KR101468942B1 - Novel Naphthalene Diimide polymers and organic electronic device - Google Patents

Abstract

The present invention relates to organic semiconductor compounds for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to synthesis of a naphthalene diimide polymer which is a new organic semiconductor compound through copolymerization of a naphthalene diimide derivative with an electron donor and an electron donating compound, and an organic electronic device using the naphthalene diimide polymer as an organic semiconductor layer.

Description

TECHNICAL FIELD [0001] The present invention relates to novel naphthalene diimide polymers and organic electronic devices using the same,

The present invention relates to organic semiconductor compounds for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to synthesis of a naphthalene diimide polymer which is a new organic semiconductor compound through copolymerization of a naphthalene diimide derivative with an electron donor and an electron donating compound, and an organic electronic device using the naphthalene diimide polymer as an organic semiconductor layer.

Organic thin film transistors (OTFTs) are now being targeted for intensive research activities due to their low cost, large size, and the possibility of producing flexible electronic devices. In particular, when a polymer organic semiconductor is used, the manufacturing cost can be reduced as compared with a low molecular weight organic semiconductor compound because it can easily form a thin film by a solution process.

Typical semiconductor compounds for polymeric organic thin film transistors developed to date include P3HT [poly (3-hexylthiophene)] and F8T2 [poly (9,9-dioctylfluorene-co-bithiophene)]. The performance of OTFT is various, but important evaluation scale is charge mobility and on / off ratio, and the most important evaluation measure is charge mobility. The charge mobility varies depending on the kind of the semiconductor material, the thin film forming method (structure and morphology), the driving voltage, and the like.

Organic thin film transistors include electrodes (source and drain), substrates and gate electrodes that require high thermal stability, insulators that have high dielectric constant and dielectric constant, and semiconductors that move charges well. There are many problems to be overcome, and the key material is organic semiconductor. Organic semiconductors can be classified into low-molecular organic semiconductors and polymeric organic semiconductors according to molecular weight, and classified into n-type organic semiconductors or p-type organic semiconductors depending on whether electrons or holes are delivered. In general, when a low molecular weight organic semiconductor is used in the formation of an organic semiconductor layer, the low molecular weight organic semiconductor is easy to purify and can remove almost any impurities. However, since such organic semiconductors can not be spin-coated and printed, a thin film must be produced by vacuum deposition, and thus the manufacturing process is complicated and costly compared to polymer organic semiconductors. In the case of polymer organic semiconductors, purification with high purity is difficult, but heat resistance is excellent, and spin coating and printing are possible, which is advantageous in manufacturing process, cost, and mass production.

Although many researches have been made so far for the development of organic semiconductor materials, the development of polymer based semiconductor materials has not been developed yet. Therefore, in order to develop an electronic device using an organic thin film transistor which is flexible and has a low manufacturing cost, development of a polymer-based semiconductor material is in urgent need. In general, the charge mobility of polymers is known to be lower than that of low molecular weight materials, but it can be said to be a material that can sufficiently overcome the manufacturing process and cost. Typically, acenes and heteroacenes are efficient p-type semiconductors, and rylene diimides, especially perylene and naphthalene derivatives, have been developed as n-type semiconductor materials with oxidation stability. However, the materials developed so far are mainly p-type semiconductor materials, and the number and performance of n-type semiconductor materials do not reach the p-type semiconductor materials which have already been developed. In particular, a number of materials have been developed using naphthalene diimide as one of the materials of interest, such as naphthalene diimide, bithiophene, and a polymer material having a charge mobility of 0.85 cm ² V ^-1 S ^-1 It has already been developed. However, it is necessary to develop a polymer semiconductor material that exhibits higher stability and higher mobility than the materials developed so far.

Korean Patent Laid-Open No. 10-2008-0063803 entitled " N-type semiconductor material for a thin film transistor " refers to an N-type semiconductor material for a thin film transistor, type channel semiconductor films, and the use of these materials in thin film transistors for electronic devices and a method for manufacturing such transistors and devices. However, thermal stability and mechanical stability also have disadvantages in that they do not exhibit sufficient effects in terms of charge mobility and flicker rate.

Korean Patent Laid-Open No. 10-2008-0063803 (2008.07.07)

The present invention provides a naphthalene diimide polymer as a novel organic semiconductor compound through copolymerization of a naphthalene diimide derivative, which is one of the electron attracting materials, with an electron donor and an electron attracting compound, and provides an organic electronic device using the naphthalene diimide polymer as an organic semiconductor layer It has its purpose.

Further, the present invention can alternately polymerize an electron-donating substance which is an aromatic material into which an aromatic vinylene group or an acetylene group is introduced, has air stability, increases the coplanarity of the main chain and has an extended conjugated structure, In which the naphthalene diimide polymer has a double bond.

The present invention also provides an organic electronic device having a high solubility, a high molecular weight, a viscosity, a spin coating process at room temperature, a solution process, and an organic electronic device used as a semiconductor layer, Naphthalene < / RTI > diimide polymer.

According to one aspect of the present invention, there is provided a naphthalene diimide derivative represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

이고;R ₁ and R ₂ are each independently C ₁ -C ₅₀ Alkyl, C ₆ -C ₅₀ Aryl, C ₁ -C ₅₀ alkoxy or

ego;

Z ₁ and Z ₂ , L _{1 ,} L _{2 and} L ₃ are each independently selected from the following structures, Z ₁ and Z ₂ may be substituted or unsubstituted;

또는

V ₁ And V ₂ is

or

≪ / RTI >

X ₁ to X ₇ are each independently S, Se, O, N, NH or NR ';

A ₁ and A ₂ are each independently hydrogen, cyano or -COOR ";

R 'and R''are independently C ₁ -C ₅₀ each Alkyl or C ₆ -C ₅₀ Aryl;

R ₃ To R ₃₁ are independently hydrogen, hydroxyl, amino, C ₁ -C ₅₀ each Alkyl, C ₆ -C ₅₀ aryl, C ₁ -C ₅₀ alkoxy, mono or di C ₁ -C ₅₀ Alkylamino, C ₁ -C ₅₀ Alkoxycarbonyl or C ₁ -C ₅₀ Alkylcarbonyloxy;

Z is an integer of 1 to 20, m or y is an integer of 0 to 2, and n is an integer of 1 to 1,000.

Another aspect of the present invention relates to an organic thin film transistor including the naphthalene diimide polymer in an organic semiconductor layer.

Hereinafter, the present invention will be described in detail.

The present invention relates to organic semiconductor compounds for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to the synthesis of naphthalene diimide polymer, which is a new p-type and n-type organic semiconductor compound, through copolymerization of a naphthalene diimide derivative with an electron donor and an electron donor compound, Device.

The organic semiconducting compound of the present invention means a naphthalene diimide polymer represented by the following formula (1). By introducing a vinylene group or an acetylene group, the coplanarity of the main chain is increased and an extended conjugated structure is obtained. To increase intermolecular interaction and to exhibit high mobility.

[Chemical Formula 1]

[In the above formula (1)

이고;R ₁ and R ₂ are each independently C ₁ -C ₅₀ Alkyl, C ₆ -C ₅₀ Aryl, C ₁ -C ₅₀ alkoxy or

ego;

Z ₁ and Z ₂ , L _{1 ,} L _{2 and} L ₃ are each independently selected from the following structures, Z ₁ and Z ₂ may be substituted or unsubstituted;

또는

으로 치환되거나 비치환 될 수 있고;V ₁ And V ₂ is

or

≪ / RTI >

X ₁ to X ₇ are each independently S, Se, O, N, NH or NR ';

A ₁ and A ₂ are each independently hydrogen, cyano or -COOR ";

R 'and R " are each independently C_One-C₅₀ Alkyl or C₆-C₅₀ Aryl;

R ₃ To R ₃₁ are independently hydrogen, hydroxyl, amino, C ₁ -C ₅₀ each Alkyl, C ₆ -C ₅₀ aryl, C ₁ -C ₅₀ Alkoxy, mono or di C ₁ -C ₅₀ Alkylamino, C ₁ -C ₅₀ Alkoxycarbonyl or C ₁ -C ₅₀ Alkylcarbonyloxy;

Z is an integer of 1 to 20, m or y is an integer of 0 to 2, and n is an integer of 1 to 1,000.

일 수 있으며, 바람직하게는

또는

에서 선택될 수 있다. In Formula 1, R ₁ and R ₂ are each independently C ₁ -C ₅₀ Alkyl, C ₆ -C ₅₀ Aryl, C ₁ -C ₅₀ alkoxy or

And preferably,

or

≪ / RTI >

[R ₃₁ To R ₃₅ are independently hydrogen, hydroxyl, amino, C ₁ -C ₅₀ each Alkyl, C ₆ -C ₅₀ aryl, C ₁ -C ₅₀ Alkoxy, mono or di C ₁ -C ₅₀ Alkylamino, C ₁ -C ₅₀ Alkoxycarbonyl or C ₁ -C ₅₀ Alkylcarbonyloxy;

The R ₃₂ Alkyl, aryl, alkoxy, alkylamino, alkoxy, or alkylcarbonyloxy of R < ₃₅ > may be further substituted with hydrogen, hydroxy or amino;

Z is an integer from 1 to 20,

하기 구조에서 선택될 수 있다.In Formula 1,

Can be selected from the following structures.

[Wherein X ₁ , X ₂ , X ₃ , A ₁ , A ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as defined in Formula 1]

하기 구조에서 선택될 수 있다.
More preferably,

Can be selected from the following structures.

The naphthalene diimide polymers of the present invention are specifically selected from the following compounds.

[Wherein n is an integer of 1 to 1,000]

More specifically, the naphthalene diimide polymers of the present invention can be selected from the following formulas.

[Wherein n is an integer of 1 to 1,000]

As a method for producing the naphthalene diimide polymer according to the present invention, a final compound can be prepared through an alkylation reaction, a Grignard coupling reaction, a Suzuki coupling reaction, a styrene coupling reaction or the like. The organic semiconductor compound according to the present invention is not limited to the above-mentioned production method, and can be produced by a conventional organic chemical reaction other than the above-mentioned production method.

The naphthalene diimide polymer according to the present invention can be used as a material for forming an organic semiconductor layer of an organic electronic device, and can be specifically used for an organic thin film transistor (OTFT) or an organic solar battery (OPV).

For example, a method of manufacturing an organic thin film transistor using the method is as follows.

Referring to FIG. 1, the substrate 11 is preferably an n-type silicon used for a typical organic thin film transistor. This substrate contains the function of a gate electrode. In addition to the n-type silicon, a glass substrate or a transparent plastic substrate having excellent surface smoothness, ease of handling, and waterproofness may be used as the substrate. In this case, the gate electrode must be added to the substrate. Examples of materials that can be used as the substrate include glass, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl alcohol (PVP), polyacrylate , Polyimide, polynorbornene, and polyethersulfone (PES).

An insulated gate constituting the OTFT device layer 12, as can be used with a large dielectric constant insulators conventionally used, specifically _{Ba 0 .33 Sr 0 .66 TiO 3} (BST), Al 2 O 3, Ta 2 O ₅ , La ₂ O ₅ , Y ₂ O ₃ and TiO ₂ , a ferroelectric insulator selected from the group consisting of PdZr _{0 .33} Ti _{0 .66} O ₃ (PZT), Bi ₄ Ti ₃ O ₁₂ , BaMgF ₄ , SrBi _{2 ) 2 O 9, Ba (ZrTi} ) O 3 (BZT), BaTiO 3, SrTiO 3, Bi4Ti 3 O 12, SiO 2, SiNx , and an inorganic insulator selected from the group consisting of AlON, or a polyimide (polyimide), BCB (benzocyclobutene ), Parylene, polyacrylate, polyvinyl alcohol, and polyvinylphenol can be used.

1, the structure of the organic thin film transistor according to the present invention includes a substrate 11, a gate electrode 16, an insulating layer 12, an organic semiconductor layer 13, a source 14, a drain electrode 15, -Bottom-contact of the substrate / gate electrode / insulating layer / source / drain electrode / organic semiconductor layer as well as the top-contact. (1,1,1,3,3,3-hexamethyldisilazane), OTS (octadecyltrichlorosilane), or OTDS (octadecyltrichlorosilane) as a surface treatment is applied between the source 14 and the drain electrode 15 and the organic semiconductor layer 13. [ It may or may not be coated.

The organic semiconductor layer employing the naphthalene diimide polymer according to the present invention may be formed into a thin film by a vacuum deposition method, a screen printing method, a printing method, a spin casting method, a spin coating method, a dipping method, or an ink jetting method. The deposition of the organic semiconductor layer may be performed using a high temperature solution at 40 DEG C or higher and a thickness of about 500 ANGSTROM is preferable.

The gate electrode 16 and the source and drain electrodes 14 and 15 may be formed of a conductive material and may be formed of a metal such as gold (Au), silver (Ag), aluminum (Al), nickel (Ni), chromium (Cr) Oxide (ITO).

The naphthalene diimide polymer according to the present invention can be used in all organic electronic devices using organic semiconductor materials such as OPV in addition to OTFTs.

The present invention can synthesize a naphthalene diimide polymer which is a new organic semiconductor compound through copolymerization of a naphthalene diimide derivative with an electron donor and an electron donating compound and can be used as an n-type or p-type polymeric material of a semiconductor. The naphthalene diimide polymer, which is an organic semiconductor compound produced according to the present invention, is highly p- and n-type organic semiconducting materials having excellent thermal and mechanical properties and high stability and high mobility, There is an effect. In addition, it has an effect of being an organic semiconductor material having high stability and high mobility characteristics, which can control the properties of the copolymer and have ambipolar characteristics.

Accordingly, the naphthalene diimide polymer according to the present invention has an advantage that it can be used in all organic electronic devices using an organic semiconductor material such as OPV in addition to an OTFT.

Figure 1 - Typical of a substrate / gate / insulating layer (source, drain) / semiconductor layer
Sectional view showing the structure of an organic thin film transistor
2 - Thermogravimetric analysis (TGA) of the organic semiconductor compound PNDIBTE prepared in Example 1
Figure 3 - Differential calorimetric analysis (DSC) of the organic semiconductor compound PNDIBTE prepared in Example 1,
4 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound PNDIBTE prepared in Example 1
5 A cyclic voltammetry curve of the organic semiconductor compound PNDIBTE prepared in Example 1
FIG. 6 is a drawing for predicting the HOMO and LUMO structure of Example 1 through computer simulation (DFT)
7 is a drawing showing the characteristics of a device manufactured using the organic semiconductor compound PNDIBTE according to Example 1
8 - Thermogravimetric analysis (TGA) of the organic semiconductor compound PNDIBTBTE prepared in Example 2
Figure 9 - Differential calorimetric analysis (DSC) of the organic semiconductor compound PNDIBTBTE prepared in Example 2,
10 is a graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound PNDIBTBTE prepared in Example 2
11 A cyclic voltammetry curve of the organic semiconductor compound PNDIBTBTE prepared in Example 2
Figure 12: Prediction of the HOMO and LUMO structure of Example 2 through computer simulation (DFT)
13 - Diagrams showing characteristics of a device manufactured using the organic semiconductor compound PNDIBTBTE according to Example 2
14 - Thermogravimetric analysis (TGA) of the organic semiconductor compound PNDIBSE prepared in Example 3
15 - Differential calorimetric analysis (DSC) of the organic semiconductor compound PNDIBSE prepared in Example 3,
16 - graph showing UV absorption in a liquid state and UV spectrum in a solid state of the organic semiconductor compound PNDIBSE prepared in Example 3
17 A cyclic voltammetry curve of the organic semiconductor compound PNDIBSE prepared in Example 3
FIG. 18 is a drawing for predicting the HOMO and LUMO structure of Example 3 through computer simulation (DFT).

Hereinafter, for the purpose of a detailed understanding of the present invention, the characteristics of the naphthalene diimide copolymer, the production method thereof, and the device according to the present invention will be described with reference to the representative compound of the present invention, , And are not intended to limit the scope of the present invention.

[Production Example 1]

 (E) -1,2- Bis ( Thiophene -2 days) Ethene ((E) -1,2- bis ( thiophen -2- yl ) ethene) Synthesis of

To the flask was added thiophene-2-carbaldehyde (5.6 g, 50 mmol), dissolved in tetrahydrofuran (THF) (100 mL), cooled to -18 ° C and treated with titanium (IV) chloride Gt; min. ≪ / RTI > After stirring for 30 minutes, zinc powder (7.8 g) is added over 30 minutes. After stirring at -18 占 폚 for 30 minutes, the mixture is warmed to room temperature and refluxed for 3 hours and 30 minutes. Then, the reaction mixture was poured into ice water and the reaction was terminated. The reaction mixture was filtered with a filter, washed with methylene chloride, and then extracted with water. The water was removed and recrystallized with hexane to obtain the desired compound (E) -1,2- Yl) ethene (4.7 g, yield: 98%). ¹ H NMR (300 MHz, CDCl ₃ ) [ppm] 隆 7.18 (d, 2H), 7.05 (s, 2H), 7.04 (d, 2H), 6.99 (m, 2H).

[Production Example 2]

(E) -1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethene) (E) synthesis

(E) -1,2-bis (thiophen-2-yl) ethene (1.78 g, 9.6 mmol) was dissolved in a mixed solvent of tetrahydrofuran / hexane (volume ratio 2/1, 50 mL) Butyllithium in cyclohexane (11 ml, 22 mmol) was added slowly at -78 [deg.] C and stirred for 30 minutes. After returning to room temperature and refluxing for 1 hour, the temperature of the reaction mixture is lowered to -78 ° C. Tetrahydrofuran (22 mL, 22 mmol) in which 1 mol of trimethyltin chloride had been dissolved was slowly added dropwise to the reaction solution at the same temperature and stirred at room temperature for 2 hours. The reaction mixture was extracted with ether, and water was removed with anhydrous magnesium sulfate. The solvent was concentrated and then recrystallized with ethanol to obtain white needle-shaped target compound (E) -1,2-bis (5- (trimethylstannyl) thiophene 2-yl) ethene (3.88 g, yield 80%). _{^{1 H NMR (300MHz, CDCl 3}} ) [ppm] δ7.11 (d, 2H), 7.08 (s, 2H), 7.07 (d, 2H), 0.36 (s, 18H).

[Production Example 3]

(E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene) (E) synthesis

(E) -1,2-bis (selenophen-2-yl) ethene (1.00 g, 3.5 mmol) was dissolved in a tetrahydrofuran solvent (50 mL), and then 2.5 mol of n-butyl lithium in cyclohexane (3.1 ml, 7.7 mmol) was added slowly at -78 [deg.] C and stirred for 30 min. After returning to room temperature and refluxing for 1 hour, the temperature of the reaction mixture is lowered to -78 ° C. Tetrahydrofuran (1.6 g, 7.7 mmol) in which 1 mol of trimethyltin chloride had been dissolved was slowly added dropwise to the reaction solution at the same temperature, and the mixture was stirred for 10 minutes and then stirred at room temperature. The solvent was concentrated and recrystallized from methanol to obtain white needle-shaped target compound (E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene (1.5 g, yield: 75%). ¹ H NMR (CD ₂ Cl ₂ , 300 MHz),? (Ppm): d 7.24-23 (d, 4H), 7.04 (d, 2H), 0.39 (s, 18H).

[ Manufacturing example  4]

 (E) -1,2- Bis (4- (trimethylstannyl) phenyl) ethene  ((E) -1,2- bis (4-( trimethylstannyl ) phenyl ) ethene) Synthesis of

After dissolving (E) -1,2-bis (4-bromophenyl) ethene (3 g, 8.7 mmol) in tetrahydrofuran (90 mL), 2 mol of n-butyllithium cyclohexane mL, 17.75 mmol) was added slowly at -78 [deg.] C and stirred for 30 minutes. Trimethyltin chloride (3.53 g, 17.75 mmol) was slowly added dropwise to the reaction mixture at the same temperature and stirred at room temperature for 2 hours. The reaction mixture was extracted with ether and water was removed with anhydrous magnesium sulfate. The solvent was concentrated and then recrystallized with ethyl alcohol to obtain (E) -1,2-bis (4- (trimethylstannyl) phenyl) (3.2 g, yield: 80%). _{^{1 H NMR (300MHz, CDCl 3}} ) [ppm] δ7.50-7.48 (m, 4H), 6.968 (s, 2H), 0.36 (s, 18H).

[Production Example 5]

 (E) -1,2- Bis (3-dodecylthiophen-2-yl) ethene  ((E) -1,2- bis (3- dodecylthiophen -2- yl ) ethene) Synthesis of

(14 g, 50 mmol), tetrahydrofuran (THF) (250 mL), titanium (IV) chloride (6.5 mL) and zinc powder (7.8 g) were added to a solution of 3-dodecylthiophene-2-carbaldehyde (E) -1,2-bis (3-dodecylthiophen-2-yl) ethene (10 g, yield: 75%) was obtained in the same manner as in Production Example 1. _{^{1 H NMR (300MHz, CDCl 3}} ) [ppm] δ 7.18 (d, 2H), 7.05 (d, 2H), 6.99 (s, 2H), 2.67 (m, 4H), 1.54 (m, 4H), 1.23 ( m, 36H), 0.88 (m, 6H)

[ Manufacturing example  6]

 (E) -1,2-bis (3- Dodecyl -5- ( Trimethylstannyl ) Thiophene Synthesis of (E) -1,2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) ethene

(E) -1,2-bis (3-dodecylthiophen-2-yl) ethene (5 g, 9.6 mmol) was dissolved in a mixed solvent of tetrahydrofuran / hexane (2/1, (E) -1,2-bis (3-dodecylbenzenesulfonyl) -2,3,4-tetrahydroisoquinoline was obtained in the same manner as in Preparation Example 2, using cyclohexane (11 ml, 22 mmol) (Trimethylstannyl) thiophen-2-yl) ethene (5.2 g, yield: 63%). _{^{1 H NMR (300MHz, CDCl 3}} ) [ppm] δ7.05 (d, 2H), 6.99 (s, 2H), 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, 6 H), 0.36 (s, 18 H).

[Production Example 7]

 (E) -1,2-bis (3-dodecylthieno [3,2-b] thiophen-2-yl) ethene -b] thiophen-2-yl) ethene)

3-dodecyl Im furnace [3,2- b] thiophene-2-hydroxy balde (17 g, 50 mmol), tetrahydrofuran (THF) (250 mL), titanium (IV) chloride (6.5 mL) (E) -1,2-bis (3-dodecylthieno [3,2-b] thiophen-2-yl) zinphosphate (7.8 g) was obtained in the same manner as in Preparation Example 1, ) Ethene (24 g, yield: 75%). _{^{1 H NMR (300MHz, CDCl 3}} ) [ppm] δ7.18 (d, 2H), 7.05 (d, 2H), 6.99 (s, 2H), 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, 6H)

[ Manufacturing example  8]

 (E) -1,2-bis (3- Dodecyl -5- ( Trimethylstannyl ) Thiophene Synthesis of (E) -1,2-bis (3-dodecyl-5- (trimethylstannyl) thieno [3,2- b] thiophen-2-yl) ethene

(5 g, 9.6 mmol) was added to a solution of (E) -1,2-bis (3-dodecylthieno [3,2- b] thiophen- (E) was obtained in the same manner as in PREPARATION 2, using 2-methyl-2-pyrrolidone as a starting material, 2/1, 100 mL), 2 mol of n-butyllithium cyclohexane (11 mL, 22 mmol), and trimethyltin chloride (4.38 g, -1,2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) ethene was obtained (5.2 g, yield 63%). 2H), 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, , ≪ / RTI > 6H), 0.36 (s, 18H).

Example 1 Synthesis of poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl-9- (5- (2- (5-methylthiophen- Yl) benzo [l, m] [3,8] phenanthroline-l, 3,6,8 (2H, 7H)

(Poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl-9- (5- (2- (5- methylthiophen- 2- yl) vinyl) thiophen- ] [3,8] phenanthroline-1,3,6,8 (2H, 7H) -tetraone] ( PNDIBTE ))

The polymer may be polymerized through a Stille coupling reaction. 4,9-dibromo-2,7-bis (2-decyltetradecyl) benzo [1,3] phenanthroline-1,3,6,8 (2H, 7H) -tetraone (0.50 g, E) -1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethene (Preparation Example 2, 0.24 g, 0.46 mmol) was dissolved in chlorobenzene (7.5 mL). Then, Pd2 (dba) 3 (8 mg, 2 mol%) and P (o-tol) 3 (11 mg, 8 mol%) were added as a catalyst and refluxed at 110 ° C for 48 hours. The reaction solution is then slowly precipitated in methanol (300 mL) and the resulting solid is filtered off. The filtered solid is purified through a soxhlet in the order of methanol, hexane, toluene and chloroform. The resulting liquid was precipitated again in methanol, filtered through a filter, and dried to obtain PNDIBTE (yield 91%) which was the title compound of a dark green solid. Mn = 70,000, polydispersity of 1.98, 1H NMR (500MHz, CDCl3, ppm):? 8.48-8.45 (broad, 2H), 7.93-7.20 (broad, 6H), 4.09-4.08 1.94 (m, 2H), 1.27-1.24 (m, 80H), 0.87 (m, 12H).

[ Example  2] Poly [(E) -2,7- Bis (2- Dodecyldecyltetradecyl ) -4- (5- Methylthiophene Yl) -9- (5 '- (2- (5-methylthiophen-2-yl) vinyl) - [ Batiotopen ]-5 days) Benzo [ lmn ] [3,8] phenanthroline-1,3,6,8 (2H, 7H) - Tetraone ]

(Poly [(E) -2,7-bis (2- decyltetradecyl -4- (5- 메틸thiophen -2- yl ) -9- (5 '-( 2- (5- 메틸thiophen -2- yl ) vinyl] - [2,2'-bithiophen-5-yl) benzo [1,3] phenanthroline-1,3,6,8 (2H, 7H) -tetraone] PNDIBTBTE ))

 The polymer may be polymerized through a Stille coupling reaction. 4,9-bis (5-bromothiophen-2-yl) -2,7-bis (2-decyltetradecyl) benzo [m] [3,8] phenanthroline- 1,3,6,8 (2H, 7H) -tetraone (E) -1,2-bis (5- (trimethylstannyl) thiophen-2-yl) ethene (Preparation 2, 0.21 g, 0.40 mmol), Pd2 (dba) 3 (Yield: 83%) was obtained in the same manner as in Example 1, using the title compound (7 mg) and P (o-tol) 3 (10 mg). (Broad, 4H), 1.97-1.95 (broad, 10H), 4.04-4.0 m, 2H), 1.35-1.17 (m, 80H), 0.80 (m, 12H).

[Example 3] Synthesis of poly [(E) -2,7-bis (2-dodecyltetradodecyl) -4-methyl- Vinyl) cerenophen-2-yl) benzo [lmn] [3,8] phenanthroline-1,3,6,8 (2H, 7H)

(Poly [(E) -2,7-bis (2-decyltetradecyl) -4-methyl-9- (5- (2- (5-methylselenophen- 2- yl) vinyl) selenophen-2-yl) benzo [ ] [3,8] phenanthroline-1,3,6,8 (2H, 7H) -tetraone] ( PNDIBSE ) Synthesis of

The polymer may be polymerized through a Stille coupling reaction. 4,9-dibromo-2,7-bis (2-decyltetradecyl) benzo [1,3] phenanthroline-1,3,6,8 (2H, 7H) -tetraone (0.50 g, 0.46 mmol) E) -1,2-bis (5- trimethylstannyl) selenophen-2-yl) ethene (Preparation 3, 0.28 g, 0.40 mmol), Pd2 (dba) 11 mg), the title compound was obtained in the same manner as in Example 1 (yield: 97%). Mn = 220,000, polydispersity of 1.13.

[ Example  4] Production of organic electronic devices

The OTFT device was fabricated by top-contact method, and 300 nm (for PNDIBTE) n-doped silicon gate was used and SiO ₂ was used as the insulator. Surface treatment was performed by surface cleaning using piranha cleaning 46-26solution (H ₂ SO ₄ : 2H ₂ O ₂ ) and then treating the surface with SAM (Self Assemble Monolayer) using ODTS (octadecyltrichlorosilane). The organic semiconductor layer was coated with a 0.2 wt% chloroform solution at a speed of 2000 rpm for 1 minute using a spin-coater. As the organic semiconductor material, PNDIBTE synthesized in Example 1 was used. The thickness of the organic semiconductor layer was confirmed to be 100 nm using a surface profiler (Alpha Step 500, Tencor). The gold used as the source and drain was deposited to a thickness of 50 nm at 1 A / s. The channel length is 160 μm and the width is 1600 μm. The characteristics of OTFT were measured using Keithley 2400 and 236 source / measure units.

The charge mobility was obtained from the slope by obtaining a graph of (ISD) ^1/2 and V _G as variables from the following formula (2) (saturation region current equation).

[Formula 2] Saturation region [

Wherein, I _SD is the source-and-drain current, μ or μ _FET is said mobile charge Doi, and C ₀ is oxide capacitance, W is the channel width, and L is channel length, V _G is the gate voltage, V _T is the threshold voltage. In addition, the blocking leakage current (I _off ) is a current flowing when the off state is obtained, and a minimum current is obtained from the off state at the current ratio.

FIG. 2 shows the results of measurement of the decomposition temperature of the organic semiconductor compound (PNDIBTE) synthesized in Example 1 using TGA. The temperature at which 5% decomposition of PNDIBTE occurs is measured at 453 ° C, and PNDIBTE has excellent thermal stability.

In FIG. 3, the thermal stability of the organic semiconductor compound (PNDIBTE) synthesized in Example 1 was measured with respect to DSC. In PNDIBTE, the melting temperature was measured at 242 ° C. and the crystallization temperature was measured at 210 ° C. .

The light absorbing region of the organic semiconductor compound (PNDIBTE) synthesized in Example 1 was measured in a solution state and a film state, and the result is shown in FIG.

In order to analyze the electrochemical characteristics of the organic semiconductor compound (PNDIBTE) synthesized in Example 1, cyclic voltammetry was performed under the condition of Bu ₄ NClO ₄ (0.1 molar concentration) in a solvent of 50 mV / s The measurement result is shown in FIG. 5, and a voltage was applied through a coating using a carbon electrode during the measurement.

The optical and electrochemical properties of the organic semiconductor compound (PNDIBTE) synthesized in Example 1 are shown in Table 1 below. Here, the LUMO value is a value calculated using the result measured in FIG. The bandgap was also obtained at the UV absorption wavelength in the film state.

In FIG. 6, the distribution of electrons according to the energy level of a molecule is shown through DFT calculation. It can be seen that electrons are distributed in the electron-donor side at the HOMO energy level of the organic semiconductor compound (PNDIBTE) synthesized in Example 1. In the LUMO energy level state, electrons in the electron donor move toward the electron acceptor.

7 is a diagram showing transfer curves of the device manufactured in Example 4 using the organic semiconductor compound (PNDIBTE) synthesized in Example 1. FIG. As shown in FIG. 7, it can be seen that the organic semiconductor compound synthesized in the present invention has excellent thermal stability and shows an increase in charge mobility when annealed, which is an excellent material.

The characteristics of the device fabricated in Example 4 were described in Table 2 below using the organic semiconductor compound (PNDIBTE) synthesized in Example 1. The device fabricated using the organic semiconductor compound (PNDIBTE) synthesized in Example 1 showed excellent n-type organic semiconductor characteristics with a charge mobility of 1.5 cm2V-1s-1, and the temperature of the annealing It was confirmed that the charge mobility increased and the blink ratio increased.

[Example 5] Production of organic electronic device

An organic electronic device was fabricated in the same manner as in Example 4, except that PNDIBTBTE synthesized in Example 2 was used as an organic semiconductor material.

The charge mobility was obtained from the slope by obtaining a graph of (ISD) ^1/2 and V _G as variables from the following formula (2) (saturation region current equation).

[Formula 2] Saturation region [

Wherein, I _SD is the source-and-drain current, μ or μ _FET is said mobile charge Doi, and C ₀ is oxide capacitance, W is the channel width, and L is channel length, V _G is the gate voltage, V _T is the threshold voltage. In addition, the blocking leakage current (I _off ) is a current flowing when the off state is obtained, and a minimum current is obtained from the off state at the current ratio.

FIG. 8 shows the results of measurement of the decomposition temperature of the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 using TGA. The temperature at which 5% decomposition of PNDIBTBTE occurs is measured at 453 ° C, so that PNDIBTBTE has excellent thermal stability.

9 shows the thermal stability of the organic semiconducting compound (PNDIBTBTE) synthesized in Example 2 against DSC. In the PNDIBTBTE, the glass transition temperature value, the melting temperature value and the crystallization temperature value are not shown, .

The light absorbing region of the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 was measured in a solution state and a film state, and the results are shown in FIG.

In order to analyze the electrochemical characteristics of the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2, cyclic voltammetry was performed under the condition of Bu ₄ NClO ₄ (0.1 molar concentration) in a solvent of 50 mV / s The measured results are shown in FIG. 11. In the measurement, a voltage was applied through a coating using a carbon electrode.

The optical and electrochemical properties of the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 are shown in Table 1 below. Here, the LUMO value is a value calculated using the result measured in FIG. The bandgap was also obtained at the UV absorption wavelength in the film state.

In FIG. 12, the distribution of electrons according to the energy level of a molecule is shown through DFT calculation. It can be seen that electrons are distributed in the electron-donor side at the HOMO energy level of the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2. [ In the LUMO energy level state, electrons in the electron donor move toward the electron acceptor.

13 is a diagram showing transfer curves of the device fabricated in Example 4 using the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2. FIG. As shown in FIG. 7, it can be seen that the organic semiconductor compound synthesized in the present invention has excellent thermal stability and shows an increase in charge mobility when annealed, which is an excellent material. The characteristics of the device fabricated in Example 5 were described in Table 2 below using the organic semiconductor compound (PNDIBTE) synthesized in Example 1. The device fabricated using the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 exhibited p-type organic semiconductor characteristics and it was confirmed that the charge mobility increased and the blink ratio increased as the annealing temperature increased .

[ Example  6] Production of organic electronic devices

An organic electronic device was fabricated in the same manner as in Example 4 except that PNDIBSE synthesized in Example 3 was used as an organic semiconductor material.

The charge mobility was obtained from the slope by obtaining a graph of (ISD) ^1/2 and V _G as variables from the following formula (2) (saturation region current equation).

[Formula 2] Saturation region [

Wherein, I _SD is the source-and-drain current, μ or μ _FET is said mobile charge Doi, and C ₀ is oxide capacitance, W is the channel width, and L is channel length, V _G is the gate voltage, V _T is the threshold voltage. In addition, the blocking leakage current (I _off ) is a current flowing when the off state is obtained, and a minimum current is obtained from the off state at the current ratio.

FIG. 14 shows the results of measurement of the decomposition temperature of the organic semiconductor compound (PNDIBSE) synthesized in Example 3 using TGA. The temperature at which 5% decomposition of PNDIBSE occurs is measured at 387 ° C, and PNDIBSE has excellent thermal stability.

15, the thermal stability of the organic semiconductor compound (PNDIBSE) synthesized in Example 3 was measured with respect to DSC. In PNDIBSE, PNDIBTBTE shows no glass transition temperature value, melting temperature value and crystallization temperature value, . ≪ / RTI >

The light absorbing region of the organic semiconductor compound (PNDIBSE) synthesized in Example 16 was measured in a solution state and a film state, and the results are shown in FIG.

In order to analyze the electrochemical characteristics of the organic semiconductor compound (PNDIBSE) synthesized in Example 3, cyclic voltammetry was performed under the condition of Bu ₄ NClO ₄ (0.1 molar concentration) in a solvent of 50 mV / s The measurement result is shown in FIG. 17, and a voltage was applied through a coating using a carbon electrode during the measurement.

The optical and electrochemical properties of the organic semiconductor compound (PNDIBSE) synthesized in Example 3 are shown in Table 1 below. Here, the LUMO value is a value calculated using the result measured in FIG. The bandgap was also obtained at the UV absorption wavelength in the film state.

In FIG. 18, the distribution of electrons according to the energy level of a molecule is shown through DFT calculation. It can be seen that electrons are distributed in the electron-donor side at the HOMO energy level of the organic semiconductor compound (PNDIBSE) synthesized in Example 3. [ In the LUMO energy level state, electrons in the electron donor move toward the electron acceptor.

[Table 1]

[Table 2]

As shown in Table 1, the compound (PNDIBTE) synthesized in Example 1, the compound (PNDIBTBTE) synthesized in Example 2, and the compound (PNDIBSE) synthesized in Example 3 absorb light in a wide wavelength range, And it has a low HOMO value, which indicates that the compound has high oxidation stability.

The characteristics of the devices fabricated in Examples 4 and 5 were described using the organic semiconductor compound (PNDIBTE) synthesized in Example 1 and the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 as shown in Table 2 above. The device fabricated using the organic semiconductor compound (PNDIBTE) synthesized in Example 1 showed excellent n-type organic semiconductor characteristics with a charge mobility of 1.5 cm ² V ^-1 s ^-1 , and annealing ) Was increased, the charge mobility and threshold voltage were increased, and it was confirmed that it had a high blink ratio. The device fabricated using the organic semiconductor compound (PNDIBTBTE) synthesized in Example 2 exhibited p-type organic semiconductor characteristics and it was confirmed that the charge mobility increased and the blink ratio increased as the annealing temperature increased .

11: substrate 12: insulating layer (insulator)
13: organic electronic device channel material 14: source material,
15: drain 16: gate (gate)

Claims (7)

A naphthalene diimide polymer represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
R ₁ and R ₂ are each independently C ₁ -C ₅₀ alkyl, C ₆ -C ₅₀ aryl, C ₁ -C ₅₀ alkoxy or

ego;
Z _1, Z ₂ , L _1, L ₂ and L < ₃ > are each independently selected from a single bond or the following structure;

V ₁ and V ₂ are

or

ego;
X ₁ to X ₇ are each independently S, Se, O, N, NH or NR ';
A ₁ and A ₂ are each independently hydrogen, cyano or -COOR ";
R 'and R " are each independently C ₁ -C ₅₀ alkyl or C ₆ -C ₅₀ aryl;
R ₃ to R ₃₁ are each independently hydrogen, hydroxy, amino, C ₁ -C ₅₀ alkyl, C ₆ -C ₅₀ aryl, C ₁ -C ₅₀ alkoxy, mono- or di-C ₁ -C ₅₀ alkylamino, C ₁ - C ₅₀ alkoxycarbonyl or C ₁ -C ₅₀ alkylcarbonyl and aryloxy;
Z is an integer of 1 to 20, m or y is an integer of 0 to 2, and n is an integer of 1 to 1,000;
Provided that m and y are 0 at the same time. The method according to claim 1,
In Formula 1,

≪ / RTI > is selected from the following structures.

[Wherein X ₁ to X ₄ , A ₁ , A ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are the same as defined in the above formula 1] 3. The method of claim 2,
remind

≪ / RTI > is selected from the following structures.

The method according to claim 1,
Wherein R < ₁ > and R < ₂ > are straight or branched C ₁ -C ₅₀ alkyl or

≪ / RTI > naphthalene diimide polymer.
[Wherein R ₃₁ and Z are the same as defined in Formula 1]. The method according to claim 1,
Lt; RTI ID = 0.0 > of: < / RTI > naphthalene diimide polymer.

[Wherein n is an integer of 1 to 1,000] 6. The method of claim 5,
Lt; RTI ID = 0.0 > of: < / RTI > naphthalene diimide polymer.

[Wherein n is an integer of 1 to 1,000] An organic thin film transistor comprising a naphthalene diimide polymer according to any one of claims 1 to 6 in an organic semiconductor layer.

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