WO2015147477A1

WO2015147477A1 - Diketopyrrolopyrrole polymer and organic electronic device adopting same

Info

Publication number: WO2015147477A1
Application number: PCT/KR2015/002653
Authority: WO
Inventors: 김윤희; 권순기; 윤희준
Original assignee: 경상대학교산학협력단
Priority date: 2014-03-27
Filing date: 2015-03-19
Publication date: 2015-10-01
Also published as: KR20150112238A; KR102099612B1

Abstract

The present invention relates to: a diketopyrrolopyrrole polymer, which is an organic semiconductor compound for an organic electronic device; and a use thereof. The diketopyrrolopyrrole polymer of the present invention, which is a polymer obtained by polymerizing three or more monomers, has a random arrangement different from that of a conventional alternating copolymer, and thus has an irregular arrangement. Therefore, the diketopyrrolopyrrole polymer has high solubility due to an increase in free volume between polymers and can be prepared for a device in an environmentally friendly manner without environmental damage by using a solution process in an environmentally friendly non-halogen solvent, enabled by high solubility.

Description

Diketopyrrolopyrrole polymer and organic electronic device employing the same

The present invention relates to a diketopyrrolopyrrole polymer which is an organic semiconductor compound for organic electronic devices and its use. The diketopyrrolopyrrole polymer of the present invention is a polymer polymerized three or more monomers, unlike the conventional alternating copolymer has a random arrangement and has an irregular arrangement, and thus free volume between the polymers (Free Volume) It has high solubility due to the increase, and high solubility makes it possible to manufacture devices in an environmentally friendly manner without destroying the environment in a solution process in an environmentally friendly non-halogen solvent.

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 a diketopyrrolopyrrole polymer having high solubility by polymerizing three or more monomers to increase the free volume between the polymers having irregular arrangement.

In addition, the present invention provides a diketopyrrolopyrrole polymer which is an organic semiconductor compound capable of environmentally friendly solution process due to the increased solubility due to the increased free volume between the polymer has an irregular arrangement unlike the conventional alternating copolymer.

The present invention also provides an organic thin film transistor comprising the novel 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 relates to a diketopyrrolopyrrole polymer having a high solubility by polymerizing three or more monomers to have an irregular arrangement to increase the free volume between the polymers and an organic electronic device using the same. .

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

[Formula 1]

In Chemical Formula 1,

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;

a is an integer of 1 or 2;

m and n are each independently an integer of 1 to 1000.

The 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 copolymer), alternating aerial Alternating copolymers, tapered copolymers, and the like.

[Formula A]

[Formula B]

(In Formulas A and B, 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) al. One or more substituents selected from kenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, amino, hydroxy, halogen, cyano, nitro, trifluoromethyl and tri (C1-C30) alkylsilyl May be further substituted; a is an integer of 1 or 2; m and n are each independently an integer of 1 to 1000.)

Since the diketopyrrolopyrrole polymer represented by the general formula (1) of the present invention polymerized three or more monomers, the arrangement is irregular, irregular free order increases the free volume between the polymer, increased free volume Due to the high solubility, the solution process in a non-halogen solvent such as THF, toluene, xylene, tetralin and the like. Conventionally, the solution process is usually performed using a solvent in which chlorine is substituted, but if a large amount of solvent in which chlorine is substituted is used for mass production, there is a problem that can lead to environmental destruction. In other words, the diketopyrrolopyrrole polymer of the present invention enables the solution process using an environmentally friendly non-halogen solvent due to the irregular arrangement.

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

It has a phosphorus structure and a structure of R ₁ and R ₂ has an integer of 3 to 7 and is a branched alkyl at the terminal, so that the charge mobility is 10 times higher than that of alkyl having no branched chain at the terminal. Have

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

And b is an integer from 3 to 10, and R ₁₁ and R ₁₂ are each independently (C 10 -C 30) alkyl.

Diketopyrrolopyrrole polymer according to an embodiment of the present invention may be more specifically and preferably in terms of having a high solubility and excellent charge mobility and flashing ratio, but is not limited thereto.

(M and n are each independently an integer of 1 to 1000.)

That is, more specifically, the thiophene-vinylene-selenophene-based diketopyrrolopyrrole polymer of the present invention, as described above, R ₁ and R ₂ in the general formula (1) has a carbon number of 24 or more, while the linear carbon number of the alkyl In the case of the structure having branched alkyl at the end of 3 to 7, the charge mobility and the flashing ratio do not decrease, and thus the organic electronic device containing the same has a very significant effect with high efficiency.

As a method for preparing the diketopyrrolopyrrole polymer according to the present invention, the final compound may be prepared through an alkylation reaction, a Grignard coupling reaction, a Suzuki coupling reaction, a Stiletto coupling reaction, and the like. 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 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 provides an organic electronic device containing the diketopyrrolopyrrole polymer.

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 diketopyrrolopyrrole polymer according to the present invention may be formed into a thin film by screen printing, printing, spin casting, spin coating, dipping or ink spraying, wherein 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.

The diketopyrrolopyrrole polymer of the present invention is a polymer polymerized three or more monomers, unlike the conventional alternating copolymer has a random arrangement and has an irregular arrangement, and thus free volume between the polymers (Free Volume) It has high solubility due to the increase, and high solubility makes it possible to manufacture devices in an environmentally friendly manner without destroying the environment in a solution process in an environmentally friendly non-halogen solvent.

1 is a UV-vis absorption spectra of the solution phase and film of the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1,

2 is a UV-vis absorption spectra of the solution phase and the film phase of the diketopyrrolopyrrole polymer (P-3-7DPP-DTT-SEVSE) synthesized in Example 2,

3 is a UV-vis absorption spectra of a solution phase and a film of the diketopyrrolopyrrole polymer (P-1-9DPP-TT-SEVSE) synthesized in Example 3,

Figure 4 shows the diketopyrrolopyrrole polymer synthesized in Examples 1 to 3 (29 Copolymer (1: 9) represents P-1-9DPP-DTT-SEVSE, 29 Copolymer (3: 7) is P-3-7DPP- DTT-SEVSE, and 37 Copolymer (5: 5) represents P-1-9DPP-TT-SEVSE) is a cyclic voltammetry diagram,

5 is a differential calorimetry (DSC) curve of the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1,

6 is a differential calorimetry (DSC) curve of the diketopyrrolopyrrole polymer (P-3-7DPP-DTT-SEVSE) synthesized in Example 2,

7 is a differential calorimetry (DSC) curve of the diketopyrrolopyrrole polymer (P-1-9DPP-TT-SEVSE) synthesized in Example 3,

8 is a thermogravimetric analysis (TGA) curve of the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1,

9 is a thermogravimetric analysis (TGA) curve of the diketopyrrolopyrrole polymer (P-3-7DPP-DTT-SEVSE) synthesized in Example 2,

10 is a thermogravimetric analysis (TGA) curve of the diketopyrrolopyrrole polymer (P-1-9DPP-TT-SEVSE) synthesized in Example 3,

11 and 12 are characteristics of the device fabricated by the solution process using THF in Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 (Transfer curve, Output curve)

13 and 14 show the characteristics of the device manufactured by the solution process using CHCl ₃ in Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 Transfer curve, Output curve)

15 and 16 are characteristics of the device manufactured by the solution process using toluene in Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 (Transfer curve, Output curve)

17 and 18 are the characteristics of the device manufactured by the solution process using the xylene in Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 Transfer curve, Output curve)

19 and 20 are characteristics of the device manufactured by the solution process using tetralin in Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 (Transfer curve, Output curve)

FIG. 21 is a graph illustrating reliability characteristics of a device fabricated by a solution process using THF in Example 4 using the diketopyrrolopyrrole polymer synthesized in Example 1 (P-1-9DPP-DTT-SEVSE). It is a drawing to show,

FIG. 22 shows the reliability characteristics of a device fabricated by a solution process using CHCl ₃ in Example 4 using a diketopyrrolopyrrole polymer synthesized in Example 1 (P-1-9DPP-DTT-SEVSE) Is a diagram representing

FIG. 23 is a graph illustrating reliability characteristics of a device fabricated in a solution process using toluene in Example 4 using the diketopyrrolopyrrole polymer synthesized in Example 1 (P-1-9DPP-DTT-SEVSE). It is a drawing to show,

FIG. 24 illustrates the reliability characteristics of a device fabricated by using a xylene solution in Example 4 using the diketopyrrolopyrrole polymer synthesized in Example 1 (P-1-9DPP-DTT-SEVSE). Is a diagram representing

FIG. 25 is a diagram illustrating reliability characteristics prepared by a solution process using tetralin in Example 4 using a diketopyrrolopyrrole polymer synthesized in Example 1 (P-1-9DPP-DTT-SEVSE). It is a figure which shows.

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.

[실시예 1] P-1-9DPP-DTT-SEVSE 의 제조Example 1 Preparation of P-1-9DPP-DTT-SEVSE

The polymer, P-1-9DPP-DTT-SEVSE, may be polymerized through a Stille coupling reaction. 3,6-bis (5-bromothiophen-2-yl) -2,5-bis ( 7-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) (0.40 g, 0.3145 mmol) and 5,5'-bis (trimethylstannyl) -2,2 ' -Biethieno [3,2-b] thiophene (5,5'-bis (trimethylstannyl) -2,2'-bithieno [3,2-b] thiophene) (0.0189 g, 0.03145 mmol) and (E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene ((E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene) (0.1731 g , 0.2830 mmol) was dissolved in chlorobenzene (6 mL) and subjected to nitrogen substitution. Thereafter, Pd ₂ (dba) ₃ (0.005 mg, 2 mol%) and P (o-tol) ₃ (0.007 g, 8 mol%) were added thereto, and the mixture was refluxed at 110 ° C. for 48 hours. Add 2-bromothiophene (0.1 g) and stir for 6 hours, add 2-tributyltin thiophene (0.1 g) and stir for 6 hours, end-capping ). The reaction solution is then slowly precipitated in methanol (300 mL) and the resulting solids are filtered off. The filtered solid was purified in the order of methanol, hexane, toluene and chloroform through soxxlet. The liquid down to the chloroform solvent was precipitated again in methanol, filtered through a filter and dried to give the title compound P-1-9DPP-DTT-SEVSE as a dark red solid (0.32 g obtained; 60% yield).

Mn = 66450, Mw = 100080, polydispersity 1.50.

[실시예 2] P-3-7DPP-DTT-SEVSE의 제조Example 2 Preparation of P-3-7DPP-DTT-SEVSE

The polymer, P-3-7DPP-DTT-SEVSE, may be polymerized through a Stille coupling reaction. 3,6-bis (5-bromothiophen-2-yl) -2,5-bis ( 7-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) (0.40 g, 0.3145 mmol) and 5,5'-bis (trimethylstannyl) -2,2 ' -Bithieno [3,2-b] thiophene (5,5'-bis (trimethylstannyl) -2,2'-bithieno [3,2-b] thiophene) (0.0569 g, 0.0943 mmol) and (E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene ((E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene) (0.1346 g , 0.2201 mmol) was dissolved in chlorobenzene (6 mL) and subjected to nitrogen substitution. Thereafter, Pd ₂ (dba) ₃ (0.005 mg, 2 mol%) and P (o-tol) ₃ (0.007 g, 8 mol%) were added thereto, and the mixture was refluxed at 110 ° C. for 48 hours. Add 2-bromothiophene (0.1 g) and stir for 6 hours, add 2-tributyltin thiophene (0.1 g) and stir for 6 hours, end-capping ). The reaction solution is then slowly precipitated in methanol (300 mL) and the resulting solids are filtered off. The filtered solid was purified in the order of methanol, hexane, toluene and chloroform through soxxlet. The liquid down to the chloroform solvent was again precipitated in methanol, filtered through a filter and dried to give the title compound P-3-7DPP-DTT-SEVSE as a dark red solid (0.30 g obtained; 65% yield).

Mn = 150160, Mw = 258930, Polydispersity 1.72.

[실시예 3] P-1-9DPP-TT-SEVSE의 제조 Example 3 Preparation of P-1-9DPP-TT-SEVSE

The polymer, P-1-9DPP-TT-SEVSE, may be polymerized through a Stille coupling reaction. 3,6-bis (5-bromothiophen-2-yl) -2,5-bis (7-decylnonadecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -da Ion (3,6-bis (5-bromothiophen-2-yl) -2,5-bis (7-decylnonadecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione) (0.40 g, 0.3145 mmol) and 2,5-bis (trimethylstannyl) thieno [3,2-b] thiophene (2,5-bis (trimethylstannyl) thieno [3,2-b] thiophene) (0.01146 g , 0.03145 mmol) and (E) -1,2-bis (5- (trimethylstannyl) selenophen-2-yl) ethene ((E) -1,2-bis (5- (trimethylstannyl) selenophen-2 -yl) ethene) (0.1731 g, 0.2830 mmol) was dissolved in chlorobenzene (6 mL) and subjected to nitrogen substitution. Thereafter, Pd ₂ (dba) ₃ (0.005 mg, 2 mol%) and P (o-tol) ₃ (0.007 g, 8 mol%) were added thereto, and the mixture was refluxed at 110 ° C. for 48 hours. Add 2-bromothiophene (0.1 g) and stir for 6 hours, add 2-tributyltin thiophene (0.1 g) and stir for 6 hours, end-capping ). The reaction solution is then slowly precipitated in methanol (300 mL) and the resulting solids are filtered off. The filtered solid was purified in the order of methanol, hexane, toluene and chloroform through soxxlet. The liquid down to the chloroform solvent was precipitated again in methanol, filtered through a filter and dried to give the title compound P-1-9DPP-TT-SEVSE as a dark red solid (0.29 g obtained; 59% yield).

Mn = 121170, Mw = 220920, polydispersity 1.81.

GPC of novel diketopyrrolopyrrole polymers synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE, P-1-9DPP-TT-SEVSE) The analytical results are shown in Table 1 below.

Table 1

	Mn	Mw	Mz	Mz + 1	PD
P-1-9DPP-DTT-SEVSE (Example 1)	66456	100086	143282	204366	1.50605
P-3-7DPP-DTT-SEVSE (Example 2)	150163	258934	519969	1173211	1.72435
P-1-9DPP-TT-SEVSE (Example 3)	121718	220923	564847	1495977	1.81505

In addition, the novel diketopyrrolopyrrole polymer synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE, P-1-9DPP-TT-SEVSE) In order to test the solubility of was measured by the following method, the results are shown in Table 2 and Table 3.

Solubility test Experimental method is to prepare a solution of each of the diketopyrrolopyrrole polymer synthesized in Examples 1 to 3 in the proportion of 0.5wt% or 0.7wt% in each solvent, and slowly heated from room temperature to dissolve the polymer sufficiently After measuring the precipitation of the polymer and whether passed through the scanning filter (0.45 micrometer) was shown in the following table.

TABLE 2

Solubility Test (0.5 wt% / mL)
	THF	toluene	Xylene	Tetralin	Chloroform (CHCl ₃ )
P-1-9DPP-DTT-SEVSE (Example 1)	++	+++	+++	+++	+++
P-3-7DPP-DTT-SEVSE (Example 2)	+++	+++	+++	+++	+++
P-1-9DPP-TT-SEVSE (Example 3)	++	+++	+++	+++	+++
+++ soluble at room temperature ++ soluble after heating + soluble after heating and insoluble during cooling-Insoluble

TABLE 3

Solubility Test (0.7 wt% / mL)
	THF	toluene	Xylene	Tetralin	Chloroform (CHCl ₃ )
P-1-9DPP-DTT-SEVSE (Example 1)	++	++	++	++	+++
P-3-7DPP-DTT-SEVSE (Example 2)	++	+++	+++	+++	+++
P-1-9DPP-TT-SEVSE (Example 3)	++	++	+++	++	+++
+++ soluble at room temperature ++ soluble after heating + soluble after heating and insoluble during cooling-Insoluble

[실시예 4] 유기전자소자 제작Example 4 Fabrication of Organic Electronic Device

The OTFT device was fabricated by top-contact, 100 nm n-doped silicon was used as a gate, and SiO ₂ was used as an insulator. Surface treatment was performed by using a piranha cleaning solution (piranha cleaning solution, H ₂ SO ₄ : 2H ₂ O ₂ ), followed by spin coating using Cytop ^TM and heat treatment at 200 ^° C. The organic semiconductor layer was prepared with 0.7 wt% of THF, chloroform, toluene, xylene, or tetralin solution, respectively, using a spin-coater at a speed of 2000 rpm. Coating for 1 minute. As the organic semiconductor material, polymers synthesized in Examples 1, 2, and 3 were used. Gold used as the source and drain was deposited to a thickness of 50 nm at 1 A / s. The channel is 50 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 mobility, 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.

Optical light of novel diketopyrrolopyrrole polymers synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE and P-1-9DPP-TT-SEVSE) Absorption area is measured in the solution state and the film state and the results are shown in Figs. Electrochemicals of Novel Diketopyrrolopyrrole Polymers Synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE and P-1-9DPP-TT-SEVSE) In order to characterize the results measured using a cyclic voltammetry (cyclo voltammetry) at 50 mV / s under a solvent of Bu ₄ NClO ₄ (0.1 molar concentration) in Figure 4, the carbon electrode was measured Voltage was applied through the coating.

The novel diketopyrrolopyrrole polymers synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE and P-1-9DPP-TT-SEVSE) The optical and electrochemical properties of) are described. Here, the HOMO value is a value calculated using the result value measured in FIG. 4. In addition, the band gap was obtained from the UV absorption wavelength in the film state.

Table 4

solvent: CHCl ₃	Optical properties				Electrochemical properties
solvent: CHCl ₃	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-1-9DPP-DTT-SEVSE (Example 1)	800455	777452	777	987	1.25	-3.92	-5.18
P-3-7DPP-DTT-SEVSE (Example 2)	803452	798455	798	1042	1.19	-4.01	-5.20
P-1-9DPP-TT-SEVSE (Example 3)	801454	800456	800	1018	1.21	-4.00	-5.21

As shown in Table 4, the diketopyrrolopyrrole polymer of the present invention has a low bandgap and a high charge mobility of the organic electronic device containing the same.

In Figures 5 to 7 novel diketopyrrolopyrrole polymer synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE and P-1-9DPP-TT -SEVSE) shows the results of measurement using DSC to determine thermal stability.

8 to 10 the novel diketopyrrolopyrrole polymer synthesized in Examples 1 to 3 (P-1-9DPP-DTT-SEVSE, P-3-7DPP-DTT-SEVSE and P-1-9DPP-TT -SEVSE) shows the result of measuring the decomposition temperature using TGA, the T _d of P-1-9DPP-DTT-SEVSE synthesized in Example 1 is 458 ℃, P- synthesized in Example 2 of 3-7DPP-DTT-SEVSE T _d is 461 ℃, and of the P-1-9DPP-TT-SEVSE synthesized in example 3 T _d is 421 ℃.

As shown in Figure 5 to 10, 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 the annealing (annealing) it can be seen that the excellent organic electronic device material have.

11 to 20 are views showing a transfer curve and an output curve of a device manufactured by the method of Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 FIG. 3 shows the organic electronic device characteristics of the polymer material for each solvent (THF, CHCl ₃ , toluene, xylene, tetralin) used in the solution process. 21 to 25 are hysteresis of the transfer curve of the device manufactured by the method of Example 4 using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 ) Shows a change in threshold voltage. The low change in the threshold voltage indicates that the stability of the device is good. As a result of measuring the hysteresis of THF, CHCl ₃ , toluene, xylene, and tetralin, the change of threshold voltage (ΔV _th (V)) was 18V, 9.54V, 9.36V, 7.77V, and 9.22V, respectively. In most cases, a stable device was realized with a change of less than 10V, and in particular, the stability of the device manufactured with xylene solvent was excellent.

Using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 in Table 5 to the characteristics of the device manufactured by the method of Example 4 solvent used in the solution process (THF , CHCl ₃ , toluene, xylene, tetralin).

Table 5

	menstruum
	THF	CHCl ₃	toluene	Xylene	Tetralin
Mobility (cm ² / Vs) (Ave)	1.40 (± 0.50)	2.16 (± 0.38)	1.91 (± 0.21)	2.61 (± 0.21)	1.89 (± 0.49)
Mobility (cm ² / Vs) (Max)	2.70	2.81	2.18	3.84	2.56
ΔV _th (V)	18.11 (12.85%)	9.54 (6.81%)	9.36 (6.68%)	7.77 (5.55%)	9.22 (6.58%)

Table 5 relates to the measurement results of the OTFT device manufactured using THF, CHCl ₃ , toluene, xylene or tetralin solvent, It can be seen that the highest charge mobility for each solvent is 2.18 cm ² / Vs, which has a high charge transfer characteristic, and also shows high characteristics in non-halogen solvents THF, toluene, xylene, and tetralyl. As a result of measuring the hysteresis of the threshold voltage, it can be confirmed that the device is stable.

In addition, using the diketopyrrolopyrrole polymer (P-1-9DPP-DTT-SEVSE) synthesized in Example 1 in Table 6 to the heat treatment temperature of the device manufactured by the method of Example 4 using xylene The characteristics according to the above are described.

Table 6

Polymer	Dielectric layer	Heat treatment temperature (℃)	μ [cm 2 / Vs]	I _on / I _off
P-1-9DPP-DTT-SEVSE (Example 1) (Xylene solvent)	Cytop / SiO ₂	Room temperature	0.97	> 10 ⁴
		100	1.09	> 10 ⁴
		120	1.42	> 10 ⁴
		140	1.56	> 10 ⁴
		160	1.80	> 10 ⁴
		180	2.59	> 10 ⁴
		200	3.84	> 10 ⁴

From Table 6, when the OTFT device was fabricated using a non-halogen solvent, xylene, the charge mobility was measured, but it was 0.97 cm ² / Vs at room temperature. At 200 ° C., it showed a high charge mobility of 3.84. This can be said that the arrangement of the organic semiconductor polymer material synthesized in Example 1 through heat treatment exhibits a high order of OTFT charge transfer characteristics, resulting in a high charge mobility.

Reliability test is an experiment to measure the life of the device, using the organic electronic material synthesized in Example 1 in the same manner as in Example 4 using xylene to fabricate an OTFT device 100V By continuously applying the voltage, the threshold voltage that is continuously measured until the lifetime of the device exceeds the gate voltage (100V) and eventually the life of the device. At this time, the parameter of the device stability is a tau value (tau: τ), the tau value of the amorphous silicon semiconductor is 8 x 10 ⁷ , the pentacene base material of the organic semiconductor is 4 x 10 ³ . . The semiconductor device life of the material synthesized in the embodiment is 5.4 x 10 ⁶ , which can be said to be high in organic semiconductors.

Claims

Diketopyrrolopyrrole polymer represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

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;

a is an integer of 1 or 2;

m and n are each independently an integer of 1 to 1000.
The method of claim 1,

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

Diketopyrrolopyrrole polymers selected from the following compounds:

(M and n are each independently an integer of 1 to 1000.)
An organic thin film transistor comprising the diketopyrrolopyrrole polymer according to any one of claims 1 to 3.
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 a diketopyrrolopyrrole polymer according to any one of claims 1 to 3.
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.