KR101496036B1 - Active layer, organic photovoltaic cell comprising the same and manufacturing method thereof - Google Patents

Abstract

The present invention provides a photoactive layer including an electron accepting material and an electron donating material, and treating the electron accepting material and the electron donating material in a non-solvent form, an organic solar cell including the same, and a method of manufacturing the same.

Description

TECHNICAL FIELD The present invention relates to a photoactive layer, an organic solar cell including the same, and a method of manufacturing the same. BACKGROUND ART [0002]

The present application claims the benefit of the filing date of Korean Patent Application No. 10-2012- 0108994 filed on September 28, 2012 to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to a photoactive layer, an organic solar cell using the same, and a method of manufacturing the same.

In 1992, Heeger of UCSB showed the first possibility of solar cell using organic polymer. This is a hetero-junction thin film element in which a light-absorbing organic polymer is mixed with a C60 fullerene derivative or a C70 fullerene derivative having a very high electron affinity. ITO (indium tin oxide) as a transparent electrode and Al A negative electrode material is used.

An electron-hole pair (electron-hole pair or exciton) is formed by absorbing light in a photoactive layer composed of an organic polymer. This electron-hole pair moves to the interface between the copolymer and the C60 fullerene derivative or the C70 fullerene derivative and is separated into an electron and a hole, and then electrons are transferred to a metal electrode and holes are transferred to a transparent electrode to generate electrons.

At present, the efficiency of organic polymer thin film solar cell using organic polymer reaches 7 ~ 8% (Nature Photonics, 2009, 3, 649-653).

However, the efficiency of organic polymer solar cells is still low compared to the maximum efficiency (~ 39%) of solar cells using silicon. Development of organic solar cells having higher efficiency is required.

Nature Photonics, 2009, 3, 649-653

The present invention provides an organic solar cell having improved efficiency, a method of manufacturing the same, and a photoactive layer used in the organic solar cell.

The present disclosure relates to a plasma display panel comprising a first electrode;

A second electrode facing the first electrode; And

And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,

Wherein the photoactive layer includes an electron accepting material and an electron donating material,

Wherein the electron accepting material and the electron donating material are non-solvent treated.

Also, the present specification discloses a plasma display panel comprising a first electrode;

A second electrode facing the first electrode; And

And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,

Wherein the photoactive layer includes an electron accepting material and an electron donating material,

(I _{c = c} / I _{c -c} ) of the antisymmetric value and the symmetric value of the absorption spectrum of the FT-IR is in the range of 110 to 150 % ≪ / RTI >

Also, the present specification discloses a plasma display panel comprising a first electrode;

A second electrode facing the first electrode; And

And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,

Wherein the photoactive layer comprises an electron accepting material and an electron donating material,

The electron accepting material and the electron donating material are treated in a non-

The efficiency of the organic solar cell is increased by 110 to 200% as compared with the case where the efficiency of the organic solar cell is higher than that of the electron-accepting material and the electron-donating material before the treatment.

Further, the present specification provides a photoactive layer comprising an electron accepting material and an electron donating material, wherein the electron accepting material and the electron donating material are non-treated.

The present invention also relates to a photoactive layer comprising an electron accepting material and an electron donating material, wherein the ratio of the antisymmetric value and the symmetric value of the absorption spectrum of FT-IR (I _{c = c} / I _{c - c} ) is increased by 110 to 150% relative to the intrinsic value of the electron accepting material and the electron donating material.

The present disclosure also provides a method of manufacturing a semiconductor device, comprising: preparing a substrate;

Forming a first electrode in one region of the substrate;

Forming an organic material layer including a photoactive layer on the first electrode;

Treating the photoactive layer with a non-solvent; And

And forming a second electrode on the organic material layer.

The photoactive layer according to one embodiment of the present specification can be manufactured through a simple process such as non-solvent treatment and, if necessary, heat treatment. Further, the photoactive layer through the above treatment is highly conductive and stable.

The photoactive layer according to one embodiment of the present invention has a good light absorptivity and forms a stabilized molecular structure through self-organization of an electron accepting material and an electron donating material. Accordingly, the organic solar cell including the photoactive layer according to one embodiment of the present invention can exhibit excellent characteristics in the open-circuit voltage rise and the efficiency increase.

In particular, the photoactive layer according to one embodiment of the present invention has a high light absorptivity, a long conjugation length, a high charge mobility, a low resistance to an electrode, and an improvement in morphology, And the efficiency of the device can be improved.

1 is a view illustrating a method of manufacturing a photoactive layer according to an embodiment of the present invention.
Fig. 2 is a diagram showing the JV curves of Example 1 and Comparative Examples 1 to 3. Fig.
Fig. 3 is a diagram showing absorption spectra of Example 1 and Comparative Examples 1 to 3. Fig.
Fig. 4 is a graph showing X-ray diffraction of Example 1 and Comparative Examples 1 to 3. Fig.
Fig. 5 is a graph showing absorption spectra of FT-IR of Comparative Examples 1 to 3. Fig.
FIG. 6 is a graph showing Auger electron spectroscopy of Example 1 and Comparative Examples 1 to 3. FIG.
FIG. 7 is a diagram of Example 1 and Comparative Examples 1 to 3 observed under an atomic force microscope (AFM). FIG.

Hereinafter, the present invention will be described in detail.

The present disclosure relates to a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And an organic material layer disposed between the first electrode and the second electrode and including a photoactive layer, wherein the photoactive layer includes an electron accepting material and an electron donating material, and the electron accepting material and the electron donating material are non- In an organic solar cell.

In the present specification, the non-solvent means that the electron donor substance or the electron accepting substance is dissolved or does not react.

In the present specification, the above-mentioned "non-wastewater treatment" refers to a "non-volatile swelling treatment" in which a non-wax penetrates between an electron donating substance and an electron accepting substance to cause swelling phenomenon when applied to an electron donating substance or an electron accepting substance do or,

Refers to a "non-cost surface treatment" in which a non-solvent acts on the surface of an electron donor or an electron accepting material through a process of applying it to an electron donating substance or an electron accepting substance and then removing the same.

The term " action " as used herein means that the surface of the electron donating substance or the electron accepting substance is affected by the formation of a dipole on the surface and / or the modification of the chemical structure of the electron donating substance or the electron accepting substance.

Further, in one embodiment of the present invention, the non-solvent causes a swelling phenomenon when applied to the photoactive layer, so that the non-solvent penetrates into the photoactive layer.

In one embodiment of the present invention, the intrinsic penetration distance into the photoactive layer is 5% or more and less than 50% of the thickness of the photoactive layer. In another embodiment, the penetration distance into the inside of the photoactive layer is 5 to 30% of the thickness of the photoactive layer.

The non-solvent can select the type of non-solvent, the treatment method, and the amount of the non-solvent upon application to the photoactive layer.

When the non-solvent is applied onto the photoactive layer for 1 minute to 60 minutes, the penetration distance of the non-solvent into the photoactive layer is 5% or more and less than 50% of the thickness of the photoactive layer.

If the penetration distance into the photoactive layer is 50% or more of the thickness of the photoactive layer, separation may occur from the substrate to which the photoactive layer is applied.

In addition, when the non-invasive distance to the inside of the photoactive layer is 5 to 30% of the thickness of the photoactive layer, the interface area between the photoactive layer and the electrode is increased and the contact property is improved, and the performance of the device can be improved.

In this specification, the non-solvent swelling method includes a method of applying a non-solvent on the photoactive layer and spin-coating or drop-coating.

In this specification, the non-solvent surface treatment method includes a method of applying a non-solvent on the photoactive layer and removing the non-solvent by spin coating.

When the non-solvent swelling method is applied to the photoactive layer, the interface between the photoactive layer and the photoactive layer and the electrode can be simultaneously controlled, which is advantageous for improving the morphology of the photoactive layer. In addition, the manufacturing process is advantageous in terms of time and cost in terms of processes such as spin coating which is relatively simple.

The applied non-solvent penetrates into the space of the photoactive layer, thereby widening the space between the polymer chains, and increasing the mobility of the polymer chains. In addition, as the mobility of the polymer chains increases, the self organization of the molecular structure forms a coordinated molecular structure. In this case, the conjugation length is increased, the mobility of the charge is increased, and the optical characteristic is increased, thereby providing a high light absorption rate and contributing to an increase in efficiency.

In one embodiment, the non-solvent swelling method applies a non-solvent for at least one minute. In another embodiment, the non-solvent is applied for 1 to 60 minutes. In one embodiment, the non-wovens are applied for 10 to 40 minutes.

In one embodiment of the present invention, the non-prepaid processing method removes the non-payment within one minute after applying the non-payment. In this case, the applied non-solvent acts on the surface of the photoactive layer more effectively than it penetrates into the photoactive layer, and is effective for the surface treatment.

When the non-solvent is applied for more than one minute, the non-penetration distance into the photoactive layer can be increased. It is possible to prevent the peeling phenomenon from progressing by preventing the penetration distance to the inside of the photoactive layer from exceeding 50% of the thickness of the photoactive layer.

In one embodiment of the present specification, the non-solvent swelling time, the non-solvent surface treatment or the non-solvent swelling and surface treatment can be simultaneously performed by adjusting the non-solvent application time as needed.

In one embodiment of the present invention, the electron accepting material and the electron donating material are heat treated before, simultaneously or after the non-expansive swelling.

In one embodiment, the electron accepting material and the electron donating material may be heat treated prior to non-solvent swelling.

In one embodiment, the electron accepting material and the electron donating material may be heat treated after the non-solvent swelling.

In another embodiment, the electron accepting material and the electron donating material may be heat treated at the same time as the non-solvent swelling. In this case, the non-solvent penetration distance to the inside of the photoactive layer increases due to the heat that is heated upon swelling by the non-solvent, the non-solvent processing time is shortened, and the heat treatment or nonsolvent is removed by spin coating or blowing The process is simplified, resulting in time and / or cost advantages.

The non-solvent is selected from the group consisting of water, an alkane compound, a halohydrocarbon compound, an ether compound, a ketone compound, an ester compound, a nitrogen compound, a sulfur compound, an acid, an alcohol compound, a phenol compound and a polyol compound.

In one embodiment of the present invention, the alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane 1 or 2 or more is selected.

In one embodiment of the present invention, the alkane-based non-solvent is dichloromethane.

Electron donating materials, such as P3HT, are not soluble in alkane based solvents, but are selectively soluble in electron accepting materials such as PCBM. In this case, when the non-solvent is used alone or in a certain amount of mixture with other solvents, there is an effect of increasing the interfacial bonding area by selectively melting the electron accepting material on the surface while swelling.

In one embodiment, the halohydrocarbon-based non-solvent is selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, Tetrachloride, chlorobenzene, o-dichlorobenzene, and 1,1,2-trichlorotrifluoranthene.

In another embodiment, the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether.

When the ether-based non-solvent is used, the boiling point is low and the solvent is easily removed after the non-solvent swelling method. Thus, the process is simple, and it is advantageous in terms of time and cost.

In another embodiment, the ketone-based solvent is selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone, and di- (isobutyl) And one or two or more are selected from the group consisting of ketones.

In one embodiment, the ester-based wastewater is selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, and isobutyl isobutylate.

In the present specification, the nitrogen compound means a solvent in which the electron donating substance or the electron accepting substance dissolves or does not react, among the compounds containing nitrogen.

In another embodiment, the nitrogenous compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethyleneamine, ethylene diemme, pyridine, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide.

In the present specification, the sulfur compound means a solvent in which the electron donating substance or the electron accepting substance dissolves or does not react, among the compounds containing sulfur

In another embodiment, the sulfur compound non-solvent is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol.

In another embodiment, the alcoholic solvent is selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, 1 or 2 in the group consisting of ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1- Or more.

When the alcohol-based non-solvent is used, a dipole is formed between the photoactive layer and the electrode to lower the hole extraction barrier, thereby increasing the voltage density. Therefore, the efficiency of the organic solar cell can be increased due to the increase of the open-circuit voltage and the fill factor (FF) due to the increase of the built-in voltage and the decrease of the surface energy trap.

In addition, when a water-soluble buffer material, metal nanoparticles, metal oxide, or the like is melted and a non-solvent treatment method is used, the non-solvent treatment and the buffer layer formation can be performed at the same time.

In one embodiment, the acid abusers are selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid and stearic acid.

When the acid abolisher is used, ionization of the electron donor proceeds to lower the interfacial charge collection barrier to increase the current density or to increase the wettability when the aqueous buffer material is subsequently applied, which is advantageous for coating.

In one embodiment, the phenolic non-wovens are selected from the group consisting of phenol, resorcinol, m-cresol, and methyl salicylate.

In one embodiment, the polyol-based non-solvent is selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol.

In one embodiment of the present disclosure, the non-solvent is a nitrogen compound non-solvent.

In one embodiment of the present disclosure, the non-solvent is acetonitrile.

In one embodiment of the present disclosure, the non-exporter is water.

In another embodiment, the non-exporter is an alkane-based non-solvent.

In another embodiment, the non-solvent is a halohydrocarbon-based non-solvent.

In one embodiment, the non-solvent is an ether based non-solvent.

In another embodiment, the non-solvent is a ketone-based solvent.

In another embodiment, the non-solvent is an ester-based solvent.

In another embodiment, the non-solvent is a sulfur compound non-solvent.

In another embodiment, the non-coster is a non-coster.

In another embodiment, the non-solvent is an alcoholic solvent.

In another embodiment, the non-solvent is a phenolic non-solvent.

In another embodiment, the non-solvent is a polyol-based non-solvent.

In one embodiment, the non-solvent is selected from one or more of alkane, ether, alcohol, and acid.

In one embodiment of the present invention, the temperature of the heat treatment is equal to or higher than the glass transition temperature (Tg) of the electron donating substance.

When the heat treatment temperature is lower than the glass transition temperature of the electron donor, the self organization of the electron donor may not occur. If the heat treatment temperature is higher than the thermal decomposition temperature of the electron donor, The photocurrent generation characteristics may be degraded.

The above heat treatment synergizes the effect of the non-solvent treating method, thereby further aligning the molecular structure, thereby increasing the conjugation length and optical characteristics. Further, the manufacturing process is relatively simple, which is advantageous in terms of time and economy in terms of process.

In one embodiment of the present invention, the heat treatment time is from 0 minutes to 5 hours. In another embodiment, the heat treatment time is from 10 minutes to 3 hours. In another embodiment, the heat treatment time is 30 minutes to 45 minutes. The time can be adjusted according to the degree of self organization.

In one embodiment of the present invention, the electron accepting material is a fullerene derivative or a non-fullerene derivative.

In one embodiment of the present invention, the fullerene derivative is a fullerene derivative of C60 to C90.

The fullerene derivative may be substituted or unsubstituted with at least one further substituent.

In one embodiment, the fullerene derivative is a C60 fullerene derivative or a C70 fullerene derivative.

In one embodiment, the C60 fullerene derivative or the C70 fullerene derivative is independently selected from the group consisting of hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be further substituted with a substituent which is bonded to each other to form a condensed ring.

In another embodiment, the fullerene derivative is selected from the group consisting of a C76 fullerene derivative, a C78 fullerene derivative, a C84 fullerene derivative, and a C90 fullerene derivative.

In one embodiment, the C76 fullerene derivative, the C78 fullerene derivative, the C84 fullerene derivative and the C90 fullerene derivative are each independently selected from the group consisting of hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be further substituted with a substituent which is bonded to each other to form a condensed ring.

The fullerene derivative has an ability to separate excitons (electron-hole pairs) and an excellent charge mobility as compared with the non-fullerene derivative, which is advantageous for the efficiency characteristics.

In another embodiment, the LUMO energy level of the non-fullerene derivative is -2.0 to -6.0 eV. In another embodiment, the LUMO energy level of the non-fullerene derivative is -2.5 to -5.0 eV. In another embodiment, the LUMO energy level of the non-fullerene derivative is -3.5 to -4.5 eV.

The injection of electrons can be easily performed within the LUMO energy level within the above range, and the efficiency of the organic solar cell is increased.

Particularly, when the LUMO energy level of the non-fullerene derivative is in the range of -3.5 to -4.5 eV, charge separation can be performed while maximizing the difference from the HOMO energy level of the electron donor, There is an advantage.

Further, in one embodiment of the present specification, the non-fullerene derivative is a non-spherical unimolecular or polymer.

In one embodiment of the present disclosure, the electron donor material comprises at least one electron donor; Or a polymer of at least one electron acceptor and at least one electron donor.

In one embodiment of the present disclosure, the electron donor material comprises at least one kind of electron donor.

In another embodiment, the electron donor material comprises a polymer of at least one electron acceptor and at least one electron donor.

In the embodiment of the present invention, the electron donor includes one or two or more in the group consisting of the following formulas.

In the above formula,

a is an integer of 0 to 4,

b is an integer of 0 to 6,

c is an integer of 0 to 8,

d and e are each an integer of 0 to 3,

f and g are each an integer of 0 to 2,

R ₂ and R ₃ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring,

X ₁ to X ₃ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '

Y ₁ and Y ₂ are the same or different and are each independently selected from the group consisting of CR, N, SiR, P and GeR,

R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjoining substituents may be bonded to each other to form a condensed ring.

In another embodiment, the electron acceptor comprises one or two or more of the group consisting of the following formulas.

In the above formula,

R ₂ to R ₅ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjoining substituents may be bonded to each other to form a condensed ring,

X ₁ and X ₂ are the same or different and each independently, CRR selected from the group consisting of ', NR, O, SiRR', PR, S, GeRR ', Se and Te from each other, Y ₁ to Y ₄ are each Are each independently selected from the group consisting of CR, N, SiR, P and GeR,

R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjoining substituents may be bonded to each other to form a condensed ring.

In one embodiment of the present invention, the electron donor material is an A unit represented by any one of the following formulas (1) to (3);

A B unit represented by the following formula (4); And

And a C unit represented by the following formula (5).

[Formula 3] < EMI ID =

[Chemical Formula 4]

In formulas (1) to (5)

f and g are each an integer of 0 to 2,

R ₂ to R ₄ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring,

X ₁ to X ₅ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '

Y ₃ to Y ₅ are the same or different and are each independently selected from the group consisting of CR, N, SiR, P and GeR,

R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjoining substituents may be bonded to each other to form a condensed ring.

In one embodiment of the present invention, the electron accepting material is a fullerene derivative. In another embodiment, the electron accepting material is a fullerene derivative of C60.

In one embodiment of the present disclosure, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM).

이다. 이 경우, X₁은 S이다. In one embodiment of the present disclosure, the electron donor material comprises

to be. In this case, X ₁ is S.

In another embodiment, the electron donor material is poly (3-hexylthiophene) (P3HT).

In one embodiment of the present disclosure, the electron donor material includes a copolymer including the A unit, the B unit, and the C unit.

In one embodiment of the present specification, the A unit is the formula (1).

In one embodiment of the present specification, the A unit is represented by formula (1), X ₁ is S, and R ₂ and R ₃ are hydrogen.

In one embodiment of the present disclosure, the X ₃ is S, and, Y ₃ and Y ₄ is N and, Y5 is CR.

In one embodiment of the present specification, R and R ₄ are the same or different and each independently represents a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R and R ₄ are the same or different and each independently an alkoxy group.

In one embodiment of the present disclosure, R and R < ₄ > are an octoxy group.

In one embodiment of the present disclosure, X ₅ is NR.

In one embodiment of the present disclosure, X ₅ is NR and R is a dodecanyl group.

In one embodiment of the present disclosure, X ₄ is S.

In one embodiment of the present invention, the electron donor material is a copolymer including a unit represented by the following formula (6).

[Chemical Formula 6]

In formula (6)

x is a molar fraction, 0 < x < 1,

y is a molar fraction, 0 <y <1, x + y = 1,

n is an integer from 1 to 10,000,

R10 to R12 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R10 is a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R10 is an octoxy group.

In one embodiment of the present specification, R11 is a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R11 is an octoxy group.

In one embodiment of the present invention, R12 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R12 is a dodecanyl group.

In one embodiment of the present disclosure, x is 0.5.

In one embodiment of the present disclosure, y is 0.5.

In one embodiment of the present invention, the terminal group of the copolymer is a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted aryl group.

In one embodiment of the present invention, the terminal group of the copolymer is a 4- (trifluoromethyl) phenyl group.

In one embodiment of the present disclosure, the electron donor material is the following polymer 1.

[Polymer 1]

In one embodiment, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) and the electron donating material is poly (3-hexylthiophene) (P3HT).

In one embodiment of the present disclosure, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) and the electron donating material is the polymer 1. [

In another embodiment, the non-solvent is acetonitrile, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) and the electron donating material is poly (3-hexylthiophene ) (P3HT).

In another embodiment, the non-solvent is acetonitrile, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) and the electron donating material is poly (3-hexylthiophene ) (P3HT), and the heat treatment temperature is not lower than the glass transition temperature of the donor material and not higher than the thermal decomposition temperature.

In one embodiment of the present disclosure, the non-solvent is methanol, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM), and the electron donating material is the polymer 1. [

In one embodiment of the present disclosure, the non-solvent is methanol, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM), the electron donating material is the polymer 1, The temperature is not lower than the glass transition temperature of the donor material and not higher than the pyrolysis temperature.

In one embodiment of the present disclosure, the non-solvent is 2-methoxyethanol, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) to be.

In one embodiment of the present disclosure, the non-solvent is 2-methoxyethanol, the electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM) , And the heat treatment temperature is not lower than the glass transition temperature of the electron donor and not higher than the thermal decomposition temperature.

In the present specification, the photoactive layer includes an electron accepting material and an electron donating material.

Further, the electron accepting material and electron donating material of the photoactive layer may form bulk heterojunction (BHJ). In one embodiment of the present disclosure, the electron accepting material and the electron donating material are mixed at a ratio (w / w) of 1:10 to 10: 1. In another embodiment, they are mixed in a weight ratio of 1: 7 to 2: 1. In another embodiment, the electron accepting material and the electron donating material are mixed in a weight ratio of 1: 4 to 5: 3. In another embodiment, the electron accepting material and the electron donating material are mixed in a weight ratio of 1: 0.4 to 1: 4.

When the content of the electron accepting material is less than 0.4 wt%, the content of the crystallized electron accepting material is insufficient, resulting in the obstruction of the generated electrons. When the amount of the electron donating material exceeds 10 wt% There is a problem that efficient absorption of light is not achieved.

In another embodiment, the organic solar cell has a ratio of an antisymmetric value and a symmetric value (Ic = c / Ic-c) of the absorption spectrum of the FT-IR to the electron accepting material and the electron Which is 110 to 150% higher than the intrinsic value of the donor material.

In another embodiment, the efficiency of the organic solar cell is 110 to 200% higher than that in the case of including the electron accepting material and the electron donating material before being treated with the non-solvent.

In another embodiment, the electron accepting material and the electron donating material are heat treated before, simultaneously or after the non-treating. In this case, the efficiency of the organic solar cell is increased by 110 to 150% as compared with the case where the electron-accepting material and the electron-donating material before the heat treatment are treated.

1 is a view illustrating a method of manufacturing a photoactive layer according to an embodiment of the present invention.

Fig. 2 is a view showing the J-V curves of Example 1 and Comparative Examples 1 to 3. Fig. FIG. 2 shows that the efficiency of the organic solar cell increases when the non-solvent swelling method is combined with the heat treatment as compared with the case where only the non-solvent swelling method or heat treatment is performed. Able to know.

Fig. 3 is a diagram showing absorption spectra of Example 1 and Comparative Examples 1 to 3. Fig. As shown in FIG. 3, a high light absorption rate is provided when the non-solvent swelling method is combined with the heat treatment, as compared with the case where only the non-solvent swelling method or the heat treatment is performed. This is an effect as the conjugation length increases.

Fig. 4 is a graph showing X-ray diffraction of Example 1 and Comparative Examples 1 to 3. Fig. As shown in FIG. 4, when the non-solvent swelling method is combined with the heat treatment, the morphology and crystallinity of the photoactive layer are improved.

Fig. 5 is a graph showing absorption spectra of FT-IR of Comparative Examples 1 to 3. Fig. In FIG. 5, it can be seen that the conjugation length becomes longer when the non-solvent swelling method or heat treatment is performed.

FIG. 6 is a graph showing Auger electron spectroscopy of Example 1 and Comparative Examples 1 to 3. FIG. As shown in FIG. 6, when the non-solvent swelling method is combined with the heat treatment, the penetration distance of the electrode into the photoactive layer is increased. In this case, the interface area between the photoactive layer and the electrode is widened, and the efficiency of the organic solar cell is increased.

FIG. 7 is a diagram of Example 1 and Comparative Examples 1 to 3 observed under an atomic force microscope (AFM). FIG. As shown in FIG. 7, when the non-solvent swelling method is combined with the heat treatment, the root mean square (RMS) value of the surface of the photoactive layer is increased. When the effective value of the surface of the photoactive layer is increased, the contact area between the photoactive layer and the electrode is increased and the electron collection efficiency is increased.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples thereof include, but are not limited to, an alkenyl group substituted with an aryl group such as a stilbenyl group or a styrenyl group.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specific examples include, but are not limited to, a methoxy group, an ethoxy group, a n-propyloxy group, an iso-propyloxy group, a n-butyloxy group, and a cyclopentyloxy group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and particularly preferably a cyclopentyl group and a cyclohexyl group.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the aryl group may be monocyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60 carbon atoms. Specific examples of the aryl group include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group, triphenyl group, terphenyl group and stilbene group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, A cyclic aromatic group such as a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluoranthene group, but is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzoxazole group, a benzthiophene group, a dibenzothiophene group, a benzfuranyl group, (phenanthroline), dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the heteroaryl group can be selected from the examples of the above-mentioned heterocyclic group.

,

등이 있다. In the present specification, a fluorenyl group is a structure in which two ring organic compounds are connected via one atom,

,

.

및

등이 있다. In the present specification, the fluorenyl group includes a group of open fluorenyl groups, wherein the open fluorenyl group is a structure in which one of the ring compounds is disconnected in the structure in which two ring compounds are connected through one atom, For example,

And

.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monocyclic diarylamine group, a substituted or unsubstituted polycyclic diarylamine group, or a substituted or unsubstituted monocyclic and polycyclic diaryl Amine group.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group and the aralkylamine group is the same as the aforementioned aryl group.

In the present specification, the alkyl group in the alkylthio group, alkylsulfoxy group, alkylamine group, and aralkylamine group is the same as the alkyl group described above.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, an arylene group, an alkenylene group, a fluorenylene group, a carbazolylene group and a heterorene group are each a divalent group of an aryl group, an alkenyl group, a fluorenyl group and a carbazole group. The description of the above-mentioned aryl group, alkenyl group, fluorenyl group and carbazole group can be applied, except that these are two groups each.

The term "substituted or unsubstituted" A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A fluorenyl group; A nitrile group; A nitro group; A heterocyclic group containing at least one of a hydroxyl group and at least one of N, O and S atoms, or has no substituent group.

In one embodiment of the present invention, the thickness of the photoactive layer is 50 to 300 nm. In another embodiment, the thickness of the photoactive layer is 100 to 250 nm. In another embodiment, the thickness of the photoactive layer is 150 nm to 230 nm.

When the thickness of the photoactive layer is less than 50 nm, there is a problem that the charge transfer distance is short and the charge factor value can be increased, but the light absorption rate is lowered. When the thickness is more than 300 nm, the current density is increased due to the sufficient photoactive layer thickness There is a problem that the generated carrier has a low ph factor value due to the long travel distance of the carrier.

Therefore, within the above-mentioned range, the resistance between the interface such as the electrode and the resistance in the bulk do not become too large, so that the value of the p factor is increased, the current characteristic is excellent, There is a merit of sufficient separation and length of movement of the carriers.

Also, the present specification discloses a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And an organic material layer disposed between the first electrode and the second electrode and including a photoactive layer, wherein the photoactive layer includes an electron accepting material and an electron donating material, and is characterized in that the absorption spectrum of the FT-IR is antisymmetric ) And a symmetric value (I _{c = c} / I _{c -c} ) of the electron-accepting material and the electron-donating material is 110 to 150% higher than the intrinsic value of the electron-accepting material and the electron-donating material.

The intrinsic value of the electron accepting material and the electron donating material refers to an absorption spectrum of the FT-IR of the photoactive layer including the electron accepting material and the electron sharing material which have not undergone any treatment, for example, heat treatment and / (I _{c = c} / I _{c -c} ) of the antisymmetric value and the symmetric value of the magnetic field.

The ratio of the antisymmetric value to the symmetric value of the FT-IR, that is, I _{c = c} / I _{c -c} , means an increase in the conjugation length.

In one embodiment of the present disclosure, the ratio of the antisymmetric to the symmetric value of the absorption spectrum of the FT-IR is increased by 110 to 150%. In another embodiment, the ratio of the antisymmetric to the symmetric value of the absorption spectrum of FT-IR is increased by 120 to 140%.

In one embodiment of the present invention, when the ratio of the antisymmetric value and the symmetric value of the absorption spectrum of the FT-IR is within the above range, the morphology of the organic solar cell is improved and the crystallinity is increased Thus, there is an advantage that the efficiency of the organic solar battery is increased.

In one embodiment of the specification, the electron accepting material and the electron donating material of the photoactive layer are treated as non-solvent.

The electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating.

Wherein an ratio of an antisymmetric value to a symmetric value of an absorption spectrum of the FT-IR (I _{c = c} / I _{c -c} ) The description of the electron accepting material, the electron donating material, and the photoactive layer of the organic solar cell which is increased by 150% is the same as described above.

A first electrode; A second electrode facing the first electrode; And an organic material layer disposed between the first electrode and the second electrode and including a photoactive layer, wherein the photoactive layer includes an electron accepting material and an electron donating material, and the electron accepting material and the electron donating material are non- And the efficiency of the organic solar cell is increased by 110 to 200% as compared with the case where the efficiency of the organic solar battery includes the electron accepting material and the electron donating material before being treated with the non-solvent.

The electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating.

Wherein the efficiency of the organic solar cell is increased by 110 to 200% as compared with the case where the efficiency of the organic solar cell is higher than that of an electron accepting material and an electron donating material before being treated with a non-solvent. And heat treatment are the same as described above.

In one embodiment of the present specification, in the photoactive layer containing an electron accepting material and an electron donating material, the electron accepting material and the electron donating material are treated in a non-sparing manner.

The electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating.

The description of the electron accepting material and the electron donating material, the non-solvent and the heat treatment of the photoactive layer is the same as described above.

The present invention also relates to a photoactive layer comprising an electron accepting material and an electron donating material, wherein the ratio (Ic = c / Ic-c) of the antisymmetric value to the symmetric value of the absorption spectrum of the FT- Is increased by 110 to 150% relative to the intrinsic value of the electron accepting material and the electron donating material.

The electron accepting material and the electron donating material of the photoactive layer are treated as non-solvent.

Further, the electron accepting material and the electron donating material of the photoactive layer are heat-treated before, simultaneously or after the non-treating.

The description of the electron accepting material and the electron donating material, the non-solvent, and the heat treatment of the photoactive layer is the same as described above.

In one embodiment of the present invention, the maximum absorption wavelength of the photoactive layer is 500 to 600 nm.

Further, in one embodiment of the present invention, the organic solar battery includes a first electrode, a photoactive layer, and a second electrode.

In another embodiment, the organic solar cell may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

In addition, in one embodiment of the present invention, a buffer layer may further be introduced between the photoactive layer and the first electrode.

In another embodiment, an electron transport layer, a hole blocking layer or an optical space layer is further introduced between the photoactive layer and the second electrode.

In one embodiment of the present invention, the first electrode may be an anode electrode, or may be a cathode electrode. The second electrode may be a cathode electrode or an anode electrode.

In one embodiment of the present invention, the organic solar cell may be arranged in the order of the anode electrode, the photoactive layer, and the cathode electrode, and may be arranged in the order of the cathode electrode, the photoactive layer, and the anode electrode.

In another embodiment, the organic solar cell may be arranged in the order of an anode electrode, a hole transporting layer, a photoactive layer, an electron transporting layer, and a cathode electrode, and the cathode electrode, the electron transporting layer, the photoactive layer, the hole transporting layer, But is not limited thereto.

In another embodiment, the organic solar cell may be arranged in the order of an anode electrode, a buffer layer, a photoactive layer, and a cathode electrode.

In this specification, the buffer layer serves to reduce the energy bandgap difference between the interfaces and increase the efficiency of the organic solar cell.

The buffer layer is selected from the group consisting of PEDOT: PSS, molybdenum oxide (MoO ₃ ), tungsten oxide (WO ₃ ), and zinc oxide (ZnO).

In one embodiment, the thickness of the buffer layer is 1 to 60 nm. In another embodiment, the thickness of the buffer layer is 10 to 50 nm. In another embodiment, the thickness of the buffer layer is 30 to 45 nm.

The buffer layer within the above range is advantageous in that it can improve the light transmittance, lower the series resistance of the solar cell, improve the interfacial properties of other layers, and manufacture a solar cell with high efficiency.

The substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in organic solar cells. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The first electrode may be a transparent material having excellent conductivity, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The second electrode may be a metal having a small work function, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The hole transporting layer and / or the electron transporting layer material may be a material for efficiently transferring electrons and holes to the photoactive layer, thereby increasing the probability that the generated charge moves to the electrode. However, the hole transporting layer and / or the electron transporting layer material are not particularly limited.

The hole transport layer material may be selected from the group consisting of poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid), N, N'-bis (3-methylphenyl) -N, N'- '-Biphenyl] -4,4'-diamine (TPD). The electron transport layer material may be selected from the group consisting of aluminum trihydroxyquinolate (Alq ₃ ), 1,3,4-oxadiazole derivative PBD (2- (4-bipheyl) -5-phenyl- (3, 4-tris [(3-phenyl-6-trifluoromethyl) quinoxaline-2-yl] benzene), a triazole derivative and the like can be used as the quinoxaline derivative.

As the electron transporting material, a material capable of transferring electrons from a cathode well into a photoactive layer can be suitably used. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The organic solar cell of the present specification can be produced by materials and methods known in the art, except that the photoactive layer is treated with a non-solvent or a non-solvent and a heat treatment are performed together.

The present disclosure provides a method of manufacturing a semiconductor device, comprising: preparing a substrate;

Forming a first electrode in one region of the substrate;

Forming an organic material layer including a photoactive layer on the first electrode;

Subjecting the photoactive layer to non-solvent treatment; And

And forming a second electrode on the organic material layer.

The step of treating the photoactive layer as non-solvent in this specification includes applying a non-solvent.

In one embodiment of the present disclosure, the step of treating the photoactive layer with the non-solvent further comprises the step of removing the applied non-solvent.

The step of removing the non-solvent can be performed by adjusting the time after the application of the non-solvent, if necessary, by non-solvent swelling, or by non-solvent surface treatment.

Further comprising a heat treatment before, simultaneously with, or after the step of treating the photoactive layer with the non-solvent.

The organic solar cell of the present invention can be manufactured, for example, by sequentially laminating a first electrode, an organic material layer including a photoactive layer, and a second electrode on a substrate. At this time, they may be coated by a wet method such as gravure printing, offset printing, screen printing, ink jet, spin coating, spray coating and the like, but not limited thereto.

In one embodiment, the photoactive layer includes an electron accepting material and an electron donating material.

The description of the electron accepting material, the electron donating material, the non-solvent, the photoactive layer, the non-solvent treatment method, and the heat treatment is the same as described above.

In another embodiment, the photoactive layer is formed from a mixed solution of poly (3-hexylthiophene) (P3HT) and [6,6] -phenyl C-butyric acid methyl ester (PCBM).

In another embodiment, the method further comprises forming the organic layer before the step of forming the second electrode after the step of performing the heat treatment.

The organic material layer includes, but is not limited to, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, and a buffer layer.

In another embodiment, the method further comprises forming an organic layer before the step of forming the photoactive layer after the step of forming the first electrode.

In another embodiment, the method further comprises forming a buffer layer after the step of forming the first electrode and before the step of forming the photoactive layer.

In another embodiment, the step of subjecting the photoactive layer to non-solvent surface treatment is a spin coating or a drop coating.

The non-solvent treatment method and the production of an organic solar cell including a heat-treated photoactive layer will be described in detail in the following examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Preparation and characterization of organic solar cell

Example  One. Expense  Swelling method and production of organic solar cell subjected to heat treatment

The organic solar cell has a structure of ITO / PEDOT: PSS / photoactive layer (P3HT: PCBM) / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes. Then, PEDOT: PSS (Clavios P) Min. For the photoactive layer coating, a mixture of P3HT: PCBM was formed at a ratio of 1: 0.6 and spin-coated to a thickness of 220 nm to form a photoactive layer. 80 [mu] l of acetonitrile was applied to the photoactive layer at intervals of 10 minutes, and spin coated at 5000 rpm and treated with the non-solvent swelling method. Al was deposited to a thickness of 150 nm using a thermal evaporator under a vacuum of 3 x 10 ^-6 torr. Further, it was heat-treated at 150 占 폚 for 30 minutes.

Comparative Example  One.

Unlike Example 1, except that the non-solvent swelling method and the heat treatment were not applied, the same procedure as in Example 1 was performed.

Comparative Example  2.

Unlike Example 1, except that heat treatment was not applied, the same procedure as in Example 1 was performed.

Comparative Example  3.

Unlike Example 1, except that the non-solvent swelling method was not applied, the same procedure as in Example 1 was performed.

The photoelectric conversion characteristics of the organic solar cell prepared in Example 1 and Comparative Examples 1 to 3 were measured under the conditions of 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

division Open-circuit voltage (V _oc ) Short circuit current density (J _sc ) Fill factor Energy Conversion Efficiency (%) Example 1 0.58 8.96 0.58 3.01 Comparative Example 1 0.41 5.74 0.54 1.28 Comparative Example 2 0.40 7.42 0.53 1.58 Comparative Example 3 0.56 8.01 0.59 2.64

2 is a graph showing an organic solar cell current-voltage curve.

As shown in Table 1, in Example 1 in which both the non-solvent swelling method and the heat treatment were applied, both the non-solvent swelling method and the heat treatment were not applied, or the efficiency was improved as compared with Comparative Examples 1 to 4 in which either of the two methods was applied .

As shown in Table 1, it can be seen that the non-solvent swelling method and the heat treatment affect the energy conversion efficiency while affecting the short-circuit current density and the fill factor.

Example  2. Expense  Manufacture of organic solar cell with surface treatment method

The organic solar cell has a structure of ITO / PEDOT: PSS / photoactive layer (polymer 1: PCBM) / Al. PEDOT: PSS (Clavios AI4083) was spin-coated on the ITO-coated glass substrate by ultrasonic cleaning using distilled water, acetone, and 2-propanol, and the ITO surface was subjected to ozone treatment for 10 minutes. Min. For the coating of the photoactive layer, a mixture of the following polymer 1: PCBM in a ratio of 1: 1.75 was formed and spin-coated to a thickness of 100 nm to form a photoactive layer. Methanol was applied to the photoactive layer and spin-coated at 5000 rpm to remove the non-solvent. Al was deposited to a thickness of 150 nm using a thermal evaporator under a vacuum of 3 x 10 ^-6 torr.

[Polymer 1]

Example  3. Expense  Manufacture of organic solar cell with surface treatment method

Example 2 was carried out in the same manner as in Example 2, except that 2-methoxyethanol was used instead of methanol.

Comparative Example  4.

Example 2 was carried out in the same manner as in Example 2, except that the non-treated surface treatment method was not used.

The organic solar cell prepared in Examples 2 and 3 and Comparative Example 4 The photoelectric conversion characteristics were measured under conditions of 100 mW / cm ² (AM 1.5), and the results are shown in Table 2 below.

V _oc  (V) J _sc  ( mA / cm ² ) FF PCE  (%) Example 2 0.830 13.227 0.560 6.14 Example 3 0.835 12.820 0.595 6.37 Comparative Example 4 0.763 13.383 0.544 5.55

As shown in Table 2, when the surface of the photoactive layer is treated with the non-solvent, the build-in potential is increased through the formation of a dipole at the interface of the photoactive layer and the open voltage And the fill factor (FF), the efficiency of the organic solar cell is increased.

Claims (51)

A first electrode;
A second electrode facing the first electrode; And
And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,
Wherein the photoactive layer includes an electron accepting material and an electron donating material,
The electron accepting material and the electron donating material are treated in a non-
The non-solvent is selected from the group consisting of water, alkane, halohydrocarbon, ether, ketone, ester, nitrogen, sulfur, acid, alcohol, phenol and polyol.
The alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane,
The halohydrocarbon based non-solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, carbon tetrachloride, chlorobenzene, o -Dichlorobenzene and 1,1,2-trichlorotrifluoranthene, and one or more of them are selected,
Wherein the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether,
The ketone-based non-solvent may be 1 or 2 in the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di- (isobutyl) Or more,
The ester-based non-solvent may be at least one selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, Isoamyl acetate and isobutyl isobutylate, one or more of them is selected,
Wherein the nitrogen compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethanolamine, ethylene diemme, pyridine, morpholine, One or more selected from the group consisting of 2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide,
Wherein the sulfur compound nonwax is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol,
The alcoholic solvent may be selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, One or more selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol,
The acid scavenger is selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid, and stearic acid,
Wherein the phenolic non-ionic agent is selected from the group consisting of phenol, resorcinol, m-cresol and methyl salicylate,
Wherein the polyol-based non-solvent is one or more selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. The method according to claim 1,
Wherein the electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating. The method according to claim 1,
Wherein the non-solvent has a penetration distance of the non-solvent into the photoactive layer of 5% or more and less than 50% of the thickness of the photoactive layer upon application to the photoactive layer for 1 to 60 minutes. delete delete delete delete delete delete delete delete delete delete delete delete The method according to claim 1,
Wherein the electron accepting material is a fullerene derivative or a non-fullerene derivative. 18. The method of claim 16,
Wherein the fullerene derivative is a fullerene derivative of C60 to C90. 18. The method of claim 16,
Wherein the non-fullerene derivative has a LUMO energy level of -2.0 to -6.0 eV. The method according to claim 1,
Wherein the electron donor material comprises at least one electron donor; Or an organic solar cell comprising at least one electron acceptor and at least one electron donor polymer. The method of claim 19,
Wherein the electron donor is one or more than one in the group consisting of the following formula:

In the above formula,
a is an integer of 0 to 4,
b is an integer of 0 to 6,
c is an integer of 0 to 8,
d and e are each an integer of 0 to 3,
f and g are each an integer of 0 to 2,
R ₂ and R ₃ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring,
X ₁ to X ₃ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '
Y ₁ and Y ₂ are the same or different and are each independently selected from the group consisting of CR, N, SiR, P and GeR,
R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring. The method of claim 19,
Wherein said electron acceptor comprises one or more than one of the following groups:

In the above formula,
R ₂ to R ₅ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjoining substituents may be bonded to each other to form a condensed ring,
X ₁ and X ₂ are the same or different and each independently, CRR selected from the group consisting of ', NR, O, SiRR', PR, S, GeRR ', Se and Te from each other, Y ₁ to Y ₄ are each Are each independently selected from the group consisting of CR, N, SiR, P and GeR,
R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring. The method of claim 19,
Wherein the electron donating substance is an A unit represented by any one of formulas (1) to (3);
A B unit represented by the following formula (4); And
An organic solar cell comprising a polymer comprising a C unit represented by the following formula
[Formula 3] &lt; EMI ID =

[Chemical Formula 4]

In formulas (1) to (5)
f and g are each an integer of 0 to 2,
R ₂ to R ₄ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring,
X ₁ to X ₅ are the same or different and each independently selected from the group consisting of CRR ', NR, O, SiRR', PR, S, GeRR '
Y ₃ to Y ₅ are the same or different and are each independently selected from the group consisting of CR, N, SiR, P and GeR,
R and R 'are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may be bonded to each other to form a condensed ring. The method according to claim 1,
Wherein the non-solvent is a nitrogen compound. The method according to claim 1,
Wherein the non-solvent is acetonitrile. The method according to claim 1,
Wherein the non-solvent is one or more selected from the group consisting of alkane, ether, alcohol and acid. The method according to claim 1,
Wherein the non-solvent is methanol or 2-methoxyethanol. The method of claim 2,
Wherein the temperature of the heat treatment is not lower than a glass transition temperature (Tg) of the donor material and not higher than a thermal decomposition temperature. The method according to claim 1,
The electron accepting material is [6,6] -phenyl C-butyric acid methyl ester (PCBM)
Wherein the electron donor material is a polymer comprising poly (3-hexylthiophene) (P3HT) or a unit represented by the following formula (6):
[Chemical Formula 6]

In formula (6)
x is a molar fraction, 0 < x < 1,
y is a mole fraction, 0 < y < 1, x + y = 1,
n is an integer from 1 to 10,000,
R10 to R12 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group. The method according to any one of claims 2, 3 and 16-28,
In the organic solar cell, the ratio of the antisymmetric value and the symmetric value (Ic = c / Ic-c) of the absorption spectrum of the FT-IR is higher than the intrinsic value of the electron accepting material and the electron donating material Lt; RTI ID = 0.0 &gt; 110-150%. &Lt; / RTI &gt; The method according to any one of claims 2, 3 and 16-28,
Wherein the efficiency of the organic solar cell is increased by 110 to 200% as compared with the case where the electron-accepting material and the electron-donating material are not before being treated with the non-solvent. The method according to any one of claims 1 to 3 and 16 to 28,
Wherein the ratio of the electron accepting material to the electron donating material is from 1:10 to 10: 1. The method according to any one of claims 1 to 3 and 16 to 28,
Wherein the thickness of the photoactive layer is 50 to 300 nm. The method according to any one of claims 1 to 3 and 16 to 28,
Wherein the organic material layer comprises a buffer layer. 34. The method of claim 33,
Wherein the buffer layer has a thickness of 1 nm to 60 nm. A first electrode;
A second electrode facing the first electrode; And
And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,
Wherein the photoactive layer includes an electron accepting material and an electron donating material,
The ratio of the antisymmetric value to the symmetric value (Ic = c / Ic-c) of the absorption spectrum of the FT-IR is 110 to 150% higher than the intrinsic value of the electron accepting substance and electron donating substance Lt; / RTI &
The electron accepting material and the electron donating material are treated in a non-
The non-solvent is selected from the group consisting of water, alkane, halohydrocarbon, ether, ketone, ester, nitrogen, sulfur, acid, alcohol, phenol and polyol.
The alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane,
The halohydrocarbon based non-solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, carbon tetrachloride, chlorobenzene, o -Dichlorobenzene and 1,1,2-trichlorotrifluoranthene, and one or more of them are selected,
Wherein the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether,
The ketone-based non-solvent may be 1 or 2 in the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di- (isobutyl) Or more,
The ester-based non-solvent may be at least one selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, Isoamyl acetate and isobutyl isobutylate, one or more of them is selected,
Wherein the nitrogen compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethanolamine, ethylene diemme, pyridine, morpholine, One or more selected from the group consisting of 2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide,
Wherein the sulfur compound nonwax is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol,
The alcoholic solvent may be selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, One or more selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol,
The acid scavenger is selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid, and stearic acid,
Wherein the phenolic non-ionic agent is selected from the group consisting of phenol, resorcinol, m-cresol and methyl salicylate,
Wherein the polyol-based non-solvent is one or more selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. delete 36. The method of claim 35,
Wherein the electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating. A first electrode;
A second electrode facing the first electrode; And
And an organic material layer provided between the first electrode and the second electrode and including a photoactive layer,
Wherein the photoactive layer comprises an electron accepting material and an electron donating material,
The electron accepting material and the electron donating material are treated in a non-
The non-solvent is selected from the group consisting of water, alkane, halohydrocarbon, ether, ketone, ester, nitrogen, sulfur, acid, alcohol, phenol and polyol.
The alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane,
The halohydrocarbon based non-solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, carbon tetrachloride, chlorobenzene, o -Dichlorobenzene and 1,1,2-trichlorotrifluoranthene, and one or more of them are selected,
Wherein the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether,
The ketone-based non-solvent may be 1 or 2 in the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di- (isobutyl) Or more,
The ester-based non-solvent may be at least one selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, Isoamyl acetate and isobutyl isobutylate, one or more of them is selected,
Wherein the nitrogen compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethanolamine, ethylene diemme, pyridine, morpholine, One or more selected from the group consisting of 2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide,
Wherein the sulfur compound nonwax is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol,
The alcoholic solvent may be selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, One or more selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol,
The acid scavenger is selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid, and stearic acid,
Wherein the phenolic non-ionic agent is selected from the group consisting of phenol, resorcinol, m-cresol and methyl salicylate,
Wherein said polyol-based non-solvent is selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol,
Wherein an efficiency of the organic solar cell is increased by 110 to 200% as compared with the case where the efficiency of the organic solar cell is higher than that of an electron accepting material and an electron donating material before being treated with a non-solvent. 42. The method of claim 38,
Wherein the electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating. In a photoactive layer containing an electron accepting material and an electron donating material,
The electron accepting material and the electron donating material are treated in a non-
The non-solvent is selected from the group consisting of water, alkane, halohydrocarbon, ether, ketone, ester, nitrogen, sulfur, acid, alcohol, phenol and polyol.
The alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane,
The halohydrocarbon based non-solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, carbon tetrachloride, chlorobenzene, o -Dichlorobenzene and 1,1,2-trichlorotrifluoranthene, and one or more of them are selected,
Wherein the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether,
The ketone-based non-solvent may be 1 or 2 in the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di- (isobutyl) Or more,
The ester-based non-solvent may be at least one selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, Isoamyl acetate and isobutyl isobutylate, one or more of them is selected,
Wherein the nitrogen compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethanolamine, ethylene diemme, pyridine, morpholine, One or more selected from the group consisting of 2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide,
Wherein the sulfur compound nonwax is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol,
The alcoholic solvent may be selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, One or more selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol,
The acid scavenger is selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid, and stearic acid,
Wherein the phenolic non-ionic agent is selected from the group consisting of phenol, resorcinol, m-cresol and methyl salicylate,
Wherein the polyol-based non-solvent is one or more selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol. delete 41. The method of claim 40,
The photoactive layer has a ratio of an antisymmetric value and a symmetric value (Ic = c / Ic-c) of the absorption spectrum of the FT-IR to an intrinsic value of the electron accepting material and the electron donating material, To &lt; RTI ID = 0.0 &gt; 150%. &Lt; / RTI &gt; In a photoactive layer containing an electron accepting material and an electron donating material,
The electron accepting material and the electron donating material are treated in a non-
The non-solvent is selected from the group consisting of water, alkane, halohydrocarbon, ether, ketone, ester, nitrogen, sulfur, acid, alcohol, phenol and polyol.
The alkane-based non-solvent is selected from the group consisting of n-butane, n-pentane, n-hexane, n-octane, isooctane, n-dodecane, dichloromethane, cyclohexane and methylcyclohexane,
The halohydrocarbon based non-solvent may be at least one selected from the group consisting of chloromethane, dichloromethane, methylene chloride, 1,1-dichloroethylene, ethylene dichloride, chloroform, 1,1-dichloroethane, trichlorethylene, carbon tetrachloride, chlorobenzene, o -Dichlorobenzene and 1,1,2-trichlorotrifluoranthene, and one or more of them are selected,
Wherein the ether-based non-solvent is selected from the group consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether and dibenzyl ether,
The ketone-based non-solvent may be 1 or 2 in the group consisting of acetone, methyl ethyl ketone, cyclohexanone, diethyl ketone, acetophenone, methyl isobutyl ketone, methyl isoamyl ketone, isophorone and di- (isobutyl) Or more,
The ester-based non-solvent may be at least one selected from the group consisting of ethylene carbonate, methyl acetate, ethyl formate, propylene-1,2-carbonate, ethyl acetate, diethyl carbonate, diethyl sulfate, n-butyl acetate, isobutyl acetate, Isoamyl acetate and isobutyl isobutylate, one or more of them is selected,
Wherein the nitrogen compound is selected from the group consisting of acetonitrile, propionitrile, nitromethane, nitroethane, 2-nitropropane, nitrobenzene, ethanolamine, ethylene diemme, pyridine, morpholine, One or more selected from the group consisting of 2-pyrrolidone, cyclohexylamine, quinoline, formamide and N, N-dimethylformamide,
Wherein the sulfur compound nonwax is selected from the group consisting of carbon disulfide, dimethyl sulfoxide and ethanethiol,
The alcoholic solvent may be selected from the group consisting of methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, benzyl alcohol, cyclohexanol, diacetone alcohol, ethylene glycol monoethyl ether, One or more selected from the group consisting of glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, 2-methoxyethanol and 1-decanol,
The acid scavenger is selected from the group consisting of formic acid, acetic acid, benzenic acid, oleic acid, and stearic acid,
Wherein the phenolic non-ionic agent is selected from the group consisting of phenol, resorcinol, m-cresol and methyl salicylate,
Wherein said polyol-based non-solvent is selected from the group consisting of ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol and dipropylene glycol,
The ratio of the antisymmetric value to the symmetric value (Ic = c / Ic-c) of the absorption spectrum of the FT-IR is 110 to 150% higher than the intrinsic value of the electron accepting substance and electron donating substance Lt; / RTI &gt; delete 41. The method of claim 40 or 43,
Wherein the electron accepting material and the electron donating material are heat-treated before, simultaneously or after the non-treating. Preparing a substrate;
Forming a first electrode in one region of the substrate;
Forming an organic material layer including a photoactive layer on the first electrode;
Subjecting the photoactive layer to non-solvent treatment; And
And forming a second electrode on the organic material layer. The method for manufacturing an organic solar battery according to any one of claims 1 to 3, 16 to 28, 35, and 37 to 39. 47. The method of claim 46,
Further comprising the step of performing a heat treatment before, simultaneously with, or after the step of performing the non-solvent treatment. 47. The method of claim 46,
After forming the first electrode,
And forming an organic layer before the step of forming the photoactive layer. 47. The method of claim 46,
After forming the first electrode,
And forming a buffer layer before the step of forming the photoactive layer. 48. The method of claim 47,
Wherein the temperature of the heat treatment step is equal to or higher than a glass transition temperature (Tg) of the donor material. 47. The method of claim 46,
Wherein the thickness of the photoactive layer is 50 to 300 nm.

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