KR101419452B1 - Alkyne bearing polymers in backbone as an charge transport layer for organic electronic devices - Google Patents

Abstract

The present invention provides a conductive polymer containing a triple bond in its main chain. The charge transport layer obtained by applying such a conductive polymer on the electrode by a solution process method and then curing it by heat treatment or light irradiation has a high charge mobility And the organic electronic device having such a charge transport layer has high efficiency.

Description

[0001] The present invention relates to an organic electronic device including a triple bond polymer in a main chain and a charge transport layer,

The present invention relates to a conductive polymer in which a triple bond is contained in a main chain and an organic electronic device manufactured by using such a conductive polymer as a charge transport layer by heat or photopolymerization.

As seen from the organic thin film solar cell (OPV) and the organic light emitting device (OLED), the organic electronic device generally constitutes a device by inserting an active organic layer between two electrodes. An example of a conductive material used for such an active organic layer is disclosed in Korean Patent Publication No. 2011-0062295.

In general, one of the two electrodes is a transparent conducting oxide (TCO) and the other is a metal electrode. In addition, in general, the active organic material is introduced onto the substrate having the transparent conductive film introduced therein. However, when the non-polar active organic material is introduced onto the transparent conductive film having a high polarity,

In general, when indium oxide (ITO) deposited on a glass substrate as a transparent electrode is used as an anode, PEDOT: PSS, WO ₃ , MO ₃ , NiO, V ₂ O ₅ And an electron transport layer composed of TiO ₂ , ZnO, CsCO ₃ or the like is used when the device is composed of an invert structure. However, when PEDOT: PSS is used as an interlayer material, indium oxide is corroded due to strong acidity of PEDOT: PSS, which inhibits the long-term stability of the active organic material.

Inorganic oxide materials also have a disadvantage in that the contact between the inorganic oxide layer and the organic photoactive layer is poor because the interface polarity is different from that of the organic photoactive layer material.

In the Marks group, a monomolecular material with trichlorosilane (-SiCl ₃ ) was synthesized, and an organic layer was formed by hydrolysis and condensation on the surface of indium oxide, (1), 175 (9), 3172, 2005. AW Hains et al., Appl. Mater. & Interfaces. , 2010). In this case, when the thickness of the interlayer material becomes thick, the conductivity is deteriorated.

The Nuyken group synthesized an oxetane group-introduced polymer capable of photo-crosslinking in a side branch, and crosslinked by irradiating with UV in the presence of a photoinitiator to use as a hole transport layer of an organic light emitting device (E. Bacher et .al., Macromolecules, 38 (5), 1640, 2005). In this case, the oxetane group itself has a non-conductive side branch, which has a negative influence on the conductivity of the thin film after crosslinking.

Heeger group introduces a hole transport layer of organic light emitting device by cross-linking perfluorocyclobutane with heat treatment of polymer containing main chain (X. Gong et al., Appl. Phys. Lett., 83 (1), 2003). In this case, the perfluorinated cyclobutane contained in the main chain interferes with the charge transfer through the main chain of the polymer, and thus is not suitable for the production of a thin film which facilitates charge transfer.

Therefore, the development and the process of the conductive polymer which is easy to manufacture the device through the solution process without deteriorating the conductivity are required.

Korean Patent Publication No. 2011-0062295 (published date 2011.06.10)

H. Yan et al., J. Am. Chem. Soc. 127 (9), 3172, 2005 A. W. Hains et al., Appl. Mater. & Interfaces., 2 (1), 175, 2010 E. Bacher et al., Macromolecules, 38 (5), 1640, 2005 X. Gong et. al., Appl. Phys. Lett., 83 (1), 2003

The present invention provides a cured conductive polymer prepared by thermally or photocuring a conductive polymer containing a triple bond in its main chain and capable of maintaining high charge mobility even after crosslinking and a conductive polymer containing a triple bond in its main chain.

The present invention also provides a material for an organic optoelectronic device comprising a conductive polymer comprising a triple bond in the main chain or the cured conductive polymer.

The present invention also provides a charge transport layer comprising the conductive polymer or the cured conductive polymer and an organic electronic device comprising the charge transport layer.

The present invention provides a conductive polymer containing a structure represented by the following general formula (1) in its main chain.

[Chemical Formula 1]

(In the formula 1,

X and Y are independently of each other C ₃ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene,

Wherein said arylene or heteroarylene is optionally substituted with one or more substituents selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, CN, C (O) ) OR, wherein R is C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ heterocycloalkyl, C ₃ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl.

In Formula (1), X or Y may be any one independently selected from the group consisting of compounds represented by the following Chemical Formulas (2) to (12).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

(In the above formulas 2 to 12,

Z is S or Se;

X is CR ₃₁ R ₃₂ , SiR ₃₃ R ₃₄ or NR ₃₅ , and R ₃₁ to R ₃₅ are C ₁ -C ₂₀ alkyl;

R ₁ to R ₁₈ are independently of each other C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₃ -C ₂₀ aryl or C ₃ -C ₂₀ Heteroaryl;

and n ₁ to n ₁₁ are integers of 1 to 100.)

The conductive polymer of formula (1) according to an embodiment of the present invention may be represented by the following formula (13) or (14).

[Chemical Formula 13]

[Chemical Formula 14]

[In the above chemical formula 13 or 14,

Z is S or Se;

X is CR ₃₁ R ₃₂ , SiR ₃₃ R ₃₄ or NR ₃₅ , and R ₃₁ to R ₃₅ are C ₁ -C ₂₀ alkyl;

A and B are independently of each other C ₃ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene;

n ₂₁ and n ₂₂ are integers of 1 to 100.]

In order to increase the efficiency of the organic optoelectronic device containing the crosslinked conductive polymer obtained by curing the conductive polymer according to the present invention, A or B in the above formulas (13) and (14) may be selected from the following structures .

(In the above formula,

Z is S or Se;

R ₄₁ to R ₄₉ are C ₁ to C ₂₀ alkyl.

The term "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention includes both linear and branched forms, and "cycloalkyl" includes not only a single ring system but also substituted or unsubstituted (C7- C30) bicycloalkyl. ≪ / RTI > &Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, and fluorenyl.

"Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5- to 6-membered monocyclic heteroaryl group and a polycyclic heteroaryl group condensed with one or more benzene rings, and may be partially saturated. The heteroaryl in the present invention also includes a form in which at least one heteroaryl is linked by a single bond.

The present invention relates to an organic optoelectronic device material comprising a conductive polymer comprising the structure represented by Formula 1 or a conductive polymer crosslinked by thermal or photo-crosslinking of the conductive polymer (hereinafter referred to as a crosslinked conductive polymer) Lt; / RTI >

The present invention also provides a charge transport layer comprising the conductive polymer or the crosslinked conductive polymer.

The conductive polymer of Formula 1 of the present invention or a crosslinked conductive polymer thereof is a material having a hole transporting property in the case of an organic electronic device having a general structure in which an anode rises on a substrate and an invert organic electronic device Can be selectively used as a material having characteristics of electron transfer.

That is, the conductive polymer of the present invention can be thermally or photo-cured and can be used as a conventional PEDOT: PSS, WO ₃ , MO ₃ , NiO It can be used as an electron transport layer of an invert structure as a hole transport layer.

The layer containing the crosslinked conductive polymer by curing the conductive polymer of the present invention is referred to as a charge transport layer, and therefore, the charge transport layer includes an electron transport layer and an electron transport layer.

The material for an organic optoelectronic device fabricated using the crosslinked conductive polymer may be prepared by first dissolving the conductive polymer of Formula 1 in chlorobenzene, 1,2-dichlorobenzene, chloroform, 1,2-dichloroethane, tetrahydrofuran, Spraying, ink jet, or the like on the organic electronic device before the active organic material is applied after dissolving in an organic solvent capable of dissolving the polymer such as toluene, xylene or the like, Followed by curing by heat treatment or light irradiation. The material for the organic optoelectronic device manufactured by this method can be introduced into the charge transport layer.

More specifically, a solution of a triple bond conductive polymer, which is dissolved in one or more kinds of organic solvents capable of easily dissolving the conductive polymer represented by the formula (1) containing a triple bond in its main chain, is applied on the electrode, the solvent is removed, Can be crosslinked by heat treatment at 170 to 250 ° C or by UV light at 140 nm to 350 nm.

The resistance of the transparent electrode can be increased at a temperature of 300 DEG C or higher, and the characteristics of the triple bonded polymer may be changed due to carbonization. The polymer may be denatured at a wavelength of 140 nm or less, and light crosslinking may not occur at a wavelength of 350 nm or more.

The crosslinking is not particularly limited, but there is a method in air and a method in an inert gas. If necessary, the unreacted portion after crosslinking can be removed by washing in a solvent.

The conductive polymer containing the structure represented by Formula 1 according to the present invention in its main chain contains a triple bond in its main chain. As shown in FIG. 2, when the crosslinked polymer is still conjugated, The crosslinked conductive polymer is insoluble, and thus a second film can be formed thereon without damaging the membrane.

An active layer such as an organic light emitting layer of an organic light emitting device or a photoelectric conversion material of an organic solar cell is introduced onto a charge transport layer in which a conductive polymer according to the present invention is thermally or photocrosslinked and then the next layer is sequentially introduced, Can be completed.

The present invention also provides an organic optoelectronic device including the crosslinked conductive polymer according to the present invention in a charge transport layer.

The present invention provides a conductive polymer comprising a triple bond in the main chain.

The charge transport layer introduced by the heat treatment or light irradiation after the conductive polymer according to the present invention is applied by the solution process has not only high charge mobility but also the work function can be controlled by changing the kind of the monomer of the conductive polymer, A hole transporting layer or an electron transporting layer capable of providing a hole transporting layer.

In addition, since the thin film cured through the reaction between the triple bonds of the conductive polymer of the present invention is insoluble in the organic solvent, when the second thin film using the organic solvent is introduced thereinto, the underlying cured film is not damaged, And it is possible to prevent the poor interface contact caused when the active organic material is introduced into the substrate or the inorganic oxide layer into which the transparent conductive film is introduced.

In addition, organic electronic devices such as an organic photovoltaic device (OPV) and an organic light emitting diode (OLED) in which a crosslinked conductive polymer crosslinked with the conductive polymer according to the present invention is introduced into a charge transport layer can realize high efficiency.

1 is a schematic diagram of a curing process of an electroconductive polymer produced according to an embodiment of the present invention,
FIG. 2 is a schematic view showing a chemical structural change at the time of crosslinking of a charge transport layer fabricated according to a preferred embodiment of the present invention,
FIG. 3 is a UV spectrum of the polymer 1 prepared in Example 1 of the present invention according to the number of cleaning cycles before and after thermal curing,
4 is a UV spectrum of the polymer 3 prepared in Example 3 of the present invention according to the number of cleaning cycles before and after thermal curing,
FIG. 5 is a UV spectrum of the polymer 4 prepared in Example 4 of the present invention according to the number of cleaning cycles before and after thermal curing,
FIG. 6 is a UV spectrum of polymer 5 prepared in Example 5 according to the number of washing cycles before and after thermal curing,
7 is a UV spectrum of the polymer 1 prepared in Example 1 before and after UV curing according to Example 7,
8 is a UV spectrum of the polymer 4 prepared in Example 4 before and after UV curing according to Example 7,
9 is a graph showing the photoelectric characteristics of the organic solar cell device manufactured in Example 8 and Comparative Example 1. FIG.

Hereinafter, the present invention will be described in more detail with reference to Examples.

The present invention is intended to more specifically illustrate the present invention, and the scope of the present invention is not limited to these embodiments.

[Example 1] Synthesis of conductive polymer 1

반응플라스크에 2,7-dibromo-9,9-didecyl-9H-fluorene(1.750 g, 2.895 mmol), 4,7-diethynyl-benzo[2,1,3]thiadiazole(533 mg, 2.895 mmol), Pd(PPh₃)₄(336 mg,10 mol%)와 CuI(111 mg, 20 mol%)을 넣은 후, Et₃N(12 mL)와 THF(24 mL)를 상온에서 넣었다. 질소로 얼렸다 진공 후 녹이는 freeze-thow를 3회 반복하여 반응 용매 중에 산소를 제거한 후, 90도에서 2일 동안 교반하여 중합시킨다. 반응용액을 메탄올에 떨어뜨려 미정제된 검은색의 분말을 얻었다. 미정제된 고분자를 소량의 클로로폼에 다시 녹인 후 600 ml의 메탄올과 아세톤 혼합용매(4/1 부피비)에 침전시킨 후, 하루 동안 교반한 후 필터하였다. 위의 침전을 3회 반복하여 900 mg의 검은 빛이 도는 갈색 고체의 고분자 1을 얻었다.

The reaction flask was charged with 2,7-dibromo-9,9-didecyl-9H-fluorene (1.750 g, 2.895 mmol), 4,7-diethynyl-benzo [2,1,3] thiadiazole (533 mg, 2.895 mmol) (PPh ₃ ) ₄ (336 mg, 10 mol%) and CuI (111 mg, 20 mol%) were added thereto. Et ₃ N (12 mL) and THF (24 mL) were added at room temperature. Freeze-thaw after melting in nitrogen is dissolved in the reaction solvent by repeating freeze-thow three times, and polymerization is carried out by stirring at 90 degrees for 2 days. The reaction solution was dropped into methanol to obtain a crude black powder. The crude polymer was redissolved in a small amount of chloroform and then precipitated in 600 ml of a mixed solvent of methanol and acetone (4/1 by volume), stirred for one day, and filtered. The above precipitation was repeated three times to obtain 900 mg of a dark brown or solid polymer 1.

The molecular weight (Mw) and distribution (PDI, Mw / Mn) of the polymer prepared in all the examples below were measured using a gel permeation chromatograph using a Young-Lin M930 pump using the following method.

The separation column was two PLgel 5mM Mixed-d columns from Varin Corp. The column size was 7.5 mm in diameter and 300 mm in length, the column temperature was 35 ° C, the moving phase was moved at 1.0 ml / min using chloroform, The sample concentration was 1 mg / 1 mL, the sample injection amount was 300 microliters, and a differential refractometer was used as a detector. Standard polystyrene was made by Varian.

 Mw = 12,214, PDI = 1.49.

[Example 2] Synthesis of conductive polymer 2

Dibromo-dithieno [3,2-b: 2 ', 3'-d] silole (209 mg, 0.362 mmol), 4 after that, insert the 7-diethynyl-benzo [2,1,3] thiadiazole (67 mg, 0.362 mmol), Pd (PPh 3) 4 (9 mg, 2 mol%) and CuI (3 mg, 4 mol% ), Et ₃ N (1.5 mL) and THF (3 mL) were added at room temperature. After freeze-thaw was dissolved in nitrogen, the freeze-thaw was repeated 3 times to remove oxygen in the reaction solvent, followed by polymerization at 90 ° C for 3 days with stirring. The reaction solution was dropped into methanol to obtain a crude black powder. The crude polymer was washed with methanol and acetone using Soxhlet, extracted with chloroform, and re-dissolved in methanol to obtain 120 mg of Polymer 2.

Mw = 30,295, PDI = 1.67.

[Example 3] Synthesis of conductive polymer 3

The reaction flask was charged with 4,7-bis (5-bromo-2-thienyl) -2,1,3-benzothiadiazole (183 mg, 0.4 mmol), 2,7-ethynyl-9,9-didecyl-9H- Et ₃ N (1.7 mL) and THF (3.4 mL) were added to the solution at room temperature after addition of Pd (PPh ₃ ) ₄ (46 mg, 10 mol%) and CuI . After freeze-thaw was dissolved in nitrogen, the freeze-thaw was repeated 3 times to remove oxygen in the reaction solvent, and polymerization was carried out by stirring at 90 ° C for 2 days. The reaction solution was dropped into methanol to obtain a crude black powder. The crude polymer is redissolved in a small amount of chloroform, and precipitated in 200 ml of a mixed solvent of methanol and acetone (4/1 by volume). After stirring for one day, the polymer is filtered. The above precipitation was repeated three times to obtain 150 mg of a red solid polymer 3.

Mw = 86,704, PDI = 2.24.

[Example 4] Synthesis of conductive polymer 4

The reaction flask was charged with N-heptadecan-9'-yl-2,7-dibromocarbazole (225 mg, 0.4 mmol), 2,7-ethynyl-9,9-didecyl-9H- After adding PPh ₃ ( ₄ ) (46 mg, 10 mol%) and CuI (15 mg, 20 mol%), Et ₃ N (1.7 mL) and THF (3.4 mL) were added at room temperature. After freeze-thaw was dissolved in nitrogen, the freeze-thaw was repeated 3 times to remove oxygen in the reaction solvent, and polymerization was carried out by stirring at 90 ° for 12 hours. The reaction solution was poured into methanol to obtain an untreated orange-colored polymer. The crude polymer was redissolved in a small amount of chloroform, and precipitated in 200 ml of a mixed solvent of methanol and acetone (4/1 by volume). After stirring for one day, the polymer was filtered. The above precipitation was repeated three times to obtain 4 mg (300 mg) of a dark red solid polymer.

 Mw = 14,019, PDI = 2.58.

[Example 5] Synthesis of conductive polymer 5

5-bromo-3-hexylthiophen-2-yl) thiazolo [5,4-d] thiazole (253 mg, 0.4 mmol), 4,7-diethynyl- (3 mL) was added with Et ₃ N (1.7 mL) and THF (3.4 mg, 0.4 mmol), Pd (PPh ₃ ) ₄ (46 mg, 10 mol%) and CuI mL) was added at room temperature. After freeze-thaw was dissolved in nitrogen, the freeze-thaw was repeated 3 times to remove oxygen from the reaction solvent. The mixture was stirred at 80 ° C for 48 hours to polymerize. The reaction solution was poured into methanol to obtain an untreated orange-colored polymer. The crude polymer was redissolved in a small amount of chloroform and then precipitated in 600 ml of a mixed solvent of methanol and acetone (4/1 by volume), stirred for one day, and filtered. The above precipitation was repeated three times to obtain 70 mg of a purple solid polymer 5 having a blackish light.

Mw = 3,514, PDI = 1.07.

[Example 6] Polymer thin film thermosetting

5 mg of a polymer containing a triple bond is dissolved in 1.0 ml of a chloroform solvent, and then coated on a quartz substrate by spin coating. The formed thin film is heated on a 200 degree heat plate for 30 minutes and then cooled. Then, it is put into a chloroform solvent to wash the hardened or hardened portion of the quartz substrate. After spin coating, heat treatment at 200 ° C, UV is measured at each step of chloroform rinse to check whether the polymer thin film remains. Particularly, chloroform washing is repeated three times to confirm whether or not the polymer is peeled off.

3 to 6 show the UV spectra obtained from the polymer thin film curing task of polymer 1, polymer 3 to polymer 5 synthesized in Example 1 and Examples 3 to 5.

The UV spectrum data of FIGS. 3 to 6 show that the polymer synthesized in Example 1, Example 3 and Example 5 was introduced into a quartz substrate by the method of Example 6 and heat-treated for 30 minutes on a 200 degree heat plate. After the first cleaning with chloroform, the UV spectrum was maintained constant even after the second to third cleaning, and after the thermal curing and the first cleaning, the hardened thin film was not dissolved in the organic solvent It can be seen that the curing has proceeded well.

[Example 7] Polymer thin film UV curing

5 mg of the polymer containing the triple bond is dissolved in 1.0 ml of a chloroform solvent, and then applied to a quartz substrate through spin coating. The resulting thin film is exposed to 1 kW of UV for 10 minutes in an argon atmosphere, and then it is put in a chloroform solvent to wash off the hardened or hardened part of the quartz substrate. After spin coating, after UV curing, UV is measured at each step after washing with chloroform to confirm whether the polymer thin film remains or not.

7 and 8 show the UV spectra obtained by the UV curing process of the polymer thin film of Polymer 1 and Polymer 4, which were synthesized in Example 1 and Example 4, respectively.

The UV spectrum data of FIGS. 7 and 8 show that the polymer synthesized in Example 1 and Example 4 was introduced into a quartz substrate by the method described above and then treated with UV light for 10 minutes. After UV treatment, It can be seen that most of the polymer remained in the thin film subjected to the first cleaning, and the curing progressed well as in the case of the heat curing treatment.

[Comparative Example 1] Invert organic solar cell element fabrication

The glass substrate coated with ITO (Indium Tin Oxide), which is a negative electrode transparent electrode, is soaked in deionized water containing washing solution, and is then washed in an ultrasonic washing machine for 15 minutes. Next, it is washed three times with deionized water, acetone, and IPA (isopropyl alcohol), and then dried in an oven at 130 ° C for 5 hours. The thus cleaned ITO glass substrate is subjected to ultraviolet / ozone treatment for 15 minutes, and then ZnO is coated on the ITO glass substrate to a thickness of 30 nm through a spin coating process. Next, an organic photoactive layer (P3HT: PC ₆₁ BM = 1: 1) is applied on the electron transporting layer through a spin coating method. Then, MoO ₃ (10 nm) and an anode Ag (80 nm) were deposited as a hole transport layer in a vacuum chamber, and IV characteristics of the fabricated device were analyzed to measure the photoelectric conversion efficiency. The results are shown in Table 1 .

[Example 8] Fabrication of Invert organic solar cell device using triple bonded polymer

The glass substrate coated with ITO (Indium Tin Oxide), which is a negative electrode transparent electrode, is soaked in deionized water containing washing solution, and is then washed in an ultrasonic washing machine for 15 minutes. Next, the substrate is washed with deionized water, acetone, and IPA three times, and then dried in an oven at 130 ° C for 5 hours. The thus cleaned ITO glass substrate is subjected to ultraviolet / ozone treatment for 15 minutes, and then ZnO is coated on the ITO glass substrate to a thickness of 30 nm through a spin coating process. After the coating, the heat treatment process is performed at 200 DEG C for 60 minutes, and the device is transferred to a glove box filled with argon to apply the organic electron transport layer. The polymer containing triple bonds is dissolved in chloroform at a concentration of 1 mg / 1 mL and applied on the ZnO layer by spin coating. Then, heat treatment is performed at 200 ^° C for 20 minutes to cure the organic solvent. Next, an organic photoactive layer (P3HT: PC ₆₁ BM = 1: 1) is applied on the charge transport layer through a spin coating method. Then, MoO ₃ (10 nm) and an anode Ag (80 nm) were deposited as a hole transport layer in a vacuum chamber, and IV characteristics of the fabricated device were analyzed to measure the photoelectric conversion efficiency. The results are shown in Table 1 .

The photoelectric conversion characteristics of the organic solar cell device fabricated in Example 8 and Comparative Example 1 Polymer V _OC (V) J _SC (mA / cm ² ) FF PCE (%) Example 7 Polymer 1 0.52 9.69 0.61 3.09 Example 7 Polymer 3 0.51 9.89 0.56 2.86 Example 7 Polymer 5 0.52 10.18 0.56 2.93 Comparative Example 1 - 0.50 9.48 0.54 2.56

Open circuit voltage (V _oc ), short-circuit current density (J _SC ), fill factor (FF), power conversion efficiency (PCE)

As shown in Table 1, the efficiency of the organic solar cell device employing the charge transport layer prepared by curing the conductive polymer of the present invention is higher than that of the organic solar cell device of Comparative Example 1 which does not employ the conductive polymer of the present invention Able to know.

In the present invention, lamination was possible because the conductive polymer was not cured by introducing the photoactive layer on the conductive polymer, and FF was increased at the same time as Jsc was increased in the case of the device in which the cured conductive polymer was introduced. It can be confirmed that the conductive polymer layer improves the interface contact without increasing the resistance between the active layer and the inorganic oxide.

Claims (9)

A conductive polymer comprising a structure represented by the following formula (1) in its main chain.
[Chemical Formula 1]

In Formula 1,
X and Y are independently selected from the compounds represented by the following formulas (2) to (12).
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

(In the above formulas 2 to 12,
Z is S or Se;
X is CR ₃₁ R ₃₂ , SiR ₃₃ R ₃₄ or NR ₃₅ , and R ₃₁ to R ₃₅ are independently of each other C ₁ -C ₂₀ alkyl;
R ₁ to R ₁₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₃ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl;
n ₁ to n ₁₁ are independently an integer of 1 to 100) delete The method according to claim 1,
The conductive polymer represented by Formula 1 is represented by Formula 13 or 14 below.
[Chemical Formula 13]

[Chemical Formula 14]

(In the above formula (13) or (14)
Z is S or Se;
X is CR ₃₁ R ₃₂ , SiR ₃₃ R ₃₄ or NR ₃₅ , and R ₃₁ to R ₃₅ are independently of each other C ₁ -C ₂₀ alkyl;
R ₇ to R ₈ are independently of each other hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ heterocycloalkyl, C ₃ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl;
A and B are independently of each other C ₃ -C ₂₀ arylene or C ₃ -C ₂₀ heteroarylene;
n ₂₁ and n ₂₂ are independently an integer of 1 to 100) The method of claim 3,
A or B is selected from the following structures.

(In the above formula,
Z is S or Se;
R ₄₁ to R ₄₉ are independently of each other C ₁ -C ₂₀ alkyl.) A material for an organic optoelectronic device manufactured using the conductive polymer of claim 1. A material for an organic optoelectronic device, which is produced by using the conductive polymer crosslinked by thermal or photo-crosslinking the conductive polymer according to claim 1. The method according to claim 6,
Wherein the thermal crosslinking is performed at a temperature of 170 to 250 ° C. A charge transport layer comprising the material for organic optoelectronic devices according to claim 5 or 6. An organic optoelectronic device comprising the charge transport layer of claim 8.

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