KR101514819B1 - organic semiconductor compound, manufacturing method thereof, and organic electronic device that contains it - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to an organic semiconductor compound having excellent electrical properties, a method for producing the same, and an organic electronic device containing the same. The organic semiconductor compound of the present invention has high thermal stability, solubility and charge mobility, High efficiency.

Description

TECHNICAL FIELD The present invention relates to an organic semiconductor compound, a method of manufacturing the same, and an organic electronic device including the organic semiconductor compound,

The present invention relates to an organic semiconductor compound, a method for producing the organic semiconductor compound, and an organic electronic device including the organic semiconductor compound. More particularly, the present invention relates to an organic semiconductor compound including perylene, a method for producing the organic semiconductor compound, and an organic electronic device including the same.

In 2009, the photovoltaic industry has installed more than 6GW in the world, forming an independent industrial country of $ 30 billion market, and it is expected to continue to grow rapidly until mid-21st century.

Current major products are crystalline silicon solar cells, which have overwhelming use in the solar power market. In recent years, however, market share of inorganic thin film solar cells such as a-Si, CdTe and CIGS has been steadily increasing. Respectively.

In addition, organic solar cells represented by dye-sensitized and organic thin-film type are not yet entering the market in earnest, but they can lead the ubiquitous solar era, which is expected in the future by promoting cheap material cost, process cost, and light, Another possibility is presented.

However, if the efficiency is higher than 10% in the future, it will be used for building integrated photovoltaic system (BIPV), which creates a beautiful appearance by installing it on a window or a balcony of a building It is expected to be largely written on. In the future, it is expected to serve as a diverse energy source supporting various flexible displays, military, indoor, and disposable solar cells.

In 1986, Eastman Kodak's CW Tang produced copper phthalocyanine (CuPc) and perylenetetracarboxylic acid (CuPc) in 1986. However, in the 1970s when the possibility of organic solar cells was first suggested, efficiency was too low to be practical. (perylene tetracarboxylic acid) derivatives, the interest and research on organic solar cell have been rapidly increasing and the development has been made. In 1995, Yu and Yu introduced the concept of bulk-heterojunction (BHJ). Fullerene derivatives such as PCBM, which have improved solubility, have been developed as n-type semiconductor materials. there was.

In particular, the research of organic solar cells has rapidly increased since 2000, and polymer solar cells capable of introducing photoactive by a solution process have introduced a bulk-hetero junction concept with PCBM in the early 2000s, By using P3HT as a photoactive layer, efficiency of 4 ~ 6% has been generally obtained. As a result, attempts to develop new materials and device structures by attracting attention from academia and industry have been made since 2005 It started in earnest.

In the case of polymer solar cells, improvement of efficiency is prominent due to new device configuration and process conditions change. In order to replace existing materials, donor materials with low bandgap and high charge mobility The development of new acceptor materials continues to require research and development.

Korean Registered Patent No. 1142207 (Apr. 25, 2012)

The present invention provides an organic semiconductor compound having excellent electrical properties.

The present invention also provides a method for producing the organic semiconductor compound of the present invention.

The present invention also provides an organic electronic device containing the organic semiconductor compound of the present invention.

The present invention provides an organic semiconductor compound that absorbs a wide range of energy and has excellent electrical characteristics, and more particularly, to an organic semiconductor compound including an electron-hole perylene.

The organic semiconductor compound of the present invention is represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

A is C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene;

R ₁ and R ₂ are independently a hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl groups to each other, wherein Alkyl, aralkyl is C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, Which may be further substituted with one or more substituents selected from halogen, trifluoromethyl, and silyl groups;

and n is an integer of 1 to 2000.]

The organic semiconducting compound of the present invention is an organic semiconducting compound that introduces perylene having a flat structure into an electron hole and efficiently absorbs light in the visible light region emitted from the sun through copolymerization with various electron acceptors and transmits electrons generated by the absorbed energy And the organic electronic device employing the organic semiconductor compound of the present invention exhibits high efficiency.

In addition, the organic semiconductor compound of the present invention is excellent in solubility in an organic solvent by controlling substituents of an electron acceptor that is thermally stable and copolymerized with perylene by introducing perylene, exhibits excellent electric characteristics because of high electron mobility, The organic electronic device including the organic semiconductor compound of the present invention has excellent short circuit current (Jsc) and fill factor (FF) characteristics.

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention may also include a form in which at least one heteroaryl is connected to a single bond, and a 5- to 6-membered monocyclic heteroaryl may be fused and partially saturated. Specific examples include, but are not limited to, pyrrolyl, thionyl, 2,5-dimethylpyrrolopyrrole-1,4-diyonyl, and the like.

In Formula 1 according to an embodiment of the present invention, A may be one or more selected from the following structures.

[In the above formula,

Z is S, O or Se,

R 'and R " are, independently of each other, hydrogen, a C ₁ -C ₃₀ alkyl group, a C ₆ -C ₃₀ aryl, a C ₃ -C ₃₀ heteroaryl or C ₆ -C ₃₀ aryl C ₁ -C ₃₀ alkyl,

R ₁₁ to R ₁₃ independently from each other are hydrogen, halogen, C ₁ -C ₃₀ alkyl group, C ₁ -C ₃₀ alkoxy, C ₆ -C ₃₀ aralkyl C ₁ -C ₃₀ alkyl,

The alkyl, aryl, heteroaryl and aralkyl of R 'and R "and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₄ are selected from C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alky Which may further be substituted with at least one substituent selected from the group consisting of halogen, C ₁ -C ₃₀ alkoxy, amino, hydroxyl, halogen, cyano, nitro, trifluoromethyl and silyl,

o, p and q are integers of 1 to 2.]

The formula 1 according to an embodiment of the present invention may be represented by the following formula 2 or 3, but is not limited thereto.

(2)

(3)

[In the above formula (2) or (3)

Z is S or Se;

R 'or R "is hydrogen or a C ₁ -C ₃₀ alkyl group;

R ₁₁ or R ₁₂ are independently, hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl, and each other;

The alkyl of R 'and R "and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₂ are selected from C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy , An amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;

n is an integer from 1 to 2000;

o and p are integers of 1 to 2.]

In the formulas 2 and 3 according to an embodiment of the present invention, R 'or R "is a C ₁₀ -C ₃₀ alkyl group and R ₁₁ or R ₁₂ may be, independently of each other, hydrogen, or a C ₁ -C ₃₀ alkyl group, more preferably R 'or R "is a C ₁₆ -C ₃₀ alkyl group; R ₁₁ or R ₁₂ may be hydrogen.

The formula 1 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

(In the above formula, n is 1 to 2000.)

The present invention also provides a method for preparing the organic semiconductor compound represented by Formula 1 by reacting the following Formula 11 with the following Formula 12.

(11)

[Chemical Formula 12]

P-A-P

[In the above formulas (11) and (12)

A is C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene;

R ₁ and R ₂ are independently a hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl groups to each other, wherein Alkyl, aralkyl is C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, Which may be further substituted with one or more substituents selected from halogen, trifluoromethyl, and silyl groups;

X is halogen;

, B(OR₂₁)₂, B(OH)₂ 또는 Sn(R₂₂)(R₂₃)(R₂₄)이며, R₂₁ 내지 R₂₄는 C₁-C₃₀알킬이며;P is

, B (OR ₂₁ ) ₂ , B (OH) ₂ or Sn (R ₂₂ ) (R ₂₃ ) (R ₂₄ ); R ₂₁ to R ₂₄ are C ₁ -C ₃₀ alkyl;

and n is an integer of 1 to 2000.]

The formula (11) according to an embodiment of the present invention may be prepared by reacting the compound of formula (13) with a halogen.

[Chemical Formula 13]

[In the formula (13)

R ₁ and R ₂ are independently a hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkylthio, C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl groups to each other, wherein Alkyl, aralkyl is C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, A trifluoromethyl group, and a silyl group.]

The reaction according to one embodiment of the present invention may be performed at 90 to 120 ° C for 4 to 20 hours, preferably at 100 to 120 ° C for 10 to 15 hours.

Formula 12 according to an embodiment of the present invention may be prepared by a method commonly known to those skilled in the art.

The present invention also provides an organic electronic device comprising the organic semiconductor compound of the present invention, particularly an organic thin film transistor or an organic solar cell.

More specifically, the present invention provides an organic electronic device containing the organic semiconductor compound of the present invention in a photoactive layer.

The organic electronic device of the present invention can be any conventional organic electronic device that a person skilled in the art can recognize. Generally, an organic solar cell is a metal-organic semiconductor (a photoactive layer) / metal (MSM, MIM) structure. ITO (Indium Tin Oxide), which has a high work function and is a transparent electrode, is used as an anode, and Al or Ca having a low work function is used as a cathode.

In particular, a BHJ (Bulk Hetero Junction) structure in which an organic semiconductor compound / C60 or an organic semiconductor compound / C70 composite is used as an electron donor and an electron acceptor, respectively, The organic semiconductor compound / C60 composite solution is coated on the ITO layer to a thickness of about 100 nm by spin coating, inkjet printing or the like. An Al or Ca metal is vacuum deposited thereon to be used as a cathode. If necessary, an EBL (exciton blocking layer) may be inserted between the electrode and the photoactive layer to improve the lifetime of the charge. As the EBL layer, a mixture of PEDOT (poly (3,4-ethylenedioxythiophene)) and PSS (poly (styrenesulfonate)) can be used.

In general, the diffusion distance of excitons in organic donor materials is about 10-30 nm, which is much shorter than the appropriate thickness (over 100 nm) of electron donor materials for solar absorption. This is one of the fundamental reasons for limiting the efficiency of organic solar cells. However, it is difficult to solve such a problem with the conventional bi-layer structure. In addition, since the two materials forming the BL (bi-layer) structure are organic monomolecules, it is necessary to deposit them. In the case of the polymer, it is difficult to manufacture by a simple process such as spin coating. On the other hand, since the polymer BHJ structure uses a mixture of electron donor (D) and electron acceptor (A) materials, the manufacturing process is simple and the surface area of the D / A interface is greatly increased. But the charge collection efficiency as an electrode also increases.

In this respect, the organic solar cell according to the present invention is preferably a BHJ structure, and an organic semiconductor compound according to the present invention is used as an electron-donating material and at least one selected from the following electron- .

Among the above-mentioned electron-accepting materials, it is more preferable to use a material such as PCBM or PCBCR which is designed to be easily dissolved in an organic solvent.

The organic semiconductor compound of the present invention has an electron mobility of perylene which is an aromatic ring and a heteroaromatic ring having a flat structure such as graphene, and has a very high electron mobility.

In addition, the organic semiconductor compound of the present invention exhibits a low band gap through extended pi-p stacking by copolymerization with perylene and various electron acceptors.

Further, the organic semiconductor compound of the present invention has high thermal stability and high solubility in an organic solvent.

Therefore, since the organic semiconductor compound of the present invention exhibits a low band gap by introducing perylene into the electron emitter and copolymerizing with various electron acceptors, the organic electronic device including the organic semiconductor compound can be produced by a process comprising the step of mixing the organic semiconductor compound of the present invention with the fullerene derivative It has a high efficiency with a breakthrough combination.

Further, the organic semiconductor compound of the present invention has high thermal stability and high solubility, so that the organic electronic device having the organic electronic compound has excellent electric characteristics and is very useful as a p-type material of an organic electronic device, particularly an organic solar cell or an organic thin film transistor .

 The present invention also provides a method for producing an organic semiconductor compound having high electrical properties.

FIG. 1 shows a BHJ (Bulk Hetero Junction) mode (a) and an organic solar cell structure (b) of an organic solar cell.
Fig. 2 shows the thermal stability (TGA) results of the polymers 1 and 2 prepared in Example 1. Fig.
3 is a UV spectrum of a solution state of Polymers 1 and 2 prepared in Example 1. Fig.
4 is a UV spectrum of the film state of Polymers 1 and 2 prepared in Example 1. Fig.
5 is a cyclic voltamogram (oxidation) of the polymer 1 prepared in Example 1. Fig.
6 is a cyclic voltamogram (reduction) of the polymer 1 prepared in Example 1. Fig.
7 is a transfer curve of the organic thin film transistor of the polymer 1 prepared in Example 1. FIG.
8 is a transfer curve of the organic thin film transistor of Polymer 2 prepared in Example 1. FIG.
9 is a JV characteristic curve of the organic solar cell of Polymers 1 and 2 prepared in Example 1. Fig.
10 shows the IPCE (Incident Photon to Current Efficiency) of the organic solar cells of the polymers 1 and 2 prepared in Example 1. Fig.
11 is a TEM (transmission electron microscopy) image of the organic solar cell of Polymer 1 prepared in Example 1. Fig.
12 is a TEM (transmission electron microscopy) image of an organic solar cell of Polymer 2 prepared in Example 1. Fig.
13 is a result of 2D-GIXS (Two-dimensional grazing incidence X-ray scattering) of Polymer 1 synthesized in Example 4. Fig.
14 is a schematic diagram showing values calculated according to the result of 2D-GIXS (Two-dimensional grazing incidence X-ray scattering) of Polymer 1 synthesized in Example 4. FIG.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following Preparation Examples and Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Here, unless otherwise defined in the technical terms and the scientific terms used, those having ordinary skill in the art to which the present invention belongs have the same meaning as commonly understood by those skilled in the art. Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

Perylene, bromine, thiophene-2-carbonitrile, dimethyl succinate, t-amylalcohol, potassium t- But are not limited to, potassium tert-butylate, tetrachlorocarbon (CCl ₄ ), triphenylphosphine, phthalimide 2-octyl-1-decanol, - 3-bromothiophene, copper (I) iodide, grinded potassium phosphate tribasic, dimethylaminoethanol, oxalyl chloride Lawesson's reagent, n-butyllithium 2.0M in hexane, diisopropylamine, tetrakis (triphenylphosphine) palladium, 2-isopropoxy-4,4,5,5, -tetramethyl- (2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane), toluene, anhydrous magnesium sulfate (MgSO ₄ ) Calcium carbonate (K ₂ CO ₃ ) and sodium hydroxide (NaOH) were purchased from Junsei, Aldrich, Alpha and Tixia. Silicagel was purchased from Merck and Chloroform, Hexane, Methanol and Acetone for HPLC used in the purification process of the material were purchased from JT Baker . The UV in the film state was measured by filtration using a 0.45 mm syringe filter before measurement and spin coating. PCBM ([6,6] -phenyl C71-butyric acid methyl ester) was used as an acceptor material of the solar cell element. ^{The 1} H NMR spectrum was measured with a Varian Mercury Plus 300 MHz spectrometer and the ultraviolet absorption spectrum was measured with JASCO JP / V-570. Cyclic voltammetry was measured using a CH Instruments Electrochemical Analyzer to determine the HOMO level of the material. The JV curve of the solar cell was 1 Kw Solar simulator (Newport 91192). The IPCE characteristics were measured by Solar cell response / Quantum efficiency / IPCE measurement system (PV Measurements, Inc.).

[Example 1] Preparation of Compound A

Preparation of 3,9-dibromoperylene (Compound A)

Perylene (5 g, 19.81 mmol) was added to carbon tetrachloride (200 mL) and thereto was added Br ₂ (8.81 g, 7.92 mmol) in the dark. The reaction mixture was stirred at 110 < 0 > C for 12 hours and 2 M HCl was added. Extracting the resulting product with chloroform and the organic layer was washed 10% sodium bisulfate, 2 M HCl and water, dried over MgSO _4. The solvent was removed to give a dark red crystal which was recrystallized with hot hexane to give 2.81 g (63%) of the title compound.

^{1 H NMR (300 MHz, CDCl} 3): δ 8.21 (dd, 2H), 7.83 (dd, 2H), 7.80 (dd, 2H), 7.40 ~ 7.37 (m, 4H)

¹³ C NMR (75 MHz, CDCl ₃ ):? 118.0, 121.3, 124.1, 125.9, 126.9, 127.1, 128.2, 128.9, 130.1, 135.8

_{Calcd for C 20 H 10: C} , 58.55; H, 2.42 Found: C, 58.30; H, 2.30.

[Example 2] Preparation of compound B

Preparation of 9- (Bromomethyl) nonadecane (Compound 1)

2-Octyldodecan-1-ol (10 g, 19.81 mmol) and triphenylphosphine (PPh ₃ ) (8.78 g, 19.81 mmol) were added to and dissolved in tetrahydrofuran (THF) 5.96 g, 19.81 mmol) and stirred for 3 hours. The reaction mixture is quenched through methanol, and then the solvent is removed. The yellow liquid obtained by filtering through hexane was subjected to column chromatography (EA: Hex = 1: 9) to remove remaining amount of triphenylphosphine to obtain 11 g (73%) of the title compound as a greenish liquid.

¹ H NMR (300 MHz, CDCl ₃ ):? 3.49 (d, 2H), 1.54 (m, 1H), 1.45-1.26 (m, 32H), 0.87 (t, 3H), 0.83 (t,

Preparation of 3,6-Dithien-2-yl-2,5-di (2-ocyl-1-decanyl) -pyrrolo [3,4-c] pyrrole-1,4-

2,5-dihydro-1,4-dioxo- 3,6-dithienylpyrrolo [3,4-c] -pyrrole in 250 mL round bottom flask equipped with a condenser (7.0g, 23.3 mmol) and K ₂ CO ₃ (9.0g , 69.9 mmol) were added, respectively. After 250 mL of DMF was added, the mixture was stirred at 130 DEG C for 1 hour. 9- (Bromomethyl) nonadecane (Compound 1) (25.3 g, 69.9 mmol) was added slowly and stirred at 130 ° C for 12 hours. After the reaction was completed, the organic layer was extracted with chloroform and brine, and the remaining water was removed with anhydrous magnesium sulfate. The solvent was evaporated and recrystallized from MC (methylene chloride) and methanol to obtain a purple solid 3,4-c] pyrrole-1,4-dione (Compound 2) (yield: 50%). %).

^{1 H NMR (300 MHz, CDCl} 3): δ 8.91 (d, 2H), 7.71 (d, 2H), 7.26 (t, 2H), 4.05 (d, 4H), 1.89 (s, 2H), 1.31-1.16 (m, 64H), 0.86 (m, 12H).

2 , 5-Bis (2-ocyldodecyl) 3,6-bis [5- (4,4,5,5-tetramethyl-1,3,2- Preparation of 5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (Compound B)

Diisopropylamine (700 mg, 6.94 mmol) was added to a 250 mL round flask with 15 mL of THF and slowly injected with n-butyllithium (2.55 mL, 6.38 mmol) at -78 ° C to generate LDA. After stirring for 30 minutes, 30 mL of THF was poured into a vacuum flask containing Compound 2, and the LDA and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.64 g, 8.79 mmol) was slowly added together. After stirring at 0 ° C for 2 hours, the organic layer was extracted with chloroform and brine, and the remaining water was removed with anhydrous magnesium sulfate. The solvent was evaporated and recrystallized from MC and methanol to obtain a purple solid 2,5-Bis (2-ocyldodecyl) 3,6-bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2- yl) thiophene- (Yield: 78%) of 5-dihydropyrrolo [3,4-c] pyrrole-1,4-dione (compound B).

^{1 H NMR (300 MHz, CDCl} 3): δ 8.91 (d, 2H), 7.71 (d, 2H), 4.05 (d, 4H), 1.89 (s, 2H), 1.36 (s, 24H), 1.31-1.16 (m, 64H), 0.86 (m, 12H).

¹³ C NMR (75 MHz, CDCl ₃ ): δ 162.17, 140.94, 138.08, 136.58, 136.08, 109.14, 85.01, 46.67, 38.19, 32.35, 32.31, 31.68, 30.45, 30.06, 30.02, 29.95, 29.79, 29.72, 29.35 , 29.27, 26.32, 26.30, 24.78, 22.69, 22.57, 14.12.

[Example 3] Preparation of compound C

Preparation of N- (2-octyldecyl) thiophen-3-amine (Compound 3)

3-bromothiophene (11.023 g, 67.6 mmol), 2-hexyldecan-1-amine (16.3 g, 67.6 mmol) and copper (I) iodide (1.3 g, 6.8 mmol) were added to a round flask equipped with a condenser , and grinded potassium phosphate tribasic (43.0 g, 200 mmol) were dissolved in dimethylaminoethanol (30 ml). And the mixture was stirred in an argon atmosphere at 90 DEG C for 48 hours. After the reaction was completed, the remaining solid was filtered and the filtrate was purified by column chromatography to obtain 7.7 g of N- (2-hexyldecyl) thiophen-3-amine (Compound 3) (yield: 35.5%).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.13 (dd, 1H), 6.61 (dd, 1H), 5.91 (dd, 2H), 4.05 (d, 2H), 1.89 (s, 1H), 1.31 -1.16 (m, 32H), 0.86 (m, 6H).

Preparation of 4- (2-octyldecyl) -4H-thieno [3,2-b] pyrrole-5,6-dione (Compound 4)

(2-octyldecyl) thiophen-3-amine (Compound 3) (7.7 g, 24 mmol) was added to a round-bottomed flask under a nitrogen atmosphere, followed by the addition of 20 mL of dichloromethane and 2.6 mL of oxalyl chloride 0.0 > 0 C. < / RTI > After stirring for 30 minutes, triethylamine (6 ml) was diluted in 40 ml of dichloromethane, slowly added, and stirred for 12 hours. After completion of the reaction, the liquid was purified by column chromatography to obtain 5.9 g of 4- (2-octyldecyl) -4H-thieno [3,2-b] pyrrole-5,6-dione (Compound 4) %).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 8.00 (d, 1H), 6.76 (d, 1H), 4.15 (d, 2H), 1.92 (s, 1H), 1.33-1.12 (m, 32H) , 0.91 (t, 3H), 0.86 (t, 3H).

(5) (4H, 4 ' H) -dione (Compound 5) Manufacturing

(2-octyldecyl) -4H-thieno [3,2-b] pyrrole-5,6-dione (Compound 4) was added to a round- And 20 mL of toluene were added slowly. After stirring at 65 ° C for 3 hours, the organic layer was extracted with chloroform and brine, and the remaining water was removed with anhydrous magnesium sulfate. The solvent was evaporated and recrystallized from MC and methanol to obtain (E) -4,4'- 1.238 g (yield: 36.3%) of bis (2-octyldecyl) - [6,6'-bithieno [3,2-b] pyrrolylidene] ).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.52 (d, J = 5.1 Hz, 2H), 6.78 (d, J = 5.1 Hz, 2H), 4.05 (d, 4H), 1.89 (s, 2H ), 1.31-1.16 (m, 64H), 0.91 (t, 6H), 0.86 (t, 6H).

(E) -2,2'-bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) -4,4'-bis (2-octyldecyl) - [ Preparation of 6,6'-bithieno [3,2-b] pyrrolylidene] -5,5 '(4H, 4'H) -dione (Compound C)

Diisopropylamine (700 mg, 6.94 mmol) was added along with 15 mL of THF to a 250 mL round flask, and n-butyllithium (2.55 mL, 6.38 mmol) was added slowly at -78 ° C to stir the mixture for 30 minutes to produce LDA. In a vacuum round flask containing Compound C, 30 mL of THF was injected and dissolved. The LDA thus prepared and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.64 g, 8.79 mmol) were slowly added together. After stirring at 0 ° C for 2 hours, the organic layer was extracted with chloroform and brine, and the remaining water was removed with anhydrous magnesium sulfate. The solvent was evaporated and recrystallized from MC and methanol to obtain (E) -2,2'- bis [5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) -4,4'-bis (2-octyldecyl) - [6,6'-bithieno [ 2-b] pyrrolylidene] -5,5 '(4H, 4'H) -dione (Compound C) (yield: 78%).

¹ H NMR (300 MHz, CDCl ₃ ):? 6.81 (s, 2H), 4.05 (d, 4H), 1.89 (s, 2H), 1.36 (t, 6H), 0.86 (t, 6H).

[Example 4] Production of organic semiconductor compound (polymer 1)

(300 mg) prepared in Example 1 and the compound B (300 mg) prepared in Examples 2 and 3 were added to a round-bottomed flask equipped with a condenser to remove moisture and oxygen. Then, toluene anhydride (10 mL). Pd ₂ (dba) ₃ and P (o-tolyl) ₃ catalyst (10 mg, 0.03 eq) were dissolved in 1 mL each of anhydrous toluene. An aqueous solution (1 mL) in which K ₂ CO ₃ was dissolved at a concentration of 2 M was added and 2 drops of aliquit 336 were injected. After completion of the reaction, the resulting solid was dissolved in chloroform, and the solid was collected by filtration to remove the catalyst. The precipitate was recrystallized in methanol to obtain a purple solid. The resulting solid was dissolved in methanol and acetone And purified by an extractor (Soxhlet) to obtain Polymer Compound 1.

Mw: 19,000 Mn: 22,000 PDI = 2.2 T d (o C) = 395

The prepared polymer was well dissolved in chloroform, THF and toluene, which are common organic solvents at room temperature.

[Example 5] Production of organic semiconductor compound (polymer 2)

Polymer 2 was obtained in the same manner as in Example 4, except that C was used in place of the compound B in Example 4. The prepared polymer 2 was also dissolved well in chloroform, THF and toluene, which are general organic solvents, at room temperature.

Mw: 12,000 Mn: 28,000 PDI = 2.3 T d (o C) = 435

The thermogravimetric analysis (TGA) curves of the polymers 1 and 2 prepared in Examples 4 and 5 are shown in FIG. 2. As shown in FIG. 2, the polymers 1 and 2, which are the organic semiconductor compounds of the present invention, Able to know.

In addition, the polymers 1 and 2 prepared in Examples 4 and 5 were dissolved in an organic solvent such as chloroform or chlorobenzene, and UV absorption spectra in a solution state and a solid film state were measured and shown in FIG. 4 and FIG.

As shown in FIG. 4, in the UV absorption spectra of the polymers 1 and 2 prepared in Examples 4 and 5 in a solution state, the polymer 1 was found to be 462, 616; Polymer 2 exhibited two large absorption spectra of 386 and 598 nm. The first absorption spectrum is the absorption spectrum of the π-π transition and the second absorption spectrum is the internal molecule charge transfer (ICT) between the electron- Spectrum.

5, in the UV absorption spectra of the films of the polymers prepared in Examples 4 and 5, Polymer 1 was observed at 403, 614; Polymer 2 showed maximum absorption at 462 and 639 nm. This spectral result showed a red-shift of about 30 nm. It is presumed that the molecules are distributed over a wide range in the solution state and move comparatively freely, but in the case of the solid film state, the aggregation tendency phenomenon of the respective groups. The band gaps were calculated using the absorption spectrum in the film state (bandgap = 1240 / λ _edge ) and the polymer 1 and 2 showed band gaps of 1.4 and 1.55 eV, respectively.

5 and 6, the HOMO level of the substance was measured by cyclic voltammetry. Ferrocene / Ferrocenium redox system (-4.8V) was measured in the solid film state as a reference. The HOMO levels of the polymers 1 and 2 were calculated to be -5.23 and -5.26 eV, respectively, and the bandgap calculated from the UV absorption spectrum The LUMO energy level of each polymer was calculated to be -3.83 and -3.71 eV, respectively.

[Example 6] Fabrication of organic solar cell device

(ITO / PEDOT: PSS / organic semiconductor compound (polymer 1, 2) + (organic compound)), which was prepared by using the polymers 1 and 2 prepared in Examples 4 and 5 as a new electron donor material, PCBM (C ₇₀ ) / Ca / Al] structure was fabricated. First, the cleaned ITO (Indium Tin Oxide) glass was treated with UV-O ₃ , and then the PEDOT: PSS layer was spin-coated to a thickness of 47 nm. Each polymer 1, 2 and PCBM (C70) were added to dichlorobenzene (3 Vol% diiodooctane with respect to dichlorobenzene) at a ratio of 1: 1 (weight ratio), followed by heating at 50 ° C for 24 hours Followed by stirring to prepare an organic semiconductor compound mixture. A glass substrate coated with PEDOT: PSS in a glove box (Ar gas) was baked at 140 ° C for 10 minutes to form a 100 nm EBL layer. The organic semiconductor compound mixture solution was spin-coated on the EBL layer, and further heat-treated at 120 ° C for 10 minutes to form a photoactive layer having a thickness of 100 nm, followed by high-temperature deposition with Ca (2.0 nm) / Al (104 nm). In order to investigate the photovoltaic characteristics of the fabricated organic solar cell device, a solar simulator and a radiant power meter were used to generate 100 mW photovoltaic cells under AM 1.5 conditions, and a 1 kW solar simulator (Newport 91192) The current density-voltage characteristics of the organic solar cell were measured using the photolithography method and the results are shown in FIG.

As shown in FIG. 9, all of the devices showed a higher open-circuit voltage value than the short-circuit current value, which can be predicted as a result of the characteristics of the polymer 1 and the polymer 2 exhibiting a low HOMO energy level.

Also, as shown in Figure 9, Polymers 1 and 2 exhibited very good short-circuit currents exceeding 13 mA / cm ² , a result of pi-pile stacking with perylene units having a flat structure. High electron and hole mobility can be said to be factors representing the short circuit current value.

Table 1 shows the electrical characteristics of the organic solar cell device prepared in Example 6, which contains the polymer 1 and the polymer 2, which are the organic semiconductor compounds prepared in Examples 4 and 5, as the photoactive layer. That is, the photovoltaic parameters of V _oc (open circuit voltage), short-circuit current density (J _SC ), fill factor (FF), and overall conversion efficiency (η) Respectively.

Organic semiconductor compound V _oc (V) J _sc (mA / cm ² ) FF PCE (%) Polymer 1 0.78 13.31 0.64 6.68 Polymer 2 0.77 13.15 0.61 6.23

As shown in Table 1, polymers 1 and 2 exhibit a fill factor close to 70%, which is also an effect of perylene. In general, P3HT, which is widely used in organic solar cells, It shows excellent fill factor value, which can be explained as a phenomenon that occurs in polymers showing crystallinity rather than amorphous polymers. When the polymers 1 and 2, which are the organic semiconductor compounds of the present invention, are used as electron spots of the photoactive layer, excellent organic solar cells having high efficiency can be obtained.

[Example 7] Fabrication of organic thin film transistor (OTFT) device

m, width W = 120

m )을 이용하여 질소하에서 제작하였다. 300 nm의 n-도핑된 실리콘 웨이퍼를 기판/게이트 전극으로, 열적으로 성장된 SiO₂ 유전체 막(200 nm)과 함께 사용하였다. 반도체 활성층을 0.5 wt % 클로로벤젠 용액으로 스핀코팅하였다. 다음, 금 소스/드레인 전극 쌍을 쉐도우 마스크를 통해 진공 증발((at ~10^-7 torr)에 의해 두께 50 nm로 열적으로 증착하였다. 채널의 길이는 12 μm 이며 폭은 120 μm이다. 고분자의 TFT 소자들은 전형적인 p-채널 트랜지스터 특징을 보였다. The devices 1 and 2 synthesized in Examples 4 and 5 were used as a p-type active layer polymer. In order to measure the electric field mobility of the charge transporting body, an organic thin film transistor (OTFT) was fabricated by bottom electrode geometry (channel length L = 12

m, width W = 120

m) under nitrogen. A 300 nm n-doped silicon wafer was used as a substrate / gate electrode with a thermally grown SiO ₂ dielectric film (200 nm). The semiconductor active layer was spin-coated with 0.5 wt% chlorobenzene solution. Next, a pair of gold source / drain electrodes was thermally deposited to a thickness of 50 nm by vacuum evaporation (at ~ 10 ^-7 torr) through a shadow mask. The channel length was 12 μm and the width was 120 μm. TFT devices showed typical p -channel transistor characteristics.

Table 2 below summarizes the TFT characteristics (output curves in ESI †).

The electric field mobility was calculated from the saturation regime using the following equation. That is, a graph was obtained from the saturation region current equation (I _ds ) ^1/2 and V _gs as variables and the slope was obtained.

C_i (V_gs - V_th)² I _ds = (W / 2L)

C _i (V _gs - V _th ) ²

In this formula,

I _ds is the drain-source current in the saturation region;

W and L are the channel width and length, respectively;

는 전계이동도;

The electric field mobility;

C _i is the capacitance per unit area of the insulating layer;

V _gs and V _th represent gate and bottom voltages, respectively.

6 and 7 show transfer curves of the polymers 1 and 2 of the present invention.

6 and 7 and the polymer 1 shown in Table 2 exhibited mobility of 10 ^-2 cm ² / Vs, which is a decisive factor for the high short-circuit current in organic solar cells. The results of this high hole mobility show that electrons and holes move smoothly due to the π-π stacking between molecules and molecules through the introduction of perylene units of flat structure.

13 is a result of 2D-GIXS (Two-dimensional grazing incidence X-ray scattering) of Polymer 1 synthesized in Example 4. Fig. The films were subjected to heat treatment at room temperature, 100 ° C, and 150 ° C for 1 hour, respectively, and then the images as shown in FIG. 13 (a) were obtained. At room temperature, (100) reflection of qz = 0.28 A ^-1 was observed, and the corresponding interlayer domain spacing (d1) was 2.24 nm.

Especially, at 100 ℃, (100) reflection intensity was increased and (200) reflection was observed. At 150 ℃, the reflection intensity of (100) It can be seen that the crystallinity of the polymer 1 is improved by the heat treatment. Therefore, the organic electronic device containing the organic semiconductor compound according to the present invention can have a very high efficiency.

There could also be observed _{(010) (d 010 = 0.46nm} ) reflection in qxy = 1.37 A ^-1, and this result is to form a high molecular lamella crystal structure 1 extremely excellent as shown in Fig. 14, domain and domain (010) reflections were observed due to the excellent pi-pi interaction between them. Also, in the case of the edge-on state polymer as shown in FIG. 14, it is arranged in the direction perpendicular to the substrate, and it can exhibit excellent mobility even in the OTFT.

Claims (9)

delete delete An organic semiconductor compound represented by the following general formula (2) or (3)
(2)

(3)

[In the above formula (2) or (3)
Z is S, O or Se;
R 'or R "is hydrogen or a C ₁ -C ₃₀ alkyl group;
R ₁₁ or R ₁₂ are independently, hydrogen, halogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy or C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl, and each other;
The alkyl of R 'and R "and the alkyl, alkoxy and aralkyl of R ₁₁ to R ₁₂ are selected from C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy , An amino group, a hydroxyl group, a halogen group, a cyano group, a nitro group, a trifluoromethyl group and a silyl group;
n is an integer from 1 to 2000;
o and p are integers of 1 to 2.] The method of claim 3,
R 'or R "is C ₁₀ -C ₃₀ alkyl group;
R ₁₁ or R ₁₂ are independently of each other hydrogen, or a C ₁ -C ₃₀ alkyl group. The method of claim 3,
(1) is selected from the following structural formulas.

A process for preparing an organic semiconductor compound represented by the following formula (1):
[Chemical Formula 1]

(11)

[Chemical Formula 12]
PAP
[In the formulas (1), (11) and (12)
A is C ₆ -C ₃₀ arylene or C ₃ -C ₃₀ heteroarylene;
R ₁ and R ₂ are independently a hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkylthio import or C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl groups to each other, wherein Alkyl, aralkyl is C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, Which may be further substituted with one or more substituents selected from halogen, trifluoromethyl, and silyl groups;
X is halogen;
P is

, B (OR ₂₁ ) ₂ , B (OH) ₂ or Sn (R ₂₂ ) (R ₂₃ ) (R ₂₄ ); R ₂₁ to R ₂₄ are C ₁ -C ₃₀ alkyl;
and n is an integer of 1 to 2000.] The method according to claim 6,
Wherein the formula (11) is prepared by reacting a halogen represented by the following formula (13).
[Chemical Formula 13]

[In the formula (13)
R ₁ and R ₂ are independently a hydrogen, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy group, C ₁ -C ₃₀ alkylthio import or C ₆ -C ₃₀ ahreu C ₁ -C ₃₀ alkyl groups to each other, wherein Alkyl, aralkyl is C ₁ -C ₃₀ alkyl, C ₂ -C ₃₀ alkenyl, C ₂ -C ₃₀ alkynyl, C ₁ -C ₃₀ alkoxy, an amino group, a hydroxyl group, a halogen group, a cyano group, A trifluoromethyl group, and a silyl group.] 8. The method of claim 7,
And the reaction is carried out at 90 to 120 DEG C for 4 to 20 hours. An organic electronic device comprising an organic semiconductor compound according to any one of claims 3 to 5.

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