KR101707028B1 - Novel organic semiconductor compounds containing benzothiadiazole group, its manufacturing method and organic semiconductor device using the same - Google Patents

Abstract

The present invention provides an organic semiconductor compound containing a novel benzothiadiazole group having high charge mobility and solubility and a process for producing the same.
The present invention also provides an organic semiconductor device containing an organic semiconductor compound containing a novel benzothiadiazole group.

Description

TECHNICAL FIELD The present invention relates to a novel benzothiadiazole group-containing organic semiconductor compound, a method for producing the same, and an organic semiconductor device using the same.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic semiconductor compound, a method for producing the organic semiconductor compound, and an organic semiconductor device employing the same. More particularly, the present invention relates to an organic semiconductor compound including a benzothiadiazole group.

The device using organic semiconductors can be formed at a room temperature by forming a semiconductor thin film on various substrates because the deposition conditions are not so complicated as compared with the conventional inorganic semiconductor devices and it is possible to realize a low cost, So that flexibility can be achieved.

Organic semiconductor materials have been applied to a wide range of devices or devices including, for example, organic solar cells (OPV), organic field effect transistors (OFET), organic light emitting diodes (OLEDs), photodetectors, sensors, memory devices and logic circuits .

At present, polyacene compounds such as anthracene, tetracene and pentacene are widely studied as an organic semiconductor material together with polyphenylene vinylene, polypyrrole, polythiophene and oligothiophene. It is expected that these polyacene compounds will have a wider π system as the length of the ring is extended, and a larger orbital overlap between adjacent molecules will be formed to improve charge mobility.

Most polyacene compounds require a high crystallinity structure to provide molecular orientation that leads to good charge mobility and have been vapor-deposited with features that are somewhat insoluble in conventional solvents.

However, such vapor deposition requires a costly and complicated apparatus, which causes a large amount of material and energy to be consumed in production.

Therefore, it is required to develop an organic semiconductor material suitable for a solution process base which can reduce this. In particular, there is a continuing demand for the development of an organic semiconductor compound having high absorption efficiency of sunlight and high mobility of electrons and hole carriers so as to compensate for disadvantages of organic semiconductor compounds.

Korean Laid-open Patent Publication No. 2014-0025266 (Publication date 2014.03.04)

The present invention provides an organic semiconductor compound containing a novel benzothiadiazole group having high charge mobility and solubility and a process for producing the same.

The present invention also provides an organic semiconductor device containing an organic semiconductor compound containing a novel benzothiadiazole group.

The present invention provides a novel organic semiconductor compound which is high in charge mobility and high in solubility to be more easily applicable to a solution process. The organic semiconductor compound of the present invention is represented by the following general formula (1).

[Chemical Formula 1]

[In the above formula (1)

Ar ₁ and Ar ₂ are, independently of one another, (C6-C20) arylene or (C3-C20) heteroarylene;

L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;

R ₁ and R ₂ are independently of each other hydrogen or halogen;

R ₃ and R ₄ are independently (C1-C20) _{alkyl, -O (R 11), -S} (R 12), -Se (R 13) or _{-Si (R 14) (R 15} ) (R 16 each ), R ₁₁ to R ₁₃ are independently of each other (C 1 -C 20) alkyl, and R ₁₄ to R ₁₆ are independently of each other hydrogen or (C 1 -C 20) alkyl;

a and b are each independently an integer of 1 to 4;

n is an integer from 1 to 500;

Arylene and heteroarylene of Ar ₁ , Ar ₂ , L ₁ and L ₂ are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and C1-C20) alkyl; < / RTI >

Said heteroarylene comprises at least one heteroatom selected from N, O, S, Se and Si.

The organic semiconductor compound of the present invention can be prepared by reacting a benzothiadiazole group having a substituent of hydrogen or a halogen which acts as an electron donor compound with an alkyl, alkoxy, alkylthio, alkylseleno, silyl, monoalkylsilyl, dialkyl A benzothiadiazole group having a substituent of a silyl or trialkylsilyl group is alternately linked and polymerized to have high charge mobility and solubility.

That is, the organic semiconductor compound of the present invention is a polymer in which a benzothiadiazole group serving as an electron donor and a benzothiadiazole group acting as an electron acceptor are connected to arylene or heteroarylene and alternately polymerized, and an extended conjugated structure The band gap energy is low and the charge mobility is high and the solubility of the benzothiadiazole group acting on the electron accepting compound is controlled by adjusting the length of the substituent,

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. &Quot; Heteroaryl " in the present invention means an aryl group having 1 to 4 hetero atoms selected from N, O, S, Se and Si as an aromatic ring skeletal atom and the remaining aromatic skeletal atom carbon, 5- to 6-membered monocyclic heteroaryl, polycyclic heteroaryl in which at least one monocyclic heteroaryl is condensed, and polycyclic heteroaryl condensed with at least one benzene ring. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

Preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 2 below.

(2)

[In the formula (2)

Ar ₁ and Ar ₂ are, independently of one another, (C6-C20) arylene or (C3-C20) heteroarylene;

L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;

R ₁ and R ₂ are independently of each other hydrogen or halogen;

D ₁ and D ₂ are independently of each other O, S or Se;

R ₁₇ and R ₁₈ are, independently of each other, (C 1 -C 20) alkyl;

n is an integer from 1 to 500;

Arylene and heteroarylene of Ar ₁ , Ar ₂ , L ₁ and L ₂ are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and C1-C20) alkyl. ≪ / RTI >

Charge mobility benzo thiadiazol asleep combination Ar ₁ and Ar in the above formula (2) according to the _second aspect of the present invention are independently (C3-C20) may renil heteroaryl each other, and preferably can heteroaryl renil selected from the following structures: However, there is no limitation.

[In the above formula,

Z ₁ to Z ₈ independently of one another are O, S or Se

R ₂₁ to R ₂₇ are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl;

q is independently an integer of 1 to 2, and when q is 2, R ₂₁ , R ₂₆ and R ₂₇ may be the same or different from each other.

In Formula 2, L ₁ and L ₂ may independently be a single bond or a (C3-C20) heteroarylene, and the heteroarylene may be selected from the following structures.

[In the above formula,

Z ₁ to Z ₈ independently of one another are O, S or Se

R ₂₁ to R ₂₇ are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl;

q is independently an integer of 1 to 2, and when q is 2, R ₂₁ , R ₂₆ and R ₂₇ may be the same or different from each other.

More preferably, Formula 1 according to an embodiment of the present invention may be represented by Formula 3 below.

(3)

[Formula 3]

이며;L ₁ and L ₂ are, independently of each other, a single bond or

;

Z ₁ , Z ₁₁ and Z ₁₂ are independently of each other S or Se;

R ₁ and R ₂ are independently of each other hydrogen or fluorine;

D ₁ and D ₂ are independently of each other O, S or Se;

R ₁₇ and R ₁₈ are, independently of each other, (C 1 -C 20) alkyl;

and n is an integer of 1 to 500.]

Preferably, D ₁ and D ₂ in Formula 3 according to an embodiment of the present invention may be O, S, or Se.

Preferably, D ₁ and D ₂ in Formula 3 according to an embodiment of the present invention are O, S, or Se, and R ₁₇ and R ₁₈ may be (C 1 -C 20) alkyl, , More preferably D ₁ and D ₂ are the same as each other, O or S, and R ₁₇ and R ₁₈ may be the same or different (C 1 -C 20) alkyl.

Preferably, n in the general formulas (1) to (3) according to an embodiment of the present invention may be 5 to 500.

The present invention also provides a process for preparing an organic semiconductor compound represented by Chemical Formula 1, and more particularly, to a process for preparing an organic semiconductor compound represented by Chemical Formula 1, wherein a benzothiadiazole tin derivative represented by Chemical Formula 11 is reacted with a benzothiadiazole halide derivative represented by Chemical Formula 12, 1 < / RTI >

[Chemical Formula 1]

(11)

[Chemical Formula 12]

[In the formulas (1), (11) and (12)

Ar ₁ and Ar ₂ are, independently of one another, (C6-C20) arylene or (C3-C20) heteroarylene;

L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;

R ₁ and R ₂ are independently of each other hydrogen or halogen;

R ₃ and R ₄ are independently (C1-C20) _{alkyl, -O (R 11), -S} (R 12), -Se (R 13) or _{-Si (R 14) (R 15} ) (R 16 each ), R ₁₁ to R ₁₃ are independently of each other (C 1 -C 20) alkyl, and R ₁₄ to R ₁₆ are independently of each other hydrogen or (C 1 -C 20) alkyl;

a and b are each independently an integer of 1 to 4;

n is an integer from 1 to 500;

R ₄₁ to R ₄₃ are independently of each other (C 1 -C 10) alkyl;

X is independently of each other halogen;

Arylene and heteroarylene of Ar ₁ , Ar ₂ , L ₁ and L ₂ are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and C1-C20) alkyl. ≪ / RTI >

The benzothiadiazole tin derivative of Formula 11 may be prepared by reacting a halide derivative of Formula 13 with a tin derivative of Formula 14 or Formula 15 to prepare a benzothiadiazole derivative of Formula 16, step; And

Reacting a benzothiadiazole derivative of the following formula (16) with a tin halide derivative of the following formula (17) to prepare a benzothiadiazole tin derivative of the formula (11).

(11)

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[In the above formulas 13 to 17,

Ar ₁ and Ar ₂ are, independently of one another, (C6-C20) arylene or (C3-C20) heteroarylene;

L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;

R ₁ and R ₂ are independently of each other hydrogen or halogen;

a and b are each independently an integer of 1 to 4;

R ₅₁ to R ₅₆ are independently of each other (C 1 -C 10) alkyl;

X ₁ is independently of each other halogen;

R ₄₁ to R ₄₃ are independently of each other (C 1 -C 10) alkyl;

X < ₁₁ > independently from each other are halogen;

Arylene and heteroarylene of Ar ₁ , Ar ₂ , L ₁ and L ₂ are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and C1-C20) alkyl. ≪ / RTI >

It is needless to say that the benzothiadiazole halide derivative of Formula 12 according to an embodiment of the present invention may be prepared by a known organic synthesis method.

(DCM), toluene (Toluene), acetonitrile (MeCN), nitromethane (Nitromethan), N, N-dimethylacetamide, and the like. It is preferable to use at least one selected from the group consisting of tetrahydrofuran (THF), N, N -dimethylformamide (DMF) and N, N -dimethylacetamide (DMA).

The reaction temperature can be used at the temperature used in conventional organic synthesis, but it can be varied depending on the amount of the reaction material and the starting material, and the reaction is completed after confirming that the starting material is completely consumed through TLC or the like. When the reaction is completed, the solvent may be distilled off under reduced pressure after the extraction process, and then the target product may be separated and purified through a conventional method such as column chromatography.

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

The organic semiconductor compound according to the present invention has high charge mobility and high solubility, and the organic semiconductor device containing the organic semiconductor compound has high efficiency.

The organic semiconductor compound according to the present invention repeatedly contains a benzothiadiazole group having different substituents, thereby improving the pi-pi stacking on the solid phase, minimizing the phase transition, and having a very high charge mobility, By introducing a long substituent at the diazo group, solubility is increased and it is very easy to apply in a solution process.

Further, the process for producing an organic semiconductor compound according to the present invention can produce a novel organic semiconductor compound by a simple process, and an organic semiconductor device containing the organic semiconductor compound produced according to the present invention has high efficiency and high solubility It is economical because it can be manufactured by a solution process, and its life stability is excellent due to high optical stability.

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

[Example 1] Production of polymer P1

Step 1. Preparation of compound 1

2-Octyldecanol (4.3 g, 14.5 mmol) was dissolved in anhydrous DMF and NaH (60% dispersion in paraffin) (0.58 g, 14.5 mmol) was added at 0 ° C. The reaction solution was stirred at 0 ° C for 1 hour, and then 5,6-difluorobenzo [c] [1,2,5] -thiadiazole (1 g, 5.8 mmol) was added. Then, after stirring at room temperature for 12 hours, 100 mL of a saturated NH ₄ Cl solution was added to terminate the reaction and extracted with diethyl ether. The extracted solution was concentrated by vacuum distillation, and Compound 1 was obtained (4.0 g, 95% yield) through silica gel column chromatography (DCM: Hexanes (1: 3)).

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 7.10 (2H, s); 3.96 (4H, d, J = 5.5 Hz); 1.89 (2 H, m); 1.26 (64H, m); 0.87 (12H, m).

Step 2. Preparation of compound 2

Br ₂ (0.4 mL, 7.44 mmol) was slowly added dropwise to a solution of Compound 1 (1.81 g, 2.48 mmol) prepared in Step 1 in CH ₂ Cl ₂ (100 mL) and glacial acetic acid (50 mL). The reaction solution was stirred at room temperature for 48 hours, and then 1M aqueous NaHSO ₃ solution (100 mL) was added to terminate the reaction. The reaction mixture was extracted with CH ₂ Cl ₂ (2 × 50 mL). The extracted solution was concentrated by vacuum distillation and then Compound 2 was obtained through silica gel column chromatography (DCM: Hexanes (1: 3)) (1.9 g, 89% yield).

¹ H NMR (300 MHz, CDCl ₃ ):? (Ppm) 4.03 (4H, d, J = 6.2 Hz); 1.92 (2 H, m); 1.56 (4 H, m); 1.26 (60H, m); 0.88 (12H, m).

Step 3. Preparation of compound 3

A mixture of 5,6-difluoro-4,7-diiodobenzo [c] [1,2,5] thiadiazole (4 g, 9.4 mmol) and tributyl (thiophen- a tributyl (thiophen-2-yl) stannane) (9.9 g, 26.4 mmol) in toluene _{(200 mL) Pd (PPh 3} ) dissolved in a solution of the ₄ (500 mg, 0.43 mmol) was added. The reaction solution was stirred at 110 ° C for 20 hours, cooled to room temperature, poured into 500 mL of ethanol to give an orange solid, and recrystallized using a mixed solvent of ethanol and MC (4: 1) to obtain Compound 3 (2.4 g, 76% yield).

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 8.30 (2H, d, J = 3.8); 7.62 (2H, doublet of J1 = 5.2 Hz, J2 = 1 Hz); 7.27 (2 H, m).

Step 4. Preparation of compound 4

A solution of the compound 3 (2.4 g, 7.13 mmol) prepared in Step 3 in THF (500 mL) was lowered to 78 ° C, and lithium diisopropylamide solution 2M in THF (9.3 mL, 18.6 mmol) Respectively. After the reaction solution was stirred for 2 hours, the reaction solution was stirred at room temperature for 48 hours, and chloro-trimethylstannane (1.0 M solution of chlorotrimethylstannane in THF) (18.6 mL, 18.6 mmol) was slowly added dropwise. The temperature of the reaction solution was raised to room temperature, stirred for 12 hours, and then extracted with diethyl ether (50 mL × 3) and water (50 mL). The extracted solution was concentrated by vacuum distillation, and the obtained solid was recrystallized from a mixed solvent of ethanol: MC (5: 1) to obtain Compound 4 (3.1 g, 66% yield).

¹ H NMR (300 MHz, CDCl ₃ ):? (Ppm) 8.35 (2H, d, J = 3.8 Hz); 7.35 (2H, d, J = 3.8 Hz); 0.45 (18H, s).

Step 5. Polymer P1 Manufacturing

Pd ₂ (dba) ₃ (5.1 mg, 5.6 μmol) and tri (o) were added to a solution of compound 2 (248 mg, 0.28 mmol) and compound 4 (185 mg, 0.28 mmol) prepared in Step 2 in chlorobenzene -Tolyl) phosphine (3.4 mg, 11.2 μmol) was treated with microwave reactor at 100 ° C for 5 minutes, 120 ° C for 5 minutes, and 140 ° C for 90 minutes. The reaction solution was cooled to room temperature and mixed with methanol to form a precipitate. The resulting precipitate was filtered and extracted with acetone (12h), hexane (12h) and chloroform (6h) sequentially using a Soxhlet apparatus. The solution extracted with chloroform was added dropwise to methanol to obtain a solid polymer P1 (199 mg, 67.0% yield).

Mn = 87,500, PDI = 2.35.

[Example 2] Production of polymer P2

Step 1 . Preparation of Compound 5

Compound 5 was prepared in the same manner as in Step 1 and Step 2 of Example 1 using 2-hexyldecanol instead of 2-octyldecanol.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 4.02 (4H, d, J = 6.2Hz); 1.92 (2 H, m); 1.58 (4 H, m); 1.33 (36H, m); 0.89 (12H, m).

MS (EI): Calcd m / z 774.82; found M ⁺ 774.

Step 2 . Polymer P2 Manufacturing

Polymer P2 was prepared in the same manner as in Step 5 of Example 1 using compound 5.

Mn = 74,500, Mw = 223,300, PDI = 2.98.

[Example 3] Production of polymer P3

Step 1. Preparation of compound 6

Compound 6 was prepared in the same manner as in Step 1 and Step 2 of Example 1 using 2-pentynonan-1-ol instead of 2-octyldecanol.

^{1 H NMR (300 MHz, CDCl} 3): δ (ppm) 4.02 (4H, d, J = 6.2Hz); 1.91 (2 H, m); 1.58 (4 H, m); 1.33 (36H, m); 0.89 (12H, m).

MS (EI): Calcd m / z 718.72; found M ⁺ 718.

Step 2. Polymer P3 Manufacturing

Polymer P3 was prepared in the same manner as in Step 5 of Example 1 using Compound 6.

Mn = 23,868, Mw = 54,852, PDI = 2.2.

[Example 4] Production of polymer P4

Step 1. Preparation of compound 7

Compound 7 was prepared in the same manner as in Step 1 and Step 2 of Example 1 using 2-decyltetradecan-1-ol instead of 2-octyldecanol.

¹ H NMR (400 MHz, CDCl ₃ ):? (Ppm) 4.01 (4H, t, J = 6.09 Hz); 1.91-1.89 (2H, m); 1.31-1.22 (2 H, m); 1.47-1.24 (78 H, m); 0.88 (12H, m).

MS (EI): Calculated m / z 999.26; found M ⁺ 999.

Step 2. Preparation of compound 8

Compound 7 (1.5 g, 1.5 mmol) and tributyl (thiophen-2-yl) Stan I (1.28 g, 3.45mmol) and dry toluene (100ml), Pd (PPh ₃₎ dissolved in a solution of the ₄ (100 mg, 5 mole%) was added and refluxed for 48 hours. The reaction solution was cooled to room temperature, concentrated and then subjected to column chromatography under a 15% MC / hexane solvent to obtain Compound 8 as an orange liquid (1.1 g, 73% yield).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 8.14 (2H, d, J = 3.73Hz); 7.50 (2H, doublet, J = 5.26 Hz); 7.21 (2 H, m); 3.91 (4H, t, J = 6.56 Hz); 1.91-1.89 (2H, m); 1.31-1.22 (2 H, m); 1.47-1.24 (78 H, m); 0.88 (12H, m).

Step 3. Compound Production of 9

NBS (N-bromosuccinimide) (0.5 g, 2.84 mmol) was added portionwise to a solution of Compound 8 (1.1 g, 1.09 mmol) in THF solvent. The reaction solution was stirred at room temperature for 8 hours, concentrated, and then separated by column chromatography with 15% MC / hexane solvent to give compound 9 as an orange liquid (0.9 g, 71% yield).

^{1 H NMR (400 MHz, CDCl} 3): δ (ppm) 8.06 (2H, d, J = 4.04Hz); 7.14 (2H, doublet, J = 4.04 Hz); 3.91 (4H, t, J = 6.68 Hz); 1.95-1.91 (2 H, m); 1.44-1.41 (2H, m); 1.47-1.24 (78 H, m); 0.88 (12H, m).

Step 4. Polymer P4 Manufacturing

Polymer P4 was prepared in the same manner as in Step 5 of Example 1 using Compound 9 and Compound 4.

Mn = 24,500, Mw = 58,555, PDI = 2.39.

[Example 5-8] Organic solar cell element fabrication

Each of the polymers P1, P2, P3 and P4 prepared in Examples 1 to 4 was used as an electron donor, C71-PCBM was used as an electron acceptor, and the mixture was mixed at a weight ratio of 1: 0.8, The material was added to chloroform (FB) solvent containing 3% by volume of diphenyl ether (DPE) in 3% by volume of chlorobenzene (CB) solvent or diphenyl ether (DPE) was dissolved, under an argon atmosphere, PEDOT (poly (3,4-ethylenedioxythiophene) by the spin coat layer is introduced on the ITO glass substrate was introduced into the photoactive layer of a thickness of 70~120nm. then a degree of vacuum of 10 ^-6 torr or less The organic solar cell was fabricated by sequentially depositing 2 nm of calcium and 100 nm of aluminum in a vacuum chamber having a thickness of 100 nm.

The current density-voltage (JV) of the organic solar cell was measured using an artificial light simulator under the condition of 100 mA / cm ² (AM 1.5G) to investigate the photovoltaic characteristics of the fabricated organic solar cell device. The open circuit voltage (V _oc ), the short-circuit current density (J _sc ), the fill factor ; FF) and energy conversion efficiency (PCE) are shown in Table 1 below.

Organic sun
Battery element compound menstruum V _oc
[V] J _sc
[mA / cm ² ] FF
[%] PCE
[%] Example 5 Polymer P1 (Example 1) CB + DPE ^* 0.90 12.74 66 7.63 Example 6 Polymer P2 (Example 2) CB + DPE ^* 0.89 12.09 68 7.31 Example 7 Polymer P3 (Example 3) CF + DPE ^** 0.91 13.04 69 8.18 Example 8 Polymer P4 (Example 4) CF + DPE ^** 0.88 11.50 66 6.67 ^* CB + DPE: Chlorobenzene (CB) solvent containing 3 vol% of diphenyl ether (DPE)
^** CF + DPE: chloroform (FB) solvent containing 3% by volume of diphenyl ether (DPE)

As shown in Table 1, all of the polymers prepared in Examples 1 to 4 repeatedly contain benzothiadiazole groups having different substituents, thereby improving the pi-pi stacking in the solid phase, And has a high V _oc value of more than 0.88 V, so that it can be used as a photoactive layer in an organic solar cell and has a high solubility of each polymer, which makes it easy to apply a solution process .

Claims (8)

delete An organic semiconductor compound represented by the following formula (2).
(2)

[In the formula (2)
L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;
R ₁ and R ₂ are independently of each other hydrogen or halogen;
D ₁ is O, S or Se;
R ₁₇ and R ₁₈ are, independently of each other, (C 1 -C 20) alkyl;
n is an integer from 2 to 500;
Wherein said L ₁ and L ₂ arylene and heteroarylene are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and (C 6 -C 20) Which may be further substituted with one or more substituents selected;
Ar ₁ and Ar ₂ are independently selected from the following structures.

[In the above formula,
Z ₁ to Z ₈ independently of one another are O, S or Se
R ₂₁ to R ₂₇ are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl;
q is independently an integer of 1 to 2, and when q is 2, R ₂₁ , R ₂₆ and R ₂₇ may be the same or different from each other] delete 3. The method of claim 2,
The organic semiconductor compound represented by Formula 2 is represented by Formula 3 below.
(3)

[Formula 3]
L ₁ and L ₂ are, independently of each other, a single bond or

;
Z ₁ , Z ₁₁ and Z ₁₂ are independently of each other S or Se;
R ₁ and R ₂ are independently of each other hydrogen or fluorine;
D ₁ is O, S or Se;
R ₁₇ and R ₁₈ are, independently of each other, (C 1 -C 20) alkyl;
and n is an integer of 2 to 500.] delete Reacting a benzothiadiazole tin derivative represented by the following formula (11) with a benzothiadiazole halide derivative represented by the following formula (12) to produce an organic semiconductor compound represented by the following formula (1).
[Chemical Formula 1]

(11)

[Chemical Formula 12]

[In the formulas (1), (11) and (12)
L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;
R ₁ and R ₂ are independently of each other hydrogen or halogen;
R ₃ and R ₄ are independently (C1-C20) _{alkyl, -O (R 11), -S} (R 12), -Se (R 13) or _{-Si (R 14) (R 15} ) (R 16 each ), R ₁₁ to R ₁₃ are independently of each other (C 1 -C 20) alkyl, and R ₁₄ to R ₁₆ are independently of each other hydrogen or (C 1 -C 20) alkyl;
a and b are each independently an integer of 1 to 4;
n is an integer from 2 to 500;
R ₄₁ to R ₄₃ are independently of each other (C 1 -C 10) alkyl;
X is independently of each other halogen;
Wherein said L ₁ and L ₂ arylene and heteroarylene are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and (C 6 -C 20) Which may be further substituted with one or more substituents selected;
Ar ₁ and Ar ₂ are independently selected from the following structures.

[In the above formula,
Z ₁ to Z ₈ independently of one another are O, S or Se
R ₂₁ to R ₂₇ are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl;
q is independently an integer of 1 to 2, and when q is 2, R ₂₁ , R ₂₆ and R ₂₇ may be the same or different from each other] The method according to claim 6,
The benzothiadiazole tin derivative of formula (11)
Preparing a benzothiadiazole derivative of Formula 16 by reacting a halide derivative of Formula 13 with a tin derivative of Formula 14 and Formula 15; And
Reacting a benzothiadiazole derivative of the following formula (16) with a tin halide derivative of the following formula (17) to prepare a benzothiadiazole tin derivative of the formula (11).
(11)

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[In the above formulas 13 to 17,
L ₁ and L ₂ independently of one another are a single bond, (C 6 -C 20) arylene or (C 3 -C 20) heteroarylene;
R ₁ and R ₂ are independently of each other hydrogen or halogen;
a and b are each independently an integer of 1 to 4;
R ₅₁ to R ₅₆ are independently of each other (C 1 -C 10) alkyl;
X ₁ is independently of each other halogen;
R ₄₁ to R ₄₃ are independently of each other (C 1 -C 10) alkyl;
X < ₁₁ > independently from each other are halogen;
Wherein said L ₁ and L ₂ arylene and heteroarylene are independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl and (C 6 -C 20) Which may be further substituted with one or more substituents selected;
Ar ₁ and Ar ₂ are independently selected from the following structures.

[In the above formula,
Z ₁ to Z ₈ independently of one another are O, S or Se
R ₂₁ to R ₂₇ are independently of each other hydrogen, halogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl;
q is independently an integer of 1 to 2, and when q is 2, R ₂₁ , R ₂₆ and R ₂₇ may be the same or different from each other] An organic semiconductor device comprising the organic semiconductor compound of claim 2 or 4.