KR102198410B1 - New compounds for eco-friendly organic electronic device, composition and eco-friendly organic electronic device - Google Patents

Abstract

The present invention relates to a novel compound, composition and an eco-friendly organic electronic device for an eco-friendly organic electronic device, and to a novel fullerene derivative that can be processed in an eco-friendly solvent, a composition for an organic electronic device including the same, and an organic electronic device.

Description

New compounds, compositions and eco-friendly organic electronic devices for eco-friendly organic electronic devices {NEW COMPOUNDS FOR ECO-FRIENDLY ORGANIC ELECTRONIC DEVICE, COMPOSITION AND ECO-FRIENDLY ORGANIC ELECTRONIC DEVICE}

The present invention provides a novel compound capable of processing in an eco-friendly solvent, a composition including the same, and an eco-friendly organic electronic device.

For the commercialization of organic solar cells, it is necessary to improve various stability of the device (light, heat, mechanical, moisture, oxidation, etc.). Since it is based on organic materials that have the advantage of being light and bendable, the possibility of application to flexible and wearable devices is very high.

Most of the photoactive layers of organic solar cells are manufactured through spin-coating using a halogenated solvent. Among non-halogen solvents, organic solar cells using solvents such as MeTHF or xylene, which are called green solvents, have been reported, but these solvents are still toxic solvents, and these toxic solvents are organic solar cells due to industrial regulations. It is difficult to use in mass production for commercialization.

In order to commercialize an organic solar cell, it is necessary to develop an eco-friendly organic solar cell based on an eco-friendly solvent process that is friendly to workers, inexpensive solvent treatment costs, and less adversely affects the environment. Since most of the materials used in the photoactive layer of organic solar cells are soluble in organic solvents and insoluble in ethanol/water, which are eco-friendly solvents, solution processing using eco-friendly solvents is not possible in the first place.

To overcome this, a method of introducing an element with a charge to the side chain to dissolve a photoactive material in an eco-friendly solvent having a polarity such as water has been reported. However, as the charges formed in the photoactive layer are trapped here, it is used as a solar cell device. There is a problem with low performance. As another method, research has been reported to improve efficiency by making a photoactive layer material into an emulsion form using water and an organic solvent, but a toxic organic solvent is still used.

The present invention is to provide a novel compound that has improved solubility in water and alcohol, which are eco-friendly solvents, can be processed in an eco-friendly solvent, and can provide an eco-friendly organic electronic device.

The present invention is to provide a composition for an organic electronic device, which can be prepared with an eco-friendly solvent, and includes a novel compound according to the present invention.

The present invention is to provide an eco-friendly organic electronic device that can be manufactured by an eco-friendly solution process using the composition for an organic electronic device according to the present invention and has improved electrical characteristics and performance.

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

According to an embodiment of the present invention, it is represented by the following Chemical Formula 1, and relates to a compound having an oligoethylene glycol-based substituent.

[Formula 1]

(Here, fullerene is selected from C60 to C860 fullerene moieties,

Ar is selected from substituted or unsubstituted phenyl and thienyl,

R ¹ is -C ₁ -C ₂₀ alkyl-,

R ² to R ⁶ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ to C _{20 It} is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ² to R ⁶ is an oligoethylene glycol-based substituent.),

및

(R⁹ 및 R¹⁰은 각각 수소 또는 C₁~C₁₀ 알킬기이고, n은 0 내지 20의 정수이고, n' 및 m'은, 각각 1 내지 20의 정수에서 선택된다.)에서 선택된다. The oligoethylene glycol-based substituent group, -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n and m are integers of 1 to 20),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n is an integer of 0 to 20, and n'and m'are each selected from an integer of 1 to 20.).

및

(R⁹ 및 R¹⁰은 각각 수소 또는 C₁~C₅ 알킬기이고, n은 0 내지 5의 정수이고, n' 및 m'은, 1 내지 10의 정수)에서 선택되는 것일 수 있다.According to an embodiment of the present invention, R ¹ is -C ₁ to C ₁₀ alkyl-, and R ² to R ⁶ are each hydrogen, a C ₁ to C ₁₀ alkyl group, -OC ₁ ~C ₁₀ alkyl group And an oligoethylene glycol-based substituent (however, at least one of R ² to R ⁶ is an oligoethylene glycol-based substituent), and the oligoethylene glycol-based substituent, -(OCH ₂ CH ₂ ) _n -OR ^7, -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₅ alkyl group, n and m are integers of 1 to 10),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₅ alkyl group, n is an integer of 0 to 5, and n'and m'are an integer of 1 to 10).

According to an embodiment of the present invention, the fullerene derivative may be represented by the following Chemical Formula 1-1.

[Formula 1-1]

(R⁹ 및 R¹⁰은, 각각 수소 또는 C₁~C₁₀ 알킬기이고, n' 및 m'은, 1 내지 10의 정수)에서 선택된다.)(Where, R ³ to R ⁵ is -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n and m are integers of 1 to 10) and

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₁₀ alkyl group, and n'and m'are selected from integers of 1 to 10).)

According to an embodiment of the present invention, the fullerene may be selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720 and C860.

According to an embodiment of the present invention, the compound may be soluble in a solvent including water, alcohol or both.

According to an embodiment of the present invention, the solubility of the compound in a solvent including water, alcohol or both may be 1 mg/ml or more at 25°C.

According to an embodiment of the present invention, the alcohol may be an alcohol having 1 to 4 carbon atoms.

According to an embodiment of the present invention, the solvent is a mixture of alcohol and water, and the volume ratio of water in the mixture may be greater than 0 to 80% by volume.

According to an embodiment of the present invention, at least one of the compounds represented by Formula 1 according to the present invention; And a solvent; It relates to a composition for an organic electronic device comprising a.

According to an embodiment of the present invention, the composition for an organic electronic device may include a solvent including water, alcohol, or both.

According to an embodiment of the present invention, the composition for an organic electronic device may further include a compound represented by Formulas 2 to 4 below.

[Formula 2]

(Where n is an integer of 1 to 1000, m is an integer of 1 to 30, X is S, Se or O, and R ¹¹ and R ¹² are each selected from hydrogen, halogen or C ₁ to C ₁₀ alkyl .)

[Formula 3]

(Wherein, R ¹³ to R ¹⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ to C ₂₀ is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent.), R is each hydrogen, a C ₁ to C ₂₀ alkyl group, and It is selected from halogen, n is an integer of 1 to 1000, and the oligoethylene glycol-based substituent is as defined above.)

[Formula 4]

(Wherein, R ¹³ to R ¹⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ ~ C _{20 It} is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent), n is an integer of 1 to 1000, and the oligoethylene glycol The system substituents are as defined above.)

According to an embodiment of the present invention, the mixing ratio of the compound represented by Chemical Formulas 2 to 4 to the compound of claim 1 may be a mass ratio of 1: 0.001 to 20 (w:w).

According to an embodiment of the present invention, an active layer comprising at least one of the compounds represented by Formula 1 according to the present invention; It relates to an organic electronic device comprising a.

According to an embodiment of the present invention, the active layer may have a thickness of 1 nm or more.

According to an embodiment of the present invention, the organic electronic device may be an organic solar cell, an organic field effect transistor, a memory device, or a photosensor.

According to an embodiment of the present invention, the organic solar cell may be an organic solar cell of an inverted type or an all-polymer organic solar cell of a normal type.

According to an embodiment of the present invention, dissolving at least one compound represented by Formula 1 according to the present invention in a solvent to form a coating composition; And coating the coating composition on a substrate. Including, and the solvent is water, alcohol, or a method for manufacturing an organic electronic device containing both.

According to an embodiment of the present invention, the coating composition may be to dissolve the compound at a temperature of room temperature or higher.

According to an embodiment of the present invention, the solvent is a mixture of alcohol and water, and the volume ratio of water in the mixture may be greater than 0 to 80% by volume.

According to an embodiment of the present invention, the substrate is an inorganic oxide thin film or cross-linked poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (cross-linked poly-(3,4-ethylenedioxythiophene) :poly(styrenesulfonate); PEDOT:PSS) may be a thin film.

The present invention introduces a hydrophilic oligoethylene glycol side chain, so that it is well dissolved in an eco-friendly polar solvent, so that a solution process is possible, and a solution process can provide a novel compound applied as an organic conductive material capable of forming a photoactive layer thin film. .

The present invention can provide a composition for an eco-friendly organic electronic device in which a solvent harmful to the human body used in an existing solution process, for example, a halogen organic solvent, is replaced with an eco-friendly solvent. In addition, the present invention can provide an all-polymer organic solar cell having a regular structure by using a solution process using a hydrophilic solvent.

The present invention can provide an eco-friendly organic electronic device having stability against an external environment, for example, high atmospheric stability, and maximizing efficiency by applying the novel compound according to the present invention.

The present invention can provide an eco-friendly organic electronic device, for example, an eco-friendly organic solar cell with improved high efficiency and electrical characteristics by using a novel compound.

1 is an exemplary diagram illustrating a device structure of a PSC having an inverted structure and a normal structure manufactured according to an embodiment of the present invention.
2 shows the JV curve and (b) EQE plots under (a) AM 1.5G and 100 mW cm ^-2 light emission of the device of the inverted structure PSC manufactured according to an embodiment of the present invention.
3 is a 2D-GIXS pattern of films of (a) PCBO12, (b) PCBO15 and (c) PCBO27 according to an embodiment of the present invention, (d) in-plane and (e) out-of-plane line It shows the analysis result of morphology according to -cut profiles.
Figure 4 is a 2D of a film of a mixture of (a) PPDT2FBT-A:PCBO12, (b) PPDT2FBT-A:PCBO15 and (c) PPDT2FBT-A:PCBO27 of a device of an inverted structure PSC prepared according to an embodiment of the present invention -GIXS pattern, showing the analysis results of morphology according to (d) in-plane and (e) out-of-plane line-cut profiles.
5 shows the evaluation results of the atmospheric stability of the structured PSC prepared according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express a preferred embodiment of the present invention, which may vary depending on the intention of users or operators, or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the contents throughout the present specification. The same reference numerals in each drawing indicate the same members.

Throughout the specification, when a member is said to be positioned "on" another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components.

Hereinafter, a novel fullerene derivative of the present invention will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these examples and drawings.

The present invention relates to a novel compound having an OEG (oligoethlene glygol) side chain, and according to an embodiment of the present invention, the compound has water-soluble, which is soluble in an aqueous solvent, and water, Solution process is possible in eco-friendly solvents such as alcohol.

According to an embodiment of the present invention, the present invention may provide a compound capable of improving processability and performance of an organic electronic device by introduction of the hydrophilic OEG side chain. More specifically, the compound may be a fullerene derivative represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1, fullerene may be selected from C60 to C860 fullerene moieties. For example, the fullerene may be selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720, and C860.

Ar may be selected from substituted or unsubstituted phenyl and thienyl. The substitution may be made by at least one substituent selected from a C ₁ -C ₂₀ alkyl group, a C2-C ₂₀ alkylene group and a halogen.

R ¹ may be -C ₁ to C ₂₀ alkyl-, preferably -C ₁ to C ₁₀ alkyl-.

R ² to R ⁶ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ to C _{20 It is selected from an} alkyl group and an oligoethylene glycol-based substituent shown below, and at least one of R ² to R ⁶ is an oligoethylene oxide glycol-based substituent.

및

(R⁹ 및 R¹⁰은 각각 수소 또는 C₁~C₁₀ 알킬기이고, n은 0 내지 20의 정수이고, n' 및 m'은, 각각 1 내지 20의 정수에서 선택된다.The oligoethylene glycol-based substituent group, -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n and m are integers of 1 to 20),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n is an integer of 0 to 20, and n'and m'are each selected from an integer of 1 to 20.

및

(R⁹ 및 R¹⁰은, 각각 수소 또는 C₁~C₅ 알킬기이고, n은 0 내지 5의 정수이고, n' 및 m'은, 1 내지 10의 정수이다)에서 선택되는 것일 수 있다. Preferably, the R ² to R ⁶ are each hydrogen, a C ₁ to C ₁₀ alkyl group, -OC ₁ ~ C ₁₀ is selected from an alkyl group and an oligoethylene glycol-based substituent, the oligoethylene glycol-based substituent is -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a -C ₁ to C ₅ alkyl group, n and m are integers of 1 to 10) ),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₅ alkyl group, n is an integer of 0 to 5, and n'and m'are an integer of 1 to 10).

More preferably, the fullerene derivative may be represented by the following Chemical Formula 1-1.

[Formula 1-1]

및

(R⁹ 및 R¹⁰은 각각 수소 또는 -C₁~C₁₀ 알킬이고, n' 및 m'은, 1 내지 10의 정수이다)에서 선택된다.)Here, R ³ to R ⁵ are -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or C ₁ to C ₁₀ alkyl, n and m are integers of 1 to 10),

And

(R ⁹ and R ¹⁰ are each hydrogen or -C ₁ to C ₁₀ alkyl, and n'and m'are integers of 1 to 10).)

According to an embodiment of the present invention, the compound may be soluble in a solvent including water, alcohol or both. For example, the solubility is in atmospheric conditions and 0° C. or higher; Above room temperature; 30° C. or higher; 50° C. or higher; 70° C. or higher; Or it may be dissolved in the solvent at a temperature of 70 ℃ to 100 ℃. For example, 0.1 mg/ml or more at 25° C. for a solvent containing water, alcohol or both; 1 mg/ml or more; 5 mg/ml or more; 10 mg/ml or more; Or, it may have a solubility of 1 mg/ml　 to 250 mg/ml.

The alcohol may be an alcohol having 1 to 4 carbon atoms, and preferably an alcohol having 1 to 2 carbon atoms.

When the water and alcohol are mixed, the volume ratio of water in the solvent mixture is greater than 0% to 80% by volume; 5% to 60% by volume; 10% to 50% by volume; Alternatively, it may be 15% to 40% by volume.

The present invention relates to a composition for an organic electronic device comprising the compound according to the present invention, and according to an embodiment of the present invention, the composition for an organic electronic device can be processed in an eco-friendly solvent such as water, alcohol, etc. It is an eco-friendly composition. The compound is included in an amount of 1 to 99 parts by weight based on 100 parts by weight of the composition, and may include a residual amount of a solvent. The solvent may contain water, alcohol, or both. Preferably it may be a mixture of alcohol and water.

According to an embodiment of the present invention, the composition for an organic electronic device is applied to an active layer of an organic electronic device, and may include a polymer receiver including the compound according to the present invention. In addition, the composition for an organic electronic device may further include at least one of a polymer donor compound represented by Chemical Formulas 2 to 4 below.

[Formula 2]

Here, n is an integer of 1 to 1000, m is an integer of 1 to 30, X is S, Se or O, and R ¹¹ and R ¹² are each selected from hydrogen, halogen or C ₁ to C ₁₀ alkyl.

[Formula 3]

[Formula 4]

In Formula 3 and Formula 4, R ¹³ to R ¹⁴ are each, hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ to C ₂₀ is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent. R is each hydrogen, a C ₁ to C ₂₀ alkyl group, and a halogen) Is selected, n is an integer of 1 to 1000, and the oligoethylene glycol-based substituent is as mentioned above.

As long as the polymer donor does not deviate from the object and scope of the present invention, optionally (poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b ']Dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophendiyl]](poly[[4,8 -bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[ 3,4-b]thiophenediyl]] (PTB7)), (poly[[4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5 -b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2 -6-diyl)])(poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6- diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)]) (PTB7-Th), poly(3-hexyl) Silthiophene) (poly(3-hexylthiophene)) (P3HT) and poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta [2,1-b:3,4-b']dithiophene-2,6-diyl]] (Poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl) )-4H-cyclopenta[2,1-b:3,4-b']dithiophene-2,6-diyl]]) (PCPDTBT) may further include at least one selected from the group consisting of.

The polymer acceptor may contain 0.001 to 99 parts by weight based on 100 parts by weight of the composition. The polymer donor may contain 0.001 to 99 parts by weight based on 100 parts by weight of the composition, and may include a residual amount of a solvent. When included within the above content range, the mixed phase of the polymer donor and the fullerene derivative is well formed, and mechanical properties and device efficiency may be improved. If it does not deviate from the object of the present invention, it may further include conventional additives, but is not specifically mentioned in the present specification.

The polymer donor: the ratio of the polymer acceptor is 1: 0.001 to 20 (w:w); 1: 0.001 to 5 (w:w); 1: 0.01 to 5 (w:w); 1: 0.1 to 3 (w:w); 1: 1 to 3 (w:w); Alternatively, it may be 1: 3 to 20 (w:w). When included within the above ratio range, the polymer donor and the polymer carrier mixed phase are well formed, so that mechanical properties are improved, damage potential due to external energy is low, and stable performance can be provided.

The present invention, the active layer comprising the compound according to the present invention; It relates to an organic electronic device comprising a.

The organic electronic device may be an organic solar cell, an organic field effect transistor, a memory device, or an optical sensor.

In one example of the present invention, the organic electronic device may include a substrate; Inorganic thin film, organic thin film or a composite film of both; And an active layer comprising the composition for an organic electronic device according to the present invention; And ternary-polymer solar cells (PSCs) including electrodes. The organic solar cell is an organic solar cell of an inverted type or a normal type, and as long as it does not depart from the scope of the present invention, components and manufacturing processes of each layer are appropriate according to the above-mentioned type. You can choose.

The substrate is a transparent substrate, and includes any one selected from the group consisting of quartz, glass, a glass substrate coated with indium thin oxide (ITO), a silicon substrate, a metal substrate, a gallium arsenide substrate, and a transparent plastic substrate. can do. The transparent plastic substrate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polystyrene (PS), polypropylene (PP), polyimide (PI), polyethylene sulfonate (PES), Group consisting of at least one transparent plastic substrate selected from the group consisting of polyoxymethylene (POM), polyetheretherketone (PEEK), polyethersulfone (PES), aromatic polyester, polyimide, and polyetherimide (PEI) It may include at least one selected from, but is not limited thereto.

The inorganic thin film or organic thin film may be formed on the substrate, and may be applied without limitation, saying that it forms an electron transport layer or a hole transport layer applicable to an organic solar cell, and aluminum tris (8-hydroxyquinoline) as an electron transport material )(aluminium tris(8-hydroxyquinoline), Alq3), lithium fluoride (LiF), lithium complex (8-hydroxy-quinolinato lithium, Liq), non-conjugated polymer, non-conjugated polymer electrolyte, conjugated polymer electrolyte, or n-type It may be a metal oxide or the like, and the n-type metal oxide is, for example, TiOx, ZnO, or Cs ₂ CO ₃ . Hole transport materials include polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene sulfide, polyphenylenevinylene, polyindole, and polypyrene. Polycarbazole, polyazulene, polyazepine, polyfluorene, polynaphthalene, poly-(3,4-ethylenedioxythiophene):poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate ); PEDOT:PSS) and a conductive polymer or a crosslinked conductive polymer including at least one selected from the group consisting of polyethylenedioxythiophene, but is not limited thereto.

For example, an inverted type organic solar cell is formed by applying an inorganic thin film/active layer containing a metal oxide-based electron transport material, and an organic thin film/active layer containing a polymer hole transport material is applied. It is possible to form a structure (normal type) organic solar cell. In addition, the organic solar cell of the normal type may be an all-polymer organic solar cell. For example, a normal type organic solar cell is a cross-linked poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (cross-linked poly-(3,4-ethylenedioxythiophene)). :poly(styrenesulfonate); PEDOT:PSS) May contain an organic thin film.

The active layer is formed on the inorganic or organic thin film, the active layer is 1 nm or more; 10 nm or more; 50 nm to 1000 nm; Or 80 nm to 150 nm.

The organic solar cell may further include a metal oxide on the active layer. For example, Ti, Zn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, Pt, Ag, Rh, Cr, V, and combinations thereof It is an oxide of at least one metal selected from the group consisting of, and more specifically, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), zinc tin oxide (Zinc Tin Oxide), gallium oxide ( Ga ₂ O ₃ ), tungsten oxide (WO ₃ ), aluminum oxide, titanium oxide, vanadium oxide (V ₂ O ₅ , VO ₂ , V ₄ O ₇ , V ₅ O ₉ , V ₂ O ₃ ) Molybdenum oxide ( MoO ₃ or MoO _x ), copper oxide (Copper(II) Oxide: CuO), nickel oxide (NiO), copper aluminum oxide (CopperAluminiumOxide: CAO, CuAlO ₂ ), rhodium zinc oxide (ZincRhodiumOxide: ZRO, ZnRh ₂ O ₄ ) , Iron oxide, chromium oxide (CrO ₃ ), bismuth oxide, IGZO (indium-Gallium Zinc Oxide), ZrO _2, etc., but is not limited thereto. Preferably it may be MoO ₃ , WO ₃ , V ₂ O ₅ and CrO ₃ .

The organic solar cell may further include an intermediate layer including an electron transport material on the active layer. The intermediate layer may include a polymer electron transport material.

The electrode includes upper and lower electrodes, and any electrode component applicable to an organic solar cell may be applied without limitation, and the upper electrode is silver (Ag), copper (Cu), gold (Au), and platinum (Pt ), titanium (Ti), aluminum (Al), nickel (Ni), zirconium (Zr), iron (Fe), manganese (Mn), and magnesium (Mg) may contain at least one selected from the group consisting of have. The lower electrode may include Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), Indium Gallium Zinc Oxide (IGZO), Indium Tin Zinc Oxide; ITZO), Ga-doped Zinc Oxide (GZO), Al-doped Zinc Oxide (AZO), F-doped Tin Oxide (FTO), Zinc Oxide (Zinc Tin Oxide; ZTO), Indium Gallium Oxide (IGO), ZnO-Ga ₂ O ₃ , ZnO-A _l2 O ₃ , SnO ₂ -Sb ₂ O ₃ It may contain at least one selected from the group consisting of However, it is not limited thereto.

As an example of the present invention, the organic thin film transistor may include an organic semiconductor layer comprising the composition according to the present invention. For example, the organic thin film transistor may include a substrate, a source-drain electrode, an organic semiconductor layer, an insulating film, and a gate electrode.

The organic thin film transistor may be manufactured with a configuration and method applied in the technical field of the present invention, and is not particularly limited unless it deviates from the object of the present invention.

The gate electrode, the source electrode, and the drain electrode may include gold (Au), silver (Ag), aluminum (Al), nickel (Ni), and indium tin oxide (ITO). For example, the organic semiconductor layer may be manufactured by a screen printing method, a printing method, a spin coating method, an ink spray method, or the like.

After the formation of the organic semiconductor layer, it may be heat-treated at 50° C. to 300° C. in a vacuum or nitrogen, argon, or air atmosphere for 1 minute to 100 minutes.

The organic semiconductor layer forms an organic semiconductor film of the composition, and the thickness of the organic semiconductor film is 1 nm or more; 10 nm or more; 50 nm to 1000 nm; Or 80 nm to 150 nm.

The organic thin film transistor may be of a top contact type in which source and drain electrodes are positioned on the organic semiconductor layer or a bottom contact type in which source and drain electrodes are formed under the organic semiconductor layer.

The present invention relates to a method of manufacturing an organic electronic device, according to an embodiment of the present invention, comprising: dissolving the compound according to the present invention in a solvent to form a coating composition; And coating the coating composition on the substrate; may include.

The step of forming the coating composition may include a temperature of room temperature or higher with the compound according to the present invention; 30° C. or higher; 50° C. or higher; 70° C. or higher; Alternatively, it may be dissolved by stirring and/or ultrasonic treatment at a temperature of 70°C to 100°C. The coating composition may be dissolved together with the ingredients added to the active layer, or may be mixed with a solution in which these are dissolved in another solvent. The solvent, as mentioned above, is an environmentally friendly solvent, and may be, for example, water, alcohol, or a mixture of both.

The substrate is a substrate on which an active layer is formed according to an organic electric device, and may be, for example, an electrode layer, an inorganic thin film, an organic thin film, or a composite film of both.

The coating may include a spray coating method, a dip coating method, a gravure coating method, a reverse offset coating method, a screen printing method, a slot-die coating method and a nozzle printing method, a dry transfer printing method, and a spin coating method. The method, ink jetting method, etc. can be applied.

It may further include drying after the coating step.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

However, the following examples are for illustrative purposes only, and the contents of the present invention are not limited to the following examples.

matter

(1) PCBM (Phenyl-C61-butyric acid methyl ester, 99%) was purchased from "NanoHoldings, Inc.," and used as received.

(2) PPDT2FBT-A(poly[(2,5-bis(1,3-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)propan-2-yloxy)phenylene)-alt- as a polymer donor (5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)]) means "Nguyen, TL; Leep, C.; Kirn, H. ; Kim, Y.; Lee, W.; Oh, JH; Kim, BJ; Woo, HY, Ethanol-Processable, Highly Crystalline Conjugated Polymers for Eco-Friendly Fabrication of Organic Transistors and Solar Cells. Macromolecules 2017, 50, 4415- 4424."

(3) PNDIT-F3N (structural formula or name) is “J. Am. Chem. Soc. 2016, 138, 2004 2013” was synthesized by reference.

Manufacturing example

[Scheme 1]

Preparation Example 1: Synthesis of 1,3-bis (3,6,9-trioxadecanyl) glycol (1,3-bis (3,6,9-trioxadecanyl) glycerol) (1)

According to Scheme 1, triethylene glycol monomethyl ether (50 g, 0.31 mol) was stirred at 100° C. in N ₂ atmosphere in a 500 mL two neck round bottom flask.

Upon reaching 100° C., Na (2.4 g, 0.11 mol) is slowly added piece by piece. It was kept at 100° C. for 1 hour in order to remove moisture in the reactant before adding Na, and stored in Na in mineral oil before cutting, and Na was added into the flask at intervals of 5 min.

After the reaction mixture was cooled to 80° C. and epichlorohydrin (9.25 g, 0.11 mol) was added dropwise, the temperature was raised to 100° C. and stirred for 12 h. After cooling to room temperature, DCM (200 mL) was added to dissolve the product, and the brownish solid was removed by filtration under reduced pressure through Celite. The crude product was purified by distillation to obtain a clear liquid product (6: 17 g, 29%). The ¹ H NMR of the product is as follows.

¹ H NMR (400 MHz, CDCl ₃ ): ?3.99-3.92 (m, 1H), 3.67-3.60 (m, 20H) 3.57-3.45 (m, 8H) 3.36 (s, 6H).

[Scheme 2]

Preparation Example 2: Synthesis of OEG tosylates (2a-c)

OEG-substituted tosylates (2a-c) are described in "Jung, SH; Kim, HJ, Supramolecular functionalization of single-walled carbon nanotubes with uncharged water-soluble porphyrins. J. Porphyrins Phthalocyanines 2008, 12, 109 -115." And "Freudenberg, J.; Kumpf, J.; Schafer, V.; Sauter, E.; Worner, SJ; Brodner, K.; Dreuw, A.; Bunz, UHF, Water-Soluble Cruciforms and Distyrylbenzenes: Synthesis, Characterization. , and pH-Dependent Amine-Sensing Properties. J. Org. Chem. 2013, 78, 4949-4959".

According to Scheme 2, NaOH (9.32 g, 0.21 mmol) was dissolved in THF (150 mL) and deionized (DI) water (40 mL) under N ₂ in a 500 mL two neck round bottom flask, respectively. Triethylene glycol monomethyl ether (8.54 g, 42 mmol), tetraethylene glycol monomethyl ether (9.33 g 42 mmol) and 1,3-bis (3,6,9-tri Oxadecanyl) glycerol (1,3-bis (3,6,9-trioxadecanyl) glycerol, (6), 20.0 g, 42 mmol)) was used as a starting material for the synthesis of 2a, b, and c, respectively. , NaOH solution was added to separate.

The reaction mixture was cooled to 0 °C, and p-toluenesulfonyl chloride (5.95 g, 31 mmol) dissolved in THF (50 mL) was added dropwise to each mixture. After 3 h hours, the organic compound was extracted with DCM, the remaining solution was washed with brine, moisture was removed with MgSO4, and evaporated under reduced pressure to obtain a clear oil product 2a-c (2a: 12.7 g, 95%, 2b: 14.3 g , 94%, 2c: 25.5 g, 91%) was obtained.

2a: ¹ HNMR (400 MHz, CDCl ₃ ): δ7.81 (d, 2H), 7.35 (d, 2H) 4.16 (t, 2H) 3.70 (t, 2H) 3.62-3.54 (m, 6H) 3.54-3.52 (m, 2H) 3.37 (s, 3H) 2.45 (s, 3H).

2b: ¹ HNMR (400 MHz, CDCl ₃ ): δ7.65 (d, 2H), 7.22 (d, 2H) 4.00 (t, 2H) 3.57-3.35 (m, 14H) 3.20 (s, 3H) 2.29 (s , 3H).

2c: ¹ HNMR (400 MHz, CDCl ₃ ): δ7.82 (d, 2H), 7.33 (d, 2H) 4.68 (qui, 1H) 3.65-3.50 (m, 28H) 3.37 (s, 6H) 2.43 (s , 3H).

Preparation Example 3: Synthesis of 3,4,5-OEG-benzoic acid methyl esters (3a-c)

3,4,5-OEG-benzoic acid methyl esters (3,4,5-OEG-benzoic acid methyl esters, 3a-c) are "Jung, SH; Kim, HJ, Supramolecular functionalization of single-walled carbon nanotubes with uncharged water. -soluble porphyrins. J. Porphyrins Phthalocyanines 2008, 12, 109-115." And "Freudenberg, J.; Kumpf, J.; Schafer, V.; Sauter, E.; Worner, SJ; Brodner, K.; Dreuw, A.; Bunz, UHF, Water-Soluble Cruciforms and Distyrylbenzenes: Synthesis, Characterization. , and pH-Dependent Amine-Sensing Properties. J. Org. Chem. 2013, 78, 4949-4959".

More specifically, referring to Scheme 2, OEG tosylate 2a-c (27.6 mmol, 2a: 8.8 g, 2b: 10 g, 2c: 14.9 g) was added to a 250 mL 3-neck round bottom flask to remove residual moisture. In order to be vacuum dried. Next, anhydrous DMF (dimethylformamide, 50 mL) was added to each reaction flask, followed by K ₂ CO ₃ (12.2 g, 88.3 mmol), KI (4.6 g, 27.6 mmol) and methyl 3,4,5-tri Hydroxybenzoate (methyl 3,4,5-trihydroxybenzoate, 1 g, 5.52 mmol) was added. The reaction mixture was refluxed overnight under N ₂ . The solution was poured into DCM (~200 mL) and washed with DI water (~50 mL). The organic layer was washed several times with 50 mL brine, and water was removed with MgSO ₄ . After removing MgSO ₄ by filtration, the organic solvent was removed by evaporation under reduced pressure, and a colorless oily residue (3a: 1.3 g, 37%, 3b: 1.5 g, 36%, 3c: 3.9 g, 33%) was obtained. .

3a: MALDI-TOF MS: calculated for C ₂₉ H ₅₀ O ₁₄ 622.7; found: 645.2 g mol ^-1 (Na ⁺ )

3b: MALDI-TOF MS: calculated for C ₃ 5H ₆₂ O ₁₇ 754.9; found: 777.4 gmol ^-1 (Na ⁺ )

3c: MALDI-TOF MS: calculated for C ₅₉ H ₁₁₀ O ₂₉ 1283.5; found: 1306.1 gmol ^-1 (Na ⁺ )

Preparation Example 4: Synthesis of 3,4,5-OEG-benzyl alcohol (4a-c)

Referring to Scheme 2, 2.65 mmol of 3a-c (3a: 1.6 g, 3b: 2 g and 3c: 3.4 g) was dissolved in dry THF (50 mL) under N ₂ gas in a 100 mL three neck round bottom flask. LiAlH ₄ solution (2.0 M in dry THF, 2 mL) was added dropwise into the solution. The mixture was stirred at room temperature overnight, and the remaining lithium aluminum hydride was quenched by slowly adding DI water at 0 °C. The product was diluted in 200 mL of DCM, and the lithium salt was filtered, followed by washing with DI water and brine (~50 mL). The organic layer was filtered after removing moisture with MgSO ₄ and collected under reduced pressure to obtain a colorless oil 4a-c (4a: 1.5 g, 97%, 4b: 1.7 g, 92%, 4c: 3.2 g, 97%).

4a: MALDI-TOF MS: calculated for C ₂₈ H ₅₀ O ₁₃ 594.7; found: 616.9 gmol ^-1 (Na ⁺ )

4b: MALDI-TOF MS: calculated for C ₃₄ H ₆₂ O ₁₆ 726.9; found: 733.0 gmol ^{-1 (} Li ⁺ )

4c: MALDI-TOF MS: calculated for C ₅₈ H ₁₁₀ O ₂₈ 1255.5; found: 1277.3 gmol ^{-1 (} Na ⁺ )

[Scheme 3]

Example 1: Synthesis of PCBO12 (6a)

(1) Synthesis of [6,6]-phenyl-C61-butyric acid ([6,6]-phenyl-C61-butyric acid (PCBA)(5))

PCBA (5) is "Qu, SX; Li, MH; Xie, LX; Huang, X.; Yang, JG; Wang, N.; Yang, SF, Noncovalent Functionalization of Graphene Attaching [6,6]-Phenyl- C61-butyric Acid Methyl Ester (PCBM) and Application as Electron Extraction Layer of Polymer Solar Cells. ACS Nano 2013, 7, 4070-4081".

More specifically, referring to Scheme 3, PCBM (1 g) was dissolved in toluene (200 mL) in a 500 mL round bottom flask and stirred under N ₂ , HCl (35 wt.% aqueous solution, 50 mL) and acetic acid. (acetic acid, 100 mL) was added. The mixture was refluxed for 12 h, cooled at room temperature, washed with DI water, and then water was removed with MgSO ₄ . After removal of MgSO ₄ , the organic layer was filtered and washed with CS2 to remove MgSO ₄ partially adsorbed on the fullerene. Finally, PCBA was purified by silica gel chromatography using toluene/methanol/acetic acid as an eluent. MALDI-TOF MS:calculated for C ₇₁ H ₁₂ O ₂ 896.9; found: 897.3 gmol ^-1 (M+).

(2) Synthesis of PCBO12 (6a)

The prepared PCBA (5, 300 mg) was dissolved in ODCB (200 mL) at 130° C. for 2 h under N ₂ . After the mixture was cooled to room temperature, 4a (433 mg) and DMAP (18 mg) were added and the mixture was stirred for 15 min to dissolve 4a and DMAP. DCC (92 mg) was added and the mixture was stirred for 3 hours. After purification, a brownish powder of PCBO12 was obtained (140 mg, 29%).

¹ HNMR (400 MHz, CDCl ₃ ): δ7.92 (d, 2H) 7.53 (t, 2H) 7.46 (t, 1H) 6.56 (s, 2H) 4.98 (s, 2H) 4.13 (m, 6H) 3.83- 3.54 (m, 30H) 3.36 (s, 9H) 2.91 (t, 2H) 2.56 (t, 2H) 2.19 (qui, 2H).

MALDI-TOF MS: calculated for C ₉₉ H ₅₀ O ₁₄ 1473.5; found: 1473.8 gmol ^-1 (M+)

Example 2: Synthesis of PCBO15 (6b)

PCBA (5, 300 mg) prepared in Example 1 was dissolved in ODCB (200 mL) at 130° C. for 2 h under N2. The mixture was cooled to room temperature, 4b (530 mg) and DMAP (18 mg) were added, and the mixture was stirred for 15 min. DCC (92 mg) was added and the mixture was stirred for 3 hours. After purification, a brown viscous liquid of PCBO15 (210 mg, 39%) was obtained.

¹ HNMR (400 MHz, CDCl ₃ ): δ7.92 (d, 2H) 7.53 (t, 2H) 7.46 (t, 1H) 6.56 (s, 2H) 4.98 (s, 2H) 4.13 (m, 6H) 3.83- 3.55 (m, 45H) 3.37 (s, 9H) 2.92 (t, 2H) 2.57 (t, 2H) 2.20 (qui, 2H)

MALDI-TOF MS: calculated for C ₁₀₅ H ₇₂ O ₁₇ 1605.7; found: 1606.1 gmol ^-1 (M+)

Example 3: Synthesis of PCBO27 (6c)

PCBA (5, 300 mg) prepared in Example 1 was dissolved in ODCB (200 mL) at 130° C. for 2 h under N ₂ . The mixture was cooled to room temperature and stirred for 15 min to dissolve 4c and DMAP after 4c (914 mg) and DMAP (18 mg) were added. DCC (92 mg) was added and the mixture was stirred for 3 hours. After purification, PCBO27 (430 mg, 60%) as a brown viscous liquid was obtained.

¹ HNMR (400 MHz, CDCl ₃ ): δ7.92 (d, 2H) 7.55 (t, 2H) 7.47 (t, 1H) 6.65 (s, 2H) 4.95 (s, 2H) 4.47 (m, 3H) 3.63- 3.53 (m, 84H) 3.37 (s, 18H) 2.93 (t, 2H) 2.57 (t, 2H) 2.20 (qui, 2H)

MALDI-TOF MS: calculated for C ₁₂₉ H ₁₂₀ O ₂₉ 2134.3; found: 2133.4 gmol ^-1 (M+)

Example 4: Fabrication of eco-friendly organic solar cell devices (eco-PSCs) of inverse structure

As shown in FIG. 1, Eco-PSC was prepared in an inverted architecture (ITO/ZnO/active layer/MoO ₃ /Ag) using a mixture of ethanol and water. More specifically, all processes except for thermal evaporation of MoOx/Ag were performed in atmospheric conditions. The ITO coated glass substrate was sonicated in acetone, DI water and IPA, dried at 80° C. for several hours, and the ZnO layer was treated with UV ozone (10 minutes) before spin coating. The ZnO layer was deposited by spin-coating on an ITO substrate using a ZnO solution, and the coated substrate was annealed at 215° C. for 15 minutes under atmospheric conditions.

The polymer donor PPDT2FBT-A ((Mn=20.5 kDa, Mw=51.5 kDa, polystyrene standards by size exclusion chromatography) and the polymer carrier prepared in the examples were respectively mixed with ethanol/water mixtures (88:12 (v/v) in solubility evaluation 1). ) Or the mixing ratio shown in Table 1 of Solubility Evaluation 2. The concentration of each mixture was 4-5 mgml ^-1 for PPDT2FBT-A, and the optimized PPDT2FBT-A:PCBOs ratio was 1:2.5 (w/ w) (PPDT2FBT-A:PCBO12) and 1:2 (w/w) (PPDT2FBT-A:PCBO15 and PPDT2FBT-A:PCBO27) The mixed solution was stirred at 80°C to 90°C for 1 hour.

Subsequently, the ITO/ZnO substrate was heated at 80° C. to 90° C. for 5 to 10 minutes, and then spin-coated at 3000 rpm for 40 seconds under atmospheric conditions to obtain an active layer having a thickness of 70 nm-90 nm.

Finally, the substrate was placed in an evaporation chamber of high vacuum (<10 ^-6 Torr) for 1 hour, and a MoO ₃ layer (10 nm) and an upper electrode Ag (120 nm) were deposited. The area of the active layer region of the device is 0.09 cm ² . The current-voltage (JV) characteristics of the device were measured under AM 1.5 G solar irradiation under atmospheric conditions.

Example 5: Preparation of eco-friendly organic solar cell devices (eco-PSCs) in regular structure

As shown in Figure 1, ITO / PEDOT: PSS (+0.1 vol% GOPS) / active layer / PNDIT-F3N / An eco-friendly PSC having a regular structure having a structure was prepared.

More specifically, the ITO substrate was subjected to ultrasonic treatment, and after washing with acetone, deionized water and isopropyl alcohol solvent, the substrate was dried in an oven at 80° C. for 20 minutes. Next, the ITO substrate was treated with UV ozone (10 minutes) before spin coating the PEDOT:PSS layer. After preparing a 40 nm-thick PEDOT:PSS layer by spin coating a PEDOT:PSS solution containing 0.1% by volume of a GOPS crosslinking agent on an ITO substrate at 3000 rpm for 40 seconds, the PEDOT: PSS layer was 150 under ambient conditions. The film was completely crosslinked by annealing at DEG C for at least 30 minutes and transferred to a glove box filled with N2.

A mixed solution was prepared by adding the electron donor PPDT2FBT-A and the electron acceptor prepared in the Example to a water/ethanol mixed solvent (88:12 (v/v) in solubility evaluation 1 or the mixing ratio shown in Table 2 in solubility evaluation 2) I did. The mixing ratio of electron donor to electron acceptor is 1:2.5 (w/w)(D:A), and the concentration of electron donor in the mixed solution is 4 mg mL-1. The mixed solution was stirred on a hot plate at 80° C. for 1 hour. This mixed solution was spin-coated on an ITO/PEDOT:PSS substrate at 2000 rpm for 40 seconds. The thickness of the prepared eco-friendly PSC was measured to be 60 ~ 70 nm by AFM measurement, and dried overnight under high vacuum conditions to remove residual solvent. Next, a coating solution in which the PNDIT-F3N polymer was dissolved in methanol with a trace amount of acetic acid was prepared, and under ambient conditions, the coating solution was spin-coated on the active layer at 2000 rpm for 60 seconds. The substrate was placed in an evaporation chamber under high vacuum (<10-6 Torr) for about 1 hour and an Ag electrode having a thickness of 120 nm was deposited. The active area of the fabricated device is 0.164 cm ² by optical microscope.

Solubility measurement

(1) The solubility of the fullerene derivatives prepared in Examples 1 to 4 was measured in 88:12 (v/v) ethanol/water mixed solvent (room temperature), respectively. The solubility gradually increases with the length of the hydrophilic OEG side chains, i.e., PCBO12, PCBO15 and PCBO27 are 11±1, 83±4 and 197±3 mg mL ^-1, respectively.

(2) PCBO12 was shown by measuring the solubility according to the mixing ratio of ethanol and water as shown in Table 1 below.

Water in Co-Solvent
(vol%) Water in Co-Solvent ^a
(mol%) Solubility
(mg mL ^-1 ) PPDT2FBT-A PC ₆₁ BO ₁₂ 0 0 2.3 0.3 5 15 7.8 2.7 10 26 9.3 11.7 15 36 17.2 27.9 25 52 42.9 40.5 35 63 29.8 26.0

Electrical characteristics of eco-friendly organic solar cell devices (eco-PSCs)

PPDT2FBT-A: The thickness of the PCBOs mixed film was measured using an atomic force microscope (AFM, FM, Veeco Dimension 3100 instrument in tapping mode) and a surface profiler (Detak-8, Veeco).

The current density-voltage (JV) characteristics of the device are in mWcm ^-2 , AM 1.5G solar irradiation (100 Peccell Technologies, Inc., PEC-L01, 100 mWcm ^-2 , solar simulator: K201 LAB55, McScience) and atmospheric conditions. Measured by Keithley 2400 SMU. This solar simulator system meets the AAB, ASTM standard class. The intensity of the solar simulator was calibrated using a standard silicon reference cell equipped with a KG-5 visible color filter.

External quantum efficiency (EQE) in a spectroscopic measurement system (K3100 IQX, MacScience, Inc.) equipped with a monochromatic light source of a 300W xenon arc lamp filtered by a monochromator (Newport) and an optical chopper (MC2000, USA) Thorlabs ) Was measured.

The J _sc value was calculated from an EQE meter equipped with an AM 1.5G solar spectrum, and the value coincided with the measured J _sc value within a 5% error range. Electron mobilities of PCBO were measured using a space-charge-limited current (SCLC) method using an electron-only device structure of ITO/ZnO/pristine films of PCBOs/LiF/Al. PCBOs were dissolved in an 88:12 (v/v) ethanol/water mixture and spin coated on the ZnO layer at atmospheric conditions (air).

Current voltage measurements were made in the range of 0 to 8V under the same atmospheric conditions, and the results were fitted by the following Mott-Gurney equation.

J _SCLC = 9εε ₀ μ V ² (8L) ^-3

ε ₀ is the dielectric constant of the free, ε is the dielectric constant of the active layer, μ is the charge-carrier mobility, V is the series resistance V _rs and the built-in potential of (V = V _appl -V _bi -V _rs ) ) V _bi is the potential across the device taking into account the potential loss, and L is the PCBO layer thickness.

result

(1) Electrical characteristics of eco-friendly organic solar cell devices

The results of evaluating the organic solar cell device to which the 88:12 (v/v) ethanol/water mixed solvent was applied are shown in FIG. 2. In FIG. 2, the highest efficiency (1.4%) is shown in the system using PCBO12, which is the least introduced OEG group, as an electron acceptor. This is the highest efficiency among the previously reported efficiency of organic solar cell devices using eco-friendly solvents, and the reason that the efficiency decreases as the OEG side chain increases is that the current density value in the device decreases.

(2) Eco-friendly organic solar cell device performance and charge mobility by fullerene derivative

(a) 88:12 (v/v) Eco-friendly organic solar cell device performance and charge mobility according to fullerene derivatives in an organic solar cell device to which an ethanol/water mixed solvent was applied are shown in Table 2. In Table 2, the shorter the OEG side chain and less running, the better the packing ability between fullerene molecules, and the better the channel for electrons to move, the higher the electron mobility and the higher the current density. have. In fact, in the evaluation of charge mobility, it can be seen that PCBO12 shows the highest charge mobility.

(b) In the organic solar cell device of the regular structure of Example 5, the performance and charge mobility of the eco-friendly organic solar cell device according to the mixing ratio of water are shown in Table 3. In addition, the performance and charge mobility of the organic solar cell device having the inverse structure of Example 4 and the normal structure of Example 5 for Water-25 of Table 2 are compared and shown in Table 4.

Device V oc
( V ) J sc
(mA cm ^-2 ) FF PCE _max
(PCE _avg ^a )
(%) Calculated J sc
(mA cm ^-2 ) Water-10
(10 vol%) 0.76 2.47 0.44 0.83 (0.62) 2.48 Water-15
(15 vol%) 0.76 5.08 0.53 2.05 (1.86) 5.00 Water-25
(25vol%) 0.74 4.80 0.49 1.74 (1.36) 4.63 Water-35
(35 vol%) 0.73 3.86 0.49 1.39 (1.16) 3.77

In Table 3 and Table 4, the same material (electron donor: PPDT2FBT-A, electron acceptor: PCBO12) was used in the photoactive layer to fabricate and compare the performance of eco-friendly organic solar cells with each device structure. Efficiency is shown, and moreover, it is possible to obtain a remarkably high efficiency (PCE = 2.05%) in the normal structure solar cell device compared to the inverse structure (PCE = 1.40%) in the Water-25 device, which has been reported so far. /It is the highest efficiency among ethanol-based organic solar cells.

(3) Morphology analysis results of thin films of fullerene derivatives according to OEG side chain length (GIWAXS)

Referring to FIG. 3, it can be confirmed through GIWAXS (grazing incidence wide angle X-ray scattering) analysis whether there is a difference in the degree of packing between fullerene molecules as the OEG side chain runs shorter. That is, it can be seen that PCBO12 shows the most regular packing in a thin film state, and it can be seen that the same tendency is shown in a mixed film (blend film, photoactive layer, FIG. 4) with PPDT2FBT-A. In other words, the shortest running of the OEG side chain (PCBO12) has a well-aligned packing structure between fullerene molecules, which facilitates the formation of electron transport channels in the mixture.

In addition, when fullerene was added to the pre-polymer organic solar cell, the current density could be improved by forming a mixing phase located at the interface between the polymer electron donor and the polymer electron acceptor. It can be predicted that the electrical properties of the device are improved by helping to separate the charges of the device.

(4) Evaluation of atmospheric stability

The organic solar cell of PPDT2FBT-A: PC ₆₁ BO ₁₂ prepared with the mixed solvent of Water-15 in Table 2 was stored for a certain time in a dark room under atmospheric conditions without a protective capsule, and the value of PCE was measured for each certain time. Referring to FIG. 5, it was confirmed that the organic solar cell of PPDT2FBT-A: PC ₆₁ BO ₁₂ maintains the initial PCE at 95%, which can be confirmed to have excellent atmospheric stability even when exposed to the atmosphere for a period of 270 hours or more.

This excellent atmospheric stability can be predicted to be due to improved interfacial adhesion properties between the hydrophilic active material and the hole/electron transport intermediate layer (i.e., PEDOT: PSS and PNDIT-F3N) in the organic solar cell of the positive structure.

In summary, the present invention can provide three GOE-substituted fullerene mono-adducts that can be utilized in the device manufacturing process using an eco-friendly ethanol/water mixed solvent. have. That is, the optical and electrochemical properties of fullerene derivatives of PCBO12, PCBO15 and PCBO27 having OEG side chains having different structures and lengths, and using the same, can be used to prepare eco-PSCs using an ethanol/water mixed solvent under atmospheric conditions. . PCBO12-based eco-PSCs show the highest PCE of 1.40% compared to the three active layer mixtures. PCBO12-based eco-PSCs, with high device performance, are due to the high electromobility of PCBO12, a single adduct, and enable more densely packed PCBO domains by reduced steric hindrance by short, linear OEG side groups. do. PPDT2FBT-A:PCBO12 has minimal charge recombination and excellent charge transfer characteristics, and moreover, the higher the purity of the PCBO12 and PCBO15 films, the more efficient charge transport is possible. Accordingly, the present invention can provide an aqueous-processable electroactive material having a high carrier mobility suitable for achieving high efficiency eco-PSCs. Moreover, by adopting a normal type device structure for the first time in a water/ethanol process-based organic solar cell, the device performance is dramatically improved (1.40% → 2.05%), and the atmospheric stability is excellent, allowing the initial PCE value to be maintained. have.

As described above, although the embodiments have been described by the limited embodiments and drawings, various modifications and variations are possible from the above description by those of ordinary skill in the art. For example, even if the described techniques are performed in a different order from the described method, and/or the described components are combined or combined in a form different from the described method, or are replaced or substituted by other components or equivalents. Appropriate results can be achieved. Therefore, other implementations, other embodiments, and claims and equivalents fall within the scope of the claims to be described later.

Claims (20)

Represented by the following formula (1), and having an oligoethylene glycol-based substituent, a compound.
[Formula 1]

(Here, fullerene is selected from C60 to C860 fullerene moieties,
Ar is selected from substituted or unsubstituted phenyl and thienyl,
R ¹ is -C ₁ -C ₂₀ alkyl-,
R ² to R ⁶ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ ~ C _{20 It} is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least two of R ² to R ⁶ are oligoethylene glycol-based substituents),
The oligoethylene glycol-based substituent group, -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n and m are integers of 1 to 20),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n is an integer of 0 to 20, and n'and m'are each selected from an integer of 1 to 20.).
The method of claim 1,
R ¹ is -C ₁ ~C ₁₀ alkyl-,
The R ² to R ⁶ are each hydrogen, a C ₁ to C ₁₀ alkyl group, -OC ₁ ~C ₁₀ alkyl group And oligoethylene glycol-based substituents (however, at least three of R ² to R ⁶ are oligoethylene glycol-based substituents),
The oligoethylene glycol-based substituent group, -(OCH ₂ CH ₂ ) _n -OR ^7, -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₅ alkyl group, n and m are integers of 1 to 10),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₅ alkyl group, n is an integer of 0 to 5, n'and m'are an integer of 1 to 10),
compound.
The method of claim 1,
The fullerene derivative is a compound represented by the following formula 1-1.

[Formula 1-1]

(Where, R ³ to R ⁵ is -(OCH ₂ CH ₂ ) _n -OR ⁷ , -O-(CH ₂ ) _n -(OCH ₂ CH ₂ ) _m -OR ⁸ (R ⁷ and R ⁸ are each hydrogen or a C ₁ to C ₁₀ alkyl group, n and m are integers of 1 to 10),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ to C ₁₀ alkyl group, and n'and m'are selected from integers of 1 to 10).)
The method of claim 1,
The fullerene is selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720 and C860,
compound.
The method of claim 1,
Wherein the compound is soluble in a solvent comprising water, alcohol or both,
compound.
The method of claim 1,
The compound, wherein the solubility in a solvent containing water, alcohol or both is 1 mg / ml or more at 25 °C,
compound.
The method of claim 5,
The alcohol is an alcohol having 1 to 4 carbon atoms,
compound.
The method of claim 5,
The solvent is a mixture of alcohol and water,
The volume ratio of water in the mixture is greater than 0 to 80% by volume,
compound.
At least one of the compounds represented by Formula 1 of claim 1; And
menstruum;
Containing,
Composition for organic electronic devices.
The method of claim 9,
The composition for an organic electronic device is to contain a solvent containing water, alcohol or both,
Composition for organic electronic devices.
The method of claim 9,
The composition for an organic electronic device further comprises a compound represented by the following formulas 2 to 4, the composition for an organic electronic device.

[Formula 2]

(Where n is an integer of 1 to 1000, m is an integer of 1 to 30, X is S, Se or O, and R ¹¹ and R ¹² are each selected from hydrogen, halogen or C ₁ to C ₁₀ alkyl .)

[Formula 3]

(Wherein, R ¹³ to R ¹⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ ~ C ₂₀ is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent.), R is hydrogen, a C ₁ ~ C ₂₀ alkyl group and halogen. Is selected, n is an integer of 1 to 1000, and the oligoethylene glycol-based substituent is as defined in claim 1.)

[Formula 4]

(Wherein, R ¹³ to R ¹⁴ are each hydrogen, a C ₁ to C ₂₀ alkyl group, -OC ₁ ~ C _{20 It} is selected from an alkyl group and an oligoethylene glycol-based substituent (however, at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent), n is an integer of 1 to 1000, and the oligoethylene glycol The system substituents are as defined in claim 1.)
The method of claim 11,
The mixing ratio of the compound represented by Chemical Formulas 2 to 4 to the compound of claim 1 is a mass ratio (w:w) of 1: 0.001 to 20,
Composition for organic electronic devices.
An active layer comprising at least one of the compounds represented by Formula 1 of claim 1;
Containing,
Organic electronic device
The method of claim 13,
The active layer, which has a thickness of 1 nm or more,
Organic electronic device.
The method of claim 13,
The organic electronic device is an organic solar cell, an organic field effect transistor, a memory device or an optical sensor,
Organic electronic device.
The method of claim 15,
The organic solar cell is an organic solar cell of an inverted type or an all-polymer organic solar cell of a normal type,
Organic electronic device.
Dissolving at least one compound represented by Formula 1 of claim 1 in a solvent to form a coating composition; And
Coating the coating composition on a substrate;
Including,
The solvent is one containing water, alcohol or both,
Method of manufacturing an organic electronic device.
The method of claim 17,
The coating composition is to dissolve the compound at a temperature of room temperature or higher,
Method of manufacturing an organic electronic device.
The method of claim 17,
The solvent is a mixture of alcohol and water,
The volume ratio of water in the mixture is greater than 0 to 80% by volume,
Method of manufacturing an organic electronic device.
The method of claim 17,
The substrate is an inorganic oxide thin film or cross-linked poly-(3,4-ethylenedioxythiophene):cross-linked poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate); PEDOT:PSS ) Which is a thin film,
Method of manufacturing an organic electronic device.

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