WO2013089323A1 - Novel diketopyrrolopyrrole polymer and organic electronic element using same - Google Patents

Abstract

The present invention relates to an organic semiconductor compound for an organic electronic element such as an organic thin film transistor (OTFT), and to a use therefor. More specifically, the present invention relates to: a diketopyrrolopyrrole polymer constituting a novel organic semiconductor compound having high pi-electron overlap by introducing an electron donor compound into a diketopyrrolopyrrole derivative; and an organic electronic element in which charge mobility and on/off ratio are improved by using the diketopyrrolopyrrole derivative as an organic semiconductor layer.

Description

 Specification

 NAME OF THE INVENTION: New Iketopy Loropyrrole Polymers and Organic Electronic Devices Using Them

 Technical Field

 [1] The present invention relates to an organic-based conductor compound for organic electronic devices such as organic thin film transistors (OTFTs) and their uses. More specifically, the present invention relates to a dieketopi-electron donor compound in a derivative. It is a novel organic-based conductor compound with a high pi-electron layered chip, which is related to organic electronic devices using dieketopy loaf as a condenser and organic-based conductor layer. Background

 [2] The development of telecommunications in the 21st century and the desire for personal handheld communication devices are capable of producing ultra-fine and ultra-integrated circuits that enable information communication devices that are small in size, light in weight, thin in thickness and easy to use. There is a need for new high-performance electronic materials and new information and communication materials that enable new-concept displays.

 Among them, organic thin film transistors (OTFT) are plastics such as display devices 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 potential for use as an important component of the circuitry has led to many studies.

 [3] The organic thin film transistor using organic semiconductor has the advantages of simple manufacturing process and low cost production compared to the organic thin film transistor using amorphous silicon and polysilicon, and plastic substrates for the implementation of flexible display. In recent years, many studies have been conducted due to the advantages of over-compatibility, especially in the case of using polymer-free conductors, which can reduce the manufacturing cost compared to low molecular weight-based conductor compounds. Have.

 [4] representative polymer fields developed to date ^ Semiconductors for thin film transistors

 Compounds include P3HT [poly (3-nucleothiophene)] and

F8T2 [poly (9,9-dioctylfluorene-co-bithiophene)]. OTFT uniqueness feature is however a number of, which is an important evaluation ^"gacheok charge mobility and off ratio (on / off ratio) to turn, the most important evaluation standard is a charge transfer. Charge transfer turning way type, the thin film formed of a semiconductor material ( Structure and morphology), driving voltage and so on.

[5] Figure 1 is a substrate / gate / insulating layer / electrode layer (source, drain) / oil-based conductor layer

A cross-sectional view showing a typical organic thin film transistor structure, in which a gate electrode is formed on the substrate. An insulating layer is formed on top of the gate electrode, and an organic base layer and a source and a drain electrode are sequentially formed thereon. The driving principle of the organic thin film transistor of the above structure is described as an example of a P-type semiconductor as follows: First, when a voltage is applied between the source and the drain, the current is proportional to the voltage under low voltage. When a positive voltage is applied to the gate here, the positive charges are driven by the electric field by the applied voltage, so that all of the positive charges are pushed up the top of the semiconductor layer. There will be a depletion layer without charge, and in this situation, the amount of low current will flow because the number of conducting charge carriers is reduced even if a voltage is applied between the source and the drain. The effect of the electric field on the applied voltage forms an accumulation layer in which the positive charge is induced in the vicinity of the insulation charge. Since there are many carriers, more current can flow. Therefore, the positive and negative voltages are applied alternately to the gates while the voltage is applied between the source and drain, so that the current flows between the source and drain. You can control it.

 [6] For organic thin film transistors composed of the above principles, electrodes (sources, drains), substrates and gate electrodes requiring high thermal stability, high

 There are insulators that must have dielectric properties and dielectric constants, and semiconductors that move charges well. Among them, there are many problems that must be overcome, and the core material is organic semiconductors. It can be divided into n-type or P-type oil-based conductors according to electron or hole transfer. In general, when molecular-weighted organic semiconductors are used to form an oil-based conductor layer, low-molecular oil-based conductors are easy to purify The charge transfer characteristics are excellent because they can be almost eliminated.However, these organic semiconductors cannot be spin coated and printed, and the thin film must be manufactured by vacuum deposition, which makes the manufacturing process more complicated and expensive compared to polymer-based conductors. In the case of polymer free-based conductors, high-purity purification is difficult, but heat resistance is excellent and spinco And the printing is possible there is a beneficial advantage in the manufacturing process and cost, mass production.

 [7] Although much research has been done to date for the development of organic semiconductor materials, the development of polymer semiconductor materials has yet to reach the development of low molecular weight semiconductor materials. Therefore, the organic thin film with low manufacturing cost is flexible.

Of polymer semiconductor materials for the development of electronic devices using transistors. In general, it is known that the charge mobility of polymers is lower than that of low molecules, but it is a material that can sufficiently overcome this in the manufacturing process and cost.Dikekepi is already developed. Currently, more than 10 PCTs have been reported from 2009 to 2011, and more than 20 SCI papers have been reported, which has a charge mobility of lcmWs and organic solar cell efficiency of 5%. Korean Patent Publication No. 2011-0091711 discloses a polymerizer in which an S-containing heteroaromatic ring is directly bonded to a diketopyrrolopyrrole group.

[9] However, the material so far has not shown a broad expansion of pi electrons.

 Therefore, it is necessary to develop a polymer semiconductor material exhibiting sufficient pie electron overlap.

 Detailed description of the invention

 Technical challenge

 [10] An object of the present invention is to alternately polymerize diketopyrrolop, one of the electron acceptor materials, and an electron donor material, which is an aromatic material in which a derivative and a vinylene bond are introduced, to have high air stability and coplanarity of the main chain. Increasing) and having an expanded conjugated structure provides a diketopylopey polymerizer containing a double bond that can exhibit a layered pi electron expansion.

Another object of the present invention is to provide a diketopyrrolopyrrole polymer, which is an organic semiconductor compound having high solubility and high molecular weight, which has viscosity and easy spin coating at room temperature, thereby allowing solution processing.

[12] Another object of the present invention is to provide a polymer of diketopyrrolopy, an organic semiconductor compound having a high charge mobility, which is used in organic electronic devices.

[13] Another object of the present invention is to provide a novel diketopyrrolopyrrole according to the present invention.

 An organic thin film transistor comprising a polymer in an organic semiconductor layer is provided. Challenge solution

 The present invention relates to an organic semiconductor compound for organic electronic devices such as an organic thin film transistor (OTFT) and its use. More specifically, the present invention is configured such that a compound containing a diketopyrrolopyrrole derivative as an electron acceptor compound and a vinylene group as an electron donor compound is alternately integrated.

 The present invention relates to a diketopyrrolopyrrole polymer, which is a p-type polymer organic semiconductor compound used as an active layer material of an organic thin film transistor, and an organic electronic device using the same.

 [15] Hereinafter, the present invention will be described in detail.

 [16] The organic semiconductor compound of the present invention is represented by the following formula (1)

 As a diketopyrrolopyrrole polymer, the introduction of the vinylene group (V)

 By increasing coplanarity and having an expanded conjugated structure, the electron density is improved, thereby increasing the intermolecular interaction and high mobility.

[17] [Formula 1]

 [19] [In Formula 1,

[20] and R ₂ are each independently (C1-C50) alkyl or (C6-C50) aryl;

[21] and L ₂ are each independently selected from the following structures;

[24]. X, to X ₃ are each independently S, Se, 0, NH, or NR ';

[25] A, and A ₂ are each independently hydrogen, cyano or -COOR ";

 [26] R 'and R "are each independently (C1-C50) alkyl or (C6-C50) aryl;

[27] R ₃ to R ₈ are each independently a hydrogen, hydroxy group, amino, (C1-C50) alkyl, (C6-C ⁵ 0) aryl, (C1-C50) alkoxy, mono- or di (C1-C50 ) Alkylamino, (C1-C50) alkoxycarbonyl or (C1-C50) alkylcarbonyloxy;

[28] m is an integer of 1 or 2, and when m is 2, each of V and L ₂ may be the same as or different from each other; and

 [29] n is an integer of 1 to 1,000.]

In Formula 1, __ _Ll- (v ᅳ L _{2) m} — is selected from the following structures.

[32] [X _l5 X ₂ , X ₃ , A _b A ₂ , R ₃ , R 4, R ₅ , R ₆ , R ₇ and are as defined in Formula 1 above. same.]

[33] More preferably, L ^ vL ^ m is selected from the following structures.

 [35]

In addition, in Formula 1, R and R ₂ are preferably (C1-C50) alkyl, and the alkyl includes linear or branched alkyl.

The diketopyrrolopyrrole polymer of the present invention is specifically selected from the following compounds.

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

[44]

 As a method for preparing the diketopyrrolopyrrole polymer according to the present invention, the final compound may be prepared through alkylation reaction, Grignard coupling reaction, Suzuki coupling reaction, steel 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 conventional organic chemical reactions in addition to the above production method.

The die ketopyrrolopy polymer according to the present invention may be used as a material for forming an organic semiconductor layer of an organic electronic device, and specific examples of the method of manufacturing the organic thin film transistor to which the polymer is applied are as follows. As the substrate 11, it is preferable to use n-type silicon used for a conventional organic thin film transistor. This substrate contains the function of the gate electrode. In addition to n-type silicon, glass substrates or transparent plastic substrates that have excellent surface smoothness, ease of handling, and water resistance may be used. In this case, a gate electrode must be added on the substrate. Substances that can be employed as the substrate include glass, polyethyienenaphthalate (PEN),

 Polyethylene terephthalate (PET),

 '' Polycarbonate (PC), Polyvinylalcohol (PVP), Polyacrylate, Polyimide,

 Polynorbornene and polyethersulfone (PES). ᅳ

As the gate insulating layer (.12) constituting the OTFT device, an insulator having a large dielectric constant, which is commonly used, may be used. Specifically, Bao. ₃₃ Sr ₀ . ₆₆ Ti0 ₃ (BST), A1 ₂ 0 ₃ ,

_{Ta 2 0 5, La 2 0} 5, Y 2 0 3 , and ferroelectric insulators, PdZr o.3 ₃ Ti ₀ .660 ₃ selected from the group consisting of _{Ti0 2 (PZT), Bi 4} Ti 3 0 12, BaMgF 4, SrBi ₂ (TaNb) ₂ 0 ₉ , Ba (ZrTi) 0 ₃ (BZT), BaTi0 ₃ ,

Insulators selected from the group consisting of SrTi0 ₃ , Bi ₄ Ti ₃ 0 ₁₂ , Si0 ₂ , SiN _x and AION, or polyimide, BCB (benzocyclobutene), parylene, polyacrylate , Polyvinylalcohol and

 Organic starch bodies such as polyvinylphenol can be used.

 The structure of the organic thin film transistor of the present invention is as shown in FIG.

 The substrate / gate electrode as well as the top-contact of the substrate 11 / gate electrode 16 / insulation layer 12 / organic semiconductor layer 13 / source 14 and drain electrode 15 / Insulating layer / source, drain electrode / includes the form of the bottom-contact (bottom-contact) of the organic conductor layer, and also the surface between the source (14) and drain electrode (15) and the organic semiconductor layer (13) HMDS (l, U, 3,3,3-hexamethyldisilazane),

 It may or may not coat octadecyltrichlorosilane (OTS) or octadecyltrichlorosilane (OTDS).

 An organic semiconductor layer employing the die ketopyrrolopyrrole copolymer according to the present invention may be formed into a thin film by vacuum deposition, screen printing, printing, spin casting, spin coating, dipping, or ink spraying. And, at this time, the deposition of the organic semiconductor layer may be formed using a high temperature solution at 40 ° C or more, the thickness is preferably around 500 persons.

 The gate electrode 16 and the source and drain electrodes 14 and 15 are conductive materials

 Possible, gold (Au), silver (Ag), aluminum (A1), nickel (Ni), chromium (Cr) and

 It is preferably formed of a material selected from the group consisting of insultin oxide (ITO).

Effects of the Invention [52] An organic semiconductor compound according to the present invention, that is, an electron acceptor compound

 Dyketopyrrolopyi containing a derivative and a vinylene group which is an electron donor compound. The diketopyrrolopy polymer, which is composed of alternating polymerization of polymers, increases the coplanarity of the main chain with the introduction of vinylene groups and has an expanded conjugated structure to enhance electron density, thereby enhancing intermolecular interactions. Excellent thermal stability. In addition, the HOMO value decreases, that is, the electron density increases in the repeating unit, thereby having excellent charge mobility and oxidation stability, and thus may be used as an organic semiconductor layer of an organic thin film transistor. Therefore, the organic thin film transistor employing these devices improves the charge mobility and the flashing ratio. When the organic thin film transistor is used, it is possible to make an electronic device having excellent efficiency and performance. Such organic thin film transistors can also be manufactured by a solution process such as vacuum deposition, spin coating or printing.

 The manufacturing cost of the electronic device using the organic thin film transistor can be reduced.

 Brief description of the drawings

 1 is a cross-sectional view showing the structure of a general organic thin film transistor fabricated from a substrate / gate / insulation layer (source, drain) / semiconductor charge.

 FIG. 2-UV-vis absorption spectra in solution and film form of organic semiconductor compound (PDPPDBTE) according to Example 1

 [55] FIG. 3-Cyclic voltammetry diagram of the organic semiconductor compound (PDPPDBTE) according to Example 1

 4-Differential Calorimetry (DSC) Curve of Organic Semiconductor Compound (PDPPDBTE) According to Example 1

FIG. 5-Thermal Capacity Analysis (TGA) Curve of Organic Semiconductor Compound (PDPPDBTE) According to Example 1

[58] Figure 6 - a view predict the HOMO and LUMO of the structure of Example 1 through a computer simulation (DFT) ^'

 7-AFM images (a: film at room temperature, a: at 200 ° C.) of the device manufactured by the method of Example 8 using the organic semiconductor compound (PDPPDBTE) according to Example 1

Annealed film state, c) drawing showing annealed film state at 250 ^o C)

8 and 9-a diagram showing the transfer cuve of the device fabricated by the method of Example 8 using the organic semiconductor compound (PDPPDBTE) according to Example 1 [room temperature, 150 ° C annealing (annealing) ), 200 ° C annealing, 250 ^o C annealing]

 [61] <Description of Symbols for Major Parts of Drawings>

 [62] 11: substrate 12: insulating layer (insulator)

 13: organic electronic element layers 14 source

[64] 15: Drain 16: Gate rL 10

 6

 8

1 _J

 Form for the implementation of the invention

And the following is to be limited to hiophen-2-yl) ethene)

 Add thiophene-2-carbaldehyde (5.6 g, 50 mmol) to the flask

 Dissolve in tetrahydrofuran (THF) (100 mL), lower the temperature to -18 ° C and slowly dropwise add titanium (IV) chloride (6.5 mL) for 30 minutes. After stirring for 30 minutes, zinc powder (7.8 g) is added over 30 minutes. After stirring at −18 ° C. for 30 minutes, the temperature is raised to room temperature and refluxed for 3 hours 30 minutes. Then pour iced water to stop the reaction, filter the minerals with a filter, wash them with methylene chloride, extract them, remove the water, recrystallize with nucleic acid, and use the yellow compound as the target compound.

 (E) -l, 2-bis (thiophen-2-yl), afforded ten (4.7 g, yield: 98%). Ή

NMR (300 MHz, CDCl ₃ ) [ppm] 67.18 (d, 2H), 7.05 (s, 2H), 7.04 (d, 2H), 6.99 (m, 2H).

 [69]

[Preparation Example 2] (E) -1,2-bis (5- (trimethylslanyl) thiophen-2-yl) ethene

Synthesis of ((E) -l, 2-bis (5- (trimethylstannyl) thiophen_ ² -yl) ethene)

 [72] The flask was charged with (E) -1,2-bis (thiophen-2-yl) ten (1.78 g, 9.6 mmol).

 After dissolving in a mixed solvent of tetrahydrofuran / nucleic acid (volume ratio 2/1, 50 mL), slowly add 2 moles of n-butyllithium cyclonucleic acid (11 ml, 22 mmol) at -78 ° C and stir for 30 minutes. Scream After raising to room temperature and refluxing for 1 hour, the reaction product is lowered to -78 ° C. 1 mole of trimeth ¾ tin in the reaction mixture in Dongeundo.

 Tetrahydrofuran (22 mL, 22 mmol) in which chloride is dissolved is slowly added dropwise, followed by H half hour at room temperature for 2 hours. Extracted with ether ，

 Water was removed with anhydrous magnesium sulfate, the solvent was concentrated, and ethane was recrystallized to give a white needle-like compound.

(E) -l, 2-bis (5- (tri methylstannyl) thiophen-2-yl) gave ten (3.88 g, yield: 80%). NMR (300 MHz, CDCl ₃ ) [ppm] 67.11 (d, 2H), 7.08 (s, 2H), 7.07 (d, 2H), 0.36 (s, 18H). [73]

[Production Example 3] (E) -1,2-bis (4- (trimethylsranyl) phenyl) ethene

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

 [76] Fulasquel was added (E) -l, 2-bis (4-bromophenyl) tene (3 g, 8.7 mmol).

 Dissolved in tetrahydrofuran (90 mL) followed by 2 moles of n-butyllithium

 Cyclonucleic acid (7.1 mL, 17.75 mmol) is added slowly at -78 ° C and stirred for 30 minutes. Trimethyltin chloride (3.53 g, 17.75 mmol) was slowly added dropwise to the reaction at the same temperature, followed by stirring at room temperature for 2 hours. Extracted with ether ，

 Water was removed with anhydrous magnesium sulfate, the solvent was concentrated and recrystallized with ethyl alcohol, which was the target compound of white powder.

Ten was obtained in (E) -l, 2-bis (4- (trimethylstannyl) phenyl) (3.2 g, yield: 80%). NMR (300 MHz, CDCl ₃ ) [ppm] 67.50-7.48 (m, 4H), 6.968 (s, 2H), 0.36 (s, 18H).

 [77]

[Production Example 4] (E) -l, 2-bis (3-dodecylthiophen-2-yl)

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

 [80] 3-dodecylthiophene-2-carbaldehyde 1 = (14 g, 50 mmol),

 Tetrahydrofuran (THF) (250 mL), titanium (IV) chloride (6.5 mL),

 Using zinc powder (7.8 g) in the same manner as in Preparation Example 1

Ten was obtained in (E) -l, 2-bis (3-dodecylthiophen-2-yl) (10 g, yield: 75%). NMR (300 MHz, CDCl ₃ ) [ppm] δ 7.18 (d, 2H), 7.05 (d, 2H), 6.99 (s, 2H), 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m , 36H), 0.88 (m, 6H)

 [81]

[82] [Preparation Example 5] (E) -1,2-bis (3-dodecyl-5- (trimethylstannyl) thiophene-2-hexyl)

((E) -l, 2-bis ( ³ -dodecyl-5- (trimethylstannyl) thiophen- ² _yl) ethe ^ synthesis

[84] Ten (5 g, 9.6 mmol) in (E) -1,2-bis (3-dodecylthiophen-2-yl) Preparation of tetrahydrofuran / nucleic acid mixed solvent (volume ratio 2/1, 100 mL), 2 moles of _n -butyllithium o cyclonucleic acid (11 ml, 22 mmol), trimethyltin chloride (4.38 g, 22 mmol) In the same manner as in Example 2

Ten was obtained (5.2 g, obtained: 63%) in (E) -l, 2-bis (3-dodecyl-5- (tri methylstannyl) thiophen-2-yl). NMR (300 MHz, CDCl ₃ ) [ppm] 67.05 (d, 2H), 6.99 (s, 2H),

 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, 6H), 0.36 (s, 18H).

 [85]

[86] [Preparation Example 6] (E) -l, 2-bis (3-dodecylthioeno [3,2-b] thiophen-2-yl)

 Synthesis of ((E) -l, 2-bis (3-dodecylthieno [3,2-b] thiophen-2-yl) ethene)

 [88] 3-dodecylthioeno [3,2-b] thiophene-2-carbaldehyde (17 g, 50 mmol)

 Tetrahydrofuran (THF) (250 mL), titanium (IV) chloride (6.5 mL),

 Using zinc powder (7.8 g) in the same manner as in Preparation Example 1

Ten was obtained (24 g, yield: 75%) from (E) -l, 2-bis (3-dodecylthioeno [3,2-b] thiophen-2-yl). NMR (300 MHz, CDCl ₃ ) [ppm] 07.18 (d, 2H), 7.05 (d, 2H), 6.99 (s, 2H),

 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, 6H)

 [89]

[90] [Preparation Example 7] (E) -1,2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) ethene

 ((E) -l, 2-bis (3-dodecyl-5- (trimethylstannyl) thieno [3,2-b] thio synthesis

 [92] Ten (5 g, 9.6 mmol) in (E) -1,2-nonaqueous (3-dodecylthioeno [3,2-b] thiophen-2-yl)

 Mixed solvent of tetrahydrofuran / nucleic acid (volume ratio 2/1, 100 mL), cyclonucleic acid with 2 moles of n-butyllithium (11 ml, 22 mmol), trimethyltin chloride (4.38 g, 22 mmol) Preparation Example 2 In the same manner as the target compound

Ten was obtained (5.2 g, yield: 63%) in (E) -l, 2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl). NMR (300 MHz, CDCl ₃ ) [ppm] 07.05 (d, 2H), 6.99 (s, 2H),

 2.67 (m, 4H), 1.54 (m, 4H), 1.23 (m, 36H), 0.88 (m, 6H), 0.36 (s, 18H).

 [93]

상기 고분자는 스틸레 (Stille) 커플링 반웅을 통해 중합할 수 있다. Example 1 Synthesis of PDPPDBTE

The polymer may 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)- Dion (() .50 g, 0.0004 mol) and

Ten (Preparation Example 2, 0.229 g, 0.0004 mmol) in (E) -1, ² -bis (5- (trimethylstannyl) thiophen- ² -yl) was dissolved in chlorobenzene (5 mL) and subjected to nitrogen substitution. do. After that, Pd ₂ (dba) ₃ (0.008 mg, 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 semi-aqueous solution is then slowly precipitated in methanol (300 mL) and the resulting solids are filtered off. The filtered solid is purified in the order of methanol, nucleic acid, toluene and chloroform via soxlet. The down liquid was again precipitated in methanol, filtered through a filter, and dried to give PDPPDBTE, the title compound as a dark green solid (90% yield). Mn = 34000, polydispersity 1.78, Ή NMR (300 MHz, CDCl ₃ ) [ppm]: δ 8.93 (broad, 4H), 6.99-6.83 (broad, 6H), 3.88 (broad, 4H), 2.11 (m 2H ), 1.31-1.25 (m, 76H), 1.04-0.88 (m, 12H).

Example 2 Synthesis of PDPPDBTE12

 The polymer may 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) Dione (0.50 g, 0.0004 mol),

 (E) -l, 2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) ethene (Preparation Example 5, 0.378 g,

0.0004 mmol), Pd ₂ (dba) ₃ (0.008 mg, 2 mol%) and P (o-tol) ₃ (0.011 g, 8 mol%) were used to prepare the title compound PDPPDBTE12 in the same manner as in Example 1.

Obtained (yield: 90%). Mn = 90,000, polydispersity 1.8, Ή NMR (300 MHz, CDC1 ₃

) [ppm]: δ 8.93 (broad, 4Η), 7.1-6.99 (broad, 4H), 3.88 (broad, 4H), 2.11 (m 2H),

1.40-1.25 (m, 120 H), 1.04-0.88 (m, 18 H).

[101] [Example 3] Synthesis of PDPPBTPE

[103]

 The polymer may 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 Ions (0.50 g, 0.0004 mol),

(E) -l, 2- bis ^(4- (trimethyl Stan) phenyl) X in (Production Example ^{3, 0. 2 02 g, 0.0004} mmol), Pd 2 (dba) 3 (0.008 mg, 2 mol% ) And P (o-tol) ₃ (0.011 g, 8 mol%) to give the title compound PDPPBTPE in the same manner as in Example 1 (yield: 90%). Mn = 90,000, polydispersity 1.8, Ή NMR (300 MHz, CDCl ₃ ) [ppm]: δ 8.93 (broad, 4H), 7.7 (broad, 8H), 6.99 (S, 2H), 3.88 (broad, 4H) , 2.1 l (m 2 H), 1.31-1.25 (m, 76H), 1.04-0.88 (m, 12H).

 [105]

Example 4 Synthesis of PDPPDTTE12

 The polymer may be polymerized through a Stille coupling reaction.

 3,6-bis (5-bromothiophene-2sylyl) -2,5-bis (2-decyltetradecyl) pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -da Ions (0.50 g, 0.0004 mol),

 (E) -l, 2-bis (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) ethene (Preparation Example 7, 0.39 g,

0.0004 mmol), Pd ₂ (dba) ₃ (0.008 mg, 2 mol%) and P (o-tol) ₃ (0.011 g, 8 mol%) were used to prepare the title compound PDPPDTTE12 in the same manner as in Example 1.

Obtained (yield 75%). Mn = 45,000, polydispersity 1.7, Ή NMR (300 MHz, CDC1 ₃

) [ppm]: δ 8.93 (broad, 4H), 7.1-6.99 (broad, 4H), 3.88 (broad, 4H), 2.1 l (m 2H),

1.40-1.25 (m, 120 H), 1.04-0.88 (m, 18 H).

 [109]

Example 5 Synthesis of PDPPDBTA

 The polymer may be polymerized through Suzuki coupling. In the flask

 Remove moisture

2,5-bis (2-decyltetradecyl) -3,6-bis (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiophene 2-yl) pyrrolo [3,4-c] pyrrole -1, ⁴ ( ² H, ⁵ H) -dione (1.20 g, 0.0010 mol) and (E) -2, 3-bis (5-bro) Add thiophen-2-yl) acrylonitrile (0.367 g, 0.0010 mmol), add 2M K ₂ CO ₃ (2.94 mL) and toluene (12 mL), and perform nitrogen bubbling for 30 minutes. Add catalyst Pd (pph ₃ ) ₄ (0.057 mg, 5 mol%) and reflux for 48 hours at 100 ° C. The solution is then slowly precipitated in methanol (300 mL) and the solids are filtered off. The filtered solid is purified in the order of methanol, nucleic acid, toluene and chloroform via soxlet. The precipitated liquid is again precipitated in methanol, filtered through a filter and dried to settle to give the title compound as a dark green solid.

PDPPDBTA was obtained (yield: 90%). Mn = 20,000, polydispersity 1.68, Ή NMR (300 MHz, CDCl ₃ ) [ppm]: δ 8.93 (broad, 4H), 6.99-6.83 (broad, 5H), 3.88 (broad, 4H), 2.11 (m 2H ), 1.31-1.25 (m, 76H), 1.04-0.88 (m, 12H).

 [113]

Example 6 Synthesis of PDPPBDTPA

 The polymer may be polymerized through Suzuki coupling. In the flask

 Remove moisture

2,5-bis (2-decyltetradecyl) -3,6-bis (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiophene 2-yl) pyrrolo [3,4-c] pi to -1,4 (2H, 5H) -dione (0.5 g, 0.0004 mol), (Z) -2,3-bis (4-bromo -2,5-dimethylphenyl) acrylonitrile (0.367 g, 0.0004 mmol), 2M K ₂ C0 ₃ (1.17 mL), toluene (5 mL), catalyst Pd (pph ₃ ) ₄ (0.023 mg, 5 mol %) To give the title compound PDPPBDTPA in the same manner as in Example 5.

Obtained (yield: 80%). Mn = 18,000, polydispersity 1.87, Ή NMR (300 MHz, CDC1 ₃ ) [ppm]: δ 8.93 (broad, 4H), 7.2-6.83 (broad, 5H), 3.88 (broad, 2H), 2.34-2. ll (m 16H), 1.31-1.25 (m, 124 H), 1.04-0.88 (m, 24 H).

 [117]

 Example 7 Synthesis of PDPPDTDTEP

 The polymer may 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 Ions (0.50 g, 0.0004 mol),

2- (4-((E) -2- (3-dodecyl-5- (trimethylstannyl) thiophen-2-yl) vinyl) -2,5-dimethylstyryl) -3-dodecyl -5- (trimethylstannyl) thiophene (0.39 g, 0.0004 mmol), Pd ₂ (dba) ₃ (0.008 mg, 2 mol%) and P (o-tol) ₃ (0.011 g, 8 mol%) In the same manner as in Example 1 to obtain the title compound PDPPDTDTEP (yield: 75%). Mn = 55,000, polydispersity 1.7, Ή NMR (300 MHz, CDCl ₃ ) [ppm]: δ 8.93 (broad, 4H), 7.1-6.99 (broad, 4H), 3.88 (broad, 4H), 2.1 l (m 2H), 1.40-1.25 (m, 120H), 1.04-0.88 (m, 18H).

 [121]

 [Example 8] Fabrication of Organic Electronic Device

 [123] The OTFT device was fabricated in a top-contact manner, and 300 nm n-doped silicon was used.

A gate was used and Si0 ₂ was used as an insulator. For surface treatment, wash the surface using piranha cleaning solution (H ₂ S0 ₄ : 2H ₂ 0 ₂ ), and then use SAM (Self Assemble) for the surface using Adrich's OTS (octadecyltrichlorosilane).

 Monolayer) was used after treatment. The organic semiconductor layer was coated with 0.7 wt% chloroform solution at a speed of 2000 rpm using a spin-coater for 1 minute. As the organic semiconductor material, PDPPDBTE synthesized in Example 1 was used. The thickness of the organic semiconductor layer was 45 nm using a surface profiler (Alpha Step 500, Tencor). Gold used as the source and drain was deposited to a thickness of 50 nm at 1 A / s. The length of the channel is 1000 μπι and the width is 2000 μιη. The measurement of the characteristics of the OTFT uses Keithley 2400 and 236 source / measure units.

The charge mobility was obtained from the saturation region with a graph of (I _SD ) ″ ² and V _G as variables from the saturation region current equation.

In the above formula, I _SD is the source-drain current, μ or μ _ΡΕΤ is the charge transfer, C ₀ is the oxide film capacitive, W is the channel width, L is the channel length, V _G is the gate voltage And V _T is the threshold voltage. The cutoff leakage current (10 _{ is the current flowing in the off state, and is obtained from the current ratio as the minimum current in the off state.

The light absorption region of the synthetic polymer compound (PDPPDBTE) synthesized in Example 1 was measured in a solution state and a film state, and the results are shown in FIG. 2. The electrical synthesis of the synthetic polymer compound (PDPPDBTE) synthesized in Example 1 was performed. In order to analyze the chemical properties, cycles were carried out at 50 mV / s under a solvent of Bu ₄ NClO ₄ (0.1 molar concentration).

 The measurement results using cyclic voltammetry are shown in FIG. 3, and voltage was applied through coating using a carbon electrode during the measurement.

 The optical and electrochemical properties of the synthetic base compound (PDPPDBTE) synthesized in Example 1 are described in Table 1. Here, the HOMO values are calculated using the results measured in FIG. The gap was obtained at the UV absorption wavelength in the film state.

 [129] Table 1

 [Table 1]

In FIG. 4, thermal stability of the oil-based conductor compound (PDPPDBTE) synthesized in Example 1 was measured. In PDPPDBTE, the glass transition temperature was measured at 260 ^° C., the melting temperature was measured at 277 ° C., and crystallization was performed. The temperature value is measured at 26 C, indicating that it has a quality characteristic.

 [131] Figure 5 shows the synthesis of the organic base compound (PDPPDBTE) synthesized in Example 1

Decomposition temperature is measured using TGA. 5% of PDPPDBTE . The temperature at which decomposition occurs was measured at 421 ⁰ C, indicating that PDPPDBTE has excellent thermal stability.

In FIG. 6, the distribution state of electrons according to the energy level of a molecule is illustrated through DFT calculation. In the HOMO energy level of the organic semiconductor compound (PDPPDBTE) synthesized in Example 1, it can be seen that electrons are spread throughout the molecular structure. In the LUMO energy level, the electrons of the electron donor move toward the electron acceptor, and these results show that the charge separation of energy is performed well.

 7 shows AFM images (a: room temperature, b: 200 ° C) of the device fabricated in Example 8 using the organic semiconductor compound (PDPPDBTE) synthesized in Example 1.

 An annealing film state, c: an annealing film state at 250 ° C.) shows an increase in the crystallinity of the molecule after annealing. ᅳ

 8 and 9 illustrate an organic semiconductor compound (PDPPDBTE) synthesized in Example 1;

 Is a diagram showing the transfer curve of the device fabricated in Example 8, showing the characteristics of the organic electronic device of the polymer material. As shown in Figure 8 and 9, the organic semiconductor compound synthesized in the present invention is excellent in thermal stability and can be seen that the charge mobility when the annealing (annealing) can be seen that the material is excellent. Table 2 below describes the characteristics of the device fabricated in Example 8 using the organic semiconductor compound (PDPPDBTE) synthesized in Example 1. As the annealing temperature increases, the charge mobility increases, the threshold voltage increases, and the flashing ratio decreases.

 [135] Table 2

 [Table 2]

 Industrial availability

 [136] An organic semiconductor compound according to the present invention, that is, an electron acceptor compound

Diketopyrrolopyrrole polymers, which are configured to alternately polymerize diketopyrrolopie derivatives and a compound containing an electron donor compound vinylene group, increase and expand coplanarity of the main chain with the introduction of vinylene groups. By having a conjugated structure, the electron density is improved, thereby increasing the intermolecular interaction and showing excellent thermal stability. In addition, the HOMO value is lowered, that is, As the electron density increases in the repeating unit, it has excellent charge mobility and oxidation stability, and can be used as an organic-based conductor layer of organic thin film transistors. Therefore, organic thin film transistors employing these organic films have improved charge mobility and flashing ratio. When using transistors, it is possible to make electronic devices with excellent efficiency and performance. These organic thin film transistors can also be manufactured by solution processes such as vacuum deposition, spin coating or printing.

The manufacturing cost of electronic devices using organic thin film transistors can be reduced.

Claims

Claims [Claim 1] A polymer of diketopyrrolepi represented by the following formula  [Formula 1]  `` R2,  ᄋ 、、 [Formula 1, R! And R ₂ are each independently (C 1 -C 50) alkyl or (C 6 -C 50) aryl; 1 ^ and 1 _{^ 2} are each independently selected from the following structures;

Xi to X ₃ are each independently S, Se, 0, NH, or NR ′; A _! And A ₂ are each independently hydrogen, cyano or -COOR ";  R 'and R "are each independently (C1-C50) alkyl or (C6-C50) aryl; R ₃ to R ₈ are each independently hydrogen, hydroxyl, amino, (C1-C50) _. Alkyl, (C6-C50) aryl, (C1-C50) alkoxy, mono or di (C1-C50) alkylamino, (C1-C50) alkoxycarbonyl or  (C1-C50) alkylcarbonyloxy; m is an integer of 1 or 2, and when m is 2, each of V and L ₂ may be the same or different from each other; and  n is an integer from 1 to 1,000.]  [Claim 2] The method according to claim 1, The ν (ν ᅳ L ₂ ) _m — is a dieketopy, characterized in that the structure selected from the following composites.

[XX ₂ , X ₃ , A _{1 (} A ₂ , R ₃ , R 4, R ₅ , R ₆ , R ₇ and ¾ are the same as defined in claim 1). [Claim 3] In paragraph 2, ᅳ--！ ^-Pyrrole polymer is a dieketope, characterized in that selected from the following structure.

 [Claim 4] In paragraph 1, And R ₂ is a (C 1 -C 50) alkyl diketopyrrole pyrrole polymer.  Clause 5] In paragraph 1,  A diketopy ropyrrole polymer characterized by being selected from the following compounds.

 [Where n is an integer of 1 to 1,000.]

In accordance with any one of paragraphs 1 to 5 An oil ₇ thin film transistor comprising a dieketopyrrolopy polymer in an oil-based conductor layer.