KR20170037175A - Method for Manufacturing Organic solar cell - Google Patents

Abstract

The present invention relates to a method for manufacturing an organic solar cell, which enables production of a high-efficiency and high-quality module through surface modification when coating. The method for manufacturing an organic solar cell comprises the steps of: forming a plurality of organic material layers on a first electrode layer laminated on a substrate; and forming a second electrode on the organic material layers. A step of treating a surface to be coated by spraying a surface treatment solvent onto the surface before forming a coating layer is included in the step of forming the plurality of organic material layers. According to the present invention, a high-efficiency and high-quality organic solar cell module can be produced by minimizing a dewetting phenomenon due to shrinkage of the coating layer through surface modification before coating.

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing an organic solar cell,

The present invention relates to a method of manufacturing an organic solar cell, and more particularly, to a method of manufacturing an organic solar cell that enables a high-efficiency high-quality module to be produced through surface modification at the time of coating.

Recently, consumption of fossil fuels has rapidly increased worldwide, and oil prices are rapidly rising, and the need for clean alternative energy is increasing due to environmental problems such as global warming. As a result, countries around the world are concentrating their efforts on renewable energy sources.

Solar cell technologies that produce electricity from sunlight, which is an infinite energy source, are among the most interested in renewable energy technologies. Solar cells are devices that convert light energy into electrical energy using a photovoltaic effect. 2. Description of the Related Art In recent years, along with the rapid development of the information electronics industry, a variety of flexible devices have been attracting attention as next-generation electric and electronic devices. Organic thin film solar cells (hereinafter referred to as "organic solar cells" , It has the advantage or the advantage that the cost of material can be greatly reduced as compared with the inorganic solar cell.

Organic solar cells can be classified into conjugated polymers such as polyparaphenylenevinylene (PPV) in which double bonds are alternated, photosensitive low molecules such as CuPc, perylene, pentacene, or (6,6) And organic semiconductor materials such as C61-butyric acid methyl ester (PCBM).

The organic solar cell basically has a thin film structure, and is generally disposed between the anode and the cathode opposite to each other, and is disposed between the anode and the cathode. The organic solar cell includes a hole acceptor such as a conjugated polymer, The electron acceptor includes a photoactive layer including an organic material having a bonding structure, and further includes an organic layer of a hole transport layer and an electron transport layer on upper and lower portions of the photoactive layer, respectively.

When light is incident on the organic solar cell from an external light source, the light passes through the anode and enters the photoactive layer, and the photons that form the incident light collide with the electrons of the valence band existing in the electron acceptor of the photoactive layer. The electrons of the valence band take energy corresponding to the wavelength of the photon from the collided photon and jump to the conduction band, and holes are left in the valence band. The holes left in the electron acceptor move to the anode, the electrons in the conduction band move to the cathode, and the electrons and holes moved to each electrode cause the organic solar cell to have an electromotive force and operate as a power source.

Such an organic solar cell is advantageous in that it can be mass-produced with ease of processability and low price, and it is possible to produce a thin film by a roll-to-roll method, thereby making it possible to fabricate a large-area electronic device having flexibility . However, despite the technical and economical advantages as described above, it is difficult to put it into practical use because of its low efficiency. Accordingly, a method for efficiently utilizing the absorbed light through the selection of an optimal organic material in the organic layer including the photoactive layer, the electron transport layer, and the hole transport layer, or the development of the organic layer manufacturing process, the shape, structure, A method of increasing the charge mobility through the increase of the electron mobility, and the like.

In the production of an organic solar cell, a patterning method of forming an organic film containing a photoactive layer in a desired pattern is one of particularly important techniques. Conventional organic film patterning methods include vacuum vapor deposition, laser induced thermal imaging (LITI), ink jet printing, slot die coating, mechanical scribing ) Were used.

1 is a manufacturing process diagram showing a state in which a pattern layer is formed on a substrate of an organic solar battery in a roll-to-roll manner. As shown in Fig. 1, a slot die 10 is provided on a substrate 1 moving path in which a film-shaped substrate 1 is continuously supplied in a roll-to-roll inline manner, To form a predetermined pattern. The slot die 10 is provided at intervals on the movement path of the substrate 1 to be supplied continuously. In the slot die 10 provided at intervals, the material is discharged and applied to the substrate. In the slot die 10 provided at intervals, the material is discharged and applied to the substrate. The material discharged from each slot die 10 is sequentially stacked so that a plurality of pattern layers 2 are sequentially stacked on one substrate 1. [ The upper electrode is laminated by screen printing using silver paste.

However, when a plurality of laminated portions are formed from different materials, it is difficult to uniformly form a coating pattern due to the instability of the interface due to the difference in surface energy between the materials. In particular, shrinkage due to surface energy difference occurs, It is difficult to realize the uniformity of the product performance because of the large thickness deviation between the center and the edge of the dried film after drying.

This problem occurs particularly when a hydrophilic layer (for example, a hole transport layer) is applied on a hydrophobic layer (for example, a photoactive layer) and shrinkage is caused when the hydrophilic layer is coated on the hydrophobic layer. A dewetting phenomenon occurs due to the presence of the catalyst. The dewetting phenomenon is a phenomenon in which the applied layer is entangled into irregularly shaped (lumpy) lumps during application.

Korean Laid-Open Patent No. 2013-0121566 (published on November 11, 2013).

Korean Laid-Open Patent No. 2013-0076609 (published on July 20, 2013).

DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the problems of the conventional organic solar cell, and it is an object of the present invention to provide an organic solar cell which can produce a high-efficiency and high-quality module by minimizing the de- And a manufacturing method thereof.

A method of manufacturing an organic solar cell according to the present invention includes the steps of forming a plurality of organic layers on a first electrode layer laminated on a substrate and forming a second electrode layer on the organic layer And a surface treatment step of spraying a surface treatment solvent onto the surface to be coated before forming the coating layer in the step of forming a plurality of organic layers.

The first electrode layer may be a cathode and the second electrode layer may be an anode. The forming the organic layer may include forming an electron transport layer on the first electrode layer, forming a photoactive layer on the electron transport layer, A surface treatment with a surface treatment solvent, and a step of forming a hole transporting layer on the surface-treated photoactive layer. The surface treatment solvent is sprayed onto the photoactive layer to form a surface to be coated before forming the hole transport layer.

In the surface treatment step, the surface to be coated is surface treated by spraying the surface treatment solvent by electrospinning. The voltage for charging the surface treatment solvent in the electrospinning method is 1 to 30 kV. The surface treatment solvent flow rate is 1 to 10 ml / min.

The surface treatment solvent is preferably an alcohol-based solvent. The surface treatment solvent preferably contains a fluorine-based additive.

The fluorine-based additive is a fluorine-based additive in which at least one end of the fluorine-containing polymer has 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. The term " functional group "

The fluorine-based polymer may be at least one selected from the group consisting of perfluoropolyether, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, poly-1,2-difluoroethylene, . ≪ / RTI >

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 contained in an amount of 0.001 to 5% by weight based on the total weight of the surface treatment solvent.

According to the method of manufacturing an organic solar cell according to the present invention, it is possible to produce a high-efficiency high-quality organic solar cell module by minimizing the de-wedging phenomenon due to shrinkage of the coating layer through surface modification before coating.

Particularly, when the hydrophilic layer (hole transport layer or the like) is coated on the hydrophobic layer (photoactive layer or the like), the photoactive layer surface-treated by the surface treatment solvent (high wetting solvent or fluorinated mixed solvent) (Second electrode layer) and the photoactive layer due to the improvement of the dewetting, thereby eliminating the damages of the thin film due to the contact between the upper electrode layer (second electrode layer) and the photoactive layer. As a result, the short circuit current density, The battery module can be manufactured.

FIG. 1 is a manufacturing process diagram showing a state in which a pattern layer is formed on a substrate of a conventional organic solar battery by a roll-to-roll method.
2 is a flowchart showing a method of manufacturing an organic solar cell according to an embodiment of the present invention.
3 is a stacked structure view showing an example of an organic solar cell manufactured by the method of manufacturing an organic solar cell according to an embodiment of the present invention.
4 is a schematic view of an overall system for manufacturing an organic solar cell according to an embodiment of the present invention.
Fig. 5 is a configuration diagram showing an electrospinning device installed before the slot die of Fig. 4; Fig.
6 (a) and 6 (b) are photographs showing a state in which the hole transport layer covers the photoactive layer before and after the surface treatment with a solvent.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Note that, in the drawings, the same components are denoted by the same reference symbols as possible. Further, the detailed description of known functions and configurations that may obscure the gist of the present invention will be omitted. For the same reason, some of the components in the drawings are exaggerated, omitted, or schematically illustrated.

FIG. 2 is a flow chart showing a method of manufacturing an organic solar cell according to an embodiment of the present invention, and FIG. 3 is a laminated structure showing an example of an organic solar cell manufactured by the method of manufacturing an organic solar cell according to an embodiment of the present invention And FIG. 4 is a schematic view of an overall system for manufacturing an organic solar cell according to an embodiment of the present invention. In this embodiment, a method of manufacturing an inverted organic solar cell in which a first electrode layer coated on a substrate is a cathode (ITO electrode) will be described as an example. In addition, in this embodiment, a method of manufacturing an organic solar cell by a roll-to-roll method using a slot die and a screen printing machine will be described as an example. It goes without saying that the present invention can be applied to a method of manufacturing an organic solar cell by various coating methods.

As shown in FIG. 2, an organic solar cell according to an embodiment of the present invention includes a first electrode layer forming step S110, an electron transport layer forming step S120, a photoactive layer forming step S130, (S140), a hole transport layer formation step (S150), and a second electrode layer formation step (S160). 3, the organic solar battery 100 manufactured according to the present invention includes a substrate P, a first electrode layer 110, an electron transport layer 120, a photoactive layer 130, a hole transport layer 150, Hole transport layer) and a second electrode layer 160. The electron transport layer 120, the photoactive layer 130, and the hole transport layer 150 are organic layers.

As shown in FIG. 4, the substrate P supplied from the unwinding roll R1 is guided and conveyed by a plurality of rolls, passes through a plurality of slot dies SD1 to SD4, a printing machine and a dryer, And the barrier layer BF is laminated to form the sealing layer PL to complete the organic solar cell. An electrospinning device 50 for performing a surface treatment step S140 is provided between the slot die SD3 forming the photoactive layer 130 and the slot die SD4 forming the hole transport layer 140 .

The substrate P may be an inorganic substrate film such as quartz or glass and may be formed of a material such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polystyrene (PS), polypropylene And any one selected from the group consisting of polyimide (PI), polyethylene sulfonate (PES), polyoxymethylene (POM), polyetheretherketone (PEEK), polyether sulfone (PES), and polyetherimide May be used. In particular, the plastic base film may be flexible and have high chemical stability, mechanical strength and transparency.

The first electrode layer 110 formed through the first electrode layer forming step S110 is a cathode layer and is formed of ITO (indium tin oxide), SnO2, IZO (In2O3-ZnO), AZO (aluminum doped ZnO) Gallium doped ZnO (GZO), Graphene, CNT, nanowire, Ag grid, and Conducting polymer (PEDOT: PSS) may be used, and they may be coated with ITO (indium tin oxide).

The cathode is formed on the substrate P and may be composed of a conductive polymer material, single-walled carbon nanotubes (SWCNT), or multi-walled carbon nanotubes (MWCNT). On the other hand, in the case of the cathode, metal oxide such as ITO (indium tin oxide) is mostly used. The first electrode layer 110 is coated on the substrate P via the slot die SD1 and then dried through a dryer.

The electron transport layer 120 formed through the electron transport layer formation step S120 is formed on the first electrode layer 110 as a space through which electrons separated from the photoactive layer 130 move. At this time, the electron transport layer 120 includes ZnO nanoparticles or TiOx nanoparticles that can be dissolved. The electron transport layer 120 increases the traveling speed of the electrons to enable the operation of the organic solar cell and blocks oxygen and moisture penetrating from the outside, so that the polymer contained in the photoactive layer 130 is deteriorated by oxygen and moisture The lifetime of the organic solar battery can be improved.

The electron transporting layer 120 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 electron transporting layer 120 is within the above range, it is possible to effectively prevent the oxygen and moisture from penetrating from the outside and influencing the photoactive layer and the hole transporting layer while improving the traveling speed of electrons.

The electron transport layer 120 contains a metal oxide, and the average particle diameter of the metal oxide may be 10 nm or less, preferably 1 to 8 nm, and more preferably 3 to 7 nm. The metal oxide is composed 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 metal selected from the group consisting of ZnO and ZnO. ZnO has a wide bandgap and a semiconducting property, so that it can further improve the movement of electrons when used together with the cathode 110. [ The electron transport layer 120 is applied to the first electrode layer 110 through a slot die (not shown), and then dried through a dryer.

The photoactive layer 130 formed through the photoactive layer forming step (S130) has a bulk heterojunction structure in which a hole receptor and an electron acceptor are mixed. The hole acceptor includes an organic semiconductor such as an electrically conductive polymer or an organic low-molecular semiconductor material. The electrically conductive polymer may be any one selected from the group consisting of polythiophene, polyphenylenevinylene, polyfulorene, polypyrrole, copolymers thereof, and combinations thereof. Wherein the organic low molecular weight semiconductor material is selected from the group consisting of pentacene, anthracene, tetracene, perylene, oligothiophene, derivatives thereof, and combinations thereof. And can be any one selected.

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-methoxy-5- (2-ethyl-hexyloxy) -1,4-phenylenevinylene, MEH-PPV] ) -1,4-phenylene vinylene, MDMOPPV], and combinations thereof. The term " poly (2-methyl-5- It can be either.

The electron acceptor may be any nanoparticle selected from the group consisting of fullerene (C60) or a fullerene derivative, CdS, CdSe, CdTe, ZnSe, and combinations thereof. The electron acceptor is also (6,6) -phenyl-C61-butyric acid methyl ester [(6,6) -phenyl-C61-butyric acid methyl ester; PCBM], (6,6) -phenyl-C71-butyric acid methyl ester [(6,6) -phenyl-C71-butyric acid methyl ester; C70-PCBM], (6,6) -thienyl-C61-butyric acid methyl ester [(6,6) -thienyl-C61-butyric acid methyl ester; ThCBM], carbon nanotubes, and combinations thereof.

The photoactive layer 130 preferably comprises a mixture of P3HT as a hole acceptor and PCBM as an electron acceptor, wherein the mixing weight ratio of P3HT and PCBM may be from 1: 0.1 to 1: 2. The photoactive layer 130 is applied to the electron transport layer 120 through the slot die SD3, and then dried through a dryer.

After the photoactive layer 130 is dried through a dryer, the surface of the photoactive layer 130 is subjected to a surface treatment step S140 by spraying a surface treatment solvent to perform surface treatment.

In the surface treatment step (S140), the surface treatment solvent is sprayed by electrospinning using an electrospraying device (ESD) to perform surface treatment. The electrospinning method is a method of realizing a continuous-phase fiber having a diameter of from 탆 to nm scale by using an electric field originally. The polymer solution is discharged at a constant rate through a pump, and when a high voltage is applied, This is how fibers are formed. When the concentration of the polymer solution is low or only the solvent is used, it can be used for surface treatment by electrospraying. Conventionally, a technique of adding a surfactant to a hole transport layer has been disclosed to solve the problem of de-wettling due to shrinkage in forming a hole transport layer on a photoactive layer, but this has not been completely improved. However, when the surface treatment is performed with a high wetting solvent by the electric spraying by the electrospinning method according to the present invention, dewetting is improved, and a high-efficiency and high-quality organic solar cell can be manufactured.

As shown in FIG. 5, the electrospinning apparatus 50 includes a nozzle vessel 51 in which a high voltage is applied and a surface treatment solvent is discharged through a nozzle, a raw material vessel 52 in which a surface treatment solvent is accommodated, A pump 53 for feeding the surface treatment solvent of the nozzle 52 to the nozzles of the nozzle vessel 51 and a pump 53 for applying a reverse electric charge to the nozzle vessel 51 provided below the substrate P of the web to be conveyed Includes an electrode portion (54) with a high voltage. Since the electrospinning apparatus is similar to a general electrospinning apparatus, detailed description is omitted.

The surface treating solvent contained in the raw material container 52 is supplied to the nozzles of the nozzle container 51 at a constant speed by the pumping force of the pump 53. Due to the high voltage applied to the nozzle container 51, And is sprayed onto the photoactive layer 130 of the web conveyed on the upper side of the collector 54 to surface-treat the photoactive layer.

The spraying height is 5 ~ 30cm and the nozzle size is surface treated in 18 ~ 30G (Gauge). The spraying height is 5 ~ 30cm and the spraying height is 1 ~ 30kV, solvent flow rate is 1 ~ 10ml / The amount of solvent treated on the photoactive layer can be controlled by adjusting the flow rate of the solvent, the intensity of the voltage, the spinning (spraying) height and the nozzle size. As the voltage increases, the surface can be treated with droplets of a wider area and fine solvent. Also, as the solvent flow rate increases, the larger the nozzle size (the smaller the G value), the greater the solvent droplet size. As the radiation (spray) height increases, the area to be treated increases. Based on the above conditions, the surface treatment condition can be optimized by adjusting the surface treatment area and the size of the droplet of the treated solvent.

The photoactive layer surface-treated with such a surface treatment solvent (a high-wetting solvent or a fluorine-based mixed solvent) has a high surface energy and improved dewetting so that the thin film due to the contact between the upper electrode (second electrode layer) Thereby eliminating the demage. As a result, the short circuit current density, the open-circuit voltage and the fill factor are increased, and thus a high-efficiency and high-quality organic solar cell module can be manufactured.

Examples of the surface treatment solvent include 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. The surface treatment solvent is preferably an alcohol-based solvent. The surface treatment solvent preferably contains a fluorine-based additive.

The fluorine-based additive is a fluorine-based additive in which at least one end of the fluorine-containing polymer has 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. The term " functional group "

The fluorine-based polymer may be at least one selected from the group consisting of perfluoropolyether, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, poly-1,2-difluoroethylene, . ≪ / RTI >

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 contained in an amount of 0.001 to 5% by weight based on the total weight of the surface treatment solvent.

The hole transport layer 150 formed through the hole transport layer formation step S150 is a layer that helps to move the holes generated in the photoactive layer 130 to the second electrode layer 160 and the anode. The hole transport layer 150 may be formed of at least one selected from the group consisting of poly (3,4-ethylenedioxythiophene) (PEDOT), poly (styrene sulfonate) (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 hole transport layer 150 is applied to the photoactive layer 130 whose surface has been treated with a material through the slot die SD4, and then dried through a dryer.

The second electrode layer 160 formed through the second electrode layer forming step S160 may be an anode layer and may be a layer of Au, Al, Ag, Ca, Mg, Ba, Mo, Al-Mg, or LiF- And is preferably coated with Ag. In this embodiment, the second electrode layer 160 is formed by screen printing using silver paste, and then dried through a dryer.

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)

A ZnO-containing coating solution was slot-die-coated on the ITO layer in a stripe form while the base film on which the ITO layer was formed was transferred in a roll-to-roll manner, and then dried to form an electron transport layer of ZnO. Then, a coating solution for forming a photoactive layer was coated on the ZnO electron transport layer by slot die coating and dried to prepare a photoactive layer.

Subsequently, a surface treatment solution containing isopropyl alcohol was sprayed onto the surface of the photoactive layer. Then, the hole transport layer coating liquid was coated on the surface-treated photoactive layer by slot die coating and dried to form a hole transport layer. Then, an Ag electrode was printed on the hole transport layer using a screen printer to produce an organic solar cell.

(Comparative Example)

An organic solar cell was prepared in the same manner as in the above example except that the surface treatment with a surface treatment solvent was not performed before forming the hole transport layer.

[Test example: evaluation of the cover area in which the hole transport layer covers the photoactive layer]

The area of the hole transport layer covering the photoactive layer was observed during the manufacturing process of the organic solar cell in the above Examples and Comparative Examples. The results are shown in the photographs of FIGS. 6 (a) and 6 (b).

6 (a) is a photograph showing a state in which the hole transporting layer is covered with the photoactive layer in the example (comparative example) in which the surface treatment with a solvent is not performed, and Fig. 6 (b) In which the hole transport layer covers the photoactive layer.

6 (a), the cover area (width) in which the hole transport layer covers the photoactive layer is about 6 mm, whereas the hole transport layer in FIG. 6 (b) Was about 9 mm.

If the hole transport layer (hole transport layer) covers 90% or more of the photoactive layer, it prevents the demage or migration due to the upper electrode and thus helps to improve the lifetime.

As described above, according to the present invention, when a hydrophilic hole transport layer is coated on a hydrophobic photoactive layer, the phenomenon of shrinkage is prevented, thereby improving the dewetting. As a result, the effective photoactive area is increased and high- Solar cells can be obtained.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of the present invention in order to facilitate the understanding of the present invention and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

50: electrospinning device 51: nozzle vessel
52: raw material container 53: pump
54:
110: first electrode layer 120: electron transport layer
130: photoactive layer 150: hole transport layer
160: Second electrode layer
BF: barrier film P: substrate
PL: sealing layer R1: take-off roll
SD1 to SD4: Slot die

Claims (13)

A method of manufacturing an organic solar cell,
Forming a plurality of organic layers on a first electrode layer stacked on a substrate,
And forming a second electrode layer on the organic material layer,
And a surface treatment step of spraying a surface treatment solvent onto the surface to be coated before forming the coating layer to form a surface treatment in the step of forming the plurality of organic layers. The method according to claim 1,
Wherein the surface treatment solvent is sprayed onto the photoactive layer prior to forming the hole transporting layer, and the surface to be coated is surface-treated. The method according to claim 1,
Wherein the first electrode layer is a cathode and the second electrode layer is an anode,
The forming of the organic material layer may include forming an electron transport layer on the first electrode layer, forming a photoactive layer on the electron transport layer, surface-treating the surface of the photoactive layer with a surface treatment solvent And a step of forming a hole transporting layer on the surface-treated photoactive layer. The method of claim 3,
Wherein the surface treatment step comprises spraying the surface treatment solvent by an electrospinning method to surface-treat the surface to be coated. The method of claim 4,
Wherein the voltage for charging the surface treatment solvent in the electrospinning method is 1 to 30 KV. The method of claim 4,
Wherein the flow rate of the surface treatment solvent in the electrospinning process is 1 to 10 ml / min. The method according to claim 1,
Wherein the surface treatment solvent is an alcohol-based solvent. The method according to claim 1,
Wherein the surface treatment solvent comprises a fluorine-based additive. The method of claim 8,
The fluorine-
Wherein at least one terminal of the fluorine-containing polymer has at least one terminal 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 functional group selected from the group consisting of combinations thereof. The method of claim 9,
The fluorine-
Polybutylene terephthalate, polytetrafluoroethylene, poly-1,2-difluoroethylene, and mixtures thereof, which is selected from the group consisting of polytetrafluoroethylene, perfluoropolyether, polyvinylidene fluoride, polyvinyl fluoride, polychlorotrifluoroethylene, ≪ / RTI > The method of claim 8,
Wherein the fluorine-based additive is 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 method of claim 8,
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 of claim 8,
Wherein the fluorine-based additive is contained in an amount of 0.001 to 5 wt% based on the total weight of the surface treatment solvent.

Images