KR101855085B1 - Selenium-containing organic semiconductor compound and producing method of the same - Google Patents

Abstract

A method for producing the selenium-containing organic semiconductor compound, and a photoelectric device including the selenium-containing organic semiconductor compound.

Description

TECHNICAL FIELD The present invention relates to a selenium-containing organic semiconductor compound and a method for producing the selenium-containing organic semiconductor compound.

The present invention relates to a selenium-containing organic semiconductor compound, a method for producing the same, and a photoelectric device including the same.

Up to now, studies for improving the charge mobility of organic semiconductors for photoelectric devices have been conducted to induce crystallization of organic molecules by heat or self-assembly. However, it is important to design the molecule so that inter-molecular conduction can easily occur.

)를 바탕으로 다양한 치환기를 도입함으로써 보다 나은 효율을 얻을 수 있다는 것은 다양한 문헌을 통해서 확인할 수 있으며, 이러한 사실은 앞으로 충분히 더 좋은 효율을 가지는 소재로서 개발 가능성이 있다는 것을 제시해 준다. 종래에 공지된 상기 치환기가 도입된 다이케토피롤로피롤은, 예를 들어,

(다이케토피롤로피롤-페닐) 또는

(다이케토피롤로피롤-티오펜) 등이 있다.For this reason, synthetic studies have been actively conducted on diketopyrrolopyrrole (DPP) -based derivatives from 1980 onwards. The DDP-based derivatives are electrons-deficient derivatives that have a low band gap and can absorb more sun light, resulting in more photon absorption. In addition, it is characterized in that a solution process can be carried out by variously introducing alkyl chains. The center of the diketopyrrolopyrrole (

), It can be confirmed through various documents that the efficiency can be improved by introducing various substituents on the basis of the substituent. This fact suggests that there is possibility of development as a material having a sufficiently high efficiency in the future. The diketopyrrolopyrrole to which the conventionally known substituent is introduced may be, for example,

(Diketopyrrolopyrrol-phenyl) or

(Diketopyrrolopyrrole-thiophene), and the like.

Recently, in the Less group, the design and synthesis of polymeric derivatives based on monomers of selenophene-diketopyrrolopyrrole compounds have shown that the base dyes can be used as 2,5-dihydro- 1,4-dioxo-3,6-dithienylpyrrolo- [3,4-c] -pyrrol) as a next generation sensitizer in consideration of stability and optical properties.

Korean Patent Publication No. 2011-0091711 discloses the use of a polymer in which diketopyrrolopyrrole is directly bonded with an aromatic hetero ring containing S as an organic semiconductor in an organic field effect transistor.

The present invention provides a selenium-containing organic semiconductor compound, a method for producing the selenium-containing organic semiconductor compound, and a photoelectric device including the selenium-containing organic semiconductor compound.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

A first aspect of the present invention provides a selenium-containing organic semiconductor compound represented by the following Formula 1:

1. A selenium-containing organic semiconductor compound represented by the following Chemical Formula 1:

 [Chemical Formula 1]

;

;

In Formula 1,

R ₁ and R ₂ each independently represent a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxycarbonyl group which may be substituted, a linear or branched C _{2- A} C _5-50 alkenyl group, a linear or branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, Or a C _3-50 heteroaryl group which may be substituted,

R ₃ is a C _6-50 aryl group which may be substituted or a C _3-50 heteroaryl group which may be substituted.

A second aspect of the present invention is a process for producing a selenium-containing organic semiconductor compound, which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3) to prepare a selenium- Lt; RTI ID = 0.0 > of:

[Chemical Formula 1]

;

;

(2)

;

;

(3)

;

;

In the above formulas,

R ₁ and R ₂ each independently represent a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxycarbonyl group which may be substituted, a linear or branched C _{2- A} C _5-50 alkenyl group, a linear or branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, Or a C _3-50 heteroaryl group which may be substituted,

R ₃ is a C _6-50 aryl group which may be substituted or a C _3-50 heteroaryl group which may be substituted,

X is a halogen.

A third aspect of the present invention provides an optoelectronic device comprising a selenium-containing organic semiconductor compound according to the first aspect or the second aspect of the present invention.

According to one embodiment of the present invention, various types of novel selenium-containing organic semiconductor compounds and methods of preparing the same can be provided, wherein the selenium-containing organic semiconductor compound includes a diketopyrrolopyrrole-selenophene organic semiconductor .

The selenium-containing organic semiconductor compound according to one embodiment of the present invention includes heterocyclic ring (selenophene) including selenium, thereby facilitating intermolecular charge transfer due to interaction of selenium molecules (Se ... Se) Has an oxidation / reduction potential lower than that of a heterocycle (thiophene) containing sulfur and has a merit that a large amount of photons can be easily absorbed due to the absorption of light having a longer wavelength than thiophene. Therefore, a photoelectric device including a selenium-containing organic semiconductor compound according to an embodiment of the present invention can provide an electronic device having excellent efficiency and performance.

Figure 1 shows the mechanism of the Suzuki cross-coupling reaction in one embodiment of the invention.
2 is an ultraviolet (UV-vis) absorption spectrum according to the state of a selenium-containing organic semiconductor compound in one embodiment of the present invention.
3 is a graph showing cyclic voltammetric measurements of selenium-containing organic semiconductor compounds in one embodiment of the present invention.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as " including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

As used herein, the terms " about, " " substantially, " and the like are used herein to refer to or approximate the numerical value of manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to prevent unauthorized exploitation by unauthorized intruders of the mentioned disclosure.

The term " step " or " step of ~ " as used throughout the specification does not imply " step for.

Throughout this specification, the term " combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B".

Throughout this specification, the term " halogen " or " halo " means that a halogen element belonging to group 17 of the periodic table is included in the compound as a functional group form and may be chlorine, bromine, fluorine or iodine, But may not be limited.

Throughout this specification, the term " alkyl group " refers to an alkyl group having from 1 to 50 carbon atoms, frequently from 1 to 40, from 1 to 30, from 1 to 20, from 1 to 10, from 1 to 8 carbon atoms, To a linear or branched alkyl group having from one to four carbon atoms, especially from one to three carbon atoms. When the alkyl group is substituted with an alkyl group, it is used interchangeably with a " branched alkyl group ". Examples of substituents include halo (for example, F, Cl, Br, I), haloalkyl (e.g., CC1 ₃ or CF ₃ ), alkoxy, alkylthio, hydroxy, carboxy (-COOH) carbonyl (-C (O) R), alkylcarbonyloxy (-OCOR), amino (-NH _2), carbamoyl (-NHCOOR- or -OCONHR-), urea (-NHCONHR-) or thiol (-SH ), But the present invention is not limited thereto. In addition, the defined alkyl groups may include, but are not limited to, one or more carbon to carbon double bonds or one or more carbon to carbon triple bonds. Butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-propyl, isopropyl, n-butyl, isobutyl, Pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, heptyl, heptyl, heptyl, heptyl, octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylbutyl, Methylhexyl, 5-methylhexyl, or all of the possible isomers thereof, but it is not limited thereto. .

Throughout this specification, the term " alkenyl group " refers to an alkenyl group that typically has from 2 to 50 carbon atoms, frequently from 2 to 40, from 2 to 30, from 2 to 20, from 2 to 10, from 2 to 8, Means a monounsaturated hydrocarbon radical having an atom, preferably 2 to 4 carbon atoms. For example, those exemplified above for the alkyl group containing a carbon-carbon double bond can be mentioned. For example, vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2- 1-yl, 1-methylbut-1-yl, 3-penten-1-yl, En-1-yl, 2-ethylprop-2-en-1-yl, and the like.

Throughout this specification, the term " alkynyl group " refers to an alkyl group having from 2 to 50 carbon atoms, frequently from 2 to 40, from 2 to 30, from 2 to 20, from 2 to 10, from 2 to 8, An unsaturated linear or branched hydrocarbon radical having one, two or three carbon atoms and optionally one or two triple bonds at any position, such as ethynyl, propargyl (2-propyn-1- 1-yl, 1-pentyn-1-yl, 3-butyne-1-yl, 1-yl, 1-ethylprop-2-yn-1-yl, and the like, But may not be limited.

Throughout this specification, the term " alkoxy group " may include a C _1-50 alkoxy group in the form of an alkyl and oxygen atom as defined above, including, for example, methoxide, ethoxide, propoxide But are not limited to, including but not limited to, butoxides, pentoses, hexoses, heptoxides, octoxides, nonoxides, dexides, or all possible isomers thereof.

Throughout this specification, the term " aryl " refers to monocyclic, such as, for example, phenyl, substituted phenyl, and the like, as well as monocyclic, such as fused bicyclic, such as naphthyl, phenanthrenyl, Refers to a click aromatic ring. Wherein the aryl group contains at least one ring having at least 6 atoms and up to 5 of the rings contain up to 22 atoms and wherein the double bonds between adjacent carbon atoms or suitable heteroatoms are alternating Resonance). The aryl group is optionally substituted with at least one substituent selected from the group consisting of halogen, alkyl, alkoxy, hydroxy, carboxy, carbamoyl, alkyloxycarbonyl, nitro, trifluoromethyl, amino, cycloalkyl, cyano, alkylS 2), or thiol. The term " alkyl " For example, the C _6-50 aryl group which is substituted or unsubstituted throughout the specification may be a benzene ring, a toluene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pentaren ring, an indene ring, a biphenylene ring, A heterocyclic ring, an acenaphthylene ring, an acenaphthylene ring, an acenaphthylene ring, a fluorene ring, a tetracene ring, a triphenylene ring, a pyrene ring, a chrysene ring, an ethyl- A heterocyclic ring, a pentachene ring, a tetraphenylene ring, a hexaphen ring, a hexachene ring, a rubisene ring, a coronene ring, a trinaphthylene ring, a heptaphene ring, a heptacene ring, a pyranthrene ring, A phenanthryl group, a 1-pyrenyl group, a chrysenyl group, a naphthacenylene group, a coronyl group, and a cyclopentadienyl group; And derivatives thereof. However, the present invention is not limited thereto. There can not be.

Throughout the present specification, the term " suzuki cross-coupling reaction ", which was first published by Akira Suzuki and his group in 1979, includes a Suzuki cross- Is a very rapid and rapid reaction that produces carbon-carbon bonds. The reaction is carried out in the presence of various catalysts with organometallic reagents and aryl halides having high reactivity and the Suzuki cross coupling reaction using an alkyl-boronic acid It is one of the reactions that form CC bonds even in the presence of relatively low toxicity and stable in the air and various functional groups. Specifically, in the present specification, the reaction utilizes aryl, vinyl- or alkyl halides catalyzed by aryl or vinyl-boronic acid and palladium. The reaction is used to synthesize polyolefins, styrenes, or substituted biphenyls (Miyaura, N., Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866-867., Suzuki A. Pure Appl. Chem. 1985, 57, 1749-1758.).

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these embodiments and examples and drawings.

A first aspect of the present invention provides a selenium-containing organic semiconductor compound represented by the following Formula 1:

[Chemical Formula 1]

;

;

In Formula 1,

R ₁ and R ₂ each independently represent a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxycarbonyl group which may be substituted, a linear or branched C _{2- A} C _5-50 alkenyl group, a linear or branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, Or a C _3-50 heteroaryl group which may be substituted,

R ₃ is a C _6-50 aryl group which may be substituted or a C _3-50 heteroaryl group which may be substituted.

In one embodiment of the present invention, the heteroatom contained in the hetero hydrocarbon ring group or the heteroaryl group may be selected from the group consisting of N, O, S, Te, Se, and combinations thereof. .

In one embodiment, R ₁ and R ₂ are each independently selected from the group consisting of halogen, optionally substituted linear or branched C _1-50 , C _1-40 , C _1-30 , C _1-20 , or C _1-10 alkyl, linear or branched optionally substituted _{C 1-50, C 1-40, C 1-30} , C 1-20, or alkoxide group of C _1-10, linear or branched C _{2 -50,} C _2-40, C _2-30, C _2-20, or C _2-10 alkenyl group, a linear or branched _{C 2-50, C 2-40, C 2-30} , C 2-20 , Or an unsaturated hydrocarbon ring group of C _2-10 , C _5-50 , C _5-40 , C _5-30 , C _5-20 , or C _5-10 , C _3-50 , C _3-40 , C _3-30, C _3-20, or unsaturated hetero ring group of C _3-10 hydrocarbons, which may be substituted with _{C 6-50, C 6-40, C 6-30} , C 6-20, or C _{6 -10} aryl group, or a C _3-50 , C _3-40 , C _3-30 , C _3-20 , or C _3-10 heteroaryl group which may be substituted.

In one embodiment herein, R ₃ is an _optionally substituted C _6-50 , C _6-40 , C _6-30 , C _6-20 , or C _6-10 aryl group or an _optionally substituted C _3-50 , C _3-40 , C _3-30 , C _3-20 , or a C _3-10 heteroaryl group.

In one embodiment of the present invention, R ₃ may include, but is not limited to, those selected from the following substituents:

;

;

;

;

;

;

;

;

;

;

;

;

;

;

;

;

Here, R ₄ to R ₆ are Each independently represents a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxy group which may be substituted, a linear or branched C _2-50 alkenyl group, Or a branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, or a C _Lt ; / RTI >

In one embodiment of the present invention, the selenium-containing organic semiconductor compound may include diketopyrrolopyrrole.

In one embodiment of the present invention, the selenium-containing organic semiconductor compound may include, but is not limited to, those selected from the following compounds:

;

;

A second aspect of the present invention is a process for producing a selenium-containing organic semiconductor compound, which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3) to prepare a selenium- Lt; RTI ID = 0.0 > of:

[Chemical Formula 1]

;

;

(2)

;

;

(3)

;

;

In the above formulas,

R ₁ and R ₂ each independently represent a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxycarbonyl group which may be substituted, a linear or branched C _{2- A} C _5-50 alkenyl group, a linear or branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, Or a C _3-50 heteroaryl group which may be substituted,

R ₃ is a C _6-50 aryl group which may be substituted or a C _3-50 heteroaryl group which may be substituted,

X is a halogen.

Although the detailed description of the parts overlapping with the first aspect of the present application is omitted, the description of the first aspect of the present invention can be applied equally to the second aspect.

In one embodiment, R ₁ and R ₂ are each independently selected from the group consisting of halogen, optionally substituted linear or branched C _1-50 , C _1-40 , C _1-30 , C _1-20 , or C _1-10 alkyl, linear or branched optionally substituted _{C 1-50, C 1-40, C 1-30} , C 1-20, or alkoxide group of C _1-10, linear or branched C _{2 -50,} C _2-40, C _2-30, C _2-20, or C _2-10 alkenyl group, a linear or branched _{C 2-50, C 2-40, C 2-30} , C 2-20 , Or an unsaturated hydrocarbon ring group of C _2-10 , C _5-50 , C _5-40 , C _5-30 , C _5-20 , or C _5-10 , C _3-50 , C _3-40 , C _3-30, C _3-20, or unsaturated hetero ring group of C _3-10 hydrocarbons, which may be substituted with _{C 6-50, C 6-40, C 6-30} , C 6-20, or C _{6 -10} aryl group, or a C _3-50 , C _3-40 , C _3-30 , C _3-20 , or C _3-10 heteroaryl group which may be substituted.

In one embodiment herein, R ₃ is an _optionally substituted C _6-50 , C _6-40 , C _6-30 , C _6-20 , or C _6-10 aryl group or an _optionally substituted C _3-50 , C _3-40 , C _3-30 , C _3-20 , or a C _3-10 heteroaryl group.

In one embodiment of the present invention, the heteroatom contained in the hetero hydrocarbon ring group or the heteroaryl group may be selected from the group consisting of N, O, S, Te, Se, and combinations thereof. .

In one embodiment of the present invention, R ₁ and R ₂ may each independently include, but are not limited to, those selected from the following substituents:

In one embodiment of the present invention, R ₃ may include, but is not limited to, those selected from the following substituents.

;

;

;

;

;

;

;

;

;

;

;

;

;

;

;

;

Here, R ₄ to R ₆ are Each independently represents a halogen, a linear or branched C _1-50 alkyl group which may be substituted, a linear or branched C _1-50 alkoxy group which may be substituted, a linear or branched C _2-50 alkenyl group, Or a branched C _2-50 alkynyl group, a C _5-50 unsaturated hydrocarbon ring group, a C _3-50 unsaturated _{heterohydrocarbon} ring group, a C _6-50 aryl group which may be substituted, or a C _Lt ; / RTI >

In one embodiment, R ₄ to R ₆ are each independently selected from the group consisting of halogen, linear or branched C _1-50 , C _1-40 , C _1-30 , C _1-20 , C _1-10 alkyl, linear or branched optionally substituted _{C 1-50, C 1-40, C 1-30} , C 1-20, or alkoxide group of C _1-10, linear or branched C _{2 -50,} C _2-40, C _2-30, C _2-20, or C _2-10 alkenyl group, a linear or branched _{C 2-50, C 2-40, C 2-30} , C 2-20 , Or an unsaturated hydrocarbon ring group of C _2-10 , C _5-50 , C _5-40 , C _5-30 , C _5-20 , or C _5-10 , C _3-50 , C _3-40 , C _3-30, C _3-20, or unsaturated hetero ring group of C _3-10 hydrocarbons, which may be substituted with _{C 6-50, C 6-40, C 6-30} , C 6-20, or C _{6 -10} aryl group, or a C _3-50 , C _3-40 , C _3-30 , C _3-20 , or C _3-10 heteroaryl group which may be substituted.

In one embodiment of the present invention, the selenium-containing organic semiconductor compound may be prepared by a Suzuki cross-coupling reaction, and by the reaction, the structure of the DA (π-bridge) But it is not limited thereto.

In one embodiment of the present invention, the selenium-containing organic semiconductor compound is a core material of the selenium-containing organic semiconductor compound, and includes diketopyrrolopyrrole derivatives containing selenium (Se) May be synthesized by introducing a thienothiophene group.

A third aspect of the present invention provides an optoelectronic device comprising a selenium-containing organic semiconductor compound according to the first aspect of the present invention. The photoelectric device according to the third aspect of the present invention is applicable to both the selenium-containing organic semiconductor compound according to the first aspect of the present invention and the method for producing the selenium-containing organic semiconductor compound according to the second aspect of the present invention But is not limited thereto.

The selenium-containing organic semiconductor compound according to one embodiment of the present invention includes heterocyclic ring (selenophene) including selenium, thereby facilitating intermolecular charge transfer due to interaction of selenium molecules (Se ... Se) Has an oxidation / reduction potential lower than that of a heterocycle (thiophene) containing sulfur and has a merit that a large amount of photons can be easily absorbed due to the absorption of light having a longer wavelength than thiophene. Therefore, a photoelectric device including a selenium-containing organic semiconductor compound according to an embodiment of the present invention can provide an electronic device having excellent efficiency and performance.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[ Example ]

< Manufacturing example  1>

Preparation of Compound T2

[Reaction Scheme 1]

Compound T2 was prepared according to the procedure described in J. Mater. Chem. 2-octylthieno [3,2-b] thiophene (T2) was synthesized by referring to the following reaction formula (1): C, 2013, 1, 3686-3694.

To a solution of thieno [3,2-b] thiophene (1 g, 7.13 mmol; T1) in THF (20 mL) was added n-BuLi (1.6 M in hexane, 4 mL, 6.42 mmol) was slowly added dropwise under argon charging conditions at -78 ° C. After stirring for 1 hour, 1-bromooctane (1.2 mL, 7.13 mmol) was slowly added dropwise. Then, the solution was stirred at -78 ° C for 30 minutes, then the temperature was raised to room temperature and stirred for 12 hours. Then, the ice water was poured out, extracted with dichloromethane, washed with Na ₂ SO ₄ To remove water. The reaction solution was concentrated, and Compound T2 (610 mg, 64%) was obtained by silica gel column chromatography (hexane).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 7.30 (d, J = 5.1Hz, 1H), 7.22 (d, J = 5.1 Hz, 1H), 6.99 (s, 1H), 2.92 (t, J = 7.6 Hz, 2H), 2.92 (t, J = 7.6 Hz, 2H), 1.77 (t, J = 7.8, 7.5 Hz, 2H), 1.52-1.35 (m, 10H), 0.97 (t, J = 6.6 Hz, 3H).

Preparation of compound T3

[Reaction Scheme 2]

Compound T3 is prepared as described in J. Mater. Chem. 2-bromo-5-octylthieno [3,2-b] thiophene (T3) (Scheme 2).

NBS (0.97 g, 5.47 mmol) was slowly added dropwise at 0 ° C to the compound T2 (1.38 g, 5.47 mmol) obtained in Preparation Example 1, slowly warmed to room temperature and stirred for 2 hours, Extraction was carried out using chloromethane, and then water was removed using Na ₂ SO ₄ . The reaction solution was concentrated, and the compound T3 (1.5 g, 83%) was isolated by flash column chromatography (hexane) .

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 7.17 (s, 1H), 6.85 (s, 1H), 2.85 (t, J = 7.5 Hz, 2H), 1.72-1.65 (m, 2H), 1.44-1.29 (m , 10H), 0.89 (t, J = 6.6 Hz, 3H).

Preparation of compound T4

[Reaction Scheme 3]

Compound T4 can be obtained by reacting 4,4,5,5-tetramethyl-2- (2-octylthieno [3,2-b] thiophen- (4,4,5,5-tetramethyl-2- (2-octylthieno [3,2-b] thiophen-5-yl) -1,3,2-dioxaborolane, T4.

N- BuLi (1.6 M in hexane solution, 0.4 mL, 0.63 mmol) was added to a dried reaction flask in which T3 (190 mg, 0.57 mmol) obtained in Preparation Example 2 was dissolved in THF (3 mL) The mixture was slowly added dropwise under 78 ° C and argon charging conditions. After stirring for 1 hour, ( i- Pro) Bpin (0.2 mL, 0.86 mmol) was slowly added dropwise at the same temperature. The solution was stirred at -78 ° C for about 30 minutes, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Then, ice water was added thereto, and the mixture was extracted with dichloromethane, followed by removal of the residue with Na ₂ SO ₄ . The reaction solution was concentrated and the compound T4 (160 mg, 74%) was obtained by silica gel flash column chromatography (EtOAc: n- Hexane = 1: 5).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 7.68 (s, 1H), 6.97 (s, 1H), 2.87 (t, J = 7.8Hz, 2H), 1.76-1.66 (m, 2H), 1.43-1.24 (m , 24H), 0.89 (t, J = 5.4 Hz, 3H).

Manufacturing example  2: Preparation of selenium-containing organic semiconductor compound

In order to utilize the Suzuki-cross coupling reaction as shown in the following Reaction Scheme 4, Compound A, which can be a core of a selenium-based organic semiconductor material which is a bridge of π- is reacted with selenophene of the Martin Heeney group - The monomers of selenophene-diketopyrrolopyrrole compounds were firstly referred to.

 [Reaction Scheme 4]

The compound A (100 mg, 0.09 mmol) and the compound T4 (84.9 mg, 0.22 mmol) were dissolved in a mixed solvent of tetrahydrofuran (THF; 0.9 mL) and water (0.3 mL) the solution was added to _{Pd (PPh 3) 4 (10} mol%) and _{K 2 CO 3 (211 mg,} 1.53 mmol). The solution was treated with N ₂ for 30 min and then refluxed at 80 ° C for 24 h. MeOH was added to the reaction solution, and the resultant precipitate was filtered. Compound TSeDPPT (86 mg, 66%) was obtained by silica gel flash column chromatography (dichloromethane: n- Hexane = 1: 1).

As shown in Reaction Scheme 4, a compound DPP (Se) -based organic semiconductor single molecule TSeDPPT having a structure of a DA (π-bridge) -D form can be successfully synthesized by Suzuki- there was.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 8.73 (d, J = 4.2 Hz, 2H), 7.40 (d, J = 4.5 Hz, 2H), 7.36 (s, 2H), 6.90 (s, 2H), 3.95 ( d, J = 7.5 Hz, 4H ), 2.88 (t, J = 7.5 Hz, 4H), 2.02-1.96 (m, 2H), 1.76-1.65 (m, 6H), 1.27-1.24 (m, 76H), 0.89 -0.84 (m, 24H).

Experimental Example  1: Optical properties

The light absorption region of the selenium-containing organic semiconductor compound (TSeDPPT) synthesized in Production Example 2 was measured in a solution state (chloroform) and a film state (FIG. 2).

As shown in Fig. 2, in the ultraviolet (UV-vis) absorption spectrum, the maximum absorption maxima λ _max in the solution state were 622 nm and 652 nm, and the optical absorption λ _onset was found to reach 715 nm. On the other hand, the maximum absorption _maxima of the film state, λ _max, was 756 nm, and the optical absorption λ _onset was shown up to 816 nm, thus confirming that the film state absorbed to a longer wavelength region than in the solution state.

In the 2011 Bazan research team's 7,7 '- [4,4-Bis (2-ethylhexyl) - (2-ethylhexyl) 4H- silolo [3,2- b : 4,5- b '] dithiophene-2,6-diyl bis [6-fluoro-4- (5'- hexyl- [2,2'- 5-yl) benzo [ c ] [1,2,5] thiadiazole] (p-DTS (FBTTh ₂ ) ₂ ) The organic semiconductor compound was reported to have a maximum absorption maximum (λ _max ) of 599 nm (chloroform in solution) in an ultraviolet (UV-vis) absorption spectrum. In comparison, the light absorption region of the synthesized selenium-containing organic semiconductor compound (TSeDPPT) according to the embodiment of the present invention is similar to the recently reported high efficiency 700 nm region of the existing material, or in the film state, It was found that the light absorption ability was improved.

Experimental Example  2: Electrochemical properties

The electrochemical properties of the selenium-containing organic semiconductor compound (TSeDPPT) synthesized in Example 1 are shown in Table 1 below. In Table 1, the highest occupied molecular orbital (HOMO) value is a value calculated using the result measured in FIG. 2 and Table 1 below show the results obtained by using cyclic voltammetry at 100 mV / s in TBAPF ₆ (0.1 molar concentration) solvent CH ₂ Cl ₂ in order to analyze electrochemical characteristics The measurement results are shown.

As shown in the following Table 1, the synthesized selenium-containing organic semiconductor compound (TSeDPPT) has a low band-like value and high charge mobility, and has excellent electrical characteristics in an organic device manufactured thereby. Compared with the known semiconductor compound of P3HT or p-DTS (FBTTh ₂ ) ₂ , it has a lower HOMO value, which not only makes it possible to form a high open-circuit voltage but also increases the oxidation stability, which is a great advantage of commercialization .

Organic semiconductor
compound E _1/2 vs SCE  (V) EF  ( eV ) Band gap  ( eV ) E _ox E _red HOMO LUMO TSeDPPT 0.678 -1.086 -5.42 -3.656 1.764 eV  = 703 nm

In Table 1, HOMO denotes the highest level occupied molecular orbital, and LUMO (lowest unoccupied molecular orbital) denotes the lowest level occupied molecular orbital.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (7)

1. A selenium-containing organic semiconductor compound represented by the following formula (1)
The selenium-containing organic semiconductor compound has a DAD-type structure,
Wherein A represents a selenophene-diketopyrrolopyrrole derivative ring represented by the following formula (1)
Wherein D represents R &lt; ₃ &gt;
Selenium-containing organic semiconductor compound:
[Chemical Formula 1]

;
In Formula 1,
R ₁ and R ₂ are each independently a C _1-30 linear alkyl group or a C _3-30 branched alkyl group,
R ₃ is

_Wherein R ₃ to R ₄ are C _1-30 linear alkyl groups or C _3-30 branched alkyl groups.
delete delete A process for producing a selenium-containing organic semiconductor compound, which comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3) to prepare a selenium-containing organic semiconductor compound represented by the following formula
The selenium-containing organic semiconductor compound has a DAD-type structure,
Wherein A represents a selenophene-diketopyrrolopyrrole derivative ring represented by the following formula (1)
Wherein D represents R &lt; ₃ &gt;
Method of preparing selenium-containing organic semiconductor compound:
[Chemical Formula 1]

;
(2)

;
(3)

;
In the above formulas,
R ₁ and R ₂ are each independently a C _1-30 linear alkyl group or a C _3-30 branched alkyl group,
R ₃ is

_Wherein R ₃ to R ₄ are C _1-30 linear alkyl groups or C _3-30 branched alkyl groups, and X is halogen.
delete 5. The method of claim 4,
Wherein the selenium-containing organic semiconductor compound is produced by a Suzuki cross-coupling reaction.
A photoelectric device comprising a selenium-containing organic semiconductor compound according to claim 1.

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