WO2015108360A1 - Asymmetric heterocycle-vinylene-heterocyclic-based diketopyrrolopyrrole polymer, organic electronic device adopting same, and monomer for preparing same - Google Patents

Abstract

The present invention relates to: an asymmetric heterocycle-vinylene-heterocyclic-based diketopyrrolopyrrole polymer which is an organic semiconductor compound for an organic electronic device; a use thereof; and a monomer for preparing the same. The asymmetric heterocycle-vinylene-heterocyclic-based diketopyrrolopyrrole polymer of the present invention is a novel organic semiconductor compound having high pi stacking, and an organic electronic device adopting the same has excellent charge mobility and on/off ratio.

Description

Asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer, organic electronic device employing the same and monomers for producing the same

The present invention relates to an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer, an organic semiconductor compound for an organic electronic device, a use thereof, and a monomer for preparing the same. The asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention is a novel organic semiconductor compound having a high pi electron overlap, and the organic electronic device employing the same has excellent charge mobility and flashing ratio.

The development of telecommunications in the 21st century and the desire for personal handheld communication devices are high performance electricity that can produce ultra-fine processing, ultra-high integrated circuits that enable small, light, thin and easy-to-use information and communication devices. There is a need for new information and communication materials that enable the display of electronic materials and new concepts. Among them, organic thin film transistors (OTFTs) are used for display drivers such as portable computers, organic EL devices, smart cards, electric tags, pagers, mobile phones, and memory devices such as cash machines and identification tags. The possibility of being used as an important component of plastic circuitry has been the subject of much research.

The organic thin film transistor using the organic semiconductor has the advantages of simpler manufacturing process and lower cost production compared to the organic thin film transistor using amorphous silicon and polysilicon, and is compatible with the plastic substrates for implementing the flexible display. Due to this superior advantage, many researches are being made recently. In particular, the use of a polymer organic semiconductor has the advantage that the manufacturing cost can be reduced compared to the low molecular organic semiconductor compound because of the advantage that the thin film can be easily formed by the solution process.

Representative semiconductor compounds for polymer-based organic thin film transistors developed to date include P3HT [poly (3-hexylthiophene)] and F8T2 [poly (9,9-dioctylfluorene-co-bithiophene)]. There are many performances of OTFT, but the most important evaluation scale is charge mobility and on / off ratio, and the most important evaluation scale is charge mobility. The charge mobility varies depending on the type of semiconductor material, thin film formation method (structure and morphology), driving voltage, and the like.

In general, an organic thin film transistor is formed of a substrate / gate / insulation layer / electrode layer (source, drain) / derivative conductor layer, and a gate electrode is formed on the substrate. An insulating layer is formed on the gate electrode, and an organic semiconductor layer, and a source and a drain electrode are sequentially formed on the gate electrode. The driving principle of the organic thin film transistor having the above structure will be described below with an example of a p-type semiconductor. First, when a current is applied by applying a voltage between the source and the drain, a current proportional to the voltage flows under a low voltage. When a positive voltage is applied to the gate, holes that are positive charges are all pushed up to the top of the semiconductor layer by the electric field by the applied voltage. Thus, the portion close to the insulating layer will have a depletion layer without conduction charge, and in such a situation, a low amount of current will flow due to the reduced number of conducting charge carriers even when a voltage is applied between the source and the drain. . On the contrary, when a negative voltage is applied to the gate, an accumulation layer in which positive charges are induced near the insulating layer is formed by the effect of the electric field caused by the applied voltage. At this time, since there are many conducting 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.

The organic thin film transistors, which are constructed on the principle described above, include electrodes (source and drain), substrates and gate electrodes requiring high thermal stability, insulators having high dielectric properties and dielectric constants, and semiconductors that transfer charges well. There are many problems to overcome, and the core material is organic semiconductor. Organic semiconductors can be classified into low molecular organic semiconductors and high molecular organic semiconductors according to molecular weight, and are classified into n-type organic semiconductors or p-type organic semiconductors according to whether electrons or holes are transferred. In general, when a low molecular weight organic semiconductor is used in forming an organic semiconductor layer, the low molecular weight organic semiconductor is easy to purify and almost removes impurities, so the charge transfer characteristics are excellent. However, such organic semiconductors are not spin coated and printed. Therefore, since the thin film must be manufactured by vacuum deposition, the manufacturing process is complicated and expensive compared with the polymer organic semiconductor. In the case of the polymer organic semiconductor, it is difficult to purify the high purity, but excellent heat resistance, spin coating and printing is possible, there is an advantage in the manufacturing process, cost, mass production.

Although many studies have been made to date for the development of organic semiconductor materials, the development of polymer semiconductor materials is still far from the development of low molecular weight semiconductor materials. Therefore, in order to develop an electronic device using a flexible, low-cost organic thin film transistor, it is urgent to develop a polymer semiconductor material. Generally, the charge mobility of a polymer is known to be inferior to that of a low molecule, but it can be said to be a material that can sufficiently overcome this in terms of manufacturing process and cost.

Korean Patent Publication No. 2011-0091711 and Korean Patent Publication No. 2009-0024832 disclose polymers in which an S-containing heteroaromatic ring is directly bonded to a diketopyrrolopyrrole group. However, there is still a need for development of a polymer semiconductor material exhibiting sufficient pi electron overlap since it still does not show sufficient pi electron expansion.

The present invention provides an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer.

In addition, the present invention provides an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer which is an organic semiconductor compound having high solubility and viscosity due to high molecular weight and easy spin coating at room temperature to enable a solution process. to provide.

The present invention also provides an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer which is an organic semiconductor compound having a high charge mobility applied to an organic electronic device.

The present invention also provides an organic thin film transistor comprising the novel asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention in an organic semiconductor layer.

The present invention relates to an organic semiconductor compound for organic electronic device such as an organic thin film transistor (OTFT) and its use. More specifically, the present invention includes an electron acceptor compound, a diketopyrrolopyro derivative, between two thiophenes, an electron donor compound, and another electron donor compound, thiophene-vinylene, in the electron donor compound thiophene. Asymmetric heterocycles such as selenophene, selenophene-vinylene-thiophene, thiophene-vinylene-furan, furan-vinylene-thiophene, selenophene-vinylene-furan or furan-vinylene-selenophene A diketopyrrolopyrrole polymer using an asymmetric heterocyclic-vinylene-heterocyclic derivative which is a p-type polymer organic semiconductor compound used as an active layer material of an organic thin film transistor in which a vinylene-heterocycle is bonded to a randomly polymerized organic thin film transistor and It relates to an organic electronic device using the same.

The novel asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention is represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

X and Y are each independently S, Se or O, provided that X and Y are not identical to each other;

R ₁ and R ₂ are each independently hydrogen or a (C ₁ -C 50) alkyl group, and the alkyl of R ₁ and R ₂ is each (C ₁ -C 30) alkyl, (C ₂ -C 30) alkenyl, (C ₂ -C 30) alky May be further substituted with one or more substituents selected from nil, (C1-C30) alkoxy, amino, hydroxy, halogen, cyano, nitro, trifluoromethyl and tri (C1-C30) alkylsilyl;

m and n are each independently an integer of 0 to 1000 and m and n are not zero at the same time.

The asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer represented by the formula (1) of the present invention is a polymer comprising a unit of formula (A) and a unit of formula (B), a block copolymer, Random copolymers, alternating copolymers, tapered copolymers, and the like.

[Formula A]

[Formula B]

(In Formulas A and B, X and Y are each independently S, Se or O, provided that X and Y are not identical to each other; R ₁ and R ₂ are each independently hydrogen or a (C 1 -C 50) alkyl group. , Wherein the alkyl of R ₁ and R ₂ is (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, amino, hydroxy, halogen, cyano , Nitro, trifluoromethyl and tri (C1-C30) alkylsilyl may be further substituted; m and n are each independently an integer of 0 to 1000 and m and n are 0 no.)

The asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer represented by the formula (1) of the present invention is coplanarity of the main chain by introducing a vinylene group (V) into the diketopyrrolopyrrole derivative The organic electronic device containing the same exhibits high mobility by increasing the molecular weight and increasing the conjugated structure, thereby enhancing the electron density and increasing the intermolecular interaction.

In addition, substituents R ₁ and R ₂ of the diketopyrrolopyrrole derivatives

It has a higher solubility by having a phosphorus structure. That is, a has a structure in which a of R ₁ and R ₂ has an integer of 1 to 10, more preferably a has a branched alkyl at the terminal, with an integer of 1 to 7, resulting in as much as 10 compared to alkyl having no branched chain at the terminal. It has more than twice the charge mobility and at the same time has a high solubility, which is more advantageous for the solution process, so that a large area organic electronic device can be manufactured in a simple and inexpensive process.

In Formula 1 according to an embodiment of the present invention R ₁ and R ₂ are each independently

And a is an integer from 1 to 10, and R ₁₁ and R ₁₂ may each independently be (C 10 -C 30) alkyl.

Asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to an embodiment of the present invention is more specifically in terms of high solubility and excellent charge mobility and flashing ratio and is preferably the following compound It may be, but is not limited thereto.

(The m and n are each independently an integer of 0 to 1000 and m and n are not 0 at the same time.)

That is, more specifically, the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention, as described above, R ₁ and R ₂ in the general formula (1) is a carbon number of 24 or more, while the linear carbon number of alkyl When the structure having a branched alkyl at the terminal of 1 to 7 has a high solubility, there is no decrease in charge mobility or flashing ratio, so that the organic electronic device containing the same has a very significant effect having high efficiency.

A method for preparing an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to the present invention, the final through the alkylation reaction, Grignard coupling reaction, Suzuki coupling reaction, Stiletto coupling reaction, etc. Compounds can be prepared. The organic semiconductor compound according to the present invention is not limited to the above production method, and may be prepared by a conventional organic chemical reaction in addition to the above production method.

In addition, the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to the present invention can be used as a material for forming an organic semiconductor layer of the organic electronic device, the present invention is an asymmetric heterocyclic-vinylene-heterocyclic An organic electronic device containing a system diketopyrrolopyrrole polymer is provided.

In particular, the organic electronic device of the present invention may be an organic thin film transistor, and specific examples of the method for manufacturing the organic thin film transistor of the present invention are as follows.

It is preferable to use n-type silicon used for a conventional organic thin film transistor as a substrate. This substrate contains the function of the gate electrode. In addition to 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, a gate electrode must be added on the substrate. Substances which can be employed as the substrate include glass, polyethylenenaphthalate (PEN), polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl alcohol (PVP), polyacrylate (Polyacrylate). , Polyimide, polynorbornene and polyethersulfone (PES).

As the gate insulating layer constituting the OTFT device, an insulator having a high dielectric constant, which is commonly used, may be used. Specifically, Ba _0.33 Sr _0.66 TiO ₃ (BST), Al ₂ O ₃ , Ta ₂ O ₅ , La ₂ O ₅ , Ferroelectric insulator selected from the group consisting of Y ₂ O ₃ and TiO ₂ , 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 Inorganic insulators selected from the group consisting of (BZT), BaTiO ₃ , SrTiO ₃ , Bi ₄ Ti ₃ O ₁₂ , SiO ₂ , SiN _x and AlON, or polyimide, BCB (benzocyclobutene), parylene, Organic precursors such as polyacrylate, polyvinylalcohol, and polyvinylphenol can be used.

The structure of the organic thin film transistor of the present invention is not only top-contact of the substrate / gate electrode / insulation layer / oil-based conductor layer / source and drain electrode but also the substrate / gate electrode / insulation layer / source, drain electrode / organic It includes all forms of bottom-contact of the semiconductor layer. In addition, HMDS (1,1,1,3,3,3-hexamethyldisilazane), octadecyltrichlorosilane (OTS) or octadecyltrichlorosilane (OTDS) may or may not be coated as a surface treatment between the source and drain electrodes and the organic semiconductor layer.

The organic semiconductor layer employing the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to the present invention is vacuum deposition, screen printing, printing, spin casting, spin coating, dipping or ink powder. It can be formed into a thin film through the method, in this case, the deposition of the organic semiconductor layer may be formed using a high temperature solution at 40 ℃ or more, the thickness is preferably about 500 kPa.

The gate electrode and the source and drain electrodes may be conductive materials, but may be formed from a group consisting of gold (Au), silver (Ag), aluminum (Al), nickel (Ni), chromium (Cr), and indium tin oxide (ITO). It is preferably formed of the selected material.

In addition, the present invention provides an asymmetric heterocyclic-vinylene-heterocyclic monomer represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

Z ₁ and Z ₂ are each independently hydrogen, halogen, B (OH) ₂ , 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl or SnR ₁₁ R ₁₂ R ₁₃ ; R ₁₁ to R ₁₃ are each independently (C 1 -C 10) alkyl.

Asymmetric heterocyclic-vinylene-heterocyclic monomers according to an embodiment of the present invention may be specifically illustrated by the following structure, but is not limited thereto.

The asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention contains a diketopyrrolopyrrole derivative, an electron acceptor compound, between two thiophenes, an electron donor compound, Thiophene-vinylene-selenophene, selenophene-vinylene-thiophene, thiophene-vinylene-furan, furan-vinylene-thiophene, selenophene-vinylene-furan or Units in which asymmetric heterocyclic-vinylene-heterocycles, such as furan-vinylene-selenophene, are bonded are randomly polymerized, and have a conjugated structure extended to the increased coplanarity of the main chain. Increasing the density increases the intermolecular interactions and shows excellent thermal stability.

In addition, the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention has a low HOMO value, that is, an electron density increases in the repeating unit, thereby having excellent charge mobility and oxidation stability. It can be very usefully used as the organic semiconductor layer of the transistor.

Therefore, the organic thin film transistor employing these devices improves the charge mobility and the flashing ratio, and when the organic thin film transistor is used, it is possible to make an electronic device having excellent efficiency and performance. The organic thin film transistor can also be manufactured by a solution process such as vacuum deposition, spin coating, or printing, thereby reducing the manufacturing cost of an electronic device using the organic thin film transistor.

In addition, the asymmetric heterocyclic -vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention is a substituent substituted by N of the diketopyrrolopyrrole derivative, that is, to have a high solubility without affecting other electrical properties, that is, The organic electronic device including the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention by introducing a substituent having a limited number of carbon atoms can be manufactured by a solution process such as vacuum deposition, spin coating or printing. Therefore, large area can be achieved by simple process and low cost.

1 is a UV-vis absorption spectra in solution and film form of thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3,

FIG. 2 is a UV-vis absorption spectra of a solution phase and a film phase of a thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4;

3 is a cyclic voltammetry diagram of the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3,

4 is a cyclic voltammetry diagram of the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4,

5 is a differential calorimetry (DSC) curve of a thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3,

6 is a differential calorimetry (DSC) curve of a thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4,

7 is a thermogravimetric analysis (TGA) curve of the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3,

8 is a thermogravimetric analysis (TGA) curve of the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4,

9 and 10 illustrate the device at room temperature prepared by the method of Example 5 using the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3. This diagram shows the characteristics (Transfer curve, Output curve),

11 and 12 are prepared by the method of Example 5 using the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3 and the device after 180 ℃ heat treatment This diagram shows the characteristics of the transfer curve (Transfer curve, Output curve),

13 and 14 show the device at room temperature fabricated by the method of Example 5 using the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4. This diagram shows the characteristics (Transfer curve, Output curve),

15 and 16 are prepared by the method of Example 5 using the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4 and the device after the 180 ° C heat treatment It is a figure which shows the characteristic (Transfer curve, Output curve) of.

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

Example 1 (E) -2-bromo-5- (2- (5-bromoselenophen-2-yl) vinyl) thiophene ((E) -2-bromo-5- (2- ( Preparation of 5-bromoselenophen-2-yl) vinyl) thiophene)

N-bromosuccinimide (NBS) (3.13 g, 17.6 mmol) and DMF (50 mL) were added and dissolved in a 250 mL three-neck flask shielded with silver foil. (E) -2- (2- (selenophen-2-yl) vinyl) thiophene ((E) -2- (2- (selenophen-2-yl) vinyl) thiophene) dissolved in DMF (30 mL) ( 2 g, 8.36 mmol) was added slowly dropwise. After stirring for 12 hours at room temperature, the reaction was terminated, 300 mL of water was added and extracted, dried over anhydrous MgSO ₄ and the solvent was removed. The obtained material was subjected to silica gel column using n-hexane to give (E) -2-bromo-5- (2- (5-bromoselenophen-2-yl) vinyl) thiophene as the target compound in solid form. Obtained in g (57%).

¹ H NMR (CDCl ₃ , 300 MHz), δ (ppm): δ7.6 (d, 1H), 7.5 (d, 1H), 7.3 (d, 1H), 7.2 (d, 1H), 7.1-7.0 (s , 2H).

Example 2 (E) -Trimethyl (5- (2- (5- (trimethylstannyl) selenophen-2-yl) vinyl) thiophen-2-yl) stannan ((E) -trimethyl Preparation of (5- (2- (5- (trimethylstannyl) selenophen-2-yl) vinyl) thiophen-2-yl) stannane)

(E) -2- (2- (Selenophen-2-yl) vinyl) thiophene ((E) -2- (2- (selenophen-2-yl) vinyl) in a well-dried 100 mL three neck round bottom flask thiophene) (1.0 g, 4.2 mmol) was added and dissolved in THF (30 mL). The temperature was lowered to −78 ° C. and n- BuLi (2.5 M in hexane, 3.51 mL, 8.8 mmol) was slowly added dropwise, stirred for 1 hour under a nitrogen stream, and then heated to room temperature and stirred for 1 hour. Then, the temperature was lowered to -78 ° C and trimethyltin chloride (1 M in THF, 3.51 mL, 8.8 mmol) was slowly added dropwise and stirred at room temperature for 2 hours. The reaction mixture was poured into iced water, extracted with Et ₂ O, the organic layer was washed with water, water was removed with anhydrous MgSO ₄ and the solvent was removed at low temperature using a rotary evaporator. Recrystallized from ethanol (Ethyl alcohol), filtered through a filter, and (E) -trimethyl (5- (2- (5- (trimethylstannyl) selenophen-2-yl) vinyl) thi Offen-2-yl) stannane was obtained in a yield of 1.7 g (71%).

¹ H NMR (CDCl ₃ , 300 MHz), δ (ppm): δ7.6 (d, 2H), 7.4 (d, 2H), 6.9 (s, 1H), 6.7 (d, 1H), 0.42 (m, 18H ).

Example 3 Preparation of P-24-DPPTVSe

The polymer P-24-DPPTVSe can be polymerized through a Stille coupling reaction. 3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-decyltetradecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -da Ion (3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-decyltetradecyl) pyrrolo [3,4-c] pyrrole -1,4 (2H, 5H) -dione) (0.50 g, 0.44 mmol) and (E) -trimethyl (5- (2- (5- (trimethylstannyl) selenophen-2-yl) vinyl) thiophen-2-yl) stannan (Example 2, 0.249 g, 0.44 mmol) was dissolved in chlorobenzene (5 mL) and subjected to nitrogen substitution. After that, Pd ₂ (dba) ₃ (0.008 mg, 2 mol%) and P (o-tol) ₃ (0.012 g, 8 mol%) were added as a catalyst and refluxed at 100 ° C. for 48 hours. The reaction solution was then slowly precipitated in methanol (300 mL) and the resulting solid was filtered off. The filtered solid was purified in the order of methanol, hexane, toluene and chloroform via soxlet. The down liquid was precipitated again in methanol, filtered through a filter and dried to give the title compound P-24-DPPTVSe as a dark green solid (90% yield).

0.42 g of amount obtained; (Mn = 33,000, Mw = 52,000, PDI = 1.57); ¹ H NMR (CDCl ₃ , 500 MHz), δ (ppm): δ 8.8 (broad, 4H), 7.4-6.75 (broad, 6H), 4.02 (broad, 4H), 1.95-1.26 (broad, 78H), 0.8 (broad, 12H).

Example 4 Preparation of P-29-DPPTVSe

The polymer P-29-DPPTVSe can be polymerized through a Stille coupling reaction. 3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-decylnonadecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H)- Dione (3,6-bis (5-bromothiophen-2-yl) -2,5-bis (7-decylnonadecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione) ( 0.50 g, 0.39 mmol) and (E) -trimethyl (5- (2- (5- (trimethylstannyl) selenophen-2-yl) vinyl) thiophen-2-yl) stannan (Example 2 , 0.220 g, 0.39 mmol) was dissolved in chlorobenzene (5 mL) and subjected to nitrogen substitution. After that, Pd ₂ (dba) ₃ (0.007 g, 2 mol%) and P (o-tol) ₃ (0.011 g, 8 mol%) were added as a catalyst and refluxed at 100 ° C. for 48 hours. The reaction solution was then slowly precipitated in methanol (300 mL) and the resulting solid was filtered off. The filtered solid was purified through soxxlet in the order of methanol, hexane and toluene. The down liquid was precipitated again in methanol, filtered through a filter and dried to give the title compound P-29-DPPTVSe as a dark green solid (yield 90%).

0.41 g of amount obtained; (Mn = 52,000, Mw = 75,000, PDI = 1.44); ¹ H NMR (CDCl ₃ , 500 MHz), δ (ppm): δ 8.78 (broad, 4H), 7.4-6.75 (broad, 6H), 4.02 (broad, 4H), 1.95-1.26 (broad, 102H), 0.85 (broad, 12H).

Example 5 Fabrication of Organic Electronic Device

The OTFT device was fabricated in a top-contact manner, using 100 nm n-doped silicon as a gate and SiO ₂ as an insulator. Surface treatment was performed using a piranha cleaning solution (H ₂ SO ₄ : 2H ₂ O ₂ ) and then using the Adrich's ODTS (octadecyltrichlorosilane) surface was used after SAM (Self Assemble Monolayer) treatment. The organic semiconductor layer was coated with 0.2 wt% chloroform solution using a spin-coater for 1 minute at 2000 rpm. P-24-DPPTVSe and P-29-DPPTVSe synthesized in Examples 3 and 4 were used as organic semiconductor materials, respectively. Gold used as the source and drain was deposited to a thickness of 50 nm at 1 A / s. The channel is 100 μm long and 1000 μm wide. The measurement of OTFT characteristics was done using Keithley 2400 and 236 source / measure units.

The charge mobility was obtained from (S _SD ) ^1/2 and V _G as variables from the saturation region current equation and obtained from the slope.

Where I _SD is the source-drain current, μ or μ _FET is the charge transfer, C ₀ is the oxide 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 cutoff leakage current I _off is a current flowing in the off state, and is determined as the minimum current in the off state in the current ratio.

The light absorption regions of the novel thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymers (P-24-DPPTVSe and P-29-DPPTVSe) synthesized in Examples 3 and 4 are in the solution state and the film state. The measurement results are shown in FIGS. 1 and 2. In order to analyze the electrochemical properties of the novel thiophene-vinylene-selenophene diketopyrrolopyrrole polymers (P-24-DPPTVSe and P-29-DPPTVSe) synthesized in Examples 3 and 4 3 and 4 show the results of using cyclic voltammetry under a condition of 50 mV / s in a solvent of Bu ₄ NClO ₄ (0.1 molarity), and the carbon electrode was used for the measurement. Voltage was applied through the coating.

Table 1 below describes the optical and electrochemical properties of the novel thiophene-vinylene-selenophene diketopyrrolopyrrole polymers synthesized in Examples 3 and 4 (P-24-DPPTVSe and P-29-DPPTVSe). It was. The HOMO value is a value calculated using the result values measured in FIGS. 3 and 4. In addition, the band gap was obtained from the UV absorption wavelength in the film state.

Table 1

Polymer	Optical properties				Electrochemical properties
	UV-S (max) (nm)	UV-F (max) (nm)	UV-ann (max) (nm)	UV-edge (nm)	Band gap (optical) (eV)	LUMO (optical) (eV)	Electrochemical (HOMO) (eV)
P-24-DPPTVSe (Example 3)	781450	816738	818	1032	1.20	4.15	5.35
P-29-DPPTVSe (Example 4)	799447	816742	798	1042	1.19	4.13	5.32

As shown in Table 1, the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer of the present invention has a low band gap and high charge mobility of the organic electronic device containing the same.

5 and 6 to measure the thermal stability for the novel thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe and P-29-DPPTVSe) synthesized in Examples 3 and 4 In order to show the results measured using DSC.

7 and 8, the decomposition temperature of the novel thiophene-vinylene-selenophene diketopyrrolopyrrole polymers synthesized in Examples 3 and 4 (P-24-DPPTVSe and P-29-DPPTVSe) was determined by TGA. shows a result of measurement by (P-24-DPPTVSe of T _d is 370 ℃; T _d of the P-29-DPPTVSe is 387 ℃).

As shown in Figure 5 to 8, the organic semiconductor compound synthesized in the present invention is excellent in thermal stability and can be seen that the charge mobility is increased when annealing (annealing) it can be seen that the excellent organic electronic device material have.

9 and 10 are manufactured by the method of Example 5 using the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3, and then room temperature A diagram showing the transfer curve and the out-put curve of the device in Figure 2, which shows the organic electronic device characteristics of the polymer material.

11 and 12 show the device of Example 5 using the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe) synthesized in Example 3, and then 180 A diagram showing a transfer curve and an out-put curve of a device after heat treatment at ℃, and a view showing the organic electronic device characteristics of the polymer material.

13 and 14 are manufactured by the method of Example 5 using the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4, and then room temperature A diagram showing the transfer curve and the out-put curve of the device in Figure 2, which shows the organic electronic device characteristics of the polymer material.

15 and 16 show the device manufactured by the method of Example 5 using the thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-29-DPPTVSe) synthesized in Example 4, and then 180 A diagram showing a transfer curve and an out-put curve of a device after heat treatment at ℃, and a view showing the organic electronic device characteristics of the polymer material.

Prepared in Example 5 using the novel thiophene-vinylene-selenophene diketopyrrolopyrrole polymer (P-24-DPPTVSe and P-29-DPPTVSe) synthesized in Examples 2 and 4 in Table 2 below The characteristics of the device were described.

TABLE 2

Polymer	Heat treatment	Surface modification	Mobility (cm 2 / (V s))	Threshold Voltage (V)	Flashing ratio on / off ratio
P-24-DPPTVSe (Example 3)	Room temperature	ODTS	0.89	10.2	5.21 X 10 4
	180 ℃	ODTS	1.8	12.88	3.58 X 10 4
P-29-DPPTVSe (Example 4)	Room temperature	ODTS	1.2	3.8	2.43 X 10 4
	180 ℃	ODTS	2.81	3.28	5.58 x 10 4

As shown in Table 2, the organic electronic device manufactured by the method of Example 5 and heat-treated at 180 ° C. is an asymmetric heterocyclic-vinylene such as the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer of the present invention. Heterocyclic diketopyrrolopyrrole polymer contains a high charge mobility and a stable flashing ratio.

The asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention comprises an electron acceptor compound, a diketopyrrolopyrrole derivative, between two thiophenes, an electron donor compound, and an electron donor compound, Thiophene-vinylene-selenophene, selenophene-vinylene-thiophene, thiophene-vinylene-furan, furan-vinylene-thiophene, selenophene-vinylene-furan or Units in which asymmetric heterocyclic-vinylene-heterocycles, such as furan-vinylene-selenophene, are bonded are randomly polymerized, and have a conjugated structure extended to the increased coplanarity of the main chain. Increasing the density increases the intermolecular interactions and shows excellent thermal stability.

In addition, the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention has a low HOMO value, that is, an electron density increases in the repeating unit, thereby having excellent charge mobility and oxidation stability. It can be very usefully used as the organic semiconductor layer of the transistor.

Therefore, the organic thin film transistor employing these devices improves the charge mobility and the flashing ratio, and when the organic thin film transistor is used, it is possible to make an electronic device having excellent efficiency and performance. The organic thin film transistor can also be manufactured by a solution process such as vacuum deposition, spin coating, or printing, thereby reducing the manufacturing cost of an electronic device using the organic thin film transistor.

In addition, the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention is a substituent substituted by N of the diketopyrrolopyrrole derivative, that is, to have high solubility without affecting other electrical properties, that is, The organic electronic device including the asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer of the present invention by introducing a substituent having a limited number of carbon atoms can be manufactured by a solution process such as vacuum deposition, spin coating or printing. Therefore, large area can be achieved by simple process and low cost.

Claims (8)

1. Asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer represented by the general formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   X and Y are each independently S, Se or O, provided that X and Y are not identical to each other;

   R ₁ and R ₂ are each independently hydrogen or a (C ₁ -C 50) alkyl group, and the alkyl of R ₁ and R ₂ is each (C ₁ -C 30) alkyl, (C ₂ -C 30) alkenyl, (C ₂ -C 30) alky May be further substituted with one or more substituents selected from nil, (C1-C30) alkoxy, amino, hydroxy, halogen, cyano, nitro, trifluoromethyl and tri (C1-C30) alkylsilyl;

   m and n are each independently an integer of 0 to 1000 and m and n are not zero at the same time.
2. The method of claim 1,

   R ₁ and R ₂ are each independently

   

   And a is an integer from 1 to 10, and R ₁₁ and R ₁₂ are each independently (C 10 -C 30) alkyl, and asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer.
3. The method of claim 2,

   Asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymers selected from the following compounds:

   

   

   (The m and n are each independently an integer of 0 to 1000 and m and n are not 0 at the same time.)
4. An organic thin film transistor comprising an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to any one of claims 1 to 3.
5. In an organic thin film transistor formed by including a substrate, a gate, a gate insulating layer, an organic semiconductor layer, and a source-drain electrode,

   An organic thin film transistor comprising an asymmetric heterocyclic-vinylene-heterocyclic diketopyrrolopyrrole polymer according to any one of claims 1 to 3, wherein the organic semiconductor layer.
6. The method of claim 5,

   The organic thin film transistor has a structure of a substrate / gate electrode / insulation layer / organic semiconductor layer / source, drain electrode, or a substrate / gate electrode / insulation layer / source, drain electrode / organic semiconductor layer.
7. Asymmetric heterocyclic-vinylene-heterocyclic monomer represented by the following formula (2).

   [Formula 2]

   

   In Chemical Formula 2,

   Z ₁ and Z ₂ are each independently hydrogen, halogen, B (OH) ₂ , 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl or SnR ₁₁ R ₁₂ R ₁₃ ; R ₁₁ to R ₁₃ are each independently (C 1 -C 10) alkyl.
8. The method of claim 7, wherein

   The asymmetric heterocyclic-vinylene-heterocyclic monomer is selected from the following structure asymmetric heterocyclic-vinylene-heterocyclic monomer.

   

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