KR101390666B1 - Diketopyrrolopyrrole- and tellurophene-based polymers derivative, organic semiconductor thin film and organic thin film transistor comprising the same - Google Patents

Abstract

The present invention relates to a diketopyrrolopyrrole and tellurophene-based polymer derivative, and an organic semiconductor thin film and an organic thin film transistor comprising the same, which produce and use the diketopyrrolopyrrole-based polymer derivative with excellent solubility in regular solvent, denoted by chemical formula 2, thereby providing the organic thin film transistor with excellent hole mobility and thermal stability.

Description

TECHNICAL FIELD The present invention relates to a polymer derivative containing diketopyrrolopyrrole and telluropene, an organic semiconductor thin film containing the same, and an organic thin film transistor and an organic thin film transistor,

The present invention relates to a diketopyrrolopyrrole polymer derivative having excellent solubility in a general solvent, high hole mobility and excellent thermal stability, an organic semiconductor thin film containing the same, and an organic thin film transistor.

Development of various devices using organic semiconductors has been actively studied more than ever in the past. In particular, organic thin film transistors have been making remarkable progress in a wide range of fields, leading to their use in active driving devices for organic EL.

Organic thin film transistors are not suitable for high-speed devices employing silicon (Si) or germanium (Ge) due to their low charge mobility due to the nature of organic semiconductors, but they are not suitable for fabrication of large area devices, low temperature processes, Can be used for fabrication, and in particular has a merit that a low-cost process is possible. Such an organic thin film transistor is composed of a substrate, a gate electrode, an insulating film, a channel layer, a source / drain electrode, and a protective layer for preventing external moisture and oxygen permeation. Among them, the channel layer has the greatest influence on the device characteristics and is a core part in which charge transfer occurs. In the organic thin film transistor, an organic compound or a polymer material that exhibits semiconductor characteristics is used instead of the conventional silicon based inorganic material. Specific examples thereof include polyphenylene compounds such as polyphenylene vinylene, polypyrrole, polythiophene, oligothiophene, or anthracene, tetracene, and pentacene. Particularly, polyacene compounds have strong intermolecular cohesion Therefore, it has an advantage that it has high crystallinity and excellent charge mobility. However, since the prior art uses a vacuum deposition process to manufacture a thin film necessary for manufacturing a device, expensive vacuum equipment is required, and the process is complicated, resulting in a disadvantage that the process cost is increased.

In order to solve this problem, studies for developing polyacene derivatives such as pentacene, which can be performed in a solution process, have been actively conducted, and a dissolvable pentacene precursor is synthesized, (PT Herwig and K. M, Adv . Mater . Vol. 11, p. 480 (1999)), a derivative in which triisopropylsilylethynyl group is bonded to both sides of pentacene to give solubility ... by developing a method used in a solution process (JE Anthony, et.al., J. Am Chem Soc, vol.123, p.9482 (2001);. JE Anthony, et.al., Tech Dig .- Int . Electron Devices Meet . , p.113 (2006)), another method for imparting solubility was to develop a pentacene derivative in which a trimethoxyphenylethynyl group was introduced as a substituent on both sides of pentacene to form an organic thin film transistor F. Wurthner, et al . , J. Mater . Chem . , Vol . 16, p . 370 (2006)). However, the precursors or derivatives have very poor thermal stability and oxidation stability, low charge mobility, and poor film performance due to their low molecular weight, making them difficult to apply to large-area devices. Therefore, it is also important to increase the solubility by introducing a substituent in order to make a polyacene-based organic semiconductor material such as pentacene suitable for a solution process. In addition to this, the stability of materials such as thermal stability and oxidation stability must be considered , It is also an important consideration to increase the intermolecular affinity and induce crystallization to improve the charge mobility.

On the other hand, since diketopyrrolopyrrole-based compounds were first developed in the early 1970's, they have been widely used in the ink, paint, and plastics industries. Recently, diketopyrrolopyrrole compounds have excellent fluorescence properties and charge carrier mobility And it has been attempted to apply it to the field of organic thin films for electronic devices. Korean Patent Laid-Open Publication No. 2001-50648 discloses an electroluminescent device comprising diketopyrrolopyrrole, specifically a electroluminescent device comprising a compound of the following formula:

Wherein Ar ₁ and Ar ₂ may be selected from the group consisting of an aryl radical, a heterocyclic radical, an unsaturated heterocyclic radical, and the like.

However, the conventional diketopyrrolopyrrole compounds have a limitation in that they can not have hole mobility enough to be used in an organic thin film transistor.

Therefore, in the present invention, the introduction of the telulophene structure excellent in electron acceptability into the diketopyrrolopyrrole excellent in planarity and excellent in electron accepting ability makes it possible to obtain a dichroic dye having excellent solubility in a solvent and high hole mobility and excellent heat stability An organic semiconductor thin film including the tofurolopyrrole polymer derivative, and an organic thin film transistor including the organic semiconductor thin film.

In order to solve the first problem,

There is provided a diketopyrrolopyrrole polymer derivative represented by the following formula (2): < EMI ID =

In Formula 2, R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; A C ₁ to C ₆₀ alkyl group; A C ₃ to C ₆₀ cycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heteroaryl group containing at least one atom selected from the group consisting of N, O, Si and S; A C ₁ to C ₆₀ heteroalkynyl group containing at least one atom selected from the group consisting of N, O, Si and S; An alkynyl group having from ₁ to ₆₀ carbon atoms; And a C ₁ to C ₆₀ heteroalkyl group containing at least one atom selected from the group consisting of N, O, Si and S,

M is at least one selected from the group consisting of alkynylene bond, or C ₂ to C ₆ alkenylene and C ₂ to C _6, the

Ar ₁ , Ar ₂ And Ar ₃ is a one selected from benzene, thiophene and celecoxib nopen and tell the group consisting of ruro pen, each independently, wherein Ar _1, Ar ₂ And Ar < ₃ > is telulophen,

a, b, c, d and e are integers of 0 or 1,

n is an integer of 1 to 100;

In order to solve the second problem, the present invention provides an organic semiconductor thin film comprising the diketopyrrolopyrrole-based polymer derivative represented by Formula 2.

According to a third aspect of the present invention, there is provided a semiconductor device comprising: a substrate; Source-drain electrodes; A channel layer; An organic thin film transistor including an insulating film and a gate electrode, wherein the channel layer includes the organic semiconductor thin film.

The diketopyrrolopyrrole-based polymer derivative of the present invention has excellent solubility in a general solvent, and can have high hole mobility and excellent thermal stability. Therefore, the diketopyrrolopyrrole-based polymer derivative of the present invention can be used in electronic and optoelectronic devices, particularly organic thin film transistors. Electronic and optoelectronic devices to which the polymer derivative of the present invention can be applied are not limited to the organic thin film transistor, but can also be applied to organic electroluminescent devices, organic solar cells, memory devices and the like.

1 is a diagram showing a general device structure of a conventional organic thin film transistor.
2 is a graph showing ¹ H NMR of a polymer derivative of formula 8 containing telethopyrrolopyrrole and telulophene prepared according to an embodiment of the present invention.
FIG. 3 is a graph of ¹ H NMR measurement of a polymer derivative of formula (12) containing a diketopyrrolopyrrole system and telulophene, prepared according to another embodiment of the present invention.
FIG. 4 is a graph showing the relationship between the ultraviolet-visible light absorbance of the polymeric derivative of formula 8 containing telethopyrrolopyrrole and telulophen prepared according to an embodiment of the present invention in a solution state and a thin film state, FIG.
FIG. 5 is a graph showing the relationship between the ultraviolet-visible light absorbance for the case where the diketopyrrolopyrrole system and the telulopene-containing polymer derivative prepared in accordance with another embodiment of the present invention are in a solution state and a thin film state, FIG.
FIG. 6 is a graph of a polymer derivative of formula 8, which contains a diketopyrrolopyrrole system and telulophene, prepared according to an embodiment of the present invention, using a thermogravimetric analyzer.
FIG. 7 is a graph of X-ray diffractometry of a thin film made of a polymer derivative of Formula 8 containing a diketopyrrolopyrrole system and tellurofen prepared according to an embodiment of the present invention.
FIG. 8 is a graph showing the X-ray diffraction spectrum of a thin film made of a polymer derivative of formula (12) containing a diketopyrrolopyrrole system and tellurofen prepared according to another embodiment of the present invention.
9 is a photograph of a thin film made of a polymer derivative of formula (8) containing a diketopyrrolopyrrole system produced according to an embodiment of the present invention and telulophen by an atomic force microscope.
10 is a graph showing an electrical characteristic of an organic thin film transistor using a thin film made of a polymer derivative of formula (8) containing a diketopyrrolopyrrole system and tellurofen prepared according to an embodiment of the present invention.
11 is a graph showing electrical characteristics of an organic thin film transistor using a thin film made of a polymeric derivative of formula (12) containing a diketopyrrolopyrrole system and tellurofen, prepared according to another embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. The present invention is not limited to the specific embodiments in which various modifications can be made to the polymer structure and the embodiments using various materials are used, and the scope of the present invention is not limited to the specific embodiments. It is therefore to be understood that within the scope of the present invention, the transformations, equivalents, and alternatives of the invention are also included. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described more fully with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown.

In the present invention, by introducing a telulophene structure excellent in electron acceptability into diketopyrrolopyrrole having excellent planarity and excellent electron accepting ability, diketopyrrolopyrrole having excellent solubility in a solvent and having high hole mobility and excellent heat stability The present invention provides a diketopyrrolopyrrole polymer derivative represented by the following formula (2): < EMI ID =

(2)

In Formula 2, R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; A C ₁ to C ₆₀ alkyl group; A C ₃ to C ₆₀ cycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heteroaryl group containing at least one atom selected from the group consisting of N, O, Si and S; A C ₁ to C ₆₀ heteroalkynyl group containing at least one atom selected from the group consisting of N, O, Si and S; An alkynyl group having from ₁ to ₆₀ carbon atoms; And a C ₁ to C ₆₀ heteroalkyl group containing at least one atom selected from the group consisting of N, O, Si and S,

M is at least one selected from the group consisting of alkynylene bond, or C ₂ to C ₆ alkenylene and C ₂ to C _6, the

Ar ₁ , Ar ₂ And Ar ₃ is a one selected from benzene, thiophene and celecoxib nopen and tell the group consisting of ruro pen, each independently, wherein Ar _1, Ar ₂ And Ar < ₃ > is telulophen,

a, b, c, d and e are integers of 0 or 1,

n is an integer of 1 to 100;

A major feature of the diketopyrrolopyrrole-based polymer derivative according to the present invention is that a telulophene structure is introduced into diketopyrrolopyrrole. The properties of the tellurium (Te) element are significantly different from those of the same 16 group (6A) elements selenium and sulfur. Only a few studies exist for polymers based on polytelulophene and telulophen, and calculations for spectroscopic studies or experimental energy band spacing have been rarely reported. Theoretically, polyetulophenes have a low energy band gap, which has the advantage of having optical absorption properties in the long wavelength region. Moreover, because tellurium has strong tellurium-tellurium interactions as a metalloid, it is expected to have very strong molecular interactions between the polymer chains. Therefore, in the present invention, tellurophen having excellent electron acceptability is introduced into diketopyrrolopyrrole having excellent planarity and excellent electron accepting ability to achieve excellent hole mobility and excellent solubility suitable for solution process, And to provide a polymer derivative having excellent stability even under the environment.

Despite these advantages, there is little research on polytelulopen because it is difficult to find a suitable way to synthesize telulophene-based monomers. In the present invention, the diketopyrrolopyrrole-based polymer including telulophene was devised and synthesized in spite of these difficulties.

The diketopyrrolopyrrole polymer derivative of the present invention is synthesized by a synthesis process of the following Reaction Scheme 1 or Reaction Scheme 2.

 [Reaction Scheme 1]

The diketopyrrolopyrrole polymer derivative prepared according to the above Reaction Scheme 1 is one in which at least one of a, b, c, d and e is 1, provided that when Ar ₁ is not telulophen, Ar ₂ Or Ar ₃ must be telulophen.

In the above Reaction Scheme 1, X ₁ is Br when Ar ₁ is benzene; Thienyl, thiophene, selenophen and tellurophene are H.

화합물을 톨루엔에서 90 내지 110 ℃에서 24 내지 64 시간 동안 반응, 또는

화합물을 톨루엔과 포타슘카보네이트(K₂CO₃) 수용액에서 24 내지 64 시간 동안 반응시켜 [화학식 2]로 표시되는 화합물을 제조한다. According to the above-mentioned Reaction Scheme 1, an aryl group (X-Ar ₁ -CN) substituted with a cyanide group, dibutyl succinate, potassium t-butoxide (t-BuOK) 2-butanol is reacted at 100 to 120 ° C for 20 to 28 hours to prepare a compound of formula (5); Next, the compound of formula (5) is reacted with potassium carbonate (K ₂ CO ₃ ), dimethylformamide (DMF), R ₁ -X ₂ And R ₂ -X ₂ compound (X ₂ = Br or I) at 120 to 160 ° C for 28 to 32 hours to prepare a compound of Formula 4; Next, when the [formula 4] the compound with N- bromosuccinimide (NBS) and chloroform at room temperature to react for 24 to 48 hours produced a compound of Formula 3 (where, X ₁ is Br step reaction . Next, the compound of Formula 3] a catalyst (Pd (PPh _{3) 4)} and

Reaction of the compound in toluene at 90 to 110 DEG C for 24 to 64 hours, or

The compound is reacted in an aqueous solution of toluene and potassium carbonate (K ₂ CO ₃ ) for 24 to 64 hours to prepare a compound represented by the formula (2).

R ₃ is a methyl or butyl group.

[Reaction Scheme 2]

화합물 또는

화합물의 a, e 가 반드시 1이고 b, c, d, 가 적어도 2 이상이라 제조가 용이하지 않을 경우 수율 향상을 위해 적용한다.[Reaction formula 2] is a monomer used in the synthesis of [formula 2] in [Reaction scheme 1]

Compound or

If a and e of the compound are necessarily 1 and b, c and d are at least 2 or more, it is applied to improve the yield when production is not easy.

When Ar ₁ and Ar ₂ are not telulophen in the above Reaction Scheme 2, at least one of b and d must be telulophen.

화합물을 톨루엔에서 90 내지 110 ℃에서 24 내지 48 시간 동안 반응, 또는

화합물을 톨루엔과 포타슘카보네이트(K₂CO₃) 수용액에서 24 내지 48시간 동안 반응시켜 [화학식 7]의 화합물 제조; 다음으로 [화학식 7]의 화합물과 N-브로모석신이미드(NBS) 및 클로로포름을 상온에서 24 내지 48시간 동안 반응시켜 [화학식 6]의 화합물 제조; 다음으로 촉매(Pd(PPh₃)₄)하에서 [화학식 6]의 화합물과

화합물을 톨루엔에서 90 내지 110 ℃에서 24 내지 64 시간 동안 반응, 또는

화합물을 톨루엔과 포타슘카보네이트(K₂CO₃) 수용액에서 24 내지 64 시간 동안 반응시켜 [화학식 2]로 표시되는 화합물을 제조한다. According to the above Reaction Scheme 2, a compound of Formula 3 of Reaction Scheme 1 and a compound of Reaction Scheme 1 under a catalyst (Pd (PPh ₃ ) ₄ )

Reaction of the compound in toluene at 90 to 110 캜 for 24 to 48 hours, or

Compound in an aqueous solution of toluene and potassium carbonate (K ₂ CO ₃ ) for 24 to 48 hours to prepare a compound of the formula 7; Next, the compound of formula (7) is reacted with N-bromosuccinimide (NBS) and chloroform at room temperature for 24 to 48 hours to prepare a compound of formula (6). Next, the compound of Formula 6] a catalyst (Pd (PPh _{3) 4)} and

Reaction of the compound in toluene at 90 to 110 DEG C for 24 to 64 hours, or

The compound is reacted in an aqueous solution of toluene and potassium carbonate (K ₂ CO ₃ ) for 24 to 64 hours to prepare a compound represented by the formula (2).

R ₃ is a methyl or butyl group.

The following are examples of the polymer of the present invention.

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; A C ₁ to C ₆₀ alkyl group; A C ₃ to C ₆₀ cycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heteroaryl group containing at least one atom selected from the group consisting of N, O, Si and S; A C ₁ to C ₆₀ heteroalkynyl group containing at least one atom selected from the group consisting of N, O, Si and S; An alkynyl group having from ₁ to ₆₀ carbon atoms; And a C ₁ to C ₆₀ heteroalkyl group comprising at least one atom selected from the group consisting of N, O, Si, and S.

) 로 정의한다.
Y ₁ and Y ₂ are S, Se Te elements, or Alkeni (

).

The present invention also provides an organic semiconductor thin film comprising a diketopyrrolopyrrole-based polymer represented by the above formula (2) and a polymer derivative containing telulophen.

The organic semiconductor thin film may be formed by dissolving the diketopyrrolopyrrole polymer derivative represented by Formula 2 in an organic solvent and coating the substrate. Examples of the coating method include spin coating, drop casting or ink jet coating. Examples of the organic solvent include at least one selected from the group consisting of chloroform, dichlorobenzene, trichloroethane, N-methylpyrrolidone and toluene , But is not limited thereto.

The present invention also provides an organic thin film transistor comprising the diketopyrrolopyrrole-based polymer derivative represented by Formula 2 or the organic semiconductor thin film.

The organic thin film transistor includes a substrate; Source-drain electrodes; A channel layer; And an organic semiconductor thin film made of a diketopyrrolopyrrole-based polymer derivative represented by Formula 2 as the channel layer.

The organic thin film transistor may include a substrate according to a general device structure; A gate electrode; Insulating film; A channel layer (organic semiconductor thin film); A bottom gate method (FIG. 1) or substrate formed in the order of the source-drain electrodes; Source-drain electrodes; A channel layer (organic semiconductor thin film); Insulating film; Gate electrodes may be formed in the order of the top gate. As the insulating film, silicon dioxide (SiO ₂ ), polyvinyl phenol, polymethyl methacrylate, or Cytop (Japan, manufactured by Asahi Glass Co., Ltd.) may be used, but the present invention is not limited thereto.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

<Examples>

Synthesis Example 1. Synthesis of diketopyrrolopyrrole polymer derivative represented by the formula (8)

(1-1) Synthesis of Compound Represented by Formula 11

3.25 g of 2-thiophenecarbonitrile, 1.5 g of dibutylsuccinate, 4 g of potassium t-butoxide and 25 ml of 2-methyl-2-butanol were reacted at 110 DEG C for 3 hours The reaction was terminated by stirring. Acetic acid and methanol were added to the reaction solution which had been cooled to 60 DEG C, and then the precipitated compound of Formula 11 was filtered and dried to obtain 2.5 g (yield: 84%) of the compound. Lt; / RTI &gt;

[Reaction Scheme 3]

(11)

(1-2) Synthesis of Compound Represented by Formula 10

(4), 3.4 g of the compound of formula (11), 11.8 g of 2-octyldodecyl iodide, 9.5 g of potassium carbonate and 100 ml of dimethylformamide (DMF) were reacted at 140 ° C. for 20 hours The reaction was terminated by stirring. Only the organic layer was extracted with dichloromethane and distilled water and purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) to obtain 2.1 g (yield: 22%) of [Chemical Formula 10].

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.88 (d, J = 4.0 Hz, 2 H), 7.62 (d, J = 4.8 Hz, 2 H), 7.27 (dd, J = 4.0 Hz, 4.8 Hz, 2 H), 4.02 (d, 4 H), 1.91 (m, 2 H), 1.25 (m, 64 H), 0.86 (m, 12 H).

[Reaction Scheme 4]

[Chemical Formula 11]

(1-3) Synthesis of Compound Represented by Formula 9

Was synthesized according to the following Reaction Scheme 5, and the reaction was terminated by stirring the compound of Formula 10 (1.25 g), N-bromosuccinimide (0.51 g) and chloroform (90 ml) at 25 ° C for 24 hours. The organic layer was extracted with dichloromethane and distilled water and purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) 0.9 g (yield: 75%).

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.63 (d, J = 4.0 Hz, 2 H), 7.21 (d, J = 4.0 Hz, 2 H), 3.91 (d, 4 H), 1.87 ( m, 2 H), 1.25 (m, 64 H), 0.86 (m, 12 H).

[Reaction Scheme 5]

[Chemical Formula 10]

(1-4) Synthesis of Compound Represented by Formula 8

400 mg (0.392 mmol) of the compound of the formula 9 was dissolved in 20 ml of toluene, and then 200 mg (0.396 mmol) of the compound of 2,5-bis (trimethylstannyl) tellurophene was added thereto, (Pd (PPh ₃ ) ₄ ) 23 mg (0.019 mmol) was added thereto, and the mixture was stirred at 90 ° C. for 52 hours. When the reaction was completed, the mixture was cooled to room temperature (25 ° C.), diluted with chloroform 100 ml, Precipitated with a solution in which 100 ml of 1N hydrochloric acid was mixed, was filtered with a filter to obtain a precipitate. After repeating this process twice, the obtained precipitate was dried and then extracted with methanol, acetone, and hexane in a soxhlet, dissolved in chloroform and reprecipitated, and then filtered to obtain 350 mg (Yield: 87%). The data for ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C) of the compound of formula (8) are shown in FIG.

[Reaction Scheme 6]

[Chemical Formula 8]

Synthesis Example 2. Synthesis of diketopyrrolopyrrole polymer derivative represented by Formula 12

(2-1) Synthesis of Compound Represented by Formula 16

, 1.4 g of the compound of the formula (11), 6 g of 2-decyltetradecyl iodide, 1.5 g of potassium carbonate and 30 ml of dimethylformamide (DMF) were reacted at 120 ° C for 24 hours The reaction was terminated by stirring. The organic layer was extracted with dichloromethane and distilled water, and the residue was purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) 1.2 g (yield: 27%).

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.88 (d, J = 4.0, 2H), 7.62 (d, J = 4.8, 2H), 7.27 (dd, J = 4.0 Hz, 4.8 Hz, 2 H ), 4.03 (d, J = 7.71,4H), 1.91 (m, 2H), 1.301.21 (m, 80H), 0.890.87 (m, 12H).

[Reaction Scheme 7]

[Chemical Formula 11]

(2-2) Synthesis of Compound Represented by Formula 15

The reaction was completed by reacting 1 g of the compound of the formula (16), 0.45 g of N-bromosuccinimide and 50 ml of chloroform at 25 DEG C for 24 hours. The organic layer was extracted with dichloromethane and distilled water and purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) 0.6 g (yield: 52%).

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.62 (d, J = 4.0, 2H), 7.21 (d, J = 4.0, 2H), 3.91 (d, 4H), 1.87 (m, 2H), 1.291.21 (m, 80H), 0.890. 86 (m, 12H).

[Reaction Scheme 8]

[Chemical Formula 15]

(2-3) Synthesis of Compound Represented by Formula 14

1.1 g of the compound of the formula 15 was dissolved in 20 ml of toluene and 5 ml of a 2M aqueous solution of potassium carbonate to obtain 4,4,5,5-tetramethyl-2- (selenophen-2 -yl) -1,3,2-dioxaborolane 0.6 g and was added to 23 mg of catalyst (Pd (PPh _{3) 4)} the reaction was terminated by stirring at 90 ℃ for 24 hours. The organic layer was extracted with dichloromethane and distilled water and purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) 0.8 g (yield: 75%).

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.91 (d, J = 4.0, 2H), 8.01 (d, J = 4.0, 2H), 7.48 (d, J = 4.0, 2H), 7.30 (m 2H), 7.25 (d, J = 4.0, 2H), 4.01 (d, 4H), 1.96 (m, 2H), 1.291.21 (m, 80H), 0.890.

[Reaction Scheme 9]

[Chemical Formula 15]

(2-4) Synthesis of Compound Represented by Formula 13

The reaction was completed by reacting 0.6 g of the compound of the formula 14, 0.18 g of N-bromosuccinimide and 30 ml of chloroform at 25 DEG C for 24 hours. The organic layer was extracted with dichloromethane and distilled water and purified by column chromatography (CH ₂ Cl ₂ / Hexane, 30:70, v / v) 0.7 mg (yield: 80%).

^{1 H NMR (400 MHz, CDCl} 3, 25 ℃): 8.86 (d, J = 4.0, 2H), 7.23 (d, J = 4.0, 2H), 7.16 (m, 4H), 4.01 (d, 4H), 1.92 (m, 2H), 1.291. 21 (m, 80H), 0.890. 86 (m, 12H).

[Reaction Scheme 10]

[Chemical Formula 14]

(2-5) Synthesis of Compound Represented by Formula 12

Was synthesized according to the [Reaction Scheme 11], wherein the toluene 15 ㎖ [Formula 13] 0.28 g of compound is dissolved and then 2,5-bis (trimethylstannyl) tellurophene compound and 0.11 g of catalyst (Pd (PPh _{3) 4)} of the After the reaction was completed, the reaction mixture was cooled to room temperature (25 ° C), diluted with chloroform 10 ml, and reprecipitated with a mixed solution of methanol 800 ml / 1N hydrochloric acid 100 ml The solution was filtered through a filter to obtain a precipitate. After repeating this process twice, the obtained precipitate was dried and then extracted with methanol, acetone, and hexane in a soxhlet, dissolved in chloroform to precipitate the precipitate. The precipitate was reprecipitated and filtered to obtain 0.21 g (Yield: 75%). The data for ¹ H NMR (400 MHz, CDCl ₃ , 25 ° C) of the compound of formula (12) are shown in FIG.

[Reaction Scheme 11]

[Chemical Formula 13]

Test Example  1. Compounds of the formula 8 ^One H NMR  Measure

Fig. 2 is a graph showing the relationship between the diketopyrrolopyrrole system and telulophen prepared according to an embodiment of the present invention &Lt; ¹ &gt; H NMR of the polymer derivative.

Test Example  2. Compounds of the formula 12 ^One H NMR  Measure

FIG. 3 is a graph showing the relationship between the diketopyrrolopyrrole system and telulopene prepared according to an embodiment of the present invention &Lt; ¹ &gt; H NMR of the polymer derivative.

Test Example  3. Ultraviolet-visible light absorbance measurement of the compound of formula (8)

FIG. 4 is a graph showing the relationship between the polymer derivative of formula (8) containing the diketopyrrolopyrrole system and telulophen prepared according to an embodiment of the present invention in a solution state and the case where the polymer derivative is formed in a thin film state, - Absorption spectrum measured with a visible light spectrometer (HP8453, Photodiode array type).

[Formula 8] Λ _max , λ _cutoff when the polymer derivative is in a solution state and a thin film state And E _g ^opt values are shown in Table 1 below.

division The compound of the formula (8) in solution The compound of the formula 8 in a thin film state λ _max 784 nm, 862 nm 810 nm, 900 nm λ _cutoff 930 nm 995 nm E _g ^OPT 1.33 eV 1.25 eV

As shown in Table 1 and FIG. 4, the maximum absorption wavelength (λ _max ) and the cutoff wavelength (λ _cutoff ) were shifted to the right, and the optical energy band gap (E _g ^opt ) Were found to be low. From these results, it can be expected that the polymer derivative having the near infrared absorption and the low energy band gap has excellent semiconductor properties and high hole mobility.

Test Example  4. Ultraviolet-visible light absorbance measurement of the compound of formula (12)

FIG. 5 shows the case where the polymer derivative of formula (12) containing the diketopyrrolopyrrole system and telulophene prepared according to an embodiment of the present invention is in a solution state and the case where the polymer derivative is formed into a thin film state, - Absorption spectrum measured with a visible light spectrometer (HP8453, Photodiode array type).

[Formula 12] Λ _max , λ _cutoff when the polymer derivative is in a solution state and a thin film state And E _g ^opt values are shown in Table 2 below.

division The compound of the formula (12) in solution The compound of the formula (12) in a thin film state λ _max 852 nm 835 nm λ _cutoff 915 nm 909 nm E _g ^OPT 1.35 eV 1.36 eV

As shown in Table 2 and FIG. 5, the maximum absorption wavelength (λ _max ) and the cutoff wavelength (λ _cutoff ) were shifted to the right and the optical energy band gap (E _g ^opt ) Were found to be low. From these results, it is predicted that the polymer derivative of formula (12) having near infrared absorption and low energy band gap has excellent semiconductor properties and high hole mobility.

Test Example  5. Measurement of thermal stability of the compound of formula (8)

FIG. 6 is a graph of a polymer derivative of formula 8, which contains a diketopyrrolopyrrole system and tellurofen, prepared according to an embodiment of the present invention, using a thermogravimetric analyzer (Mettler TGA50). The polymer derivative of the formula (8) was carried out at a temperature raising rate of 10 ° C / min under a nitrogen atmosphere at a temperature range of 35 to 600 ° C.

As shown in FIG. 6, the polymer derivative of formula (8) had a thermal decomposition temperature of 5% at a high temperature of 400 ° C or more, indicating excellent thermal stability.

Test Example  6. Compounds of formula 8 XRD  Measure

FIG. 7 is a graph showing the X-ray diffractometer (Rigaku D / Max Ultimata 3, Fig. 7) showing a thin film made of a polymer derivative of formula (8) containing a diketopyrrolopyrrole system and tellurofen prepared according to an embodiment of the present invention, Cu K?:? = 1.54).

The polymer was spin-coated at a temperature of 250 ° C., and a diffraction pattern was measured for a sample prepared by the heat treatment at a temperature of 250 ° C. The thin film was formed on a silicon wafer by drop-casting. At this time, chloroform was used as a solvent, and the concentration was 10 mg / ml.

As shown in FIG. 7, when the thin film was prepared using the compound of the formula (8) prepared according to the example, a high diffraction intensity was exhibited at a temperature of 250 ° C., and it was confirmed that the film had a high crystallinity.

Test Example  7. Compounds of formula 12 XRD  Measure

FIG. 8 is a graph showing the X-ray diffractometer (Rigaku D / Max Ultimata 3, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) using a thin film made of a polymer derivative of formula (12) containing a diketopyrrolopyrrole- Cu K?:? = 1.54).

The polymer was spin-coated at a temperature of 250 ° C., and the diffraction pattern of the sample was measured. The thin film was formed on a silicon wafer by drop-casting. At this time, chloroform was used as a solvent, and the concentration was 10 mg / ml.

As shown in FIG. 8, when the thin film was prepared using the compound of the formula (12) prepared according to the example, a high diffraction intensity was shown at a temperature of 250 ° C., and it was confirmed that the film had a high crystallinity.

Test Example  8. Compounds of formula 8 AFM  Image investigation

FIG. 9 is a graph showing the results of a scanning electron microscope (AFM) (Advanced Scanning Probe Microscope, XE-100) using a thin film made of a polymer derivative of Formula 8 containing a diketopyrrolopyrrole system and telulophene prepared according to an embodiment of the present invention. , PSIA).

As a thin film sample, a polymer sample was spin-coated on a silicon wafer and then heat-treated at 250 ° C for 10 minutes. Chloroform was used as a solvent for spin coating, and the concentration was 10 mg / ml. The atomic force microscope (AFM) observed the surface of each thin film using a silicon cantilever in the tapping mode.

As shown in FIG. 9, the non-heat-treated thin films already exist in the form of organic packing between the molecules before the heat treatment, and the heat-treated thin films are superior to the non- It was confirmed that the organic packing between the molecules was increased and the crystallinity was further increased.

Test Example  9. Organic thin film transistor of compound

10 is a graph showing an electrical characteristic of an organic thin film transistor using a thin film made of a polymer derivative of formula (8) containing a diketopyrrolopyrrole system and tellurofen prepared according to an embodiment of the present invention.

The organic thin film transistor used in this test example was prepared by treating the surface with octyltrichlorosilane (OTS) to form a hydrophobic SiO ₂ dielectric surface on a highly doped n-doped Si / SiO ₂ substrate, 8] was spin-coated to a thickness of 40 to 50 nm and then heat-treated at 250 ° C for 10 minutes. The gold electrodes of the source and drain were fabricated by vacuum deposition through a shadow mask having a length of 1.5 mm and a width of 0.1 mm.

As shown in FIG. 10, the organic thin film transistor using the organic thin film of the present invention has a high hole mobility of 1.51 cm 2 / Vs. 10, the graph on the right is an output characteristic graph showing a change in I _DS with respect to the output voltage V _DS for each V _G. At this time, V _G was measured with sequential changes of 0, -20, -40, -60, -80, -100, and 120 V, respectively. All field effect charge mobility was calculated by μ _sat = (2I _DS L) / (WC (V _G -V _TH ) ² ) where I _DS saturation drain current, C is the capacitance of oxide dielectric, V _G is the gate bias, and V _TH is the threshold voltage. The performance of the fabricated equipment was measured with a Keithley 4200 semiconductor characterizer in air at room temperature.

Test Example  10. Organic thin film transistor of compound

11 is a graph showing electrical characteristics of an organic thin film transistor using a thin film made of a polymer derivative of formula (12) containing a diketopyrrolopyrrole system and tellurofen, prepared according to an embodiment of the present invention. As a thin film sample, a sample obtained by spin coating a diketopyrrolopyrrole polymer derivative, which is a compound of formula (12), on a silicon wafer treated with octyltrichlorosilane (OTS), and then heat-treating at 200 ° C for 10 minutes was used.

As shown in FIG. 11, the organic thin film transistor using the organic thin film of the present invention has a high hole mobility of 0.63 cm 2 / Vs. 11, the graph on the right is an output characteristic graph showing a change in I _DS with respect to the output voltage V _DS for each V _G. At this time, V _G was measured with sequential changes of 0, -20, -40, -60, -80, -100, and 120 V, respectively.

Claims (3)

A diketopyrrolopyrrole polymer derivative represented by the following formula (2):
(2)

In Formula 2, R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; A C ₁ to C ₆₀ alkyl group; A C ₃ to C ₆₀ cycloalkyl group; A C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heteroaryl group containing at least one atom selected from the group consisting of N, O, Si and S; A C ₁ to C ₆₀ heteroalkynyl group containing at least one atom selected from the group consisting of N, O, Si and S; An alkynyl group having from ₁ to ₆₀ carbon atoms; And a C ₁ to C ₆₀ heteroalkyl group containing at least one atom selected from the group consisting of N, O, Si and S,
M is at least one selected from the group consisting of alkynylene bond, or C ₂ to C ₆ alkenylene and C ₂ to C _6, the
Ar ₁ , Ar ₂ And Ar ₃ is a one selected from benzene, thiophene and celecoxib nopen and tell the group consisting of ruro pen, each independently, wherein Ar _1, Ar ₂ And Ar &lt; ₃ &gt; is telulophen,
a, b, c, d and e are integers of 0 or 1,
n is an integer of 1 to 100; An organic semiconductor thin film comprising a diketopyrrolopyrrole-based polymer derivative represented by Formula (2) according to Claim 1. Board; Source-drain electrodes; A channel layer; An organic thin film transistor comprising an insulating film and a gate electrode, wherein the channel layer comprises the organic semiconductor thin film according to claim 2.

Images