WO2012165670A1 - Procédé de fabrication d'une cellule solaire comprenant une nanostructure - Google Patents

Procédé de fabrication d'une cellule solaire comprenant une nanostructure Download PDF

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Publication number
WO2012165670A1
WO2012165670A1 PCT/KR2011/003960 KR2011003960W WO2012165670A1 WO 2012165670 A1 WO2012165670 A1 WO 2012165670A1 KR 2011003960 W KR2011003960 W KR 2011003960W WO 2012165670 A1 WO2012165670 A1 WO 2012165670A1
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Prior art keywords
layer
electron donor
solar cell
donor material
electrode
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PCT/KR2011/003960
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English (en)
Korean (ko)
Inventor
김태환
양희연
손동익
Original Assignee
한양대학교 산학협력단
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Priority to PCT/KR2011/003960 priority Critical patent/WO2012165670A1/fr
Publication of WO2012165670A1 publication Critical patent/WO2012165670A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • nanostructures such as nanorods or nanowires into the photoactive layer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the crystallinity of the electron donor material may be improved through the heat treatment, charge transfer efficiency may be further improved.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • FIGS. 2A to 2F are perspective views illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • FIG. 3a and 3b are SEM images (Fig. 3b is a cross-sectional SEM image) of the nanostructures prepared according to Experimental Example 1.
  • FIG. 4 is an SEM image of a nanostructure prepared according to Experimental Example 2.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • FIGS. 2A to 2F are perspective views illustrating a method of manufacturing a solar cell according to an embodiment of the present invention.
  • 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).
  • PVC polyvinyl chloride
  • PVP polyvinyl pyrrolidone
  • PI polyimide
  • PE polyethylene
  • PEN polyethylene naphthalate
  • PAR polyarylate
  • 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.
  • 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.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • FTO fluorine-doped tin oxide
  • ZnO zinc oxide
  • Al-doped ZnO AZO
  • Ga Doped ZnO Ga Doped ZnO
  • IGZO In / Ga-doped ZnO
  • MZO Mg-doped ZnO
  • Mo-doped ZnO Al-doped M
  • 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.
  • 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.
  • 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, ⁇ -NPB, TPD, Spiro-TPD, Spiro-NPB, DMFL-TPD, DMFL-NPB, DPFL-TPD, DPFL-NPB, ⁇ -NPD, Spiro-TAD, BPAPF, NPAPF , NPBAPF, Spiro-2NPB, PAPB, 2,2'-Spiro-DBP, Spiro-BPA, TAPC, Spiro-TTB, ⁇ -TNB, HMTPD, ⁇ , ⁇ -TNB, ⁇ -TNB, ⁇ -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.
  • the process of forming the hole transport layer 115 may be omitted.
  • 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).
  • the present invention is not limited thereto.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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 °C to 300 °C depending on its molecular weight. .
  • the crystallinity of the electron donor material may be improved, thereby increasing the transfer efficiency of the charge generated in the photoactive layer.
  • 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";
  • the n-type metal oxide layer may be, for example, a layer including any one selected from ZnO, TiO 2, and SnO 2 .
  • 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
  • the present invention is not limited thereto.
  • 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.
  • 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.
  • 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.
  • 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.
  • a texturing effect of suppressing total reflection of light incident on the solar cell may be obtained, light absorption efficiency may be improved.
  • 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.
  • a solution process such as spin coating
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • PEG polyethylene glycol
  • 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).
  • FIG. 3a and 3b are SEM images (Fig. 3b is a cross-sectional SEM image) of the nanostructure prepared according to Experimental Example 1.
  • 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.
  • P3HT poly (3-hexylthiophene-2,5-diyl)
  • PEG polyethylene glycol
  • 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).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une cellule solaire comprenant une nanostructure, lequel procédé comprend les étapes consistant à : préparer un substrat comportant une première électrode ; former sur la première électrode une couche mince de mélange, dans laquelle sont mélangés un matériau donneur d'électrons et un polymère sacrificiel qui n'est pas miscible avec le matériau donneur d'électrons ; former la nanostructure du matériau donneur d'électrons par enlèvement du polymère sacrificiel dans la couche mince de mélange par traitement thermique ; former une couche de matériau accepteur d'électrons sur la nanostructure du matériau donneur d'électrons ; et former une seconde électrode sur la couche de matériau accepteur d'électrons. Selon la présente invention, une nanostructure peut être introduite à l'intérieur d'une couche photoactive par une méthode simple, de telle sorte que les coûts de fabrication d'une cellule solaire peuvent être diminués. De plus, l'efficacité d'absorption optique, l'efficacité de séparation électrons-trous et l'efficacité de déplacement peuvent être augmentées, améliorant ainsi le rendement photovoltaïque d'une cellule solaire.
PCT/KR2011/003960 2011-05-30 2011-05-30 Procédé de fabrication d'une cellule solaire comprenant une nanostructure WO2012165670A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019107790A1 (fr) * 2017-11-28 2019-06-06 주식회사 엘지화학 Couche photoactive et cellule photovoltaïque organique la comprenant
US11502255B2 (en) 2017-11-28 2022-11-15 Lg Chem, Ltd. Photoactive layer and organic solar cell comprising same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100988206B1 (ko) * 2008-12-12 2010-10-18 한양대학교 산학협력단 탄소 나노튜브 복합재료를 이용한 태양 전지 및 그 제조방법
KR101033028B1 (ko) * 2009-06-25 2011-05-09 한양대학교 산학협력단 태양 전지 및 그 제조 방법
KR101036453B1 (ko) * 2009-07-06 2011-05-24 한양대학교 산학협력단 ｐ-ｉ-ｎ 나노선을 이용한 태양전지

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100988206B1 (ko) * 2008-12-12 2010-10-18 한양대학교 산학협력단 탄소 나노튜브 복합재료를 이용한 태양 전지 및 그 제조방법
KR101033028B1 (ko) * 2009-06-25 2011-05-09 한양대학교 산학협력단 태양 전지 및 그 제조 방법
KR101036453B1 (ko) * 2009-07-06 2011-05-24 한양대학교 산학협력단 ｐ-ｉ-ｎ 나노선을 이용한 태양전지

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019107790A1 (fr) * 2017-11-28 2019-06-06 주식회사 엘지화학 Couche photoactive et cellule photovoltaïque organique la comprenant
US11502255B2 (en) 2017-11-28 2022-11-15 Lg Chem, Ltd. Photoactive layer and organic solar cell comprising same

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