KR20150110127A - Asymmetric diketopyrrolopyrrole polymer and organic electronic device using the same - Google Patents

Abstract

The present invention relates to a novel asymmetric diketopyrrolopyrrole polymer and uses thereof. According to the present invention, the diketopyrrolopyrrole polymer has high π-electron stacking by introducing an electron donor compound, has high asymmetric arrangement, and thus has high solubility due to an increase in free volume. A solution process is available in an eco-friendly non-halogenated solvent due to the high solubility. The organic electronic device applying the same is capable of performing excellent charge mobility and a remarkable on/off ration, and can be broadly applied to a semiconductor device.

Description

Asymmetric diketopyrrolopyrrole polymer and organic electronic device using the same [0002]

The present invention relates to novel asymmetric diketopyrrolopyrrole polymers and their uses, and more particularly to asymmetric diketopyrrolopyrrole polymers which are capable of solution processing in environmentally friendly non-halogen solvents due to their high solubility, To an organic electronic device.

The development of information communication in the 21st century and the desire for personal portable communication devices are required for ultra-fine processing that enables information communication devices that are small in size, light in weight, thin in thickness, and easy to use, Electronic materials, and new information communication materials that enable new concept display. Among them, the organic thin film transistor (OTFT) can be applied to a display device such as a portable computer, an organic EL device, a smart card, an electric tag, a pager, a cellular phone, The possibility of being used as an important component of the plastic circuit part has been the subject of much research.

Organic thin film transistors using organic semiconductors have advantages over conventional amorphous silicon and polysilicon organic thin film transistors because they are simple to manufacture and can be manufactured at low cost. Compatibility with plastic substrates for the implementation of flexible displays And the advantages such as the superiority of the recent research is being done. 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.

Generally, an organic thin film transistor has a structure including a substrate / gate / insulating layer / electrode layer (source, drain) / organic semiconductor layer, and a gate electrode is formed on the substrate. An insulating layer is formed on the gate electrode, and an organic semiconductor layer, a source and a drain electrode are sequentially formed on the insulating layer. The driving principle of the organic thin film transistor having the above structure will be described as an example of a p-type semiconductor as follows. First, when a voltage is applied between a source and a drain to flow a current, a current proportional to the voltage flows under a low voltage. When a positive voltage is applied to the gate, the positive charges are all pushed up to the top of the semiconductor layer by the electric field due to the applied voltage. Therefore, a depletion layer having no conduction charge is generated in a portion close to the insulating layer, and in such a situation, a low amount of current will flow because a potential carrier between the source and the drain is reduced even when a conduction charge carrier is reduced . On the contrary, when a negative voltage is applied to the gate, an accumulation layer is formed in which a positive charge is induced in the vicinity of the insulating layer by the effect of the electric field by the applied voltage. At this time, since there are many conduction charge carriers between the source and the drain, more current can flow. Therefore, the current flowing between the source and the drain can be controlled by alternately applying a positive voltage and a negative voltage to the gate while a voltage is applied between the source and the drain.

Electrodes (sources and drains), substrates and gate electrodes requiring high thermal stability, insulators having high dielectric constant and dielectric constant, and semiconductors capable of transferring charges well can be used for organic thin film transistors having the above- There are many problems to be overcome, but the key material is organic semiconductors. 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 organic semiconductor is used in the formation of an organic semiconductor layer, the low-molecular organic semiconductor is easy to purify and can remove impurities hardly, so that the charge transfer property is excellent. However, such an organic semiconductor can not be spin- Therefore, the manufacturing process is complicated and costly as compared with the polymer organic semiconductor, because the thin film must be manufactured through vacuum deposition. 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.

Korean Patent Publication No. 2011-0091711 and Korean Patent Publication No. 2009-0024832 disclose a polymer in which a heteroaromatic ring containing S is directly bonded to a diketopyrrolopyrrole group. However, since it still does not show sufficient expansion of the pi electron, it is necessary to develop a polymer semiconductor material showing sufficient pi electron overlap.

Accordingly, the present inventors have synthesized a novel asymmetric diketopyrrolopyrrole polymer by introducing an electron donor compound into a diketopyrrolopyrrole polymer, which is an electron acceptor compound, and have a high pi electron overlap according to this asymmetric arrangement, Free volumetric flame retardant, the present inventors have completed the present invention by confirming that a solution process in an environmentally friendly nonhalogen solvent is possible due to high solubility.

Korean Patent Publication No. 2011-0091711 (2011.08.12.) Korean Patent Publication No. 2009-0024832 (2009.03.09.)

It is an object of the present invention to provide a novel asymmetric diketopyrrolopyrrole polymer which has a high pi electron overlapping and asymmetric arrangement, and an organic electronic device capable of performing an environmentally friendly solution process using the same.

The present invention includes a diketopyrrolopyrrole polymer represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

R1 to R4 are each independently hydrogen or a (C1-C50) alkyl group,

Each of which may be further substituted with a substituent of (C1-C30) alkyl or (C1-C30) alkoxy, respectively;

X1 is S or Se;

m is an integer from 1 to 1,000;

and n is an integer of 0 to 1,000.

The diketopyrrolopyrrole polymers according to one embodiment of the present invention may be selected from the following compounds.

[Wherein m and n are each independently an integer of 1 to 1,000]

이고, a는 2 내지 10의 정수이고, R₁₁및 R₁₂은 각각 독립적으로 (C10-C30)알킬일 수 있다.According to one embodiment of the present invention, each of R1 to R4 independently represents

, A is an integer from 2 to 10, and R ₁₁ and R ₁₂ are each independently (C 10 -C 30) alkyl.

The present invention provides an organic electronic device comprising the diketopyrrolopyrrole polymer.

The organic electronic device according to an embodiment of the present invention may include a substrate, a gate, a gate insulating layer, an organic semiconductor layer, and a source-drain electrode.

The diketopyrrolopyrrole polymer according to an embodiment of the present invention may be an organic electronic device included in the organic semiconductor layer.

Unlike conventional alternating copolymers, the novel asymmetric diketopyrrolopyrrole polymers of the present invention have a random arrangement and thus have irregular arrangement, resulting in a high pi electron overlap and an increase in free volume between polymers And has high solubility. Because of this high solubility, environmentally friendly non-halogen solvents can be used to produce devices in a solution process without environmental degradation.

Figure 1 is a UV-vis absorption spectrum of a solution phase and film on an asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Se) according to Example 1,
Figure 2 is a UV-vis absorption spectrum on a solution and film of an asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Th) according to Example 2,
3 is a cyclic voltammetry diagram of an asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Se, P29DPP-TT-Th) according to Examples 1 to 2,
4 is a thermogravimetric analysis (TGA) curve of an asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Se) according to Example 1,
5 is a thermogravimetric analysis (TGA) curve of an asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Th) according to Example 2,
6 and 7 are diagrams showing the characteristics (transfer curve, output curve) of the device fabricated by the method of Example 3 using the asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Se) according to Example 1 ,
8 and 9 are diagrams showing the characteristics (transfer curve, output curve) of the device manufactured by the method of Example 4 using the asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Th) according to Example 2 .

 The present invention relates to novel asymmetric diketopyrrolopyrrole polymers which are organic semiconducting compounds for organic electronic devices and their uses. More specifically, the present invention comprises a compound comprising an electron donor group in a diketopyrrolopyrrole polymer, which is an electron donor compound, characterized by having an irregular arrangement. The present invention also relates to an organic electronic device containing a diketopyrrolopyrrole polymer which is a p-type polymeric organic semiconductor compound used as an active layer material of an organic thin film transistor.

The present invention provides a diketopyrrolopyrrole polymer represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

R1 to R4 are each independently hydrogen or a (C1-C50) alkyl group,

Each of which may be further substituted with a substituent of (C1-C30) alkyl or (C1-C30) alkoxy, respectively;

X1 is S or Se;

m is an integer from 1 to 1,000;

and n is an integer of 0 to 1,000.

The asymmetric diketopyrrolopyrrole polymer represented by the formula (1) of the present invention can be obtained by graft polymerization of an asymmetric asymmetric monomer of a polymer main chain, thereby increasing the coplanarity of the main chain, Thereby improving the electron density and enhancing the intermolecular interaction, and thus the organic electronic device containing the same exhibits high mobility.

인 구조를 가짐으로써 보다 높은 용해도를 가질 수 있다. 이때, R₁ 내지 R₄의 a는 2 내지 10의 정수를 가지고 말단에 가지쇄를 가지지 않은 알킬에 비해 무려 10배 이상 높은 전하이동도를 가지며 동시에 높은 용해도를 가져 용액공정에 보다 유리하여 간단하고 저렴한 공정으로 대면적의 유기 전자 소자를 제작할 수 있다.Also, R1 to R4, which are substituents of the diketopyrrolopyrrole polymer,

Can have a higher solubility. In this case, a of R ₁ to R ₄ has a charge mobility of 10 times or more higher than that of an alkyl having an integer of 2 to 10 and no branch at the terminal, and at the same time, has high solubility, An organic electronic device with a large area can be manufactured with an inexpensive process.

이고, a는 2 내지 10의 정수이고, R₁₁및 R₁₂은 각각 독립적으로 (C10-C30)알킬일 수 있다. R 1 to R 4 in the formula (1) according to an embodiment of the present invention are each independently

, A is an integer from 2 to 10, and R ₁₁ and R ₁₂ are each independently (C 10 -C 30) alkyl.

The diketopyrrolopyrrole polymer according to an embodiment of the present invention may be selected from the following compounds in view of having high solubility and good charge mobility and flicker ratio, but the present invention is not limited thereto.

[Wherein m and n are each independently an integer of 1 to 1,000]

의 구조를 가지며, 알킬의 직쇄의 탄소수인 a가 2 내지 10일 수 있다. 또한 상기 알킬기의 직쇄에 연결된 가지쇄의 구조를 가질 경우, 전하이동도나 점멸비의 저하가 일어나지 않아 이를 함유하는 유기 전자 소자는 높은 효율을 가지는 매우 현저한 효과를 가질 수 있다. That is, more specifically, the asymmetric diketopyrrolopyrrole polymer according to the present invention is such that R1 to R4 in Formula 1 are each independently an alkylene group having a carbon number of 25 or more

And a, which is the number of carbon atoms of the straight chain of alkyl, may be 2 to 10. In addition, when a structure of the branch chain connected to the straight chain of the alkyl group is provided, the charge mobility and the blink rate do not decrease, and the organic electronic device containing the same has a remarkable effect with high efficiency.

Also, as a method for producing an asymmetric diketopyrrolopyrrole 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 asymmetric diketopyrrolopyrrole polymer according to the present invention is not limited to the above-mentioned production method but can be produced by a conventional organic chemical reaction in addition to the following Production Method 1.

(Production Method 1)

[In Production Method 1,

X1 is S or Se;

m is an integer from 1 to 1,000;

and n is an integer of 0 to 1,000.

The asymmetric diketopyrrolopyrrole polymer according to the present invention can be used as a material for forming an organic semiconductor layer of an organic electronic device, and the present invention provides an organic electronic device including the asymmetric diketopyrrolopyrrole polymer.

The organic electronic device of the present invention may include a substrate, a gate, a gate insulating layer, an organic semiconductor layer, and a source-drain electrode, and more preferably an organic thin film transistor having the above-described structure. At this time, a specific example of the method for fabricating the organic thin film transistor is as follows.

As the substrate, n-type silicon used in a typical organic thin film transistor is preferably used. 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).

As the gate insulating layer constituting the OTFT device, an insulating material having a high dielectric constant can be used. Typically, 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 (TaNb) ₂ O ₉ , Ba (ZrTi) O ₃ (BZT), an inorganic insulator selected from the group consisting of BaTiO ₃ , SrTiO ₃ , Bi ₄ Ti ₃ O ₁₂ , SiO ₂ , SiN _x and AlON, or an inorganic insulator selected from the group consisting of polyimide, benzocyclobutene, parylene, Polyacrylate, polyvinylalcohol and polyvinylphenol can be used as the organic binder.

The structure of the organic thin film transistor of the present invention is not limited to the top-contact of the substrate / gate / gate insulating layer / organic semiconductor layer / source-drain electrode as well as the substrate / gate / gate insulating layer / And the bottom-contact type of the semiconductor layer. Also, HMDS (1,1,1,3,3,3-hexamethyldisilazane), octadecyltrichlorosilane (OTS), or octadecyltrichlorosilane (OTDS) may be coated between the source and drain electrodes and the organic semiconductor layer.

The organic semiconductor layer employing the asymmetric diketopyrrolopyrrole polymer 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 and source-drain electrodes may be formed of a conductive material, but may be selected from the group consisting of Au, Ag, Al, Ni, Cr, and ITO It is preferably formed of one or more materials.

The present invention can be more clearly understood by the following examples, and the following examples are merely illustrative of the present invention and are not intended to limit the scope of the invention.

(Example 1) Production of P29DPP-TT-Se

(Step 1) Preparation of 2- (selenophen-2-yl) thieno [3,2-b] thiophene

2-bromothieno [3,2-b] thiophene (5.5 g, 0.0251 mol), tributyl (selenophen-2-yl) stannane (15.81 g, 0.0376 mol), tetrakis (triphenylphosphine) palladium ) (0.29 g, 0.251 mmol) were added and dissolved in Toluene (250 ml). This was refluxed at 80 DEG C for 24 hours. Then, the reaction solution was cooled to room temperature and filtered on a cellite. The reaction solvent was removed by distillation under reduced pressure, and column purification was carried out by column chromatography. This was recrystallized from methyl alcohol to give 3.2 g (47%) of the solid compound.

^{1 H-NMR (300 MHz,} CD 2 Cl 2): δ 7.98-7.96 (d, 1 H), 7.43-7.41 (, m 2 H), 7.37 (s, 1H), 7.31-7.26 (m, 2H)

EI, MS m / z (%): 269.2 (100, M < + &

(Step 2) Trimethyl (5- (5- (trimethylstannyl) selenophen-2-yl) thieno-

[3,2-b] thiophen-2-yl) stannane

2- (selenophen-2-yl) thieno [3,2-b] thiophene (1.0 g, 3.714 mmol) was added to a 100 mL three-neck round bottom flask and dissolved in THF (30 ml). The temperature was lowered to -78 ° C and n- BuLi (2.5 M in hexane, 3.41 mL, 8.542 mmol) was slowly added dropwise and stirred for 1 hour under a stream of nitrogen. This was lowered to a temperature of -78 < trimethyltin chloride (1.70 g, 8.542 mmol) was added dropwise and the mixture was stirred at RT for 2 hours. The reaction solution was poured into ice water and extracted with ether. The extracted organic layer was washed with water, dried over MgSO4, and then the solvent was removed at low temperature using a rotary evaporator. This was recrystallized with methyl alcohol to obtain a solid compound with a yield of 0.91 g (41%).

¹ H-NMR (300 MHz, CD 2 Cl 2):? 7.46-7.42 (m, 2 H), 7.30

EI, MS m / z (%): 594.8 (100, M +)

(Step 3) Preparation of P29DPP-TT-Se

The polymer can be polymerized through a steel coupling reaction. 3, 6-bis (5-bromothiophen-2-yl) -2,5-bis (7-decylnonadecyl) pyrrolo [3,4-c] pyrrole- ) And trimethyl (5- (trimethylstannyl) selenophen-2-yl) thieno [3,2-b] thiophen-2-yl) stannane (0.187 g, 0.0004 mmol) were dissolved in 6 mL of chlorobenzene solvent, Substitutions were made. Then, Pd ₂ (dba) ₃ (0.007 mg, 2 mol%) and p (o-tol) ₃ (0.095 g / 8 mol%) were added as a catalyst and refluxed at 110 ° C for 48 hours. 2-Bromothiophene (0.1 g) was added to the reaction solution, refluxed for 6 hours, and 2-thiophenemethyltin (0.1 g) was added thereto, followed by refluxing for 6 hours to terminate the terminal group reaction. The solution was then slowly precipitated in methanol (300 mL) and the solid filtered. The filtered solid was purified by centrifugation in the order of methanol, hexane, toluene and chloroform. The descending liquid was precipitated again in methanol, filtered through a filter, and dried to obtain a dark green solid. (Yield: 75%).

¹ H NMR (300 MHz, CDCl ₃ ) [ppm]: 8.93 (broad, 4H), 6.92-6.48 (broad, 4H), 3.82 (broad, 4H), 2.13 ), 1.08-0.79 (m, 12H).

(Example 2) Preparation of P29DPP-TT-Th

(Step 1) Preparation of 2- (thiophen-2-yl) thieno [3,2-b] thiophene

A solution of 2-bromothieno [3,2-b] thiophene (5.5 g, 0.0251 mol), tributyl (thiophen-2-yl) stannane (14.05 g, 0.0376 mol), tetrakis (triphenylphosphine) palladium ) (0.29 g, 0.251 mmol) were added and dissolved in Toluene (250 ml). This was refluxed at 80 DEG C for 20 hours. Then, the reaction solution was cooled to room temperature and filtered on a cellite. The reaction solvent was removed by distillation under reduced pressure, and column purification was carried out by column chromatography. This was recrystallized again with methyl alcohol to give a solid compound (4.4 g, 78%).

^{1 H-NMR (300 MHz,} CD 2 Cl 2): δ 7.88-7.76 (d, 1 H), 7.44-7.40 (, m 2 H), 7.38 (s, 1H), 7.33-7.26 (m, 2H)

EI, MS m / z (%): 222.3 (100, M < + &

(Step 2) Trimethyl (5- (5- (trimethylstannyl) thiophen-2-yl) thieno-

[3,2-b] thiophen-2-yl) stannane

2- (thiophen-2-yl) thieno [3,2-b] thiophene (1.0 g, 4.497 mmol) was added to a 100 mL three-neck round bottom flask and dissolved in THF (30 ml). The temperature was lowered to -78 ° C and n- BuLi (2.5 M in hexane, 4.12 mL, 10.344 mmol) was slowly added dropwise and stirred for 1 hour under a stream of nitrogen. This was lowered to a temperature of -78 < trimethyltin chloride (2.06 g, 10.344 mmol) was added dropwise and the mixture was stirred at RT for 2 hours. The reaction solution was poured into ice water and extracted with ether. The extracted organic layer was washed with water, dried over MgSO4, and then the solvent was removed at low temperature using a rotary evaporator. This was recrystallized with methyl alcohol to obtain a solid compound with a yield of 0.91 g (41%).

¹ H-NMR (300 MHz, CD 2 Cl 2):? 7.44-7.40 (m, 2H), 7.38 (s, 1H), 7.32-7.30

EI, MS m / z (%): 547.9 (100, M < + &

(Step 3) Preparation of P29DPP-TT-Th

The polymer can be polymerized through a steel coupling reaction. 3, 6-bis (5-bromothiophen-2-yl) -2,5-bis (7-decylnonadecyl) pyrrolo [3,4-c] pyrrole- ) And trimethyl (5- (trimethylstannyl) thieno [3,2-b] thiophen-2-yl) thiophen-2-yl) stannane (0.172 g, 0.0004 mmol) were dissolved in 6 mL of chlorobenzene solvent, Respectively. After that, Pd2 (dba) 3 (0.007 mg, 2 mol%) and p (o-tol) 3 (0.095 g / 8 mol%) were added as a catalyst and refluxed at 110 ° C for 48 hours. 2-Bromothiophene (0.1 g) was added to the reaction solution, refluxed for 6 hours, and 2-thiophenemethyltin (0.1 g) was added thereto, followed by refluxing for 6 hours to terminate the terminal group reaction. The reaction solution was slowly precipitated in methanol (300 mL) and the solid was filtered. The filtered solid was purified by centrifugation in the order of methanol, hexane, toluene and chloroform. The descending liquid was precipitated again in methanol, filtered through a filter, and dried to obtain a dark green solid. (Yield 79%).

^{1 H NMR (300 MHz, CDCl3} ) [ppm]: 8.96 (broad, 4H), 6.99-6.65 (broad, 4H), 3.78 (broad, 4H), 2.15 (m 2H), 1.32-1.26 (m, 76H) , 1.08-0.78 (m, 12H).

The GPC results of the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se and P29DPP-TT-Th) synthesized in Examples 1 and 2 are shown in Table 1 below, Respectively.

The solubilities of the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se and P29DPP-TT-Th) synthesized in Examples 1 and 2 were measured and the results are shown in Table 2 below.

(Examples 3 to 4) Organic electronic device fabrication

The OTFT device was fabricated by top contact method, and 100 nm n-doped silicon gate was used and SiO ₂ was used as an insulator. Surface treatment was performed by surface cleaning using piranha cleaning solution (H ₂ SO ₄ : 2H ₂ O ₂ ) and then surface treatment with SAM (Self Assemble Monolayer) using Alfa's OTS-18 (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, the P29DPP-TT-Se and the P29DPP-TT-Th synthesized in Examples 1 and 2 were used. The gold used as the source and drain was deposited at a thickness of 100 nm at 1 A / s. The channel length is 15 μm and the width is 1500 μm. The OTFT characteristics were measured using Keithley 4800.

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

Where I _SD is the source-drain current, μ or μ _FET is the charge transfer, C ₀ is the oxide film capacitance, W is the channel width, L is the 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.

The light absorption regions of the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se and P29DPP-TT-Th) synthesized in Examples 1 and 2 were measured in a solution state and a film state, Respectively. To analyze the electrochemical characteristics of the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se and P29DPP-TT-Th), organic semiconductor compounds synthesized in Examples 1 and 2, Bu ₄ NClO ₄ ) And 50 mV / s using a cyclic voltammetry. The results are shown in FIG. 3. The voltage was applied through a coating using a carbon electrode during the measurement.

 The optical and electrochemical properties of the asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se, P29DPP-TT-Th) synthesized in Examples 1 to 2 are shown in Table 3 below. Here, the HOMO 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.

As shown in Table 3, it can be seen that the asymmetric diketopyrrolopyrrole polymer of the present invention has a low band gap, and thus the charge mobility of the organic electronic device containing the same is high.

 4 to 5 show the measurement results of the decomposition temperatures of the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se and P29DPP-TT-Th) synthesized in Examples 1 and 2 using TGA .

 6 to 7 are diagrams showing transfer curves of the device fabricated in Example 3 using the novel asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Se) synthesized in Example 1. The transfer curves of the organic electronic 1 is a diagram showing device characteristics,

8 to 9 are diagrams showing transfer curves of the device fabricated in Example 4 using the novel asymmetric diketopyrrolopyrrole polymer (P29DPP-TT-Th) synthesized in Example 2. The transfer curve of the polymer material Fig. 5 is a view showing electronic device characteristics,

The characteristics of the devices fabricated in Examples 3 to 4 are shown in Table 4 using the novel asymmetric diketopyrrolopyrrole polymers (P29DPP-TT-Se, P29DPP-TT-Th) synthesized in Examples 1 and 2 Respectively.

As shown in Table 4, the organic electronic device manufactured by the methods of Examples 3 to 4 and heat-treated at 200 ° C contains the diketopyrrolopyrrole polymer of the present invention and has a high charge mobility, I have.

Claims (6)

A diketopyrrolopyrrole polymer represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

[In the above formula (1)
R1 to R4 are each independently hydrogen or a (C1-C50) alkyl group,
Each of which may be further substituted with a substituent of (C1-C30) alkyl or (C1-C30) alkoxy, respectively;
X1 is S or Se;
m is an integer from 1 to 1,000;
and n is an integer of 0 to 1,000. The method according to claim 1,
A diketopyrrolopyrrole polymer selected from the following compounds.

[Wherein m and n are each independently an integer of 1 to 1,000] The method according to claim 1,
Each of R1 to R4 independently represents

, A is an integer from 2 to 10, and R ₁₁ and R ₁₂ are each independently (C 10 -C 30) alkyl.
An organic electronic device comprising a diketopyrrolopyrrole polymer according to any one of claims 1 to 3.
5. The method of claim 4,
Wherein the organic electronic device comprises a substrate, a gate, a gate insulating layer, an organic semiconductor layer, and a source-drain electrode.
6. The method of claim 5,
Wherein the diketopyrrolopyrrole polymer is included in the organic semiconductor layer.

Images