KR20200074779A - 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 for an eco-friendly organic electronic device, a composition therefor and an eco-friendly organic electronic device. The present invention, more specifically, relates 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 environmentally friendly solvent, a composition comprising the same, and an environmentally friendly organic electronic device.

In order to commercialize the organic solar cell, it is necessary to improve various stability (light, heat, machine, moisture, oxidation, etc.) of the device. Because it is based on an organic material that has the advantage of being lightweight and bendable, it is highly applicable to flexible and wearable devices.

Most of the photoactive layer of the organic solar cell is produced by spin-coating using a halogenated solvent. Among the non-halogen solvents, organic solar cells using a solvent such as MeTHF or xylene called green solvent 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 for 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 worker-friendly, has a low solvent treatment cost, and has little adverse effect on the environment. Most of the materials used in the photoactive layer of the organic solar cell are soluble in an organic solvent and not soluble in ethanol/water, which is an eco-friendly solvent.

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

The present invention is to provide a novel compound that can improve the solubility in water and alcohol, which are environmentally friendly solvents, process in an environmentally friendly solvent, and provide an environmentally friendly organic electronic device.

The present invention is to provide a composition for an organic electronic device that can be manufactured with an eco-friendly solvent and contains the novel compound according to the present invention.

The present invention, by using the composition for an organic electronic device according to the present invention can be manufactured by an environmentally friendly solution process, to provide an environmentally friendly organic electronic device with improved electrical properties and performance.

However, the problems to be solved by the present invention are not limited to the problems mentioned above, and other problems 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]

(Where 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 alkyl groups and oligoethylene glycol-based substituents (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, -(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 ~C ₁₀ alkyl group, n and m are integers from 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 from 0 to 20, and n'and m'are each selected from integers from 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 (wherein 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 from 1 to 10),

And

(R ⁹ and R ¹⁰ are each a hydrogen or C ₁ ~ C ₅ alkyl group, n is an integer of 0 to 5, n'and m', may be selected from 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 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 a C ₁ ~C ₁₀ alkyl group, n and m are integers from 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 containing water, alcohol, or both.

According to an embodiment of the present invention, the compound, the solubility in water, alcohol or a solvent containing both, may be at least 1 mg / ml at 25 ℃.

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 solvents; 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 water, alcohol, or a solvent containing both.

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

[Formula 2]

(Where n is an integer from 1 to 1000, m is an integer from 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 alkyl group and an oligoethylene glycol-based substituent is selected (but at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent.), R are each hydrogen, C ₁ ~ C ₂₀ alkyl group and Selected from halogen, n is an integer from 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 Alkyl group and oligoethylene glycol-based substituent is selected from (but at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent.), n is an integer from 1 to 1000, the oligoethylene glycol 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 and the compound of claim 1 may be 1: mass ratio (w:w) of 0.001 to 20.

According to an embodiment of the present invention, the 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 be one having 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 an optical sensor.

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

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. It includes, and the solvent is water, alcohol, or both of these, relates to a method of manufacturing an organic electronic device.

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

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 one embodiment of the present invention, the substrate is an inorganic oxide thin film or a 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, by introducing a hydrophilic oligoethylene glycol side chain, it is possible to provide a novel compound applied as an organic conductive material that can be dissolved in an environmentally friendly polar solvent, solution process is possible, and a solution process can form 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 a human body used in a conventional solution process, for example, a halogen organic solvent is replaced with an eco-friendly solvent. In addition, the present invention, by using a solution process with a hydrophilic solvent can provide an all-polymer organic solar cell in the form of a crystal structure.

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

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 properties using a novel compound.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms used in the present specification are terms used to appropriately represent a preferred embodiment of the present invention, which may vary according to a user's, operator's intention, or customs in the field to which the present invention pertains. Accordingly, definitions of these terms should be made based on the contents throughout the specification. The same reference numerals in each drawing denote the same members.

Throughout the specification, when one member is positioned “on” another member, this includes not only the case where one member abuts 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 the other component may be further included instead of excluding the other component.

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 oligoethlene glygol (OEG) side chain, and according to an embodiment of the present invention, the compound has water-soluble in water-soluble solvent, water, Solution processing is possible in environmentally friendly solvents such as alcohol.

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

[Formula 1]

In 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 C ₁ -C ₂₀ alkyl group, C2-C ₂₀ alkylene group and halogen.

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

R ² to R ⁶ are each hydrogen, a C ₁ ~C ₂₀ alkyl group, -OC ₁ ~ C _{20 It is selected from} alkyl groups and oligoethylene glycol-based substituents 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 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 ~C ₁₀ alkyl group, n and m are integers from 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 from 0 to 20, and n'and m'are each selected from integers from 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, R ² to R ⁶ are each hydrogen, C ₁ to C ₁₀ alkyl, -OC ₁ ~ C _{10 It} is selected from alkyl groups and oligoethylene glycol-based substituents, the oligoethylene glycol-based substituents, -(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, and n and m are integers from 1 to 10 ),

And

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

According to an embodiment of the present invention, the compound may be soluble in a solvent containing water, alcohol, or both. For example, the solubility may include 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, at least 0.1 mg/ml at 25° C. for solvents containing water, alcohol or both; 1 mg/ml or more; 5 mg/ml or more; 10 mg/ml or more; Or 1 mg/ml to 250 mg/ml.

The alcohol is an alcohol having 1 to 4 carbon atoms, preferably an alcohol having 1 to 2 carbon atoms.

When mixing the water and alcohol, the volume ratio of water in the solvent mixture is greater than 0% by volume to 80% by volume; 5% to 60% by volume; 10% to 50% by volume; Or 15% to 40% by volume.

The present invention relates to a composition for an organic electronic device comprising a 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 environmentally friendly solvent such as water, alcohol, etc. It is an environmentally friendly composition. The compound is contained in 1 to 99 parts by weight with respect to 100 parts by weight of the composition, it may include a residual amount of solvent. The solvent may include water, alcohol, or both. Preferably it can 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 the active layer of an organic electron assister, and may include a polymer receiver comprising a 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 the following Chemical Formulas 2 to 4.

[Formula 2]

Here, n is an integer from 1 to 1000, m is an integer from 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 ~ C ₂₀ alkyl group and an oligoethylene glycol-based substituent (but at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent. R is hydrogen, C ₁ to C ₂₀ alkyl, and halogen, respectively) Selected, n is an integer from 1 to 1000, and the oligoethylene glycol-based substituent is as mentioned above.

(Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b), if necessary, as long as it does not depart from the object and scope of the present invention. ']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-hex 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).

The polymer acceptor may include 0.001 to 99 parts by weight based on 100 parts by weight of the composition. The polymer donor contains 0.001 to 99 parts by weight with respect to 100 parts by weight of the composition, and may include a residual amount of solvent. When included in the content range, a mixed phase of the polymer donor and a fullerene derivative is well formed, and mechanical properties and device efficiency can be improved. If it does not depart from the object of the present invention, it may further include a conventional additive, it 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); Or 1: 3 to 20 (w:w). When included in the ratio range, the polymer donor and the polymer acceptor mixed phase are well formed to improve mechanical properties, and have low potential for damage due to external energy, and provide stable performance.

The present invention, the active layer containing 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.

As an example of the present invention, the organic electronic device, a substrate; Inorganic thin film organic thin film or a composite film of the two; And an active layer comprising the composition for an organic electronic device according to the present invention; And an organic solar cell (PSCs) including an electrode. The organic solar cell is an organic solar cell of an inverted type or a normal type, and the components and manufacturing processes of each layer are appropriate according to the above-mentioned form unless it is within the scope of the present invention. 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), polyether ether ketone (PEEK), polyether sulfone (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 the organic thin film may be formed on the substrate, and can be applied without limitation as it forms an electron transport layer or a hole transport layer applicable to an organic solar cell, and can be applied without limitation, 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, and the n-type metal oxide is, for example, TiOx, ZnO or Cs ₂ CO ₃ . As a hole transport material, polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene sulfide, polyphenylene vinylene, polyindole, polypyrene. Polycarbazole, polyazulene, polyazepine, polyfluorene, polynaphthalene, poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonate ); PEDOT:PSS) and polyethylenedioxythiophene may include a conductive polymer or a crosslinked conductive polymer including at least one selected from the group, but is not limited thereto.

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

The active layer is formed on the inorganic thin film or the organic thin film, and 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, more specifically, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), zinc 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(II) Oxide: CuO, nickel oxide (NiO), copper aluminum oxide (CopperAluminiumOxide:CAO, CuAlO ₂ ), zinc oxide (ZincRhodiumOxide: ZRO, ZnRh ₂ O ₄ ) , Iron oxide, chromium oxide (CrO ₃ ), bismuth oxide, indium-gallium zinc oxide (IGZO), ZrO _{2 and the} like, but is not limited thereto. It may be preferably MoO ₃ , WO ₃ , V ₂ O ₅ and CrO ₃ .

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

The electrode may include, without limitation, upper and lower electrodes, and any electrode component applicable to the organic solar cell. The upper electrode may include silver (Ag), copper (Cu), gold (Au), and platinum (Pt). ), titanium (Ti), aluminum (Al), nickel (Ni), zirconium (Zr), iron (Fe), manganese (Mn), and magnesium (Mg). have. The lower electrode may include indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium zinc oxide (IGZO), indium tin zinc oxide (Indium Tin Zinc Oxide); ITZO), Gallium-doped Zinc Oxide (GZO), Aluminum-doped Zinc Oxide (AZO), F-doped Tin Oxide (FTO), Zinc Oxide 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 include 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 including 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 by a configuration and method applied in the technical field of the present invention, and is not particularly limited as long as it does not depart 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 spraying method, or the like.

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

The organic semiconductor layer forms an organic semiconductor film by 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 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 for manufacturing an organic electronic device, according to an embodiment of the present invention, dissolving the compound according to the present invention in a solvent to form a coating composition; And coating the coating composition on the substrate.

The step of forming the coating composition is a temperature of the compound according to the invention above room temperature; 30°C or higher; 50°C or higher; 70°C or higher; Or it may be dissolved by stirring and / or ultrasonic treatment at a temperature of 70 ℃ to 100 ℃. The coating composition may be dissolved with a component added to the active layer or mixed with a solution in which they are dissolved in other solvents. The solvent, as mentioned above, is an environmentally friendly solvent, and may be, for example, water, alcohol, or a mixture of the two.

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 the two.

The coating step, spray coating method, dip coating method, gravure coating method, reverse offset coating method, screen printing method, slot-die coating method and nozzle printing method, dry transfer printing method (dry transfer printing), spin coating Method, ink spraying method and the like can be applied.

After the coating step may further include a step of drying.

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

However, the following examples are only for illustrating the present invention, 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 was used as received.

(2) PPDT2FBT-A(poly((2,5-bis(1,3-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)propan-2-yloxy)phenylene)-alt- (5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)]), "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) means “J. Am. Chem. Soc. 2016, 138, 20042013”.

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 the N ₂ atmosphere in a 500 mL 2-neck round bottom flask.

When 100° C. is reached, Na (2.4 g, 0.11 mol) is slowly added piece by piece. To remove moisture in the reactant before adding Na, it was maintained at 100° C. for 1 hour, and stored in Na in mineral oil before cutting, and Na was added to the flask at 5 min intervals.

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

¹ H NMR (400 MHz, CDCl ₃ ): δ3.99-3.92 (m, 1H), 3.67-3.60 (m, 20H) 3.57-3.45 (m, 8H) 3.36 (s, 6H).

[Scheme 2]

Preparation 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 synthesizing 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, water was removed with MgSO 4 and evaporated under reduced pressure to give a clear oil product 2a-c (2a: 12.7 g, 95%, 2b: 14.3 g). , 94%, 2c: 25.5 g, 91%).

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 (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 described as "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) is added to a 250 mL 3-neck round bottom flask to remove residual moisture. For vacuum drying. Next, anhydrous DMF (dimethylformamide, 50 mL) was added to the reaction flask, respectively, and 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 removal of MgSO ₄ by filtration, the organic solvent was removed by evaporation under reduced pressure to obtain a colorless oil residue (3a: 1.3 g, 37%, 3b: 1.5 g, 36%, 3c: 3.9 g, 33%). .

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 (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) were 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 overnight at room temperature, and the residual 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 and then washed 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), "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 to 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 in fullerene. Finally, PCBA was purified by silica gel chromatography using toluene/methanol/acetic acid as 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 cooling 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)

The PCBA (5, 300 mg) prepared in Example 1 was dissolved in ODCB (200 mL) at 130° C. temperature for 2 h under N2. After 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, brownish viscous 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)

The 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 4c (914 mg) and DMAP (18 mg) were added, followed by stirring for 15 min to dissolve 4c and DMAP. DCC (92 mg) was added and the mixture was stirred for 3 hours. After purification, brownish viscous PCBO27 (430 mg, 60%) 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: Preparation of eco-PSCs of eco-friendly organic solar cells in reverse structure

As shown in FIG. 1, Eco-PSC was prepared with an inverted architecture (ITO/ZnO/active layer/MoO ₃ /Ag) using a mixture of ethanol and water. More specifically, all the processes except for the thermal vapor deposition of MoOx/Ag were performed under atmospheric conditions. The ITO coated glass substrate was sonicated in acetone, DI water and IPA, dried for several hours at 80° C. and UV ozone (10 min) treated before spin coating the ZnO layer. 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 acceptor prepared in the examples were respectively ethanol/water mixture (88:12 of solubility evaluation 1 (v/v ) Or the mixing ratio shown in Table 1 of Solubility Assessment 2. The concentration of each mixture is 4-5 mgml ^-1 for PPDT2FBT-A, and the optimized PPDT2FBT-A:PCBOs ratio is 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, followed by spin-coating 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 a high vacuum (<10 ^-6 Torr) evaporation chamber 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-PSCs as an organic solar cell device in the form of a regular structure

As shown in Figure 1, ITO / PEDOT: PSS (+0.1% by volume GOPS) / active layer / PNDIT-F3N / Ag structure was prepared in the form of an environmentally friendly PSC having a structure.

More specifically, after the ITO substrate was sonicated and washed 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 the GOPS crosslinker on an ITO substrate at 3000 rpm for 40 seconds, the PEDOT:PSS layer was 150 at ambient conditions. The film was completely crosslinked by annealing at 30° C. for at least 30 minutes and transferred to a glove box filled with N 2.

The electron donor PPDT2FBT-A and the electron acceptor prepared in the Examples were added to a water/ethanol mixed solvent (88:12 (v/v) of solubility evaluation 1 or a mixing ratio shown in Table 2 of solubility evaluation 2) to prepare a mixed solution. Did. The mixing ratio of the electron donor to the electron acceptor is 1:2.5 (w/w) (D:A), and the concentration of the electron donor in the mixed solution is 4 mg mL-1. The mixed solution was stirred for 1 hour on a hot plate at 80°C. This mixed solution was spin coated on an ITO/PEDOT:PSS substrate at 2000 rpm for 40 seconds. The thickness of the produced eco-friendly PSC was measured by AFM measurement to 60 to 70 nm, and dried under high vacuum conditions overnight 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 to deposit a 120 nm thick Ag electrode. The active area of the fabricated device was 0.164 cm ² by optical microscopy.

Solubility measurement

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

(2) PCBO12 is 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 properties 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) characteristic of the device is 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 AAB, ASTM standard classes. 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) Thorlabs in a spectroscopic measurement system (K3100 IQX, MacScience, Inc.) equipped with a monochromatic light source of a 300 W xenon arc lamp filtered by a monochromator (Newport) and an optical chopper (MC2000, USA) ) Was measured.

The J _sc values were calculated from an EQE meter equipped with an AM 1.5G solar spectrum, and the values matched the J _sc values measured 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 a 88:12 (v/v) ethanol/water mixture and spin coated onto the ZnO layer in atmospheric conditions (air).

Current voltage measurements were made in the range of 0 to 8 V under the same atmospheric conditions, and the results were fit 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 is the potential across the device taking into account the potential losses due to _bi , and L is the PCBO layer thickness.

result

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

The result of evaluating the organic solar cell device to which the 88:12 (v/v) ethanol/water mixed solvent was applied is shown in FIG. 2. In FIG. 2, the highest efficiency (1.4%) is shown in a system using PCBO12 with the lowest OEG group as an electron acceptor. This is the highest efficiency of the organic solar cell device efficiency using the previously reported eco-friendly solvent, and the longer the OEG side chain is, the lower the efficiency is because 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 mixture solvent was applied are shown in Table 2. In Table 2, the shorter and shorter the OEG side chain is, the better the packing ability between fullerene molecules is, and it can be predicted that the electron density increases due to the well formed channel through which electrons can move, resulting in an increase in current density. have. In fact, in the evaluation of charge mobility, it can be confirmed that PCBO12 shows the highest charge mobility.

(b) The performance and charge mobility of the environment-friendly organic solar cell device according to the mixing ratio of water in the organic solar cell device having the structure of Example 5 are shown in Table 3. In addition, the performance and charge mobility of the organic solar cell device of the reverse structure of Example 4 and the positive structure of Example 5 for Water-25 in 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 for the photoactive layer to produce and produce eco-friendly organic solar cells with each device structure. Efficiency, furthermore, it is possible to obtain significantly higher efficiency (PCE= 2.05%) in a solar cell device of a fixed structure compared to an inverse structure (PCE= 1.40%) in a device of Water-25, which has been reported to date. / 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 that the packing degree between fullerene molecules differs as the OEG side chain runs shorter. That is, it can be confirmed that PCBO12 shows the most regular packing in the thin film state, and also shows the same tendency in a mixed film with PPDT2FBT-A (blend film, photoactive layer, FIG. 4). That is, as the OEG side chain runs the shortest (PCBO12), it has a well-aligned packing structure between fullerene molecules, and electron transport channels are well formed 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 to form a polymer-polymer interface at the polymer-polymer interface. It can be predicted that the electrical properties of the device are improved by helping to separate the charges of the.

(4) Evaluation of atmospheric stability

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

This excellent atmospheric stability can be expected to be attributed to the improved interfacial adhesion properties between the hydrophilic active material and the hole/electron transport intermediate layer (ie, PEDOT: PSS and PNDIT-F3N) in the organic solar cell having a structure.

Overall, the present invention can provide three GOE-substituted fullerene mono-adducts that can be utilized in device manufacturing processes using environmentally friendly ethanol/water mixed solvents. have. That is, the optical and electrochemical properties of the fullerene derivatives of PCBO12, PCBO15 and PCBO27 having OEG side chains having different structures and lengths, and using them, 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 electrical mobility of PCBO12, a single adduct, enabling 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 properties, and further, the higher the purity of the PCBO12 and PCBO15 films, the more efficient charge transport is possible. Accordingly, the present invention can provide aqueous-processable electroactive materials with high carrier mobility suitable for achieving high-efficiency eco-PSCs. Moreover, by adopting the normal type device structure for the first time in the organic solar cell based on the water/ethanol process, the device performance is dramatically improved (1.40% → 2.05%), and the air stability is excellent to maintain the initial PCE value. have.

As described above, although the embodiments have been described by a limited embodiment and drawings, those skilled in the art can make various modifications and variations from the above description. For example, even if the described techniques are performed in a different order than the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (20)

A compound represented by Formula 1 below and having an oligoethylene glycol-based substituent.
[Formula 1]

(Where 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 alkyl groups and oligoethylene glycol-based substituents (however, at least one of R ² to R ⁶ is an oligoethylene glycol-based substituent),
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 ~C ₁₀ alkyl group, n and m are integers from 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 from 0 to 20, and n'and m'are each selected from integers from 1 to 20.).
According to claim 1,
R ¹ is -C ₁ ~C ₁₀ alkyl-,
R ² to R ⁶ are each hydrogen, a C ₁ ~C ₁₀ alkyl group, -OC ₁ ~C ₁₀ alkyl group And an oligoethylene glycol-based substituent (where at least one of R ² to R ⁶ is an oligoethylene glycol-based substituent),
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 from 1 to 10),

And

(R ⁹ and R ¹⁰ are each hydrogen or a C ₁ ~C ₅ alkyl group, n is an integer from 0 to 5, n'and m'are selected from integers of 1 to 10,
compound.
According to claim 1,
The fullerene derivative is a compound represented by the following Chemical Formula 1-1.

[Formula 1-1]

(Where 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 a C ₁ ~C ₁₀ alkyl group, n and m are integers from 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 claim 1,
The fullerene is selected from the group consisting of C60, C70, C74, C76, C78, C82, C84, C720 and C860,
compound.
According to claim 1,
The compound is soluble in a solvent containing water, alcohol, or both,
compound.
According to claim 1,
The compound, the solubility in water, alcohol or a solvent containing both, is at least 1 mg / ml at 25 ℃,
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 compound 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 includes 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 comprising a compound represented by the following Formula 2 to Formula 4, the composition for an organic electronic device.

[Formula 2]

(Where n is an integer from 1 to 1000, m is an integer from 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 alkyl group and an oligoethylene glycol-based substituent is selected (but at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent), R is hydrogen, C ₁ ~ C ₂₀ alkyl group and halogen Selected, n is an integer from 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 Alkyl group and oligoethylene glycol-based substituent is selected from (but at least one of R ¹³ to R ¹⁴ is an oligoethylene glycol-based substituent.), n is an integer from 1 to 1000, the oligoethylene glycol 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 1: mass ratio (w:w) of 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, having 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 inverted type organic solar cell or a normal type organic polymer solar cell,
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 to include 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 above room temperature,
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):poly(styrenesulfonate):poly(styrenesulfonate); PEDOT:PSS ) Is a thin film,
Method of manufacturing an organic electronic device.

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