WO2012165670A1 - Method for fabricating solar cell including nanostructure - Google Patents

Abstract

Provided is a method for fabricating a solar cell including a nanostructure, which includes the steps of: preparing a substrate formed with a first electrode; forming a mixture thin film layer, in which an electron donor material and a sacrificial polymer which is immiscible with the electron donor material are mixed, on the first electrode; forming the nanostructure of the electron donor material by removing the sacrificial polymer in the mixture thin film layer by heat treatment; forming an electron acceptor material layer on the nanostructure of the electron donor material; and forming a second electrode on the electron acceptor material layer. According to the present invention, a nanostructure may be introduced to the inside of a photoactive layer via a simple method, so that the manufacturing costs of a solar cell may decrease. In addition, optical absorption efficiency, electron-hole separation efficiency and movement efficiency may increase, thereby improving the photovoltaic efficiency of a solar cell.

Description

Solar cell manufacturing method including nanostructure

The present invention relates to a solar cell manufacturing method, and more particularly to a solar cell manufacturing method comprising a nanostructure in the photoactive layer.

A solar cell is a semiconductor device that converts light energy directly into electrical energy using a photovoltaic effect. Recently, many studies have been conducted as part of clean alternative energy technologies in the face of environmental problems and high oil price problems.

Among them, the organic solar cell has a high absorption coefficient of the organic molecules used as the photoactive layer can be manufactured in a thin device, can be manufactured with a simple manufacturing method and a low equipment cost, due to the characteristics of the organic material has good flexibility and processability, etc. There are several advantages that can be applied in the field. However, it is pointed out that the conventional organic solar cell has a low photovoltaic efficiency due to its low charge trap density, low charge lifetime, low mobility, short diffusion length, and low photoelectric conversion efficiency.

In order to generate a photocurrent in a solar cell, excitons generated in the photoactive layer by absorption of light must be separated into electrons and holes at a junction interface between an electron donor material and an electron acceptor material. However, in general, the distance that excitons can move is very small compared to the thickness of the light absorbing layer, which is about 10 nm, which is a fundamental factor limiting the efficiency of the solar cell. In order to improve the donor-acceptor interface area by introducing nanostructures such as nanorods or nanowires into the photoactive layer, research is being conducted. However, the conventional electrochemical method using the porous alumina template has a problem of device contamination by impurities contained in the electrolyte, and the chemical vapor growth method and the vapor phase epitaxy growth method require expensive equipment and high vacuum, resulting in high manufacturing costs. Has a problem.

The technical problem to be solved by the present invention is to provide a solar cell manufacturing method that can improve the photoelectric conversion efficiency, and can reduce the manufacturing cost.

In order to achieve the above technical problem, an aspect of the present invention provides a method of manufacturing a solar cell including a nanostructure in a photoactive layer.

The method includes preparing a substrate on which a first electrode is formed, forming a mixed thin film layer on which the electron donor material and a sacrificial polymer that is incompatible with the electron donor material are mixed, and the sacrificial polymer in the mixed thin film layer. Heat treatment to form a nanostructure of the electron donor material, forming an electron acceptor material layer on the nanostructure of the electron donor material, and forming a second electrode on the electron acceptor material layer. Include.

The sacrificial polymer may be polyalkylene glycol, preferably polyethylene glycol or polypropylene glycol.

The electron donor material is pentacene, coumarin 6, ZnPC, CuPC, TiOPC, Spiro-MeOTAD, F16CuPC, SubPc, N3, P3HT, P3KT, PT, P3OT, PCPDTBT, PCDTBT, PFDTBT, MEH-PPV, MDMO-PPV, PFO And PFO-DMP.

The electron acceptor material layer may be an n-type organic semiconductor layer or an n-type metal oxide layer.

In this case, the n-type organic semiconductor layer is C ₆₀ , PC ₆₁ BM, PC ₇₁ BM, PC ₈₁ BM, PDCDT, PenPTC, PTCBI, ADIDI, PTCDA, PTCDI, NTDA, MePTC, HepPTC, Liq, TPBi, PBD, BCP , Bphen, BAlq, Bpy-OXD, BP-OXD-Bpy, TAZ, NTAZ, NBphen, Bpy-FOXD, OXD-7, 3TPYMB, 2-NPIP, HNBphen, POPy2, BP4mPy, TmPyPB and BTB The n-type metal oxide layer may be a layer including any one selected from ZnO, TiO _2, and SnO ₂ .

The nanostructure of the electron donor material may be a thin film electron donor material layer having a plurality of holes or a protrusion type electron donor material layer composed of a plurality of protrusions.

Forming the mixed thin film layer may be performed by a spin coating method.

Further, before forming the mixed thin film layer, the method may further include forming a hole transport layer on the first electrode.

Another aspect of the present invention to achieve the above technical problem is to prepare a substrate on which a first electrode is formed, forming a mixed thin film layer in which an electron donor material and polyethylene glycol is mixed on the first electrode, polyethylene in the mixed thin film layer Removing glycol by heat treatment to form a nanostructure of an electron donor material, forming an electron acceptor material layer on the nanostructure of the electron donor material, and forming a second electrode on the electron acceptor material layer It provides a solar cell manufacturing method comprising a.

According to the present invention as described above, by introducing a nanostructure in the photoactive layer, it is possible to increase the light absorption efficiency, the separation efficiency of the electrons and holes and the transfer efficiency to improve the photoelectric conversion efficiency of the solar cell.

In addition, since the nanostructure can be manufactured through a simple solution process and heat treatment, the manufacturing cost of the solar cell can be lowered, and a large area device can be manufactured. In addition, since the crystallinity of the electron donor material may be improved through the heat treatment, charge transfer efficiency may be further improved.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a flowchart illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.

2A to 2F are perspective views illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.

3a and 3b are SEM images (Fig. 3b is a cross-sectional SEM image) of the nanostructures prepared according to Experimental Example 1.

4 is an SEM image of a nanostructure prepared according to Experimental Example 2. FIG.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the present invention to those skilled in the art. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. Like numbers refer to like elements throughout. In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.

1 is a flowchart illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.

2A to 2F are perspective views illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.

Referring to FIGS. 1S10 and 2A, a substrate 100 on which a first electrode 110 is formed is prepared.

The substrate 100 is used to support a solar cell, a transparent inorganic substrate selected from glass, quartz, Al ₂ O ₃ and SiC, or polyethylene terephthlate (PET), polyethersulfone (PES), polystyrene (PS), and PC ( It may be a light-transmissive plastic substrate selected from polycarbonate, polyvinyl chloride (PVC), polyvinyl pyrrolidone (PVP), polyimide (PI), polyethylene (PE), polyethylene naphthalate (PEN), and polyarylate (PAR).

The first electrode 110 is positioned on the substrate 100, and is preferably a light transmissive material so that light passing through the substrate 100 reaches the photoactive layer. The first electrode 110 is a conductive material having a low resistance, and may serve as an anode that receives holes generated in the photoactive layer disposed thereon and transfers the holes to the external circuit.

In this case, the first electrode 110 may be formed of indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), Al-doped ZnO (AZO), Ga Doped ZnO (GZO), In / Ga-doped ZnO (IGZO), Mg-doped ZnO (MZO), Mo-doped ZnO, Al-doped MgO, Ga-doped MgO and CuAlO ₂ It can be one act.

In addition, the first electrode 110 may be an organic electrode of any one of graphene, carbon nanotubes, C ₆₀ (fullerenes, fllerene), conductive polymers, and composites thereof. When the first electrode 110 is formed of an organic material electrode, a solar cell can be easily formed on a flexible plastic substrate.

The first electrode 110 may be appropriately selected from a thermal evaporation method, an e-beam evaporation method, a sputtering method, a chemical vapor deposition method, or a similar method.

Referring to FIGS. 1S11 and 2B, a hole transport layer 115 is formed on the first electrode 110.

The hole transport layer 115 may easily transfer holes generated in the photoactive layer to the first electrode 110, and may act as a buffer layer to reduce the surface roughness of the first electrode 110.

The hole transport layer 115 is NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, DMFL-TPD, DMFL-NPB, DPFL-TPD, DPFL-NPB, α-NPD, Spiro-TAD, BPAPF, NPAPF , NPBAPF, Spiro-2NPB, PAPB, 2,2'-Spiro-DBP, Spiro-BPA, TAPC, Spiro-TTB, β-TNB, HMTPD, α, β-TNB, α-TNB, β-NPP, PEDOT: It may be formed of any one selected from PSS and PVK. However, the present invention is not limited thereto, and other materials having an energy level between the HOMO level of the electron donor material and the work function (or HOMO level) of the first electrode may be used.

However, the process of forming the hole transport layer 115 may be omitted.

1 (S12) and FIG. 2C, an incompatible sacrifice with an electron donor material and an electron donor material is performed on the hole transport layer 115 (if the hole transport layer is omitted, the first electrode 110). The mixed thin film layer 120 is formed of the polymer.

The sacrificial polymer is a material that is removed after the mixed thin film layer 120 is formed, and a material that becomes a means for converting the mixed thin film layer 120 into a nanostructure of an electron donor material as described below by removing the mixed thin film layer 120. to be. The sacrificial polymer may be a polyether based compound, for example, polyalkylene glycol, preferably polyethylene glycol or polypropylene glycol, and more Preferably it may be polyethylene glycol (polyethylene glycol). However, the present invention is not limited thereto.

On the other hand, throughout the present specification, the polyalkylene glycol (polyalkylene glycol) refers to the oligomer (oligomer) or polymer (alkyl) of the alkylene oxide (alkylene oxide), polyalkylene oxide (polyalkylene oxide) and polyoxy It is to be understood as encompassing polyoxyalkylenes.

The electron donor material absorbs sunlight incident from the outside to form electron-hole pairs (exitons, excitons), and moves holes separated from the pn junction interface between the electron donor material and the electron acceptor material in an anode direction. It means a substance that makes. That is, the electron donor material may be a low molecular or high molecular organic material that can be used as a p-type semiconductor, for example, pentacene, coumarin 6 (coumarin 6, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin), zinc phthalocyanine (ZnPC), copper phthalocyanine (CuPC), titanium oxide phthalocyanine (TiOPC), Spiro-MeOTAD (2,2 ', 7,7'-tetrakis (N, Np-dimethoxyphenylamino) -9,9'- spirobifluorene), F16CuPC (copper (II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H, 31H-phthalocyanine), SubPc (boron subphthalocyanine chloride) and N3 (cis-di (thiocyanato) -bis (2,2'-bipyridyl-4,4'-dicarboxylic acid) -ruthenium (II)), or P3HT (poly ( 3-hexylthiophene-2,5-diyl)), P3KT (poly [3- (potassium-6-hexanoate) thiophene-2,5-diyl]), PT (poly (thiophene-2,5-diyl)), P3OT (poly (3-octylthiophene-2,5-diyl)), PCPDTBT (poly [2,6- (4,4-bis- (2-ethylhexyl) -4H-cyclopenta [2,1-b; 3,4- b '] dithiophene) -alt-4,7- (2,1,3-benzothiadiazole)]), PCDTBT (poly [N-9 "-hepta-decanyl-2,7- carbazole-alt-5,5- (4 ', 7'-di-2-thienyl-2', 1 ', 3'-benzothiadiazole)]), PFDTBT (poly (2,7- (9- (2'- ethylhexyl) -9-hexyl-fluorene) -alt-5,5- (4 ', 7'-di-2-thienyl-2', 1 ', 3'-benzothiadiazole))), MEH-PPV (poly [1 -methoxy-4- (2-ethylhexyloxy-2,5-phenylenevinylene)]), MDMO-PPV (poly [2-methoxy-5- (3,7-dimethyloctyloxy) -1,4-phenylenevinylene]), PFO (poly (9,9-dioctylfluorenyl-2,7-diyl)) and PFO-DMP (poly (9,9-dioctylfluorenyl-2,7-diyl) end capped with dimethylphenyl). However, the present invention is not limited thereto.

On the other hand, the mixed thin film layer 120 is a casting method, a spin coating method, an ink-jet printing method, a screen printing (casting method) of the mixed solution containing the electron donor material and the sacrificial polymer It may be formed by coating by a screen printing method, a doctor blade method, or the like, and preferably by a spin coating method.

In this case, the solvent of the mixed solution is not particularly limited as long as it is a solvent capable of dissolving both the electron donor material and the sacrificial polymer. For example, when P3HT is used as the electron donor material and polyethylene glycol is used as the sacrificial polymer, Organic solvents such as chlorobenzene or dichlorobenzene may be used.

Referring to FIGS. 1S14 and 2D, the sacrificial polymer in the mixed thin film layer 120 is removed by heat treatment to form the nanostructure 130 of the electron donor material.

The nanostructure 130 of the electron donor material may be formed through phase separation between the electron donor material and the sacrificial polymer and removal of the sacrificial polymer by heat treatment in the process of forming the mixed thin film layer 120.

The nanostructure 130 of the electron donor material may be, for example, a thin film electron donor material layer having a plurality of holes or a protrusion type electron donor material layer composed of a plurality of protrusions (nano shown in FIG. 2D). The structure 130 is an exaggerated representation of the projection electron donor material layer).

In this case, the width and height of the hole and the protrusion may be adjusted in the range of several to several hundred nanometers (nm) by adjusting the concentration and spin coating speed of the mixed solution containing the electron donor material and the sacrificial polymer.

In addition, the heat treatment temperature may be selected in an appropriate range depending on the type of sacrificial polymer used, for example, when using polyethylene glycol may be selected in a temperature range of about 160 ℃ to 300 ℃ depending on its molecular weight. .

In particular, since the solvent and the sacrificial polymer are removed through the heat treatment process, the crystallinity of the electron donor material may be improved, thereby increasing the transfer efficiency of the charge generated in the photoactive layer.

Referring to FIGS. 1S16 and 2E, an electron acceptor material layer 140 is formed on the nanostructure 130 of the electron donor material.

The electron acceptor material layer 140 forms a photoactive layer 150 together with the nanostructure 130 of the electron donor material, and moves the separated electrons at the pn junction interface 135 in the direction of the cathode. Means.

The electron acceptor material layer 140 may be an n-type organic semiconductor layer or an n-type metal oxide layer.

The n-type organic semiconductor layer is, for example, C ₆₀ (fullerene), PC ₆₁ BM ([6,6] -phenyl-C ₆₁ -butyric acid methyl ester), PC ₇₁ BM ([6,6] -phenyl-C ₇₁ -butyric acid methyl ester), PC ₈₁ BM (([6,6] -phenyl-C ₈₁ -butyric acid methyl ester), PDCDT (N, N'-bis (2,5-di-tert -butylphenyl) -3,4,9,10-perylene-tetracarboxylic acid diimide), PenPTC (perylene-3,4,9,10-tetracarboxylic acid N, N'-dipenthylimide), PTCBI (perylene-3,4,9) , 10-tetracarboxylic bis-benzimidazde), ADIDI (antra [2 ", 1", 9 ";4,5,6,6", 5 ", 10"; 4 ', 5', 6 '] diisoquino [2, 1-a; 2 ', 1'-a'] diperimidine-12,25-dione), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), perylene-3,4,9,10- tetracarboxylic acid dimide), NTDA (1,4,5,8-naphthalenetetracarboxylic dianhydride), meptc (perylene-3,4,9,10-tetracarboxylic acid N, N'-dimethylimide), HepPTC (perylene-3,4,9) , 10-tetracarboxylic acid N, N'-diheptylimide), Liq (8-hydroxyquinolinolato-lithium), TPBi (2,2 ', 2 "-(1,3,5-benzinetriyl) -tris (1-phenyl-1- H-benzimidazole)), PBD (2,9-dimethyl-4,7-diphenyl-1,10- phenanthroline), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2-methyl-8-quinolinolate ) -4- (phenylphenolato) aluminium), Bpy-OXD (1,3-bis [2- (2,2'-bipyridine-6-yl) -1,3,4-oxadiazo-5-yl] benzene), BP-OXD-Bpy (6,6'-bis [5- (biphenyl-4-yl) -1,3,4oxadiazo-2-yl] -2,2'-bipyridyl), TAZ (3- (4-biphenyl ) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole), NTAZ (4- (Naphthalen-1-yl) -3,5-diphenyl-4H-1,2,4-triazole), NBphen (2,9-bis (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline), Bpy-FOXD (2,7-bis [2- (2,2'-bipyridine-6- yl) -1,3,4-oxadiazo-5-yl] -9,9-dimethylfluorene), OXD-7 (1,3-bis [2- (4-tert-butylphenyl) -1,3,4-oxadiazo -5-yl] benzene), 3TPYMB (tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl) borane), 2-NPIP (1-methyl-2- (4- (naphthalen- 2-yl) phenyl) -1H-imidazo [4,5f] [1,10] phenanthroline), HNBphen (2- (naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline), POPy2 ( phenyl-dipyrenylphosphine oxide), BP4mPy (3,3 ', 5,5'-tetra [(m-pyridyl) -phen-3-yl] biphenyl), TmPyPB (1,3,5-tri [(3-pyridyl) -phe n-3-yl] benzene) and BTB (4,4'-bis (4,6-diphenyl-1,3,5-triazin-2-yl)).

The n-type metal oxide layer may be, for example, a layer including any one selected from ZnO, TiO _2, and SnO ₂ .

Meanwhile, the electron acceptor material layer 140 may cast, spin coat, inkjet print, or screen a solution containing the n-type organic semiconductor or the n-type metal oxide (specifically, a metal oxide in the form of nanoparticles). It can apply | coat and form by the printing method. However, the present invention is not limited thereto.

Through this process, the photoactive layer 150 may form a structure in which the electron acceptor material layer 140 meshes with the nanostructure 130 of the electron donor material in nanoscale, resulting in an increase in the pn junction interface 135. Therefore, it is possible to improve the electron-hole resolution of excitons generated by light absorption.

Referring to FIGS. 1S18 and 2F, a second electrode 160 is formed on the electron acceptor material layer 140.

The second electrode 160 is a conductive material having a low resistance, and may serve as a cathode that receives electrons generated by the photoactive layer 150 disposed below and transfers the electrons to an external circuit.

The second electrode 160 may be a metal electrode made of any one selected from Al, Au, Cu, Pt, Ag, W, Ni, Zn, Ti, Zr, Hf, Cd, Pd, and alloys thereof.

In addition, the second electrode 160 may be an organic electrode including any one selected from graphene, carbon nanotubes, fullerenes, conductive polymers, and composites thereof, and the second electrode 160 may be formed of a transparent organic electrode. In this case, light reception at the top of the battery is possible.

The second electrode 160 may be formed by applying a thermal image deposition method, an electron beam deposition method, a sputtering method, a chemical vapor deposition method or an electrode forming paste containing a metal and then heat treatment.

As described above, according to the present invention, by introducing nanostructures into the photoactive layer, it is possible to increase the light absorption area and increase the effective separation region where the excitons generated by the increased pn junction interface can be separated into electrons and holes. Therefore, the separation efficiency of excitons can be improved. In addition, unlike the conventional bulk heterojunction structure, the electron donor material and the electron acceptor material have a continuous phase structure in which the electron donor material and the electron acceptor material are respectively connected to the anode and the cathode. Can be moved to improve the transfer efficiency of the charge. In addition, since a texturing effect of suppressing total reflection of light incident on the solar cell may be obtained, light absorption efficiency may be improved.

In addition, the nanostructure formation in the present invention can be formed by a simple method of applying a mixture of the electron donor material and the sacrificial polymer through a solution process such as spin coating, and then heat treatment to lower the manufacturing cost of the solar cell There is this. In addition, it is possible to improve the crystallinity of the electron donor material through the heat treatment process, which can further improve the transfer efficiency of the charge to contribute to the photoelectric conversion efficiency.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Experimental Example 1 Preparation of Nanostructure (1)

P3HT (poly (3-hexylthiophene-2,5-diyl)) and PEG (polyethylene glycol) were dissolved in 1 ml of chlorobenzene in a weight ratio of 5: 1 (30 mg: 6 mg), respectively, to prepare a mixed solution. Next, the mixed solution was spin coated on the substrate at 2000 rpm for 5 seconds to form a mixed thin film containing a mixture of P3HT and PEG. The substrate was then placed on a hot plate and heat treated at 180 ° C. for 10 minutes to remove PEG (and chlorobenzene).

3a and 3b are SEM images (Fig. 3b is a cross-sectional SEM image) of the nanostructure prepared according to Experimental Example 1.

Referring to FIGS. 3A and 3B, it can be seen that a thin film P3HT layer having a plurality of holes can be formed by removing PEG from the mixed thin film containing P3HT and PEG by heat treatment.

Experimental Example 2: Fabrication of Nanostructures (2)

P3HT (poly (3-hexylthiophene-2,5-diyl)) and PEG (polyethylene glycol) were dissolved in 3 ml of chlorobenzene in a weight ratio of 5: 1 (50 mg: 10 mg), respectively, to prepare a mixed solution. Next, the mixed solution was spin coated on the substrate at 5000 rpm for 40 seconds to form a mixed thin film containing a mixture of P3HT and PEG. The substrate was then placed on a hot plate and heat treated at 180 ° C. for 10 minutes to remove PEG (and chlorobenzene).

4 is an SEM image of a nanostructure prepared according to Experimental Example 2.

Referring to Figure 4, it can be seen that through the removal of PEG by heat treatment in the mixed thin film containing P3HT and PEG, it is possible to form a projection-like P3HT layer consisting of a plurality of projections.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. Changes are possible.

[Description of the code]

100 substrate 110 first electrode

115: hole transport layer 120: mixed thin film layer

130: nanostructure of the electron donor material 135: p-n junction interface

140: electron acceptor material layer 150: photoactive layer

160: second electrode

Claims (12)

Preparing a substrate on which the first electrode is formed; Forming a mixed thin film layer on which the electron donor material and the sacrificial polymer which are incompatible with the electron donor material are mixed on the first electrode; Removing the sacrificial polymer in the mixed thin film layer by heat treatment to form a nanostructure of an electron donor material; Forming an electron acceptor material layer on the nanostructure of the electron donor material; And Forming a second electrode on the electron acceptor material layer. The method of claim 1, The sacrificial polymer is a polyalkylene glycol solar cell manufacturing method. The method of claim 2, The polyalkylene glycol is a polyethylene glycol or polypropylene glycol solar cell manufacturing method. The method of claim 1, The electron donor material is pentacene, coumarin 6, ZnPC, CuPC, TiOPC, Spiro-MeOTAD, F16CuPC, SubPc, N3, P3HT, P3KT, PT, P3OT, PCPDTBT, PCDTBT, PFDTBT, MEH-PPV, MDMO-PPV, PFO And PFO-DMP any one selected from the solar cell manufacturing method. The method of claim 1, The electron acceptor material layer is an n-type organic semiconductor layer or n-type metal oxide layer solar cell manufacturing method. The method of claim 5, The n-type organic semiconductor layer is C ₆₀ , PC ₆₁ BM, PC ₇₁ BM, PC ₈₁ BM, PDCDT, PenPTC, PTCBI, ADIDI, PTCDA, PTCDI, NTDA, MePTC, HepPTC, Liq, TPBi, PBD, BCP, Bphen, Containing any one selected from BAlq, Bpy-OXD, BP-OXD-Bpy, TAZ, NTAZ, NBphen, Bpy-FOXD, OXD-7, 3TPYMB, 2-NPIP, HNBphen, POPy2, BP4mPy, TmPyPB and BTB Layer solar cell manufacturing method. The method of claim 5, The n-type metal oxide layer is a solar cell manufacturing method of a layer containing any one selected from ZnO, TiO ₂ and SnO ₂ . The method of claim 1, The nanostructure of the electron donor material is a thin film type electron donor material layer having a plurality of holes solar cell manufacturing method. The method of claim 1, The nanostructure of the electron donor material is a solar cell manufacturing method is a projection type electron donor material layer consisting of a plurality of projections. The method of claim 1, Forming the mixed thin film layer is a solar cell manufacturing method that is performed by a spin coating method. The method of claim 1, Forming a hole transport layer on the first electrode before forming the mixed thin film layer further comprises a solar cell manufacturing method. Preparing a substrate on which the first electrode is formed; Forming a mixed thin film layer on which the electron donor material and polyethylene glycol are mixed on the first electrode; Removing the polyethylene glycol in the mixed thin film layer by heat treatment to form a nanostructure of an electron donor material; Forming an electron acceptor material layer on the nanostructure of the electron donor material; And Forming a second electrode on the electron acceptor material layer.

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