KR102400724B1 - Stretchable organic semiconducting polymer, manufacturing method thereof, and organic electronic devices containing the same - Google Patents

Abstract

The present invention relates to a stretchable organic semiconductor polymer, a method for manufacturing the same, and an organic electronic device comprising the same. Specifically, it is prepared by polymerizing a crystalline monomer and a flexible monomer into which carbazole and DPP are introduced, thereby providing an organic semiconductor polymer that realizes elasticity while maintaining electrical properties.

Description

Stretchable organic semiconductor polymer, manufacturing method thereof, and organic electronic device including same

The present invention relates to an organic semiconductor compound having elasticity, a method for manufacturing the same, and an organic electronic device including the same.

Recently, demand for and interest in new devices, such as flexible and wearable devices that can be freely deformed, are rapidly increasing. In a situation in which market expectations for these new electronic devices are gradually increasing, research for the development of a semiconductor material having elasticity, which is a key element of a flexible electronic device, is being actively conducted.

Organic semiconductors have excellent compatibility with flexible substrates, a simple manufacturing process, and low cost production. In particular, polymer semiconductors can be solution processed, thin film formation is easy due to excellent mechanical flexibility, electrical properties can be controlled by changing molecular structure, and manufacturing cost can be reduced compared to low molecular weight organic semiconductor compounds. With this advantage, it is emerging as a next-generation material for realizing flexible electronic devices.

Recently, in order to develop an organic semiconductor polymer having elasticity, research on preparing a semiconductor polymer by polymerizing a crystalline monomer having a conjugated structure and a flexible monomer without crystallinity has been reported. . A crystalline monomer (Crystalline part) provides electrical properties of the semiconductor, and a flexible monomer (Flexible part) without electrical properties provides elasticity of the semiconductor. However, it is very difficult to develop a semiconductor polymer that simultaneously realizes excellent elasticity and excellent electrical properties. In the case of a semiconductor polymer having stretchability reported so far, since the crystallinity of the crystalline part is not or very weak, when the content of the flexible monomer having no electrical properties is increased, the electrical properties of the semiconductor are greatly increased. There is a problem of degradation. Due to this, the content of the flexible monomer is reduced, the thermoplastic elastomer properties of the semiconductor polymer are not great, and the crystallinity properties are also reduced.

Non-patent literature 1. Macromo. Rapid Commun. 2016, 37, 1623 Non-Patent Document 2. Nature 2016, 539, 411

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel organic semiconductor polymer that maintains electrical properties of a semiconductor and realizes excellent elasticity, and a method for manufacturing the same.

Another object of the present invention is to provide an organic electronic device comprising the organic semiconductor polymer of the present invention.

The organic semiconductor polymer according to the present invention for achieving the above object includes repeating units represented by Chemical Formulas 1 and 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₄ are each independently hydrogen, C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C1-30 alkoxy, C2-C30 heterocycloalkyl, C2-C30 alkenyl or C2-C30 alkynyl ego;

R ₅ to R ₁₃ are each independently hydrogen or C 1 -C 30 alkyl;

Z ₁ and Z ₂ are each independently O, S, Se or NR _a , wherein R _a is hydrogen or C1-C30 alkyl;

Ar ₁ and Ar ₂ are each independently C6-C30 arylene or C3-C30 heteroarylene;

Ar ₃ to Ar ₅ are each independently a single bond, C6-C30 arylene, or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, -C(O)NR _b -, -NR _c C(O)-, -CO-, -COO-, -SO ₂ -or -SO-, wherein R _b and Rc are each independently hydrogen or C1-C30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 30.

According to an aspect of the present invention, R ₁ to R ₄ in Formula 1 may each independently be hydrogen or C1-C10 alkyl, and e and f may each independently be an integer of 1 to 20.

According to an aspect of the present invention, in terms of excellent crystallinity of the organic semiconductor polymer, Ar ₁ and Ar ₂ of Formula 1 may each independently be selected from the following structural formula.

In the above structural formula, R ₁₄ to R ₁₈ are each independently hydrogen or C1-C20 alkyl, Z ₃ to Z ₇ are each independently O, S, Se or NR _d , where R _d is hydrogen or C1-C20 alkyl am.

According to an aspect of the present invention, Ar ₃ and Ar ₅ of Formula 2 may each independently be any one selected from the following structural formula.

In the above structural formula, Z ₆ to Z ₈ are each independently O, S or Se, and R ₁₇ to R ₂₁ are each independently hydrogen or C1-C10 alkyl.

According to one aspect of the present invention, the organic semiconductor polymer of the present invention is represented by the following formula (3).

[Formula 3]

In Formula 3,

R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;

Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;

Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, -C(O)NR _b - or -NR _c C(O)-, wherein R _b is R _c are each independently hydrogen or C1-C30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 20;

n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1.

According to an aspect of the present invention, in Formula 3, R ₁ to R ₄ may be each independently hydrogen or C1-C5 alkyl, and R ₅ to R ₁₃ may each independently be hydrogen or C5-C20 alkyl.

According to an aspect of the present invention, Ar ₁ and Ar ₂ of Formula 3 may each independently be represented by the following structural formula.

In the above structural formula, R ₁₄ is hydrogen or C 1 -C 10 alkyl, and Z ₃ is S or Se.

According to an aspect of the present invention, Ar ₃ and Ar ₅ of Formula 3 may each independently be any one selected from the following structural formula.

In the above structural formula,

Z ₆ to Z ₈ are each independently S or Se, and R ₁₇ to R ₂₁ are each independently hydrogen or C1-C5 alkyl.

According to one aspect of the present invention, the organic semiconductor polymer of the present invention is represented by the following formula (4).

[Formula 4]

In Formula 4,

R ₁ to R ₄ are each independently hydrogen or C1-C20 alkyl;

R ₅ to R ₉ are each independently hydrogen or C 1 -C 20 alkyl;

Z ₁ , Z ₂ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C20 heteroarylene;

a, b, c and d are each independently an integer from 1 to 3;

s is an integer from 1 to 20;

n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1.

In addition, in the method for producing an organic semiconductor polymer according to the present invention, an organic semiconductor polymer represented by the following formula (3) is prepared by polymerizing a monomer represented by the following formula (11), a monomer represented by the following formula (12), and a monomer represented by the following formula (13) including the steps of

[Formula 3]

[Formula 11]

[Formula 12]

[Formula 13]

In Formula 3 and Formula 11 to Formula 13,

X ₁ to X ₄ are each independently halogen;

R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;

R ₂₂ to R ₂₄ are each independently hydrogen or C 1 -C 30 alkyl;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;

Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;

Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, —C(O)NR _b — or —NR _c C(O)—, wherein R _b is Rc each independently hydrogen or C 1 -C 30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 20;

n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1.

Another object of the present invention is to provide an organic semiconductor polymer as described above included in an organic electronic device.

According to an aspect of the present invention, the organic electronic device may be a liquid crystal display device, an organic light emitting display device, an organic transistor, an organic solar cell, or an organic sensor.

In addition, the present invention provides a crystalline compound represented by the following formula (7) having excellent crystallinity.

[Formula 7]

In Formula 7,

R ₁ to R ₄ are each independently hydrogen or C1-C20 alkyl;

R ₅ to R ₁₃ are each independently hydrogen or C5-C20 alkyl;

R ₃₀ and R ₃₁ are each independently hydrogen or halogen;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C20 heteroarylene;

a, b, c and d are each independently an integer of 1 to 3.

According to an aspect of the present invention, the crystalline compound may have a T _m value of 30 to 280° C. and a T _c value of 20 to 270° C. in a differential scanning calorimetry curve.

The semiconductor polymer of the present invention realizes excellent elasticity while maintaining electrical properties. Specifically, by using a compound in which DPP (Diketopyrrolopyrrole) is introduced on both sides of carbazole, which is a central skeleton, as a crystalline part, the crystallinity of the crystalline monomer can be very excellent. The semiconductor polymer including the crystalline monomer may maintain the electrical properties of the semiconductor even when a flexible monomer having no electrical properties is included.

In addition, carbazole and DPP, which are crystalline monomers, have electrochromic properties, and flexible monomers have excellent compatibility with electrolytes, which are essential for electrochromic implementation. The electrochromic properties are improved due to excellent mixing properties with the electrolyte.

In addition, the organic electronic device of the present invention has excellent electrical properties, electrochromic properties and elasticity by including the organic semiconductor polymer of the present invention.

Accordingly, the organic semiconductor polymer of the present invention can be usefully applied to various device fields such as a liquid crystal display device, an organic light emitting display device, an organic transistor, an organic solar electricity or an organic sensor.

1 is a differential calorimetry (DSC) curve of (a) compound 1 synthesized in Example 1, (b) compound 2 synthesized in Example 2.
2 is a differential calorimetry (DSC) curve of (a) P7, (b) P5, (c) P3, and (d) P1.
3 is a differential calorimetry (DSC) curve of (a) P10, (b) P0.
4 is a thermogravimetric analysis (TGA) curve of (a) P7, (b) P5, (c) P3, and (d) P1.
5 is a thermogravimetric analysis (TGA) curve of (a) P10, (b) P0.
6 is a UV-vis absorption spectrum of (a) P7, (b) P5, (c) P3, (d) P1 in solution and film phases.
7 illustrates organic transistors according to Examples 9 to 12 and Comparative Example 3 of the present invention.
8 is a view showing the measurement results of the charge mobility of the organic transistors according to Examples 9 to 12 and Comparative Example 3 of the present invention.
9 shows electrochromic results according to Examples 13 to 15 and Comparative Example 4 of the present invention.

Hereinafter, a novel organic semiconductor polymer according to the present invention, a method for manufacturing the same, and an organic electronic device including the same will be described in more detail through Preparation Examples and Examples. However, the following Preparation Examples and Examples are only references for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms. In addition, all technical and scientific terms, unless otherwise defined, have the meanings commonly understood by those of ordinary skill in the art to which the present invention belongs, and may unnecessarily obscure the subject matter of the present invention in the following description. A description of possible known functions and configurations will be omitted.

As used herein, the term “comprises” is an open-ended description having an equivalent meaning to expressions such as “comprises”, “contains”, “has” or “characterizes”, and is an element not listed in addition; Materials or processes are not excluded.

As used herein, all substituents including “alkyl” and other “alkyl” moieties refer to monovalent organic radicals having one bonding position derived from a straight-chain or pulverized hydrocarbon.

As used herein, the term “alkoxy” refers to an *-O-alkyl radical, where “alkyl” is as defined above.

As used herein, the term “alkenyl” refers to an organic radical derived from a hydrocarbon containing one or more double bonds.

As used herein, the term “alkynyl” refers to an organic radical derived from a hydrocarbon containing one or more triple bonds.

As used herein, the term “cycloalkyl” refers to a non-aromatic monocyclic or multicyclic ring system having 3 to 30 carbon atoms.

As used herein, the term “heterocycloalkyl” refers to a substituted or unsubstituted non-aromatic 3 to 15 membered ring radical consisting of carbon atoms and 1 to 5 heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur, and heterocycloalkyl Alkyl radicals may be monocyclic, bicyclic or tricyclic ring systems, which may be fused, bridged, or include spiro ring systems, and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocycloalkyl radical may be present in various oxidation states. may be oxidized in some cases. Also, the nitrogen atom may be quaternized in some cases.

As used herein, the term “arylene” is a divalent organic radical of an aromatic ring derived from an aromatic hydrocarbon, and is preferably a single or fused ring having 4 to 7, preferably 5 or 6 ring atoms in each ring. It includes a system, and includes a form in which a plurality of aryls are connected by a single bond. The 'aryl' refers to an organic radical derived from an aromatic hydrocarbon ring by removal of one hydrogen, and specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, etc. , but is not limited thereto.

As used herein, the term "heteroarylene" is an organic radical derived from an aromatic hydrocarbon by the removal of two hydrogens, and includes one or more heteroatoms selected from B, N, O, S, P(=O), Si and P may be a monocyclic or polycyclic aromatic hydrocarbon radical containing 3 to 8 ring atoms, and a single or fused ring system comprising suitably 3 to 7, preferably 5 or 6 ring atoms in each ring It includes, and includes a form in which a plurality of heteroaryls are connected by a single bond.

As used herein, the term "halogen" refers to a fluorine (F), chlorine (Cl), bromine (Br) or iodine (I) atom.

As used herein, the term “single bond” refers to a case in which an atom does not exist in the corresponding site. For example, when Y is a single bond in the structure of X-Y-Z, X and Z are directly connected to form the structure of X-Z.

As seen in the background art, the present inventors have intensified research on novel organic semiconductor polymers that realize excellent stretchability while maintaining the electrical properties of semiconductors. As a result, it was confirmed that when the compound in which DPP was introduced into both carbazoles was used as a crystalline monomer (Crystalline part), it was confirmed that very excellent crystallinity was exhibited. Accordingly, it was confirmed that the semiconductor polymer including the crystalline monomer can maintain the electrical properties of the semiconductor even when a flexible part having no electrical properties is included, and thus can be developed as a semiconductor polymer having elasticity. In addition, carbazole and DPP, which are crystalline monomers, have electrochromic properties, and flexible monomers have excellent compatibility with electrolytes, which are essential for electrochromic implementation. It was confirmed that the electrochromic properties were improved due to excellent mixing properties with the electrolyte. Accordingly, the present invention provides a semiconductor polymer having such structural characteristics, a method for manufacturing the same, and an organic electronic device including the same.

Hereinafter, the semiconductor polymer according to the present invention will be described in detail.

The semiconductor polymer of the present invention is characterized in that it includes a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). With such structural features, the semiconductor polymer of the present invention can realize excellent elasticity while maintaining electrical properties.

[Formula 1]

[Formula 2]

(In Formula 1 and Formula 2,

R ₁ to R ₄ are each independently hydrogen, C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C1-30 alkoxy, C2-C30 heterocycloalkyl, C2-C30 alkenyl or C2-C30 alkynyl ego;

R ₅ to R ₁₃ are each independently hydrogen or C 1 -C 30 alkyl;

Z ₁ and Z ₂ are each independently O, S, Se or NR _a , wherein R _a is hydrogen or C1-C30 alkyl;

Ar ₁ and Ar ₂ are each independently C6-C30 arylene or C3-C30 heteroarylene;

Ar ₃ to Ar ₅ are each independently a single bond, C6-C30 arylene, or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, -C(O)NR _b -, -NR _c C(O)-, -CO-, -COO-, -SO ₂ -or -SO-, wherein R _b and Rc are each independently hydrogen or C1-C30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 30.)

Since the semiconductor polymer according to an embodiment of the present invention includes the repeating units represented by Chemical Formulas 1 and 2, it is possible to realize excellent elasticity while maintaining the electrical properties of the semiconductor.

Preferably, R ₁ to R ₄ in Formula 1 according to an embodiment of the present invention are each independently hydrogen or C 1 -C 10 alkyl, and e and f may each independently be an integer of 1 to 20. More preferably, R ₁ to R ₄ in Formula 1 may each independently be hydrogen or C1-C5 alkyl.

에서 선택되는 어느 하나일 수 있으며, 상기 구조식에서 R₁₄ 내지 R₁₈는 각각 독립적으로 수소 또는 C1-C20알킬이고, Z₃ 내지 Z₇은 각각 독립적으로 O, S, Se 또는 NR_d이고, 여기서 R_d는 수소 또는C1-C20 알킬이다.In Formula 1 according to an embodiment of the present invention, Ar ₁ and Ar ₂ are each independently

may be any one selected from, in the structural formula, R ₁₄ to R ₁₈ are each independently hydrogen or C 1 -C 20 alkyl, Z ₃ to Z ₇ are each independently O, S, Se or NR _d , where R _d is hydrogen or C1-C20 alkyl.

Preferably, in the structural formula according to an embodiment of the present invention, R ₁₄ to R ₁₈ are each independently hydrogen or C 1 -C 5 alkyl, and Z ₃ to Z ₇ may each independently be S or Se.

에서 선택되는 어느 하나일 수 있으며, 상기 구조식에서 Z₆ 내지 Z₈은 각각 독립적으로 O, S 또는 Se이고, R₁₇ 내지 R₂₁은 각각 독립적으로 수소 또는 C1-C10알킬이다. 바람직하게는, Z₆ 내지 Z₈은 각각 독립적으로 S 또는 Se이고, R₁₇ 내지 R₂₁은 각각 독립적으로 수소 또는 C1-C5알킬일 수 있다.In Formula 2 according to an embodiment of the present invention, Ar ₃ and Ar ₅ are each independently

may be any one selected from, in the above structural formula Z ₆ To Z ₈ are each independently O, S or Se, R ₁₇ to R ₂₁ are each independently hydrogen or C1-C10 alkyl. Preferably, Z ₆ to Z ₈ may each independently be S or Se, and R ₁₇ to R ₂₁ may each independently be hydrogen or C 1 -C 5 alkyl.

Preferably, in terms of having better electrical properties, the semiconductor polymer according to an embodiment of the present invention may be represented by the following formula (3).

[Formula 3]

(In Formula 3,

R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;

Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;

Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, -C(O)NR _b - or -NR _c C(O)-, wherein R _b is Rc each independently hydrogen or C1-C30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 20;

n and m are each independently real numbers greater than 0 and less than 1 as a mole fraction, and n+m=1.)

In Formula 3 according to an embodiment of the present invention, R ₁ to R ₄ may each independently be hydrogen or C1-C5 alkyl, and R ₅ to R ₁₃ may each independently be hydrogen or C5-C20 alkyl. Preferably, R ₅ to R ₉ may each independently be C6-C18 alkyl.

Preferably, Ar ₁ and Ar ₂ of Formula 3 according to an embodiment of the present invention are each independently

이며, 상기 구조식에서 R₁₄는 수소 또는 C1-C10알킬이고, Z₃는 S 또는 Se이다. 바람직하게는, R₁₄는 수소 또는 C1-C5알킬이고, Z₃는 S일 수 있다.

and, in the above structural formula, R ₁₄ is hydrogen or C1-C10 alkyl, and Z ₃ is S or Se. Preferably, R ₁₄ is hydrogen or C 1 -C 5 alkyl, and Z ₃ may be S.

에서 선택되는 어느 하나일 수 있으며, 상기 구조식에서 Z₆, Z₇ 및 Z₈은 각각 독립적으로 S 또는 Se이고, R₁₇ 내지 R₂₁은 각각 독립적으로 수소 또는 C1-C5알킬이다.Ar ₃ and Ar ₅ of Formula 3 according to an embodiment of the present invention are each independently

may be any one selected from, in the above structural formula Z ₆ , Z ₇ and Z ₈ are each independently S or Se, and R ₁₇ to R ₂₁ are each independently hydrogen or C1-C5 alkyl.

More preferably, the organic semiconductor polymer according to an embodiment of the present invention may be represented by the following formula (4).

[Formula 4]

(In Formula 4, R ₁ to R ₄ are each independently hydrogen or C1-C20 alkyl;

R ₅ to R ₉ are each independently hydrogen or C 1 -C 20 alkyl;

Z ₁ , Z ₂ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C20 heteroarylene;

a, b, c and d are each independently an integer from 1 to 3;

s is an integer from 1 to 20;

n and m are each independently real numbers greater than 0 and less than 1 as a mole fraction, and n+m=1.)

Preferably, in Formula 4 according to an embodiment of the present invention, R ₁ to R ₄ are each independently hydrogen or C1-C5 alkyl, R ₅ to R ₉ are each independently hydrogen or C7-C20 alkyl, Z ₁ , Z ₂ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently S or Se, Ar ₁ and Ar ₂ are each independently C3-C9 heteroarylene, a, b, c and d are each independently 1 to It is an integer of 3, and s may be an integer of 1 to 10.

Hereinafter, a method for producing an organic semiconductor polymer according to the present invention will be described in detail.

In the method for producing a polymer semiconductor according to an embodiment of the present invention, a compound represented by the following formula (3) is prepared by polymerizing a monomer represented by the following formula (11), a monomer represented by the following formula (12), and a monomer represented by the following formula (13) includes steps.

[Formula 3]

[Formula 11]

[Formula 12]

[Formula 13]

(In Formula 3 and Formula 11 to Formula 13,

X ₁ to X ₄ are each independently halogen;

R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;

R ₂₂ to R ₂₄ are each independently hydrogen or C 1 -C 30 alkyl;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;

Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;

Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;

D ₁ and D ₂ are each independently a single bond, -C(O)NR _b - or -NR _c C(O)-, wherein R _b is Rc each independently hydrogen or C1-C30 alkyl;

a, b, c and d are each independently an integer from 1 to 3;

e and f are each independently an integer from 1 to 20;

n and m are each independently real numbers greater than 0 and less than 1 as a mole fraction, and n+m=1.)

The compound represented by Formula 3 according to an embodiment of the present invention is prepared by a stille coupling reaction of a monomer represented by Formula 11, a monomer represented by Formula 12, and a monomer represented by Formula 13 under a catalyst.

The catalyst according to an embodiment of the present invention may be any catalyst used for stille coupling, but may be Pd (Palladium) as a specific example. It may be 10 mol%.

The solvent used in the preparation method according to an embodiment of the present invention is a conventional organic solvent, and 1,4-dioxane (1,4-dioxane), dichloromethane (DCM), dichloroethane (DCE), toluene (Toluene) ), acetonitrile (MeCN), nitromethan, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA) and chlorobenzene ( CB) is preferably used, and chlorobenzene or toluene is more preferably used as a solvent. The reaction time may vary depending on the reactant, the type of the solvent, and the amount of the solvent.

Hereinafter, a crystalline monomer which is a factor providing excellent crystallinity of the organic semiconductor polymer of the present invention will be described.

The crystalline monomer of the semiconductor polymer according to an embodiment of the present invention may be represented by the following formula (7).

[Formula 7]

(In Formula 7,

R ₁ to R ₄ are each independently hydrogen or C1-C20 alkyl;

R ₅ to R ₁₃ are each independently hydrogen or C5-C20 alkyl;

R ₃₀ and R ₃₁ are each independently hydrogen or halogen;

Z ₁ and Z ₂ are each independently S or Se;

Ar ₁ and Ar ₂ are each independently C3-C20 heteroarylene;

a, b, c and d are each independently an integer from 1 to 3.)

Preferably, in Formula 7 according to an embodiment of the present invention, R ₁ to R ₄ are each independently hydrogen or C1-C5 alkyl; R ₅ to R ₁₃ are each independently hydrogen or C7-C20 alkyl; Z ₁ and Z ₂ are each independently S; Ar ₁ and Ar ₂ are each independently C3-C9 heteroaryl.

The compound represented by Formula 7 according to an embodiment of the present invention may have a T _m value of 30° C. to 280° C. and a T _c value of 20° C. to 270° C. in a differential scanning calorimetry curve, more preferably 80° C. It may have a T _m value of from to 200° C. and a T _c value from 50° C. to 180° C. Through this, it can be seen that the semiconductor polymer of the present invention including the compound represented by Chemical Formula 7 as a crystalline monomer has excellent crystallinity.

Hereinafter, the use of the semiconductor polymer according to the present invention will be described.

An aspect of the present invention may be an organic electronic device including the semiconductor polymer, and the organic electronic device may be a liquid crystal display device, an organic light emitting display device, an organic transistor, an organic solar cell, or an organic sensor.

Hereinafter, the semiconductor compound of the present invention and a manufacturing method thereof will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely references for describing the present invention in detail, and the present invention is not limited thereto and may be implemented in various forms.

[Method of measuring physical properties]

1. NMR Spectroscopy

¹ H NMR spectroscopy was measured using a Bruker AM-300 spectrometer.

2. Weight average molecular weight measurement

The weight average molecular weight is a weight average molecular weight value in terms of standard polystyrene measured by gel permeation chromatography (GPC) using chloroform as a solvent.

GPC equipment: M930 of Younglin Kigi,

Column: Agilent's PLgel 5um Mixed-D

Column temperature: 30 ℃

Input amount: 300 μl

Flow rate: 1.0 ml/min

3. Measurement of glass transition temperature (T _g ), crystallization temperature (T _c ) and melting point (T _m )

In order to evaluate crystallinity and ductility, the glass transition temperature (T _g ), the crystallization temperature (T _c ) and the melting temperature (T _m ) were measured according to the Differential Scanning Calorimetry (DSC) method ISO 11357-3. .

4. Decomposition temperature (T _d ) measurement

To measure thermal stability, volatility, and decomposition temperature, thermogravimetric analysis (TGA) was used. The TGA method was measured under nitrogen gas injection at a pressure of 1.5 bar/min while warming the obtained title compound to 800°C at a rate of 5°C/min.

5. Charge mobility measurement

Charge mobility was measured through transistor fabrication. To this end, the synthesized polymer is used as an active layer and a transistor with source, drain, and gate three electrodes is fabricated. Then, while the gate electrode voltage is kept constant, flowing between the source and drain according to the source-drain voltage The current was measured. The measured current-voltage curve is divided into a linear section at a low voltage and a saturation section at a high voltage. Mobility was measured and calculated from the linear curve, which is a low voltage.

6. Electrochromic Efficiency Measurement

For electrochromism, decolorization/discoloration experiments were performed under the conditions of 0.5V, which discolors, and 0.1V, where discoloration occurs due to the oxidation reaction of the synthesized polymer. Visible light transmittance was measured over time using an SD2400 transmittance meter (EDTM Inc.), and the discoloration efficiency (discoloration efficiency = ΔT/charge, ΔT: difference in transmittance during coloring and decolorization) was calculated by changing the transmittance with respect to the amount of charge. .

[Example 1] Preparation of unimolecular organic semiconductor compound 1

Compound A (5.92 g, 9.0 mmol), compound C (12.07 g, 20.0 mmol), and Pd (pph ₃ ) ₄ (0.416 g, 0.36 mmol) were placed in a 500 mL flask and dissolved in 250 ml THF. Then, 60 ml of 2M K ₂ CO ₃ was added and stirred at 70° C. for 48 hours, followed by cooling at room temperature. The resulting mixture was extracted with dichloromethane, the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate (MgSO ₄ ) and concentrated. The product was purified by flash chromatography on silica gel to obtain a purple solid compound 1 (12.51 g, 96%).

H-NMR (300 MHz, CDCl ₃ , ppm): δ 9.10 (d, 2H, J=22 Hz), 8.90 (d, 2H, J=3 Hz), 8.14 (q, 2H, J=23 Hz), 7.86(s, 1H), 7.715(m, 7H), 7.28(m, 2H), 4.63(s, 1H), 4.14(tt, 8H), 2.35(s, 2H), 2.01(s, 4H), 1.89 (s, 2H), 1.45 (m, 38H), 1.13 (m, 18H), 0.97 (d, 6H, J=6.5 Hz), 0.91 (m, 18H), 0.79 (t, 6H, J=13.5 Hz) .

[Example 2] Preparation of unimolecular organic semiconductor compound 2

Compound B (8.0 g, 8.93 mmol), compound C (12.37 g, 20.5 mmol), and Pd (pph ₃ ) ₄ (0.405 g, 0.35 mmol) were placed in a 500 mL flask and dissolved in toluene 60 mL and DMF 10 mL. After stirring at 110° C. for 48 hours, it was cooled at room temperature. The resulting mixture was extracted with dichloromethane, the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate (MgSO ₄ ) and concentrated. The product was purified by flash chromatography on silica gel to obtain a purple solid compound 2 (7.32 g, 51%).

H-NMR (300 MHz, CDCl ₃ , ppm): δ 8.99(d, 2H), 8.89(d, 2H), 8.09(t, 2H), 7.79(m, 1H), 7.62(m, 3H), 7.51 (br, 2H), 7.36 (m, 6H), 7.29 (d, 2H), 4.66 (br, 1H), 4.05 (br, 8H), 2.38 (br, 4H), 1.94 (br, 8H), 1.14 ( m, 52H), 0.89 (m, 30H).

[Example 3] Preparation of unimolecular organic semiconductor compound 3

N-bromosuccimide (N-bromosuccimide, NBS; 1.56 g, 8.75) in 400 ml of chloroform (CHCl ₃ ) was added to a solution of compound 1 (5.80 g, 4.00 mmol) obtained in Example 1 at 0 ° C. mmol) was added slowly in 3 portions. The reaction was stirred at room temperature over 12 hours. The resulting mixture was extracted with dichloromethane and the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The product was purified by flash chromatography on silica gel to give a purple solid compound 3 (5.2 g, 81 %).

H-NMR (300 MHz, CDCl ₃ , ppm): δ 9.11(d, 2H), 8.64(d, 2H), 8.13(m, 2H), 7.85(s, 1H), 7.66(m, 5H), 7.24 (d, 2H), 4.63(s, 1H), 4.11(t, 4H), 3.99(t, 4H), 2.35(s, 2H), 2.01(s, 4H), 1.87(s, 2H), 1.44( m, 38H), 1.12 (m, 18H), 0.97 (d, 6H), 0.92 (m, 18H), 0.79 (t, 6H).

[Example 4] Preparation of unimolecular organic semiconductor compound 4

In 100 ml of chloroform (CHCl ₃ ), the compound 2 (1.62 g, 1.00 mmol) obtained in Example 2 was added to a solution of N-bromosuccimide (N-bromosuccimide, NBS; 0.38 g, 2.15) at 0° C. mmol) was added slowly in 3 portions. The reaction was stirred at room temperature over 12 hours. The resulting mixture was extracted with dichloromethane and the organic phase was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated. The product was purified by flash chromatography on silica gel to give a purple solid compound 4 (1.4 g, 79 %).

H-NMR (300 MHz, CDCl ₃ , ppm): δ 9.01(d, 2H), 8.82(d, 2H), 8.13(t, 2H), 7.75(m, 1H), 7.58(m, 3H), 7.53 (br, 2H), 7.33 (m, 4H), 7.31 (d, 2H), 4.65 (br, 1H), 4.04 (br, 8H), 2.33 (br, 4H), 1.96 (br, 8H), 1.13 ( m, 52H), 0.89 (m, 30H).

[Example 5] Preparation of organic semiconductor polymer P5

Compound 3 (0.5 mmol), 2,5-bis (trimethylstannyl) thiophene (1 mol), 2-bromo-5- (12- (5-bromothiophen-2-) in 4.5 ml of toluene and 1.5 ml of DMF under nitrogen atmosphere yl)dodecyl)thiophene (0.5mmol) was dissolved, Pd ₂ (dba) ₃ (2 mol%) and P(o-tol) ₃ (8 mol%) were added, stirred at 100° C. for 48 hours, and cooled at room temperature after reaction did After the produced polymer was precipitated in methanol, the precipitated polymer was washed in the order of methanol, acetone, and hexane through Soxhlet purification, and the polymer dissolved in chloroform was precipitated in methanol. The precipitated polymer was filtered and dried in vacuum to obtain polymer P5 in a 5:5 ratio.

[Examples 6 to 8]

In the method of Example 5, polymerization was carried out in the same manner except for changing the molar ratio of the starting material to obtain P1, P3 and P7 corresponding to Examples 6 to 8, respectively, and Physical properties are shown in Table 1 below.

[Comparative Examples 1 to 2]

Except for changing the molar ratio of the starting material in the method of Example 5, polymerization was carried out in the same manner to obtain compounds P0 and P10 corresponding to Comparative Examples 1 and 2, respectively, and the properties of the prepared semiconductor polymer were It is shown in Table 1 below.

1 shows the DSC measurement results for the compounds 1 and 2 synthesized in Examples 1 and 2 above. In the semiconductor polymer, T _m and T _c are indicators indicating the degree of crystallinity, and since both compounds show strong T _m and T _c values, it can be said that the crystalline form is excellent (T _m of Compound 1 is 166-172℃, T _c is 124°C; T _m of compound 2 is 93°C, T _c is 60°C).

Figure 2 shows the DSC measurement results for the polymers P7, P5, P3 and P1 synthesized in Examples 5 to 8. In semiconductor polymers, the T _g value is an important indicator of the degree of ductility. It has a T _g value at 100 ° C or less in P7 where 30% of flexible part is introduced. As the content of flexible monomer increases, the T g value of the polymer It was confirmed that the _g value was lowered.

3 shows the DSC measurement results for the polymers P0 and P10 synthesized in Comparative Examples 1 and 2. When the T _g value of P10 in which 0% of the flexible monomer was introduced was 100 ° C. or higher, it was confirmed that the polymer synthesized through the method of the present invention could implement elasticity. That is, since the semiconductor polymer of the present invention has excellent crystallinity and elasticity, it was confirmed that excellent elasticity can be realized while maintaining the electrical properties of the semiconductor.

4 shows the results of measuring the decomposition temperatures of the polymers P7, P5, P3 and P1 synthesized in Examples 5 to 8 using TGA, and FIG. 5 is the polymer synthesized in Comparative Examples 1 and 2 Decomposition temperatures for P0 and P10 are shown using TGA. It can be seen that all of the T _d95% values, which are the temperature at which a 5% weight loss of the compound occurs, are above 400°C and have excellent thermal stability (T _d95% of P10 is 415°C; T _d95% of P7 is 417°C; P5 T _d95% of P3 is 415 °C; T _d95% of P3 is 409 °C; T _d95% of P1 is 416 °C; T _d95% of P0 is 424 °C).

Figure 6 shows the light absorption regions of P7, P5, P3 and P1 measured in solution state, film state and 110 ℃ annealing film state, P7, P5 in which 30%, 50%, and 70% of flexible monomers are introduced, respectively. And a vibronic peak was observed in the vicinity of 780 nm in P3. Through this, it could be confirmed that P7, P5 and P3 had crystalline properties, and as the content of the flexible monomer increased, the absorption at 400 nm increased.

[Examples 9 to 12] Organic transistor fabrication

Transistors were fabricated using the polymers P1, P3, P5 and P7 synthesized in Examples 5 to 8 above. 5 mg of each polymer was dissolved in 1 mL chlorobenzene, and then spin-coated on Eagle 2000 glass patterned with a thickness of 15 nm and 5 nm of Au/Ni as source-drain electrodes, respectively, and heat-treated at 100° C. for 30 minutes to form an active layer. A PMMA solution (80 mg/mL in nBA) was spin-coated on the active layer, heat-treated at 80° C. to form an insulating layer, and then 50 nm of Al was thermally deposited as a gate electrode.

[Comparative Example 3] Organic transistor production

A transistor was manufactured in the same manner as in Example 9 using the polymer P10 synthesized in Comparative Example 2.

8 is a view showing the measurement results of the charge mobility of the devices manufactured in Examples 9 to 12 and Comparative Example 3 at all times. The device made of polymer P10 made of only crystalline monomer showed the highest charge mobility, and as the flexible monomer content of the polymer increased, the charge mobility decreased. low can be seen. That is, it was confirmed that the semiconductor polymer of the present invention can maintain the electrical characteristics while increasing the flexibility characteristics through the low decrease in the charge mobility even though the increase in the flexible monomer content is very large.

[Examples 13 to 15] Confirmation of electrochromic properties

After coating the polymers P3, P5 and P7 synthesized in Examples 5 and 7 to 8 on ITO transparent electrodes, electrochromic evaluation was performed in an electrolyte solution in which 0.1 M concentration of LiClO ₄ was dissolved in propylene carbonate.

[Comparative Example 4] Confirmation of electrochromic properties

Using the polymer P10 synthesized in Comparative Example 2, electrochromic evaluation was performed in the same manner as in Example 11.

9 shows the results of Examples 11 to 13 and Comparative Example 4. P10, P3 and P5 showed discoloration efficiencies of 81 cm ² /C, 71 cm ² /C, and 70 cm ² /C, respectively, and the discoloration efficiency of P7 was 151 cm ² /C, a crystalline monomer with electrochromic properties. It showed superior discoloration efficiency than P10 made of only. Through this, it was confirmed that the semiconductor polymer of the present invention in which a flexible monomer is partially introduced into a crystalline monomer having electrochromic properties has superior electrochromic properties than general electrochromic polymers.

As described above, the present invention has been described by specific matters and limited examples, but these are provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the field to which the present invention belongs Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (14)

An organic semiconductor polymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ₁ to R ₄ are each independently hydrogen, C1-C30 alkyl, C3-C30 cycloalkyl, C6-C30 aryl, C1-30 alkoxy, C2-C30 heterocycloalkyl, C2-C30 alkenyl or C2-C30 alkynyl ego;
R ₅ to R ₁₃ are each independently hydrogen or C 1 -C 30 alkyl;
Z ₁ and Z ₂ are each independently O, S, Se or NR _a , wherein R _a is hydrogen or C1-C30 alkyl;
Ar ₁ and Ar ₂ are each independently C6-C30 arylene or C3-C30 heteroarylene;
Ar ₃ to Ar ₅ are each independently a single bond, C6-C30 arylene, or C3-C30 heteroarylene;
D ₁ and D ₂ are each independently a single bond, -C(O)NR _b -, -NR _c C(O)-, -CO-, -COO-, -SO ₂ -or -SO-, wherein R _b and R _c are each independently hydrogen or C1-C30 alkyl;
a, b, c and d are each independently an integer from 1 to 3;
e and f are each independently an integer from 1 to 30. According to claim 1,
In Formula 1, R ₁ to R ₄ are each independently hydrogen or C1-C10 alkyl;
e and f are each independently an integer of 1 to 20 organic semiconductor polymer. According to claim 1,
Ar ₁ and Ar ₂ of Formula 1 are each independently any one selected from the following structural formula:

In the above structural formula, R ₁₄ to R ₁₈ are each independently hydrogen or C1-C20 alkyl, Z ₃ to Z ₇ are each independently O, S, Se or NR _d , where R _d is hydrogen or C1-C20 alkyl am. The method of claim 1,
Ar ₃ and Ar ₅ of Formula 2 are each independently any one selected from the following structural formula.

In the above structural formula, Z ₆ to Z ₈ are each independently O, S or Se, and R ₁₇ to R ₂₁ are each independently hydrogen or C1-C10 alkyl. The method of claim 1,
An organic semiconductor polymer represented by the following formula (3):
[Formula 3]

In Formula 3,
R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;
Z ₁ and Z ₂ are each independently S or Se;
Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;
Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;
Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;
D ₁ and D ₂ are each independently a single bond, -C(O)NR _b - or -NR _c C(O)-, wherein R _b is R _c are each independently hydrogen or C1-C30 alkyl;
a, b, c and d are each independently an integer from 1 to 3;
e and f are each independently an integer from 1 to 20;
n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1. In claim 5,
In Formula 3, R ₁ to R ₄ are each independently hydrogen or C1-C5 alkyl;
R ₅ to R ₁₃ are each independently hydrogen or C5-C20 alkyl. In claim 5,
Ar ₁ and Ar ₂ of Formula 3 are each independently an organic semiconductor polymer represented by the following structural formula:

In the above structural formula, R ₁₄ is hydrogen or C 1 -C 10 alkyl, and Z ₃ is S or Se. In claim 5,
Ar ₃ and Ar ₅ of Formula 3 are each independently any one selected from the following structural formula.

In the above structural formula,
Z ₆ , Z ₇ and Z ₈ are each independently S or Se, and R ₁₇ to R ₂₁ are each independently hydrogen or C1-C5 alkyl. In claim 5,
Formula 3 is an organic semiconductor polymer represented by Formula 4 below.
[Formula 4]

In Formula 4,
R ₁ to R ₄ are each independently hydrogen or C1-C20 alkyl;
R ₅ to R ₉ are each independently hydrogen or C 1 -C 20 alkyl;
Z ₁ , Z ₂ , Z ₁₁ , Z ₁₂ and Z ₁₃ are each independently S or Se;
Ar ₁ and Ar ₂ are each independently C3-C20 heteroarylene;
a, b, c and d are each independently an integer from 1 to 3;
s is an integer from 1 to 20;
n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1. An organic compound represented by the following formula (3) comprising the step of preparing an organic semiconductor polymer represented by the following formula (3) by polymerizing a monomer represented by the following formula (11), a monomer represented by the following formula (12), and a monomer represented by the following formula (13) A method for producing a semiconductor polymer.
[Formula 3]

[Formula 11]

[Formula 12]

[Formula 13]

In Formula 3 and Formula 11 to Formula 13,
X ₁ to X ₄ are each independently halogen;
R ₁ to R ₁₃ are each independently hydrogen or C1-C30 alkyl;
R ₂₂ to R ₂₄ are each independently hydrogen or C1-C30 alkyl;
Z ₁ and Z ₂ are each independently S or Se;
Ar ₁ and Ar ₂ are each independently C3-C30 heteroarylene;
Ar ₃ and Ar ₅ are each independently a single bond, C6-C30 areylene or C3-C30 heteroarylene;
Ar ₄ is a single bond, C6-C30 arylene or C3-C30 heteroarylene;
D ₁ and D ₂ are each independently a single bond, -C(O)NR _b - or -NR _c C(O)-, wherein R _b is Rc each independently hydrogen or C 1 -C 30 alkyl;
a, b, c and d are each independently an integer from 1 to 3;
e and f are each independently an integer from 1 to 20;
n and m are each independently a real number greater than 0 and less than 1 as a mole fraction, and n+m=1. An organic electronic device comprising the organic semiconductor polymer of any one of claims 1 to 10. 12. The method of claim 11,
The organic electronic device may be a liquid crystal display device, an organic light emitting display device, an organic transistor, an organic solar cell, or an organic sensor. delete delete

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