.57 mmol) obtained from Preparation Example 9, THF (5 mL) , toluene (30 mL) and 2M-K₂CO₃

(50 mL) , and the mixture was bubbled with nitrogen. Under nitrogen atmosphere, added was Pd(PPh₃) ₄ (0.1 g) as a catalyst, and the reaction was continued at 90^°Cfor 24 hours. Then the reaction mixture was poured to 2N-HC1 to quench the reaction, and the solid produced was filtered, extracted with methanol and toluene by using a Soxlet device, and recrystallized from CHCl₃.

Yield: 1.01 g (80%)

¹H-NMR (300 MHz, CDCl₃, ppm) : 9.14 (s, IH), 8.92 (s, IH), 8.81 (d, IH), 8.58-8.45 (m, 3H), 8.19-8.06 (m, 4H), 7.67-7.50

(m, 2H), 1.36-1.27 (m, 21H)

[Example 8] Preparation of 2 , 6-distyryl-9, 10- bis [ (triisopropylsilanyl) ethynyl] anthracene (Compound 108)

Heck reaction

108

To a 100 mL 2 -necked round bottomed flask, charged were 2, 6-dibromo-9, 10-bis ( triisopropyl silyl) acetyl anthracene (Compound 9) (4 g, 5.72 mmol) obtained from Preparation Example 6, styrene (3.5 g, 35.7 mmol), THF (20 mL) , triethylamine (40 mL) , tri-o-tolylphospine (0.08 g) , Pd(OAc)₂ (0.16 g) , and the mixture was stirred. Reaction was continued at 70^°Cfor 6 hours, and then quenched by pouring the mixture to 2N-HC1. The reaction mixture was extracted with dichloromethane, dried over MgSO₄ and evaporated by using a rotary evaporator to remove the solvent . The product was isolated via column chromatography (eluent: hexane/MC = 10/1) .

Yield: 3.1 g (73%)

¹H NMR (300 MHz, CDCl₃, ppm) : 8.69 (s, IH), 8.60 (d, IH), 7.85 (d, IH), 7.60 (d, 2H), 7.43 (t, 2H), 7.34 (t, 3H), 1.34- 1.28 (m, 21H)

[Example 9] Preparation of 2 , 6-bis-phenylethynyl-9, 10- bis [ ( triisopropylsilanyl) ethynyl] anthracene (Compound 109)

Sonogashira reaction

109

To a 100 mL 2-necked round bottomed flask, charged were 2 , 6-dibromo-9, 10-bis (triisopropyl silyl) acetyl anthracene (Compound 9) (4 g, 5.72 tnmol) obtained from Preparation Example 6, phenylacetylene (4.6 g, 45.7 mmol) , toluene (20 mL) , triethylamine (40 mL) , coppor iodide (0.2 g) and Pd(pph₃)₂Cl₂ (0.24 g) , and the mixture was stirred. Reaction was continued at 100 ^°C for 24 hours, and then quenched by pouring the mixture to 2N-HC1. The reaction mixture was extracted with chloroform, dried over MgSO₄ and evaporated by using a rotary evaporator to remove the solvent. The product was isolated via column chromatography (eluent: hexane/MC = 8/1).

Yield: 2.8 g (66%)

¹H NMR (300 MHz, CDCl₃, ppm) : 8.88 (s, IH), 8.59 (d, IH), 7.71 (d, IH), 7.61 (d, 2H), 7.40 (t, 3H), 1.36-1.27 (m, 21H)

[Example 10] Preparation of Compound (110)

18

To 100 mL of THF and 2M aqueous solution of K₂CO₃, added were 2 , 6-dibromo-9, 10-dihydroanthracene (Compound 15) (5 g, 0.015 mol) obtained from Preparation Example 11 and 6- methoxynaphthalen-2-yl-2-boronic acid (Compound 18) (14.9 g, 0.033 mol) obtained from Preparation Example 13, and the mixture was stirred under nitrogen atmosphere for 30 minutes. After adding tetrakis (triphenylphosphine-palladium) (0.5 g, 0.4 mmol) , the resultant mixture was stirred at 85-95 ^°C for about 24 hours . Then the reaction was quenched by pouring the mixture to 2N-HC1. The precipitate produced was filtered, and extracted with toluene by using a Soxhlet device. Recrystallization from chlorobenzene gave the desired compound

(110) (yield: 40%) .

FT-IR (KBr, cm^"1): 2955, 2889 (aliphatic C-H), 3008 cm^"1

(aromatic C=C) , 1240 cm^"1 (Ar-C-O)

[Example 11] Preparation of Compound (111)

18

Desired compound (111) was obtained according to the same procedure as described in Example 10, but using 2-bromo-5- (5- bromothiophen-2-yl) thiophene (Compound 16) (0.015 mol) obtained from Preparation Example 12, and 6-methoxynaphthalen- 2-yl-2-boronic acid (Compound 18) (0.033 mol) obtained from Preparation Example 13. Yield: 51%.

FT-IR (KBr, cm^"1): 2953, 2990 (aliphatic C-H), 3010 cm -1

(aromatic C=C) , 1241 cm^"1 (Ar-C-O)

[Example 12] Preparation of Compound (112)

20

Desired compound (112) was obtained according to the same procedure as described in Example 10, but using 2-bromo-5- (5- bromothiophen-2-yl) thiophene (Compound 16) (0.015 mol) obtained from Preparation Example 12, and 6- (hexyloxy) naphthalen-2-yl-2-boronic acid (Compound 20) 0.033 mol) obtained from Preparation Example 14. Yield: 45%.

FT-IR (KBr, cm^"1): 2953, 2920, 2880 (aliphatic C-H), 3010 cm^"1 (aromatic C=C) , 1235 cm^"1 (Ar-C-O)

[Example 13] Preparation of Compound (113!

Preparation of 6- (hexyloxy) naphthalene-2 -carbaldehyde (Compound 23 )

To a 250 mL 2-necked round bottomed flask, charged were 2 -bromo- 6- (hexyloxy) naphthalene (Compound 19) (5 g, 16.3 mmol) obtained from Preparation Example 14 and refined THF (75 mL) , and the temperature was lowered to -78 ^°C by using liquefied nitrogen under nitrogen atmosphere. To the mixture, n-BuLi (7.8 mL, 19.5 mmol) was slowly added dropwise, and the resultant mixture was stirred for 1 hour. After cooling the mixture to -40 ^°C by using liquefied nitrogen, 1- formylpiperidine (2.2 g, 19.5 mmol) was injected thereto, and the resultant mixture was stirred at ambient temperature. After 3 hours, the reaction was quenched by adding 20% NH₄Cl solution. The reaction mixture was extracted with ether, dried over MgSO₄, and evaporated by using a rotary evaporator to remove the solvent. Recrystallization from hexane gave the desired compound, 6- (hexyloxy) naphthalene-2 -carbaldehyde (Compound 23) (2.9 g, yield: 68.4%). Preparation of Compound (113)

To a 100 mL 2 -necked round bottomed flask, charged were phosphonium salt (2.05 g, 2.6 mmol) , NaH (0.62 g, 26 mmol) and toluene (50 mL) , and the mixture was stirred at 120^°C for 4 hours. After cooling it to ambient temperature, added was 6- (hexyloxy) naphthalene-2 -carbaldehyde (Compound 23) (2 g, 7.8 mmol), and the temperature was raised again to 120 ^°C After stirring for 12 hours, the reaction mixture was added to 2N- HCl (200 mL) to quench the reaction. The reaction mixture was then stirred for 1 hour, filtered, and washed with methylene chloride, H₂O and ethanol, to obtain the desired compound (113) . Yield: 0.8 g (52.8%)

FT-IR (KBr) (cm^"1) : 3051-3022 (aromatic, vinyl C-H) , 1617 (vinyl C=C) , 1595-1510 (aromatic C=C) , 1417 (CH₂) , 1361 (CH₃) ;

MS(EI) (m/z) : 582.0 (M+)

[Example 14] Preparation of Compound (114)

Preparation of 2 -bromo- 6 - (octyloxy) naphthalene (Compound 24 )

According to the same procedure for preparing Compound (19) as described in Preparation Example 14, but using S- bromonaphthalen-2-ol (0.135 raol) and 1-bromooctane (0.145 mol) , the desired compound, 2-bromo-6- (octyloxy) naphthalene (Compound 24) was obtained. Yield: 44.6%

Preparation of 6- (octyloxy) naphthalene-2-carbaldehyde (Compound 25 )

According to the same procedure for preparing Compound (23) as described in Example 13, but using 2 -bromo- 6- (octyloxy) naphthalene (Compound 24) (16.3 mmol) and 1- formylpiperidine (19.5 mmol), the desired compound, 6- (octyloxy) naphthalene-2 -carbaldehyde (Compound 25) was obtained. Yield: 75%

Preparation of Compound (114)

According to the same procedure as described in Example 13, but using 6- (octyloxy) naphthalene-2-carbaldehyde (Compound 25) (7 mmol) and the phosphonium salt (2.3 mmol), the desired compound (114) was obtained. Yield: 50%

FT-IR (KBr) (cm^"1) : 2923-2851 (aromatic, vinyl C-H) , 1602 (vinyl C=C) , 1474 (aromatic C=C) , 1383 (CH₂) , 1247 (CH₃) ; MS(EI) (m/z) : 638.0 (M⁺)

[Example 15] Preparation of Compound (115)

22

According to the same procedure as described in Example 10, but using 2 , 6-dibromo-9 , 10-dihydroanthracene (Compound 15) (0.015 mol) obtained from Preparation Example 11 and 6- (decyloxy) naphthalene-2 -yl-2 -boronic acid (Compound 22) (0.033 mol) obtained from Preparation Example 15, the desired compound (115) was obtained. Yield: 43%

FT-IR (KBr, cm^"1): 2958, 2930 (aliphatic C-H), 3118 cm^"1 (aromatic C=C), 1240 cm^"1 (Ar-C-O); MS (EI) (m/z) : 743.07 (M⁺)

[Example 16] Preparation of Compound (116)

22

According to the same procedure as described in Example

10, but using 2-bromo-5- (5-bromothiophen-2-yl) thiophene

(Compound 16) obtained from Preparation Example 12 and 6-

(decyloxy) naphthalene-2-yl-2-boronic acid (Compound 22) (0.033 mol) obtained from Preparation Example 15, the desired compound (116) was obtained. Yield: 49%

FT-IR (KBr, cm^"1): 2953, 2920, 2860 (aliphatic C-H)₇ 3010 cm^"1 (aromatic C=C) , 1237 cm^"1 (Ar-C-O)

[Example 17] Preparation of Compound (117]

Preparation of 6- (decyloxy) naphthalene-2 -carbaldehyde (Compound 26 )

According to the same procedure for preparing Compound

(23) as described in Example 13, but using 2-bromo-6-

(decyloxy) naphthalene (Compound 21) (16.3 mmol) obtained from

Preparation Example 15 and 1-formylpiperidine (19.5 mmol), the desired compound (26), 6- (decyloxy) naphthalene-2 -carbaldehyde was obtained. Yield: 73.4%

Preparation of Compound (117)

According to the same procedure as described in Example 13, but using 6- (decyloxy) naphthalene-2 -carbaldehyde (Compound 26) (7.9 mmol) and the phosphonium salt (2.6 mmol), the desired compound (117) was obtained. Yield: 50% FT-IR (KBr, cm^"1) : 2923-2851 (aromatic, vinyl C-H) , 1602 (vinyl C=C) , 1474 (aromatic C=C) , 1383 (CH₂) , 1247 (CH₃) ; MS (EI) (m/z) : 694.0 (M⁺)

[Example 18] Preparation of Compound (118]

Preparation Of 2-bromo-6- (dodecyloxy) naphthalene

(Compound 27)

According to the same procedure for preparing Compound (19) as described in Preparation Example 14, but using 6- bromonaphthalen-2-ol (0.135 mol) and 1-bromododecane (0.145 mol) , the desired compound (27) , 2-bromo-6- (dodecyloxy) naphthalene (Compound 27) was obtained. Yield: 41.3%

Preparation of 6- (dodecyloxy) naphthalene-2-carbaldehyde (Compound 28)

According to the same procedure for preparing Compound (23) as described in Example 13, but using 2-bromo-6- (dodecyloxy) naphthalene (Compound 27) (16.3 mmol) and 1- formylpiperidine (19.5 mtnol) , the desired compound (28), 6- (dodecyloxy) naphthalene-2-carbaldehyde (Compound 28) was obtained. Yield: 84.14%

Preparation of Compound (118)

According to the same procedure as described in Example 13, but using 6- (dodecyloxy) naphthalene-2-carbaldehyde (Compound 28) (7.8 mmol) and the phosphonium salt (2.6 mmol) , the desired compound (118) was obtained. Yield: 55.1%

FT-IR (KBr, cm^"1) : 2915-2851 (aromatic, vinyl C-H) , 1623- 1620 (vinyl C=C) , 1468 (aromatic C=C) , 1381 (CH₂) , 1247 (CH₃) ^■ MS (EI) (m/z) : 750.0 (M⁺)

[Example 19] Manufacturing an organic thin film transistor

On a cleansed glass substrate (11) , aluminum was vacuum deposited as a gate electrode (16) with a thickness of 65θA and then PVP as a gate insulator (12) was coated by spin coating with a thickness of 5500 A Gold (Au) as source-drain electrodes (14 and 15) was then vacuum deposited thereto with a thickeness of 450A The length of the channel was 30 μm, and the width 150 μm. Compound (101) obtained from Example 1 was vacuum deposited at 80^°Cof substrate temperature at a rate of 0.3 Asec with a thickness of 500 A to prepare an OTFT device of bottom-contact mode as shown in Fig. 1. By using the device, the current transmission property was measured, and the current transmission curves are shown in Fig. 2. The measured values of several physical properties of the device are listed in Table 1. Charge mobility was calculated from the current formula of the saturation region as shown below, by means of the current transmission curve. Thus, a graph is plotted with variables (I_SD)^1//2 and V_G from the current formula of the saturation region, and the charge mobility was obtained from the slope of the graph.

(I_SD)^1/2= (μC₀W/2L)^1/2(V_G-V_τ) slope = ( μC₀W/2L) ^1/2 μ_FET = ( slope) ² ( 2L/C₀W)

In the formulas, I_SD is source-drain current, μ or μ_FEτ is charge mobility, C₀ is electrostatic capacity of insulating film, W is channel width, L is channel length, V_G is gate voltage, and V_τ is threshold voltage.

Interrupting leakage current (I_Off) is the current flowing under off-state, that is obtained as minimum value under off- state from the current ratio. Subthreshold slope (SS) shows the extent of change in drain current versus change in gate voltage before reaching the threshold voltage. It is obtained as the amount of change in gate voltage required for 10 -fold increase of drain current. Threshold voltage (V_th) is minimum voltage required to drive an OTFT device, and obtained as the point of intersection of the slope of the linear portion of the I_D-V_G graph and the value under off-state.

[Example 20] Evaluation of thermal properties of organic semiconductor compounds

Thermal properties of organic semiconductor compounds prepared from Examples 1 to 4 (Compounds 101, 102, 103, 104) were examined by means of thermal gravity analysis (TGA) and differential scanning calorimeter (DSC) with heating them from 40^°C to 700^°Cat a rate of loVmin under nitrogen atmosphere. The results are shown in Figs. 3 and 4. For Compound (101), weight reduction was observed at 285 ^°C and 490 ^°Q this shows decomposition of the triple bond occurring at 285 °C and decomposition of the material occurring again at 490 ^°C In case of Compounds (102, 103 and 104), 5% of weight reduction was observed at 453 "Q 438°Cand 417^°C In case of Compound (101), phase transition occurred at 325 °C It is recognized that the phase transition occurred with decomposition of the triple bond. It is measured that Compound (102) has phase transition points at 152 "Q 178 ^°C and 218 ^°C It is indirectly recognized from the observation of several phase transition temperatures in DSC, that Compound (101) has liquid crystallinity . [Example 21] Evaluation of properties of organic thin film transistor

Hole mobility and on/off property of the organic thin film transistor manufactured according to Example 19 were evaluated. Features of the organic thin film transistor employing Compound (101) according to the present invention as channel material are shown in Fig. 2. The semiconductor property of Compound (101) was p-type. Several measured physical properties of the OTFT device employing the same are shown in Table 1.

[Comparative Example 1]

An OTFT device was manufactured according to the same procedure described in Example 19, but using pentacene, of which the chemical structure is shown below, as a substance for creating channel material. The current transmission property of the device was measured, and several measured physical properties are shown in Table 1.

[Table 1]

As can be seen from Table 1, the device of Example 19 employing Compound (101) according to the present invention exhibited higher charge mobility and current on/off ratio, and much lower interrupting leakage current, threshold voltage and subthreshold slope, as compared to the device of Comparative Example 1. Thus it is confirmed that the compounds according to the present invention provide excellent performance when being employed in an organic thin film transistor.

[Example 22] Manufacturing an organic thin film transistor by using an oligoanthracene derivative

On a cleansed glass substrate (11) , chromium was vapor- deposited by sputtering process as a gate electrode (16) with a thickness of IOOOA and then SiO₂ as a gate insulator (12) was vapor-deposited by CVD process with a thickness of 1000 A ITO as source-drain electrodes (14 and 15) was then vapor- deposited thereon by sputtering process with a thickness of 1200 A Before vapor-depositing the organic semiconductor material, the substrate was washed with isopropyl alcohol over 10 minutes. The sample was soaked in a solution of octadecyltrichlorosilane diluted in hexane to 10 mM of concentration over 30 seconds, washed with acetone, and dried. Then, the oligoanthracene derivative (Compound 105) obtained from Example 5 was dissolved and spin-coated thereto with a thickness of 7OθA to provide an OTFT device of bottom-contact mode .

Charge mobility was calculated from the current formula of the saturation region as shown below, by means of the current transmission curve. Thus, a graph is plotted with variables (I_SD)^1/2 and V_G from the current formula of the saturation region, and the charge mobility was obtained from the slope of the graph.

(I_SD)^1/2= (μC₀W/2L)^1/2(V_G-V_τ) slope = ( μC₀W/2L) ^1/2 μ_FET = ( slope) ² (2L/C₀W)

In the formulas, I_SD is source-drain current, μ or μ_FET is charge mobility, C₀ is electrostatic capacity of insulating film, W is channel width, L is channel length, V_G is gate voltage, and V_τ is threshold voltage.

Interrupting leakage current (I_Off) is the current flowing under off-state, that is obtained as minimum value under off- state from the current ratio.

When the oligoanthracene derivative according to the present invention is applied to an OTFT, high charge mobility of 2.3 x 10^"2 cm²/Vs was measured for the OTFT.

[Example 23] Manufacturing of organic thin film transistor

As the substrate (11) , n-type silicon was employed, and the substrate comprises the fuction of a gate electrode. On the upper part of the gate electrode, silicon dioxide (SiO₂) thermally expanded to 300 nm of thickness was employed as an insulator (capacitance per unit area Ci = 10 nF/cm²) . On this silicon dioxide, titanium (10 nm) and gold (80 nm) were vapor- deposited to form a source and a drain electrode. The gap between the source and drain had 25 μm to 500 μm of width (W) , and 5 μm to 50 μm of length (L) . The organic semiconductor compounds prepared from Example 12-14 and 16-18 (Compounds 112, 113, 114, 116, 117 and 118) were spin-cast to form channel material having 5OθA of thickness, and an organic thin film transistor of bottom-contact mode (as shown in Fig. 1) was manufactured therefrom.

[Example 24] Evaluation of thermal properties of organic semiconductor compounds Thermal properties of organic semiconductor compounds prepared from Example 12-14 and 16-18 (Compounds 112, 113, 114, 116, 117 and 118) were examined by means of thermal gravity analysis (TGA) and differential scanning calorimeter (DSC) with heating them from 40^°Cto 700^°Cat a rate of 10^°(7min under nitrogen atmosphere. The results are shown in Figs. 9 and 10.

As the results of thermal gravity analysis, the reduction of weight of the individual organic semiconductor compounds by 5 wt% was observed at above 380 ^°C As the results of differential scanning calorimeter, the glass transition temperature was not clearly distinguished, but it was measured that various phase transition phenomena such as liquid crystal phase transition and melting point occurred. The observation of various transition temperature from DSC indirectly shows liquid crystallinity of the organic semiconductor compounds according to the present invention.

[Example 25] Evaluation of properties of organic thin film transistor

Hole mobility and on/off property of the organic thin film transistor manufactured according to Example 23 were evaluated. Features of the organic thin film transistor employing Compound (113) according to the present invention as channel material are shown in Fig. 11. The semiconductor property of Compound (113) was p-type. The hole mobility of the organic thin film transistor employing the compound was 0.015 cm²/Vs, the subthreshold slope (Vss) was 0.69, and the on/off ratio was 1.18 x 10⁵. Consequently, the hole mobility of Compound (113) was somewhat lower than or approximately same as that of pentacene . However, the on/off ratio (which is beneficial in practical operation of the device) was higher than that of an organic thin film transistor employing pentacene, while the interrupting leakage current (A) and subthreshold slope (Vss) were very low as compared to those of an OTFT employing pentacene. Thus, it is confirmed that the organic semiconductor compounds according to the present invention have excellent semiconductor properties to give excellent performances when applied to an OTFT. [Table 2]

[industrial Applicability]

As described above, a novel organic semiconductor compound according to the present invention, being a mono- molecular organic semiconductor having inherent structure, is stable at ambient temperature, and can be easily synthesized by means of various processes. When being used as an active layer in an OTFT, it is able to form a thin film via vacuum deposition process and is coatable via wet process at ambient temperature. By using the compound, an OTFT having both sufficiently high electron mobility and low interrupting leakage current can be manufactured. The excellent liquid crystallinity of the compounds facilitates intermolecular arrangement and provides remarkable crystallinity.

The organic thin film transistor manufactured by applying the novel organic semiconductor compound according to the present invention facilitates intramolecular or intermolecular charge mobility due to the introduction of various substituent (s) and substituent group (s) . By virtue of excellent semiconductor properties (including excellent crystallinity and strong π-stacking) , the OTFT exhibits improved hole and electron mobility, excellent on/off ratio, as well as very low interrupting leakage current, threshold voltage and subthreshold slope, as measured. Thus, the compounds according to the present invention can be utilized as an active layer for organic thin film transistor devices.

Accordingly, an electronic device having excellent efficiency and performance can be manufactured by utilizing an OTFT employing the novel organic semiconductor compound according to the present invention. The OTFT can be also manufactured by means of vacuum deposition, or solution process such as spin coating and printing, so that the production cost of an electronic device employing an OTFT can be lowered.

Claims

[CLAIMS]

[Claim l]

An organic semiconductor compound selected from the compounds represented by one of Chemical Formulas (1) to (3) : [Chemical Formula 1]

(Ari)_m—≡≡-A-≡—(Ar₂)_n

[In Chemical Formula (1), A represents (C₆-C₃₀) arylene or (C₆-C₃₀) heteroarylene; Ari and Ar₂ independently represent (C₆- C₃₀) aryl or (C₄-C₃₀) heteroaryl; m and n independently represent an integer of 1 to 4 ;

A, Ari or Ar₂ may be independently substituted by at least one substituent (s) selected from the group consisting of hydroxyl group, linear, branched or cyclic (Ci-C₃₀) alkyl group, linear, branched or cyclic (C₁-C₃₀JaIkOXy group, (C₁- C₃₀)alkoxy (C₁-C₃₀) alkyl group, (C₅-C₃₀) ar (Ci-C₃₀) alkyl group, (C₅- C₃₀) aryl group, amino group, mono- or di (C₆-C₃₀) alkylamino group, mono- or di (C₆-C₃₀) arylamino group, (C₁-C₃₀) alkoxycarbonyl group, cyano group and halogen . ] [Chemical Formula 2]

[In Chemical Formula (2) , Ai and A₂ are independently selected from the group consisting of C, Si and Ge,- Rn, R₁₂, R₁₃ and Ri₄ are independently selected from the group consisting of hydrogen; linear, branched or cyclic (C₁-C₃₀) alky1 group; linear, branched or cyclic (C₂-C₄₀) alkenyl group; linear, branched or cyclic (C₃-C₄₀) alkynyl group; linear, branched or cyclic (Ci-C₃₀) alkoxy group; (C₆-C₄₀) aryl group; (C₄- C₃₀) heteroaryl group, (C₆-C₃₀) ar (Ci-C₃₀) alkyl group; (C₁- C₃₀) alkoxy (Ci-C₃₀) alkyl group,- (Ci-C₃₀) alkoxy (C₂-C₃₀) alkenyl group; (C₆-C₅₀) heteroaryl (C₁-C₃₀) alkyl group; (C₁-C₄₀) carbyl; hydro (C₁-C₄₀) carbyl group; (C₆-C₄₀) aryloxy group; (C₁- C₄₀) alkoxycarbonyl group; (C₆-C₄₀) aryloxycarbonyl group; cyano group; carbamoyl group (-C(=O)NH₂) ; haloformyl group (-C(=O)-X, wherein X represents a halogen atom); formyl group (-C(=O)-H); isocyano group; isocyanate group; thiocyanate group; thioisocyanate group; mono- or di (Ci-C₃₀) alkylamino group,- mono- or di (C₆-C₃₀) arylamino group,- hydroxyl group; halogen group; nitro group and silyl group; or Rn, R₁₂, R₁₃ and R₁₄ are independently cross-linked with carbon of adjacent anthracene group via alkylene or alkenylene to form saturated or unsaturated (C₄-C₃₀) ring, wherein the carbon atom in the saturated or unsaturated ring may be substituted by oxygen atom, sulfur atom or chemical formula -N(R₃)- [R_a represents a hydrogen atom or (Ci-C₃₀) alkyl group] ; and the alkyl, alkenyl, alkynyl, alkoxy, aryl or heteroaryl group of R₁₁, R₁₂, R₁₃ or R₁₄ may be further substituted by at least one substituent (s) selected from the group consisting of (C₁-C₃₀) alkyl ; (C₂- C₃₀) alkenyl; (C₃-C₃₀) alkynyl; (C₁-C₃₀JaIkOXy; (C₆-C₄₀) aryloxy group; (C₆-C₃₀) aryl ; (C₄-C₃₀) heteroaryl ; formyl group; amino group; hydroxy1 group; nitro group; halogen and siIyI group;

Ri5, Ri6/ Ri7/ Ri8/ Ri9 and R₂₀ are independently selected from the group consisting of hydrogen; linear, branched or cyclic (C₁-C₃₀) alkyl group; linear, branched or cyclic (C₂- C₄₀) alkenyl group; linear, branched or cyclic (C₃-C₄₀) alkynyl group; linear, branched or cyclic (C₁-C₃₀) alkoxy group; (C₆- C₄₀) aryl group; (C₄-C₃₀) heteroaryl group, (C₆-C₃₀) ar (C₁-C₃₀) alkyl group; (C₁-C₃₀) alkoxy (C₁-C₃₀) alkyl group; (C₁-C₃₀) alkoxy (C₂- C₃₀) alkenyl group; (C₆-C₅₀) heteroaryl (C₁-C₃₀) alkyl group; (C₁- C₄₀)carbyl; hydro (C₁-C₄₀) carbyl group; (C₆-C₄₀) aryloxy group; (Ci-C₄₀) alkoxycarbonyl group; (C₆-C₄₀) aryloxycarbonyl group; cyano group,- carbamoyl group (-C(=O)NH₂); haloformyl group (- C(=O)-X, wherein X represents a halogen atom); formyl group (- C(=O)~H); isocyano group; isocyanate group; thiocyanate group,- thioisocyanate group; mono- or di (Ci-C₃₀) alkylamino group,- mono- or di (C₆-C₃₀) arylamino group; hydroxyl group; halogen group; nitro group and silyl group; and the alkyl, alkenyl, alkynyl, alkoxy, aryl or heteroaryl group of R₁₅, Ri₆, Ri₇, Ris, Ri₉ or R₂₀ may be further substituted by at least one substituent (s) selected from the group consisting of (Ci- C₃₀) alkyl; (C₂-C₃₀) alkenyl; (C₃-C₃₀) alkynyl ; (Ci-C₃₀) alkoxy; (C₆- C₄₀)aryloxy group; (C₆-C₃₀) aryl; (C₄-C₃₀) heteroaryl; formyl group; amino group; hydroxyl group,- nitro group; halogen and silyl group.]

[Chemical Formula 3]

[In Chemical Formula (3), Ar₃ represents (C₆-C₃₀) arylene or (C₆-C₃₀) heteroarylene,- R₂₁ and R₃₂ independently represent hydrogen, linear, branched or cyclic (Ci-C₂₅) alkyl, (C₅-C₂₅) aryl, (C₄-C₂₅) heteroaryl, (Ci-C₂₅) alkoxy (Ci-C₂₅) alkyl, (C₅-C₂₅) ar (Ci- C₂₅) alkyl, (C₄-C₂₅) heteroaryl (Ci-C₂₅) alkyl, linear, branched or cyclic (C₂-C₂₅) alkenyl, linear, branched or cyclic (C₂- C₂₅) alkynyl, mono-, di- or tri (Ci-C₂₅) alkylsilyl, mono-, di- or tri (C₅-C₂₅) arylsilyl, saturated or unsaturated 3- to 7-membered heterocycloalkyl comprising oxygen, nitrogen or sulfur atom in the heterocycle, or saturated or unsaturated 3- to 7-membered heterocycloalkyl (C₁-C₂₅) alkyl comprising oxygen, nitrogen or sulfur atom in the heterocycle; provided that if both R₃₁ and R₃₂ are hexyl, Ar₃ is not anthracene or thienothiophene;

Xi and X₂ are independently selected from the group consisting of 0, N, S and (C₁-C₂₅) alkylene; x and y independently represent an integer of 1 or 2,- p and r independently represent an integer of 0, 1 or 2 ; q is an integer from 1 to 4 ;

Ar₃ may be further substituted by at least one substituent (s) selected from the group consisting of hydroxyl, linear, branched or cyclic (C₁-C₂₅) alkyl, linear, branched or cyclic (C₁-C₂₅) alkoxy, (Ci-C₂₅) alkoxy (C₁-C₂₅) alkyl, (C₅-C₂₅) ar (C₁- C₂₅) alkyl, (C₅-C₂₅) aryl, amino, mono- or di (C₅-C₂₅) alkylamino, mono- or di (C₆-C₂₅) arylamino, cyano and halogen; and the alkyl, aryl, heteroaryl, alkoxyalkyl, aralkyl, heteroarylalkyl, alkenyl, alkynyl, alkylsilyl, arylsilyl, heterocycloalkyl or heterocycloalkylalkyl group of R₃₁ or R₃₂ may be further substituted by at least one substituent (s) selected from the group consisting of (C₁-C₂₅) alkyl, (C₂- C₂₅) alkenyl, (C₃-C₂₅) alkynylamino group, hydroxyl group, [C₁- C₂₅) alkoxy, (C₆-C₂₅) aryloxy group, (C₆-C₂₅) aryl, (C₄- C₂₅) heteroaryl, halogen or silyl group.] [Claim 2]

An organic semiconductor compound according to claim 1, wherein A is selected from the group consisting of phenylene, naphthylene, anthrylene, phenanthrylene, tetracenylene, pentacenylene, pyrenylene, chrysenylene or fluorenylene . [Claim 3]

An organic semiconductor compound according to claim 2, wherein A is selected from the groups represented by following chemical formulas :

[Claim 4]

An organic semiconductor compound according to claim 1, wherein Ar₁ and Ar₂ independently represent aryl or heteroaryl represented by one of the following chemical formulas:

wherein, Ri is independently selected from the group consisting of hydrogen, hydroxyl group, linear, branched or cyclic (Ci-C₃₀) alkyl group, linear, branched or cyclic (Ci- C₃₀)alkoxy group, (Ci-C₃₀) alkoxy (Ci-C₃₀) alkyl group, (C₅- C₃₀) ar (Ci-C₃₀) alkyl group, (C₅-C₃₀) aryl group, amino group, mono- or di (C₅-C₃₀) alkylamino group, mono- or di (C₆-C₃₀) arylamino group, (C₁-C₃₀) alkoxycarbonyl group and cyano group; and the position of linkage where the substituent is bonded is selected from the carbons in the substituent ring. [Claim 5]

An organic semiconductor compound according to claim 4, which is selected from the compounds represented by one of the following formulas:

[Claim 6 ]

An organic semiconductor compound according to claim 1, wherein aryl or heteroaryl of Rn to R₁₄ is selected from the substituents represented by one of the following chemical formulas :

wherein, R₂i, R₂₂, R23/ R24, R25 and R₂₆ are independently selected from the group consisting of hydrogen, (Ci-C₃₀) alkyl group, (Cg-C₃₀) aryl group and (Ci-C₃₀) alkoxy (C₆-C₃₀) aryl group,- and alkyl or aryl of R₂₁, R₂₂, R23, R24, R25 or R₂₅ may be substituted by at least one substituent (s) selected from the group consisting of (C_x-C₃₀) alkoxy and halogen; and the position of linkage where the substituent is bonded is selected from the carbons in the substituent ring. [Claim 7]

An organic semiconductor compound according to claim 6, wherein R₁₅, R₁₆, R₁₇, R₁₈, Ri9 and R₂₀ are independently selected from the group consisting of (C₁-C₁₀) alkyl group, tri (C₁- C₁₀) alkylsilyl group; tri (C₁-C₁₀) alkoxysilyl group or tri (C₆- C₁₀) arylsilyl group.

[Claim δ]

An organic semiconductor compound according to claim 7, wherein said tri (C₁-C₁₀) alkylsilyl group; tri (C₁-C₁₀) alkoxysilyl group or tri (C₆-C₁₀) arylsilyl group is selected from the group consisting of trimethylsilyl, triethylsilyl, tripropylsilyl, dimethylethylsilyl, diethylmethylsilyl, dimethylpropylsilyl, dimethylisopropylsilyl , dipropylmethylsilyl , diisopropylmethylsilyl , dipropylethylsilyl , diisopropylethylsilyl , diethylisopropylsilyl , triisopropylsilyl, trimethoxysilyl, triethoxysilyl and triphenylsilyl .

[Claim S>]

An orgnanic semiconductor compound according to claim 8, which is selected from the compounds represented by one of the following formulas : 87

[Claim lθ]

An organic semiconductor compound according to claim 1, wherein Ar₃ is selected from the structures represented by one of the following chemical formulas:

wherein, R₄₁ to R₄₇ are independently selected from the group consisting of hydrogen, (Ci-C₂₅) alkyl, (C₅-C_2S) aryl and (C₅-C₂₅) ar (Ci-C₂₅) alkyl, and the alkyl and aryl of said R_4x to R₄₇ may be further substituted by at least one substituent (s) selected from the group consisting of (Ci-C₂₅) alkoxy and halogen. [Claim ll]

An organic semiconductor compound according to claim 10, wherein the aryl and heteroaryl of R₃₁ or R₃₂ are selected from the substituents represented by following chemical formulas:

wherein, R₅₁, R₅₂, R53 , R54 , R55 and R₅₅ are independently selected from the group consisting of hydrogen, amino, linear, branched or cyclic (Ci-C₂₅) alkyl, linear, branched or cyclic (Ci-C₂₅) alkoxy, (Ci-C₂₅) alkoxy (Ci-C₂₅) alkyl, (C₅-C₂₅) ar (C₁- C₂₅) alkyl, (C₅-C₂₅) aryl, mono- or di (C₆-C₂₅) alkylamino, mono- or di (C₆-C₂₅) arylamino group; and the position of linkage where the substituent is bonded is selected from the carbons in the substituent ring. [Claim 12]

An organic semiconductor compound according to claim 11, which is selected from the compounds represented by one of the following chemical formulas:

[Claim 13 ]

An organic thin film transistor which comprises a first electrode; a second electrode; and an organic semiconductor compound selected from the compounds represented by one of Chemical Formulas (1) to (3) according to claim 1 between the first electrode and the second electrode. [Claim 14]

An organic thin film transistor according to claim 13, wherein said organic semiconductor compound is formed as a thin film via vacuum deposition, screen printing, printing process, spin coating process, dipping process or ink-jet process . [Claim 15]

An organic thin film transistor comprising a substrate (11) , a gate electrode (16) , a gate insulator (12) , channel material (13) and source/drain electrodes (14 and 15), wherein the channel material is formed of an organic semiconductor compound selected from the compounds represented by Chemical Formulas (1) to (3) according to claim 1.

[Claim 16]

An organic thin film transistor according to claim 15, wherein the structure of the organic thin film transistor is characterized by top-contact or bottom-contact.

[Claim 17]

An organic thin film transistor according to claim 15, wherein the gate electrode (16) and the source-drain electrodes (14 and 15) are formed of a substance selected from the group consisting of gold (Au) , silver (Ag) , aluminum (Al) , nickel (Ni) , chromium (Cr) and indium tin oxide (ITO) .

[Claim 18]

An organic thin film transistor according to claim 15, wherein the channel material (13) is formed as a thin film via vacuum deposition, screen printing, printing process, spin casting process, spin coating process, dipping process or ink- jet process.

[Claim 19]

An organic thin film transistor according to claim 15, wherein the substrate (11) is formed of a substance selected from the group consisting of glass, polyethylenenaphthalate (PEN) , polyethyleneterephthalate (PET) , polycarbonate (PC) , polyvinylalcohol (PVP) , polyacrylate, polyimide, polynorbornene and polyethersulfone (PES) .

[Claim 20]

An organic thin film transistor according to claim 15, wherein the gate insulator (12) is selected fromm a strongly dielectric insulator selected from the group consisting of Ba_0.33Sr_C65TiO₃ (BST), Al₂O₃, Ta₂O₅, La₂O₅, Y₂O₃ and TiO₂; an inorganic insulator selected from the group consisting of PdZr_0.33Ti_0.eeθ₃ (PZT), Bi₄Ti₃O₁₂, BaMgF₄, SrBi₂ (TaNb) ₂O₉, Ba(ZrTi)O₃ (BZT) , BaTiO₃, SrTiO₃, Bi₄Ti₃Oi₂, SiO₂, SiN_x and AlON; or polyimide, benzocyclobutene (BCB) , parylene, polyacrylate, polyvinylalcohol and polyvinylphenol .