KR20140077593A - Method for manufacturing organic device and organic device manufactured by using the same - Google Patents

Abstract

The present invention provide a method for manufacturing an organic device capable of improving efficiency of an organic device by forming a stable multi-layered thin film structure of of a flat and even surface; and an organic device manufactured using the same. The manufacturing method comprises a step of forming a thin film layer on the substrate by coating the substrate with a coating solution while transferring the substrate in a roll-to-roll method.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an organic device,

The present invention relates to a method of manufacturing an organic device and an organic device manufactured using the same.

An organic device is a device using a charge-transporting organic compound such as an organic solar cell, an organic electroluminescent device, and an organic field effect transistor, and generally has a multilayer thin film structure. Since organic compounds can be designed and synthesized in a variety of ways, the organic devices using the organic compounds have unlimited potential for development.

The organic device having a multilayer thin film structure can be manufactured by various coating methods such as slot die coating, spray coating, spin coating, and gravure coating, and a roll-to-roll slot die coating method It is mainly used. However, when the multi-layer thin film structure is formed through the slot die coating, spreadability and wettability are not good due to the surface energy of the thin film formed first and the surface tension of the coating liquid to be coated later. As a result, There is a problem that it is difficult. Also, if the roll-to-roll process is repeated several times, there is a high possibility that the surface of the web is contaminated. Also, the contamination caused by the roll-to-roll process causes imbalance of the surface tension of the coating liquid and causes defects on the surface of the thin film.

Various techniques have been researched and developed to solve such problems in slot die coating. Specifically, Korean Patent Laid-Open Publication No. 2008-0020283 discloses a method of discharging a plurality of coating liquids through a plurality of slots in one slot die. However, this method has a problem that the kinds of usable solvents are limited. Korean Patent Laid-Open Publication No. 2010-0062742 discloses a method in which one material is first coated, and then another material is coated, thereby coating a plurality of layers of a heterogeneous material. However, in the case of the above method, the spreadability and the wettability are poor due to the mutual properties of the materials, so that the coating process can not proceed smoothly.

Korean Patent Publication No. 2008-0020283 (published on March 5, 2008) Korean Patent Publication No. 2010-0062742 (Published on June 10, 2010)

 Solar Energy Materials & Solar Cells 98 (2012) 118-123  Solar Energy Materials & Solar Cells 95 (2011) 731-734

It is an object of the present invention to provide a method of manufacturing an organic device capable of improving the efficiency of an organic device by forming a stable multilayer thin film structure of a flat and even surface.

Another object of the present invention is to provide an organic device manufactured by the above manufacturing method.

According to an embodiment of the present invention, there is provided a method of forming a thin film on a substrate, the method comprising: coating a coating solution while transferring the substrate in a roll-to-roll manner to form a thin film layer on the substrate; The organic semiconductor layer being formed on the substrate.

The fluorine-based additive preferably has at least one terminal of the fluorine-containing polymer with at least one terminal of the fluorine-containing polymer is a carboxyl group, an ester group, an amide group, an alkylamide group, an alcohol group, a urethane group, a siloxane group, a phosphoric acid group, a polyether group, , A nonionic functional group, and combinations thereof.

Wherein the fluorine-based polymer is at least one selected from the group consisting of perfluoropolyether, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, poly-1,2-difluoroethylene, It can be chosen from the group.

Preferably, the fluorine-based additive may be a compound of the following formula 1 or 2:

[Chemical Formula 1]

X ₁ -CF ₂ O- (CF ₂ -CF ₂ -O) p- (CF ₂ O) q-OCF ₂ -X ₂

(2)

X ₃ -CF ₂ O- (CF ₂ -O-CF ₂ -CF ₂ -O) r-CF ₂ -X ₄

X ₁ to X ₄ each independently represent a functional group selected from the group consisting of a carboxyl group, an ester group, an amide group, an alkylamide group, an alcohol group, a urethane group, a siloxane group, a phosphoric acid group, a polyether group, an anionic functional group, a cationic functional group, And a combination thereof. The ratio of p / q is an integer of 1 to 4, and r is an integer of 1 or more.

Preferably, X ₁ to X ₄ each independently represent -COOH, -COOR, -CONH ₂ , -CONHR, -ROH, -R (OR ') _x OH, -NHCOOR, (-NHRSi (OR') ₃ , HO (P = O) (OH ) O-, -RO (P = O) (OH) 2, -O (RO) x -, COONR 3 H +, NR 3 H + COCH 3 O- , and a combination thereof Wherein R and R 'are each independently an alkyl group having 1 to 10 carbon atoms and x is an integer of 1 or more. More preferably, X ₁ to X ₄ each independently represent -COOH, -COOCH _{2 CH 3, -CONHC 18 H 37} , -CH 2 OH, -CH 2 (OCH 2 CH 2) OH, -CH 2 OCH 2 CH (OH) CH 2 OH, -CH 2 O (P = O) (OH ) ₂ , and NR ₃ H + COCH ₃ O-.

The fluorine-based additive may be a fluorine-based polymer having a polystyrene reduced weight average molecular weight of 1,000 to 2,000 g / mol by gel permeation chromatography.

The fluorine-based additive may have a ratio (Mw / Mn) of the weight-average molecular weight to the number-average molecular weight of 1 to 4.

The fluorine-based additive may be included in an amount of 0.001 to 5% by weight based on the total weight of the coating solution.

Preferably, the step of forming the thin film layer may be carried out by forming a thin film layer on the substrate by slot-coating the coating solution while transferring the substrate in a roll-to-roll manner.

The step of forming the thin film layer may be a step of forming a transparent conductive thin film layer on the substrate by coating a coating solution containing a substance for forming a transparent conductive thin film layer, a fluorine-based additive and a solvent while transferring the substrate by a roll-to-roll method.

The transparent conductive thin film material for forming a tin-doped indium oxide (ITO: tin-doped indium oxide ), fluorine-doped tin oxide (FTO: fluorine-doped tin oxide ), ZnO-Ga 2 O 3, ZnO-Al 2 O 3, SnO ₂ -Sb ₂ O ₃ , a conductive polymer, graphene, graphene oxide, carbon nanotubes, precursors thereof, and mixtures thereof.

The step of forming the thin film layer may be a step of forming a metal oxide thin film layer on the substrate by coating a coating solution containing a metal oxide thin film layer forming material, a fluorine based additive and a solvent while transferring the substrate by a roll-to-roll method.

The metal oxide thin film layer forming material may be at least one selected from the group consisting of metal chloride, metal acetate, metal citrate, metal (meth) acrylate, metal bromide, metal cyanide the metal oxide precursor may be a metal oxide precursor selected from the group consisting of cyanide, cyanide, metal phosphate, metal sulfate, metal sulfide and mixtures thereof, or metal oxide particles prepared therefrom, And is selected from the group consisting of Ti, Zn, Si, Mn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, .

The step of forming the thin film layer may be a step of forming a photoactive layer on the substrate by coating a coating solution containing an electron acceptor, a hole receptor, a fluorine-based additive and a solvent while transferring the substrate by a roll-to-roll method.

The electron acceptor (6,6) -phenyl -C ₆₁ - butyric rigs Acid methyl ester _{[(6,6) -phenyl-C 61} -butyric acid methyl ester; PCBM], (6,6) - phenyl -C ₇₁ - butyric rigs Acid methyl ester _{[(6,6) -phenyl-C 71} -butyric acid methyl ester; _{C 70 -PCBM], (6,6)} - thienyl -C ₆₁ - butyric rigs Acid methyl ester _{[(6,6) -thienyl-C 61} -butyric acid methyl ester; ThCBM], carbon nanotubes, precursors thereof, and mixtures thereof, and the hole acceptor is any one selected from the group consisting of poly-3-hexylthiophene (P3HT), poly- Poly-3-octylthiophene (P3OT), poly-p-phenylenevinylene (PPV), poly (9,9'-dioctylfluorene) (2-methoxy, 5- (2-ethylhexyloxy) -1,4-phenylenevinylene, MEH- PPV], poly (2-methyl, 5- (3 ', 7'-dimethyloctyloxy) ) -1,4-phenylene vinylene, MDMOPPV], precursors thereof, and mixtures thereof.

The step of forming the thin film layer may include a step of forming a hole transporting layer on the substrate by coating a coating solution containing a hole transporting material, a fluorine-based additive and a solvent while transferring the substrate by a roll-to-roll method.

The hole transport material may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), poly (styrenesulfonate) (PSS), polyaniline, phthalocyanine, pentacene, polydiphenylacetylene, Acetylene, poly (trifluoromethyl) diphenylacetylene, copper phthalocyanine (Cu-PC) poly (bistrifluoromethyl) acetylene, polybis (t- butyldiphenyl) acetylene, poly (trimethylsilyl) diphenylacetylene, There can be mentioned, for example, polyacetals such as poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t- Methyl) phenylacetylene, poly (trimethylsilyl) phenylacetylene, precursors thereof, and mixtures thereof.

The step of forming the thin film layer may be a step of forming an electrode layer on the substrate by coating a coating solution containing an electrode-forming material, a fluorine-based additive and a solvent while transferring the substrate by a roll-to-roll method.

The electrode layer forming material may be at least one selected from the group consisting of Ag, Cu, Au, Pt, Ti, Al, Ni, Zr, , And manganese (Mn); Or a precursor containing the metal element.

According to another embodiment of the present invention, there is provided an organic device manufactured by the above manufacturing method.

Preferably, the organic device may be an organic solar cell.

Other details of the embodiments of the present invention are included in the following detailed description.

According to the manufacturing method of the present invention, it is possible to form a stable thin film on a flat and even surface in a multilayer coating process by using an additive capable of lowering the surface tension of the coating solution without changing the surface energy of the pre-formed thin film, Thus, the efficiency of the organic device can be improved. Further, by improving the process stability by the above-described manufacturing method, the defective rate can be greatly reduced.

1 is a perspective view illustrating an organic solar cell according to an embodiment of the present invention.
FIG. 2 is a photograph (observed magnification 7 times) of a hole transport layer formed after the formation of a hole transport layer in a manufacturing process of an organic solar cell according to an embodiment. FIG.
FIG. 3A is a photograph (observed magnification 7 times) of a center portion of a hole transporting layer formed after forming a hole transporting layer in a manufacturing process of an organic solar cell according to a comparative example, and FIG. 3B is a photograph It is a photograph (observation magnification 7 times).

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In the roll-to-roll coating method, particularly when forming a multilayer thin film using a slot die of a roll-to-roll method, the surface energy of the pre-formed thin film is increased or the surface tension Can be considered. However, the method of controlling the surface energy of the preformed thin film has a risk of changing the properties of the thin film.

Accordingly, in the present invention, by using the fluorine-based additive capable of lowering the surface tension of the coating solution in forming the multilayer thin film structure of the organic device, a flat and uniform thin film can be stably formed, thereby improving the efficiency of the organic device .

That is, a method of manufacturing an organic device according to an embodiment of the present invention includes forming a thin film layer by coating a coating solution while transferring the substrate by a roll-to-roll method. The thin film layer may be at least one selected from the group consisting of a transparent conductive thin film layer, a photoactive layer, a hole transport layer, a metal oxide thin film layer and an electrode layer. The coating solution may contain at least one of a coating material for forming a thin film layer and a solvent .

The fluorine-based additive is a fluorine-based polymer exhibiting water solubility by a functional group substituted on at least one terminal of both ends of the polymer. The fluorine-based additive is not sensitive to the dispersing power, And the fluorine portion having a high electronegativity serves to lower the polarizability at the interface of the coating solution.

If the surface tension is not uniform in the coating solution, the surface of the thin film after the coating is aggregated. In particular, when contaminants are present on the substrate, a slope of the surface tension is generated in the coating liquid coated on the substrate, and as a result, the crater phenomenon occurs. On the contrary, the fluorine-based additive reduces the attraction force by the fleeting dipole at the interface of the coating solution coated on the substrate, that is, weakens the attracting force between the molecules, thereby reducing the surface tension of the coating solution, The spreadability and wettability are improved and the occurrence of surface defects is reduced.

The fluorine-based polymer specifically includes a perfluoropolyether (PFPE), polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene or poly-1,2-difluoroethylene And is preferably a perfluoropolyether.

The functional group substitutable at the terminal of the fluorine-containing polymer specifically includes a carboxyl group (-COOH), an ester group (-COOR wherein R is an alkyl group having 1 to 10 carbon atoms, for example, -COOCH ₂ CH ₃ ), an amide group (-CONH ₂ ), an alkylamido group (-CONHR wherein R is an alkyl group having 1 to 10 carbon atoms, such as -CONHC ₁₈ H ₃₇ ), an alcohol group (-ROH or -R (OR ') _x OH (Wherein R and R 'are each independently an alkyl group having 1 to 10 carbon atoms and x is an integer of 1 or more, preferably an integer of 1 to 10), for example, -CH ₂ OH, -CH ₂ (OCH ₂ CH _{2) OH, -CH 2 OCH 2} CH (OH) CH 2 OH and the like), urethane group (-NHCOOR (wherein, R is an alkyl group having 1 to 10 carbon atoms), siloxane group (-NHRSi (OR ') ₃ (wherein , R and R 'is an alkyl group having 1 to 10 carbon atoms, each independently)), phosphate groups (e.g., HO (P = O) (OH) O-, -RO (P = O) (OH) ₂ (wherein , R is an alkyl group having 1 to 10 carbon atoms)), a polyether group (-O (RO) _x - (wherein, R is C 1 An alkyl group of paper 10, x is an integer of 1 or more integer, preferably from 1 to 30), anionic (anionic) functional groups (e.g., COONR ₃ H + (where R is an alkyl group having 1 to 10 carbon atoms)), In the group consisting of a cationic functional group (e.g., NR ₃ H + COCH ₃ O-, where R is an alkyl group of 1 to 10 carbon atoms), a non-ionic functional group, It can be selected.

Preferably, the fluorine-based additive is a compound having a structure represented by the following formula (1) or (2):

[Chemical Formula 1]

X ₁ -CF ₂ O- (CF ₂ -CF ₂ -O) p- (CF ₂ O) q-OCF ₂ -X ₂

(2)

X ₃ -CF ₂ O- (CF ₂ -O-CF ₂ -CF ₂ -O) r-CF ₂ -X ₄

In the above formula, X ₁ to X ₄ each independently may be the above-mentioned substituent, the ratio of p / q is an integer of 1 to 4, and r is an integer of 1 or more.

Preferably, X ₁ to X ₄ each independently represent -COOH, -COOR, -CONH ₂ , -CONHR, -ROH, -R (OR ') _x OH, -NHCOOR, (-NHRSi (OR') ₃ , HO (P = O) (OH ) O-, -RO (P = O) (OH) 2, -O (RO) x -, COONR 3 H +, NR 3 H + COCH 3 O- , and a combination thereof (Wherein R and R 'are each independently an alkyl group having 1 to 10 carbon atoms and x is an integer of 1 or more), more preferably X ₁ to X ₄ are each independently -COOH, - _{COOCH 2 CH 3, -CONHC 18 H} 37, -CH 2 OH, -CH 2 (OCH 2 CH 2) OH, -CH 2 OCH 2 CH (OH) CH 2 OH, -CH 2 O (P = O) ( OH) ₂ , and NR ₃ H + COCH ₃ O-.

The fluorine-based additive preferably has a fluorine content of 30 to 70%.

The fluorine-based additive preferably has a kinematic viscosity (cSt) of 5 to 20,000 cSt.

The fluorine-based additive preferably has a weight average molecular weight (hereinafter referred to as "Mw") in terms of polystyrene by gel permeation chromatography (GPC) of 1,000 to 2,000 g / mol.

The fluorine-based additive preferably has a weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) of 1 to 4.

The fluorine-based additive may be included in an amount of 0.001 to 5% by weight based on the total weight of the coating solution. If the content of the fluorine-based additive is less than 0.001% by weight, the effect of using the additives is insignificant. If the content is more than 5% by weight, the properties of the thin film may be deteriorated.

The coating material may be an organic or inorganic material included in each thin film constituting the organic device. Specifically, the coating material may be any one selected from the group consisting of a material for forming a transparent conductive thin film layer, a material for forming a photoactive layer, a material for forming a hole transporting layer, a material for forming a metal oxide thin film layer, This can be appropriately selected depending on the kind of the coating layer to be formed.

Specifically, when the step of forming the thin film layer is a step of forming a transparent conductive thin film layer, the coating material may be a tin-doped indium oxide (ITO), a fluorine-doped tin oxide : fluorine-doped tin oxide), ZnO-Ga 2 O 3, ZnO-Al 2 O 3, SnO 2 -Sb 2 O 3, a conductive polymer, graphene (graphene), graphene oxide (graphene oxide), carbon nanotubes, And a mixture thereof, or a precursor thereof.

When the step of forming the thin film layer is a step of forming a metal oxide thin film layer, the coating material may be a metal oxide thin film layer forming material such as metal chloride, metal acetate, metal citrate, metal (Meth) acrylate, a metal bromide, a cyanide, a metal phosphate, a metal sulfate, a metal sulfide, and a mixture thereof. And metal oxide particles prepared therefrom. The metal may be selected from the group consisting of Ti, Zn, Si, Mn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, Pt, Ag, Rh, And the like.

Also, when the step of forming the thin film layer is a step of forming a photoactive layer, the coating material may be a hole receptor, an electron acceptor or a precursor thereof as a material for forming a photoactive layer. Specifically, the hole acceptor may be a poly-3-hexylthiophene (P3HT), a poly-3-octylthiophene (P3OT), a polyparaphenylenevinylene -phenylenevinylene, PPV, poly (9,9'-dioctylfluorene), poly (2-methoxy, 5- (2-ethyl- hexyloxy) Poly (2-methoxy, 5- (2-ethyle-hexyloxy) -1,4-phenylenevinylene, MEH-PPV] ) -1,4-phenylene vinylene, MDMOPPV]. The poly (2-methyl) -5- (3 ', 7'-dimethyloctyloxy) (6,6) -phenyl-C61-butyric acid methyl ester [(6,6) -phenyl-C61-butyric acid methyl ester; PCBM] Butyric acid methyl ester [(6,6) -thienyl (C7-PCBM), (6,6) -thienyl-C61-butyric acid methyl ester -C61-butyric acid methyl ester (ThCBM), and carbon It may be any one selected from the group consisting of tubes.

When the step of forming the thin film layer is a step of forming a hole transporting layer, the coating material may be at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), poly (styrenesulfonate) (PSS), polyaniline, phthalocyanine, pentacene, polydiphenylacetylene, poly (t-butyl) diphenylacetylene, polytrifluoromethyldiphenylacetylene, copper phthalocyanine (Cu- (Methyl) acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene , Poly (methylmethacrylate), polymethylphenylacetylene, poly (t-butyl) phenylacetylene, polynitrophenylacetylene, poly (trifluoromethyl) phenylacetylene and poly (trimethylsilyl) phenylacetylene Ball transfer may be a material or a precursor thereof.

In addition, when the step of forming the thin film layer is a step of forming an electrode, the coating material may be formed of Ag, Cu, Au, Pt, Ti, Metal particles such as aluminum (Al), nickel (Ni), zirconium (Zr), iron (Fe), and manganese (Mn); Or a precursor containing the metal element, for example, silver nitrate _{(AgNO 3), Cu (HAFC} ) 2 (Cu (hexafluoroacetylacetonate) 2,), Cu (HAFC) (1,5-Cyclooctanediene), Cu (HAFC) (1 , 5-Dimethylcyclooctanediene), Cu ( HAFC) (4-Methyl-1-pentene), Cu (HAFC) (Vinylcyclohexane), Cu (HAFC) (DMB), Cu (TMHD) 2 (Cu (tetramethylheptanedionate) 2), DMAH (dimethylaluminum hydride), TMEDA (tetramethylethylenediamine ), DMEAA (dimethylethylamine alane, NMe 2 Et · AlH 3), TMA (trimethylaluminum), TEA (triethylaluminum), TBA (triisobutylaluminum), TDMAT (tetra (dimethylamino) titanium), TDEAT (tetra (dimethylamino) titanium). When the coating material is a metal particle, the particle size of the metal particle may be 1 nm to 50 nm, preferably 3 nm to 20 nm.

The content of the coating material may be appropriately determined depending on the use of the thin film to be formed, and may be 5 to 99% by weight based on the total weight of the coating solution.

The solvent is not particularly limited as long as it can dissolve or disperse the coating material. Specifically, the solvent is water; Alcohols such as ethanol, methanol, propanol, isopropanol and butanol; (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMF), tetrahydrofuran (DMF), or the like, or a solvent such as acetone, pentane, toluene, benzene, diethyl ether, methyl butyl ether, N-methylpyrrolidone (DMSO), carbon tetrachloride, dichloromethane, dichloroethane, trichlorethylene, chloroform, chlorobenzene, dichlorobenzene, trichlorobenzene, cyclohexane, cyclopentanone, cyclohexanone, dioxane, terpineol, methyl An organic solvent such as ether ketone, or a mixture thereof, and it is preferable that the solvent is appropriately selected from among the above-mentioned solvent materials depending on the type of the coating material when preparing the coating liquid.

The solvent may be contained in an amount of the remainder in the coating solution, and preferably 1 to 95% by weight based on the total weight of the coating solution. When the content of the solvent exceeds 95 wt%, it is difficult to obtain the function of the desired coating layer. When the content of the solvent is less than 1 wt%, it is difficult to form a thin film having a uniform thickness.

The coating solution having the above-described constitution can be prepared by dispersing or dissolving the coating material in a solvent.

The substrate includes a substrate film.

The base film is not particularly limited as long as it has transparency, and may be a transparent inorganic base film such as quartz or glass, a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN), a polycarbonate (PC), a polystyrene (PEI), polyether sulfone (PES), and polyetherimide (PEI), in the group consisting of propylene (PP), polyimide (PI), polyethylene sulfonate (PES), polyoxymethylene Any one selected transparent plastic substrate film can be used. Particularly, the transparent plastic substrate film is preferably flexible and has high chemical stability, mechanical strength and transparency.

The base film preferably has a transmittance of at least 70% or more, preferably 80% or more at a visible light wavelength of about 400 to 750 nm.

The substrate may be a thin film layer or a multilayer structure thereof selected from the group consisting of a transparent conductive thin film layer, a photoactive layer, a hole transport layer, a metal oxide thin film layer and an electrode layer constituting an organic device, for example, a transparent conductive thin film layer and a metal oxide thin film layer A transparent conductive thin film layer, a metal oxide thin film layer, and a photoactive layer are sequentially stacked, a multi-layer structure in which a transparent conductive thin film layer and a photoactive layer are sequentially stacked, a transparent conductive thin film layer, a metal oxide thin film layer, Layer structure in which a sequentially stacked multilayer structure, a transparent conductive thin film layer, a photoactive layer, and a hole transport layer are sequentially stacked, a transparent conductive thin film layer, a metal oxide thin film layer, a photoactive layer, and a hole transport layer are sequentially stacked You may.

When the thin film layer is formed on the substrate, the speed at which the substrate is transported by the roll-to-roll method may be from 0.01 m / min to 20 m / min, and preferably from 0.1 m / min to 5 m / min. The feed rate may be optimized according to the coating and drying speed of the thin film layer using the roll-to-roll equipment.

The coating of the coating solution on the transferred substrate may be carried out by a method such as slot-die coating, spraying, spin coating, dipping, printing, or doctor blading, . After coating the coating solution, a post-treatment process may be carried out by selectively drying or heat-treating the coated substrate. The drying may be carried out by hot air drying, NIR drying, or UV drying at 50 to 400 ° C, preferably 70 to 200 ° C for 1 to 30 minutes.

For example, in the case of a photoactive layer, post-treatment may be performed after drying and heat treatment at 25 to 150 ° C for 5 to 145 minutes after the coating process. By appropriately controlling the drying step and the heat treatment step, appropriate phase separation can be induced between the electron acceptor and the hole acceptor, and the orientation of the electron acceptor can be induced. If the temperature is less than 25 ° C, the mobility of the electron acceptor and the hole acceptor may be low and the heat treatment effect may be insignificant. If the annealing temperature exceeds 150 ° C, Can be degraded. If the heat treatment time is less than 5 minutes, the mobility of the electron acceptor and the hole acceptor may be low and the heat treatment effect may be insufficient. If the heat treatment time exceeds 145 minutes, the performance deteriorates due to deterioration of the electron acceptor .

The thickness of the thin film layer formed according to the above-described method can be appropriately determined according to the application, and may be preferably 10 nm to 10 탆, more preferably 20 nm to 1 탆. When the thickness of the thin film layer is within the above range, the efficiency of the organic device manufactured is the most excellent.

By using the fluorine-based additive capable of lowering the surface tension of the coating solution as described above, it is possible to stably form a flat and uniform thin film, and the multilayer structure of the thin film produced by the above- ≪ / RTI > can exhibit improved efficiency.

According to another embodiment of the present invention, there is provided an organic device manufactured by the above manufacturing method.

The organic device may be one or more of the multi-layered thin films constituting the organic device by the above manufacturing method. Specifically, the organic device may be an organic solar cell, an organic electroluminescent device, or an organic field effect transistor, and preferably an organic solar cell.

Specifically, the organic solar cell includes a transparent conductive thin film layer formed on a base film using a coating solution for forming a transparent conductive thin film layer; Forming a photoactive layer on the transparent conductive thin film layer using a coating solution for forming a photoactive layer; And forming an electrode layer on the photoactive layer by using a coating solution for forming an electrode layer. At least one of the layers may be formed by a roll-to- Coated with a slot die. The method may further include a step of forming a metal oxide thin film layer after forming the transparent conductive thin film layer or a step of forming a hole transporting layer after forming the photoactive layer, and these steps may further include a step of forming a coating solution containing a fluorine- Lt; RTI ID = 0.0 > die-coating < / RTI >

Accordingly, the thin film layer not formed by the slot die coating method according to the roll-to-roll method can be manufactured by a conventional method such as spraying, spin coating, dipping, printing, doctor blading or sputtering. For example, when a transparent conductive thin film layer is prepared by a conventional method, an etch resist is screen-printed while transferring the substrate in a roll-to-roll manner, UV-cured, and then etched using an etching solution such as a copper chloride aqueous solution Followed by stripping with a stripping agent such as sodium hydroxide to form a pattern, followed by washing and drying. In the case of the anode, the anode forming material is formed on the hole transporting layer by screen printing, gravure printing, gravure-offset printing, thermal vapor deposition, electron beam deposition, RF or magnetron sputtering, chemical vapor deposition or the like You may.

1 is a perspective view illustrating an organic solar cell according to an embodiment of the present invention. 1 is an example of the present invention, but the present invention is not limited thereto. Also. The organic solar cell may be an inverted organic solar cell including a metal oxide thin film layer formed between a cathode and a photoactive layer.

1, the organic solar battery 100 includes an anode 160 and a cathode 120 disposed opposite to each other, and a light emitting layer 130 disposed between the anode 160 and the cathode 120, And a metal oxide thin film layer 170 formed between the cathode 120 and the photoactive layer 140.

The cathode 120 may include a base film 110 for supporting a cathode, and the base film is the same as described above.

The cathode 120 is a path for allowing light passing through the base film 110 to reach the photoactive layer 140, and thus includes a transparent conductive material having conductivity and high transparency. Specific examples of the anode forming material for forming the cathode 120 include tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), ZnO-Ga ₂ O ₃ , A transparent oxide selected from the group consisting of ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ and a mixture thereof, or a conductive polymer, a graphene thin film, a graphene oxide thin film, a carbon nanotube Organic-transparent electrodes such as thin films, and organic-inorganic transparent electrodes such as metal-bonded carbon nanotube thin films.

The anode 160 may be formed of a material selected from the group consisting of Ag, Cu, Au, Pt, Ti, Al, Ni, Zr, Fe), manganese (Mn), and combinations thereof.

The photoactive layer 140 has a bulk heterojunction structure in which a hole receptor and an electron acceptor are mixed.

The hole-transporting material may be an organic semiconductor such as an electrically conductive polymer or an organic low-molecular semiconductor material. The electrically conductive polymer may be a polythiophene, polyphenylenevinylene, polyfulorene, polypyrrole, , Copolymers thereof, and mixtures thereof. The organic low-molecular semiconductor material may be at least one selected from the group consisting of pentacene, anthracene, tetracene, perylene, Oligothiophenes, oligothiophenes, derivatives thereof, and combinations thereof. Preferably, the hole acceptor is selected from the group consisting of poly-3-hexylthiophene (P3HT), poly-3-octylthiophene (P3OT), poly- p-phenylenevinylene, PPV, poly (9,9'-dioctylfluorene), poly (2-methoxy, 5- (2-ethyl-hexyloxy) Poly (2-methyloxy) -5- (3 ', 7'-dimethyloctyloxy) ) -1,4-phenylene vinylene, MDMOPPV], and mixtures thereof. The term " poly (2-methyl) It can be either.

The electron acceptor may be any nanoparticle selected from the group consisting of fullerene (C ₆₀ ) or a fullerene derivative, CdS, CdSe, CdTe, ZnSe, and mixtures thereof. Preferably, the electron acceptor (6,6) -phenyl -C ₆₁ - butyric rigs Acid methyl ester _{[(6,6) -phenyl-C 61} -butyric acid methyl ester; PCBM], (6,6) - phenyl -C ₇₁ - butyric rigs Acid methyl ester _{[(6,6) -phenyl-C 71} -butyric acid methyl ester; _{C 70 -PCBM], (6,6)} - thienyl -C ₆₁ - butyric rigs Acid methyl ester _{[(6,6) -thienyl-C 61} -butyric acid methyl ester; ThCBM], carbon nanotubes, and mixtures thereof.

The photoactive layer 140 preferably includes a mixture of P3HT as the hole acceptor and PCBM as the electron acceptor, wherein the mixing weight ratio of the P3HT and PCBM may be 1: 0.1 to 1: 2.

The organic solar battery 100 may further include a hole transporting layer 150 between the anode 160 and the photoactive layer 140. The hole transport layer 150 is a layer that helps to move the holes generated in the photoactive layer 140 to the anode 160. The hole transport layer 150 may be formed of at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), poly (styrenesulfonate) (PSS), polyaniline, phthalocyanine, pentacene, polydiphenylacetylene, ) Poly (trimethylsilyl) di (triphenylmethyl) diphenyl acetylene, poly (trifluoromethyl) diphenylacetylene, copper phthalocyanine (Cu-PC) poly (bistrifluoromethyl) acetylene, (Meth) acrylates, such as phenylacetylene, poly (acetylenes), phenylacetylene, poly (carbazole) diphenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, (Trifluoromethyl) phenylacetylene, poly (trimethylsilyl) phenylacetylene, a derivative thereof, and a mixture thereof, preferably, the hole transporting material is selected from the group consisting of A mixture of PEDOT and PSS.

The organic solar battery 100 includes a metal oxide thin film layer 170 between the cathode 120 and the photoactive layer 140. The metal oxide thin film layer 170 serves as a negative electrode to increase the traveling speed of electrons to enable operation of the organic solar cell 100 and to block oxygen and moisture penetrating from the outside, The life of the organic solar battery 100 can be improved by preventing the polymer from being deteriorated by oxygen and moisture.

The metal oxide thin film layer 170 may have a thickness of 10 to 500 nm, preferably 20 to 300 nm, more preferably 20 to 200 nm. When the thickness of the metal oxide thin film layer 170 is within the above range, it is possible to effectively prevent the oxygen and moisture from penetrating from the outside and affecting the photoactive layer and the hole transporting layer while enhancing the electron moving speed.

The metal oxide contained in the metal oxide thin film layer 170 may have an average particle diameter of 10 nm or less, preferably 1 to 8 nm, and more preferably 3 to 7 nm.

The metal oxide may be selected from the group consisting of Ti, Zn, Si, Mn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, Pt, Ag, Rh, And may be an oxide of any one of metals selected from the group consisting of ZnO, and preferably ZnO. The ZnO has a broad bandgap and a semiconducting property, so that when the ZnO is used together with the cathode 120, the movement of electrons can be further improved.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

[Production Example: Production of Organic Solar Cell]

(Example)

(Prepared by mixing 247 mg of ZnO-containing coating solution (Zn (OAC) ₂ .2H ₂ O, 126 mg of KOH and 1 ml of 1-butanol) onto the ITO layer while transferring the base film on which the ITO layer was formed, Was coated on a slot die in a stripe form and then dried at 120 ° C. to form a metal oxide thin film layer of ZnO. The slot die coating had a line speed of 12 mm / sec, a slot die height of 1300 μm, and a coating liquid flow rate of 0.4 ml / min.

Then the coating solution for forming the optically active layer on the ZnO thin film layer of metal oxide (prepared by mixing lisicon SP001 ^® (Merck ^{Ltd.) 15mg, lisicon ® A-600} ( Merck & Co.), and 12mg of 1,2-dichlorobenzene (Dichlorobenzene) 1ml) Was coated on a slot die and dried at 120 DEG C to prepare a photoactive layer. The slot die coating had a line speed of 12 mm / sec, a slot die height of 1500 m, and a coating liquid flow rate of 1.2 ml / min.

Next, the optically active layer on a PEDOT: a weight ratio of 1: ^{PSS (Orgacon ® EL-P 5010} , agfa , Ltd.) with isopropyl alcohol, and fluorine-based additive (FLUOROLINK ^® P54, Solvay Solexis, Inc.) 50: 49 Was coated by slot die coating and dried at 120 캜 to form a hole transporting layer. The slot die coating was performed at a line speed of 5 mm / sec, a slot die height of 800 m, and a coating fluid flow rate of 3.0 ml / min.

Then, an Ag electrode was printed on the hole transport layer using a screen printer to produce an organic solar cell.

(Comparative Example)

And is carried out in the same manner as in Example except for using the coating solution containing the ^{PSS (Orgacon ® EL-P 5010} , agfa , Ltd.) and isopropyl alcohol in a weight ratio of 50: 50: hole transport layer formed during PEDOT Thereby preparing an organic solar cell.

[Test Example: Evaluation of Formability of Coating Layer]

The hole transport layer formed after the formation of the hole transport layer in the manufacturing process of the organic solar cell in the above Examples and Comparative Examples was observed using a microscope. The results are shown in Figs. 2, 3a and 3b.

FIG. 2 is a photograph of the hole transporting layer prepared in Example, and FIG. 3 (a) and FIG. 3 (b) are microscopic photographs of the central portion and the edge portion of the hole transporting layer prepared in Comparative Example.

Figures 2, 3a and 3b show the thin film layer formed with dark portions. As shown in FIG. 2, PEDOT: PSS was flat and uniformly coated on the formed photoactive layer in the case of forming the hole transport layer using the fluorine-based additive, whereas in the comparative example in which the fluorine-based additive was not used, It can be seen that PEDOT: PSS is coated on the center or the edge portion of the photoactive layer as shown in FIG.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

100: Organic solar cell
110: base film
120: cathode
140: photoactive layer
150: hole transport layer
160: anode
170: metal oxide thin film layer

Claims (22)

And coating the coating solution while transferring the substrate in a roll-to-roll manner to form a thin film layer on the substrate,
Wherein the coating solution comprises a fluorine-based additive. The method according to claim 1,
Wherein the fluorine-based additive has a structure in which at least one end of the fluorine-containing polymer has at least one terminal of a carboxyl group, an ester group, an amide group, an alkylamide group, an alcohol group, a urethane group, a siloxane group, a phosphate group, a polyether group, an anionic functional group, Nonionic functional groups and combinations thereof. ≪ RTI ID = 0.0 > 11. < / RTI > 3. The method of claim 2,
Wherein the fluorine-based polymer is at least one selected from the group consisting of perfluoropolyether, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, poly-1,2-difluoroethylene, Lt; RTI ID = 0.0 > (I) < / RTI > The method according to claim 1,
Wherein the fluorine-based additive is a compound having a structure represented by the following formula (1) or (2).
[Chemical Formula 1]
X ₁ -CF ₂ O- (CF ₂ -CF ₂ -O) p- (CF ₂ O) q-OCF ₂ -X ₂
(2)
X ₃ -CF ₂ O- (CF ₂ -O-CF ₂ -CF ₂ -O) r-CF ₂ -X ₄
X ₁ to X ₄ each independently represent a functional group selected from the group consisting of a carboxyl group, an ester group, an amide group, an alkylamide group, an alcohol group, a urethane group, a siloxane group, a phosphoric acid group, a polyether group, an anionic functional group, Functional group and combinations thereof, wherein the ratio of p / q is an integer of 1 to 4 and r is an integer of 1 or more. 5. The method of claim 4,
Wherein X ₁ to X ₄ are each independently selected from _{-COOH, -COOR, -CONH 2, -CONHR} , -ROH, -R (OR ') x OH, -NHCOOR, -NHRSi (OR') 3, HO (P = O (OH) O-, -RO (P = O) (OH) ₂ , -O (RO) _x- , COONR ₃ H +, NR ₃ H + COCH ₃ O- and combinations thereof. , Wherein R and R 'are each independently an alkyl group having 1 to 10 carbon atoms, and x is an integer of 1 or more. 5. The method of claim 4,
X ₁ to X ₄ each independently represent -COOH, -COOCH ₂ CH ₃ , -CONHC ₁₈ H ₃₇ , -CH ₂ OH, -CH ₂ (OCH ₂ CH ₂ ) OH, -CH ₂ OCH ₂ CH CH ₂ OH, -CH ₂ O (P═O) (OH) ₂ , and NR ₃ H + COCH ₃ O-. The method according to claim 1,
Wherein the fluorine-based additive has a polystyrene-reduced weight average molecular weight of 1,000 to 2,000 g / mol by gel permeation chromatography. The method according to claim 1,
Wherein the fluorine-based additive has a ratio (Mw / Mn) of a weight-average molecular weight to a number-average molecular weight of 1 to 4. The method according to claim 1,
Wherein the fluorine-based additive is contained in an amount of 0.001 to 5% by weight based on the total weight of the coating solution. The method according to claim 1,
Wherein the step of forming the thin film layer is carried out by performing slot die coating of a coating solution while transferring the substrate in a roll-to-roll manner to form a thin film layer on the substrate. The method according to claim 1,
Wherein the step of forming the thin film layer is a step of forming a transparent conductive thin film layer on the substrate by coating a coating solution containing a material for forming a transparent conductive thin film layer, a fluorine-based additive and a solvent while transferring the substrate in a roll- ≪ / RTI > 12. The method of claim 11,
Wherein the transparent conductive thin film layer forming material is selected from the group consisting of tin-doped indium oxide, fluorine-doped tin oxide, ZnO-Ga ₂ O ₃ , ZnO-Al ₂ O ₃ , SnO ₂ -Sb ₂ O ₃ , a conductive polymer, a graphene, a graphene oxide, a carbon nanotube, a precursor thereof, and a mixture thereof. The method according to claim 1,
Wherein the step of forming the thin film layer is a step of coating a coating solution containing a metal oxide thin film layer forming material, a fluorine based additive and a solvent while transferring the substrate in a roll-to-roll manner to form a metal oxide thin film layer on the substrate Way. 14. The method of claim 13,
Wherein the metal oxide thin film layer forming material is selected from the group consisting of metal chloride, metal acetate, metal citrate, metal acrylate, metal bromide, metal cyanide, wherein the metal oxide precursor is a metal oxide precursor selected from the group consisting of cyanide, metal phosphate, metal sulfate, metal sulfide and mixtures thereof,
The metal may be selected from the group consisting of Ti, Zn, Si, Mn, Sr, In, Ba, K, Nb, Fe, Ta, W, Sa, Bi, Ni, Cu, Mo, Ce, Pt, Ag, Rh, Lt; RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the step of forming the thin film layer is a step of forming a photoactive layer on the substrate by coating a coating solution containing an electron acceptor, a hole acceptor, a fluorine additive and a solvent while transferring the substrate in a roll-to-roll manner. 16. The method of claim 15,
Wherein the electron acceptor is (6,6) -phenyl -C ₆₁ - butyric rigs Acid methyl ester _{[(6,6) -phenyl-C 61} -butyric acid methyl ester], (6,6) - ₇₁ -C-phenyl-butyric Rick Acid methyl ester _{[(6,6) -phenyl-C 71} -butyric acid methyl ester], (6,6) - thienyl -C ₆₁ - butyric rigs Acid methyl ester [(6,6) -thienyl-C ₆₁ -butyric acid methyl ester], carbon nanotubes, precursors thereof, and mixtures thereof.
Wherein said hole acceptor is selected from the group consisting of poly-3-hexylthiophene, poly-3-octylthiophene, poly-p-phenylenevinylene, Dioctylfluorene), poly (2-methoxy, 5- (2-ethylhexyloxy) -1,4-phenylenevinylene) [poly (2- methoxy, 5- (2-ethyle-hexyloxy) -1,4-phenylenevinylene], poly (2-methyl, 5- (3 ', 7'-dimethyloctyloxy) (2-methyl, 5- (3 ', 7'-dimethyloctyloxy)) - 1,4-phenylene vinylene], precursors thereof, and mixtures thereof. The method according to claim 1,
Wherein the step of forming the thin film layer is a step of forming a hole transporting layer on the substrate by coating a coating solution containing a hole transporting material, a fluorine-based additive and a solvent while transferring the substrate in a roll-to-roll manner. 18. The method of claim 17,
Wherein the hole transport material is selected from the group consisting of poly (3,4-ethylenedioxythiophene), poly (styrenesulfonate), polyaniline, phthalocyanine, pentacene, polydiphenylacetylene, poly (t- (T-butyldiphenyl) acetylene, poly (trimethylsilyl) diphenylacetylene, poly (carbazole) di (Meth) acrylates, such as phenylacetylene, polydiacetylene, polyphenylacetylene, polypyridine acetylene, polymethoxyphenylacetylene, polymethylphenylacetylene, poly (t-butyl) phenylacetylene, polynitrophenylacetylene, (Trimethylsilyl) phenylacetylene, a precursor thereof, and a mixture thereof. The method according to claim 1,
Wherein the step of forming the thin film layer is a step of forming an electrode layer on the substrate by coating a coating solution containing an electrode forming material, a fluorine-based additive and a solvent while transferring the substrate in a roll-to-roll manner. 20. The method of claim 19,
Wherein the electrode layer forming material is at least one selected from the group consisting of Ag, Cu, Au, Pt, Ti, Al, Ni, Zr, , And manganese (Mn); Or a precursor containing the metal element. An organic device produced by the manufacturing method according to claim 1. 22. The method of claim 21,
Wherein the organic device is an organic solar cell.

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