WO2015167285A1 - Cellule solaire et son procédé de fabrication - Google Patents

Cellule solaire et son procédé de fabrication Download PDF

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WO2015167285A1
WO2015167285A1 PCT/KR2015/004406 KR2015004406W WO2015167285A1 WO 2015167285 A1 WO2015167285 A1 WO 2015167285A1 KR 2015004406 W KR2015004406 W KR 2015004406W WO 2015167285 A1 WO2015167285 A1 WO 2015167285A1
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group
substituted
unsubstituted
charge transport
electrode
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Korean (ko)
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이행근
이지영
이재철
김진석
최두환
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LG Chem Ltd
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LG Chem Ltd
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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
    • H10K30/50—Photovoltaic [PV] devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • 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
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • 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 specification relates to a solar cell and a method of manufacturing the same.
  • the solar cell refers to a battery that generates current-voltage using a photovoltaic effect of absorbing light energy from sunlight and generating electrons and holes.
  • Solar cells are devices that can directly convert solar energy into electrical energy by applying the photovoltaic effect.
  • Solar cells can be divided into inorganic solar cells and organic solar cells according to the material constituting the thin film.
  • An object of the present specification is to provide a solar cell and a method of manufacturing the same.
  • a second electrode provided to face the first electrode
  • a photoactive layer provided between the first electrode and the second electrode
  • It provides a solar cell comprising a charge transport layer comprising a charge transport material represented by the following formula (1) between the photoactive layer and the first electrode or the second electrode.
  • n is the number of repeats of the structure in parentheses 1 to 3,
  • X1 to X4 are the same as or different from each other, and each independently O, S or NR,
  • R and R1 to R16 are the same as or different from each other, and each independently hydrogen; Halogen group; Carboxylic acid groups; Nitro group; Nitrile group; Imide group; Amide group; Imine group; Thioimide; Anhydride group; Hydroxyl group; Substituted or unsubstituted ester group; Substituted or unsubstituted thioester group; Substituted or unsubstituted thioester group; Substituted or unsubstituted carbonyl group; Substituted or unsubstituted thio group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted arylalkyl group; Substituted or unsubstituted aryloxy group; Substituted or unsub
  • the present specification comprises the steps of preparing a substrate; Forming a first electrode on the substrate; Forming at least two organic material layers including at least two organic material layers including a photoactive layer and a charge transport layer on the first electrode; And it provides a method of manufacturing the above-described solar cell comprising the step of forming a second electrode on the organic material layer.
  • the solar cell according to the exemplary embodiment of the present specification is excellent in electron transfer capability, thereby realizing an increase in optical short circuit current density (Jsc) and an increase in efficiency.
  • Formula 1 may include a metal particle or an ionic group.
  • the light absorption through redistribution of the incident light increases, and due to the increase of the interfacial dipole, the barrier of charge is adjustable.
  • high efficiency solar cells can be expected due to increased conductivity.
  • the solar cell according to the exemplary embodiment of the present specification may implement a high efficiency by improving a fill factor (FF).
  • FF fill factor
  • the solar cell according to the exemplary embodiment of the present specification may shorten the production cost and / or increase the efficiency of the process due to a simple manufacturing process.
  • the solar cell according to the exemplary embodiment of the present specification may be a wound structure, in which case it is possible to efficiently absorb light in various directions to increase efficiency.
  • 1 to 4 illustrate organic solar cells according to one embodiment.
  • FIG. 5 is a view showing a change in device efficiency when each of the organic solar cells manufactured according to the experimental example according to an embodiment of the present disclosure when the heat treatment at 80 °C temperature.
  • first electrode A first electrode; A second electrode provided to face the first electrode; A photoactive layer provided between the first electrode and the second electrode; And a charge transport layer comprising a charge transport material represented by Formula 1 between the photoactive layer and the first electrode or the second electrode.
  • the crown type includes a charge transport material of the crown type (crown type).
  • metal oxides have been used as the charge transport layer of the inverted structure.
  • the metal oxide is used as the charge transport layer, it is difficult to apply to a flexible substrate due to the high heat treatment in order to have a high charge mobility, it is difficult to control the energy barrier with the applied photoactive layer material.
  • the charge transport layer including the charge transport material represented by Formula 1 has excellent charge mobility and is easily applied to a flexible substrate because there is no separate heat treatment for forming a nanostructure required for charge transport. It may be possible. In addition, it is easy to control the charge mobility and work function by inserting a substituent of the crown-type material represented by the formula (1) and / or an ionic group in the center of the formula (1). Therefore, there is an advantage that the control of the energy barrier with the photoactive layer material is easy.
  • the thermal stability of the formed charge transport layer is increased to increase the life of the device, and at least two kinds of ions
  • the combined crown material is mixed, there is an effect of forming a uniform mixed layer.
  • the charge transport material represented by Formula 1 may be represented by the following Formula 1-1 or Formula 1-2.
  • n X1 to X4, R5 to R8 and R13 to R16 are the same as defined above,
  • Cy1 to Cy4 are the same as or different from each other, and each independently a substituted or unsubstituted aromatic ring; Or a substituted or unsubstituted heterocycle.
  • X1 is O.
  • X 1 is NR.
  • X2 is O.
  • X2 is NR.
  • X3 is O.
  • X3 is NR.
  • X4 is O.
  • X4 is NR.
  • R is hydrogen
  • Cy1 to Cy4 are benzene rings.
  • crosslinkable substituent is a substituent in which a compound is a vehicle capable of binding several compounds directly or through a linker.
  • the crosslinkable substituent is a substituted or unsubstituted vinyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted acrylate group; Hydroxyl group; Or an isocyanate group.
  • n 1
  • n is 2.
  • n 3.
  • the charge transport material represented by Formula 1 may be selected from the following structures.
  • hydrogen substituted in the carbon of the base structure may be substituted with the aforementioned crosslinkable substituent.
  • the charge transport material represented by Formula 1 may be selected from the following structures.
  • a is an integer from 4 to 4.
  • the charge transport material represented by Formula 1 includes 0.01 wt% to 2 wt% based on the total mass of the charge transport layer. In one embodiment of the present specification, the charge transport material represented by Formula 1 is 0.02 wt% to 0.5 wt% based on the total mass of the charge transport layer.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • substituted or unsubstituted is deuterium; Halogen group; An alkyl group; Alkenyl groups; An alkoxy group; Ester group; Carbonyl group; Carboxyl groups; Hydroxyl group; Cycloalkyl group; Silyl groups; Aryl alkenyl group; Aryloxy group; Alkyl thioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Boron group; Alkylamine group; Aralkyl amine groups; Arylamine group; Heteroaryl group; Carbazole groups; Arylamine group; Aryl group; Nitrile group; Nitro group; Hydroxyl group; And one or more substituents selected from the group consisting of a heterocyclic group or no substituent.
  • the halogen group may be fluorine, chlorine, bromine or iodine.
  • carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.
  • the thiimide group is one in which C ⁇ O of the imide group is substituted with C ⁇ S.
  • the anhydride group is one in which the N atom of the imide group is substituted with O.
  • the amide group may be substituted with one or two of the nitrogen of the amide group is hydrogen, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • the amide group also includes a ring group such as lactam.
  • R ' is hydrogen; An alkoxy group having 1 to 60 carbon atoms; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; Substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms; Heteroarylalkyl group having 2 to 60 carbon atoms; Substituted or unsubstituted ester group having 1 to 40 carbon atoms; Substituted or unsubstituted carbonyl group having 1 to 40 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms containing at least one of N, O and S atoms.
  • the ester group herein includes a ring group such as a lactone group.
  • the carbonyl group It may be represented as.
  • R ' is hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; Substituted or unsubstituted arylalkyl group having 7 to 50 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.
  • the cation group of the present specification is a group in which the O atom of the carbonyl group is substituted with an S atom.
  • R 'and R are the same as or different from each other, and are hydrogen; a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 25 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
  • the ether group It may be represented as.
  • R is a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 25 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
  • Z1 to Z3 are the same as or different from each other, a linear, branched or cyclic substituted or unsubstituted alkyl group having 6 to 25 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-o
  • the cycloalkyl group is not particularly limited, but preferably 3 to 60 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. Do not.
  • the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C20. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.
  • the arylalkyl group is not particularly limited in carbon number, but in one embodiment of the present specification, the arylalkyl group has 7 to 50 carbon atoms. Specifically, the aryl moiety has 6 to 49 carbon atoms, and the alkyl moiety has 1 to 44 carbon atoms.
  • benzyl group p-methylbenzyl group, m-methylbenzyl group, p-ethylbenzyl group, m-ethylbenzyl group, 3,5-dimethylbenzyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl Group, ⁇ , ⁇ -methylphenylbenzyl group, 1-naphthylbenzyl group, 2-naphthylbenzyl group, p-fluorobenzyl group, 3,5-difluorobenzyl group, ⁇ , ⁇ -ditrifluoromethylbenzyl group , p-methoxybenzyl group, m-methoxybenzyl group, ⁇ -phenoxybenzyl group, ⁇ -benzyloxybenzyl group, naphthylmethyl group, naphthylethyl group, naphthylisopropyl group, pyrrolylmethyl group, pyrroleeth
  • the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • carbon number of the said acrylate is not specifically limited, It is preferable that it is 3-40. Specific examples include methyl acrylate, ethyl acrylate, methacrylate, 3- (acryloyloxy) propyl methacrylate, and the like, but are not limited thereto.
  • the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like.
  • the present invention is not limited thereto.
  • the aryl group may be monocyclic, and the carbon number is not particularly limited, but is preferably 6 to 60 carbon atoms.
  • Specific examples of the aryl group include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group, and terphenyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetrasenyl group, chrysenyl group, fluorenyl group, Polycyclic aromatics, such as an acenaphthasenyl group, a triphenylene group, and a fluoranthene group, etc., are mentioned, but it is not limited to these.
  • the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.
  • the heterocyclic group or heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms include an atom selected from the group consisting of O, N, S, Si, and Se. It can contain more.
  • carbon number of the said heterocyclic group is not specifically limited, It is preferable that it is C2-C60.
  • heterocyclic group examples include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, triazine group, acridil group, pyridazine group , Quinolinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthrroline group (phenanthroline) and dibenzofuranyl group, but are not limited thereto.
  • the heteroaryl in the heteroaryloxy group may be selected from the examples of the heteroaryl group described above.
  • the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group and aralkylamine group is the same as the aryl group described above.
  • aryloxy group phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, and the like.
  • arylthioxy group examples include a phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenyl.
  • Thioxy groups and the like, and aryl sulfoxy groups include, but are not limited to, benzene sulfoxy groups and p-toluene sulfoxy groups.
  • the alkyl group in the alkylthioxy group, the alkyl sulfoxy group, the alkylamine group and the aralkylamine group is the same as the example of the alkyl group described above.
  • the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group
  • the alkyl sulfoxy group includes mesyl, ethyl sulfoxy, propyl sulfoxy and butyl sulfoxy groups. Etc., but is not limited thereto.
  • the amine group is not particularly limited, but is preferably 1 to 30.
  • Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group.
  • examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group.
  • the aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group.
  • the arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.
  • aryl amine group examples include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra Cenylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group and the like, but are not limited thereto.
  • heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.
  • Adjacent groups herein means substituents substituted on adjacent carbons.
  • the adjacent groups are bonded to each other to form a hydrocarbon ring or hetero ring, wherein adjacent substituents form a bond to each other, and include one or more of 5- to 8-membered monocyclic or polycyclic hydrocarbon rings or heteroatoms. It means forming a 5- to 8-membered monocyclic or polycyclic hetero ring.
  • the hydrocarbon ring is a cycloalkyl group; Cycloalkenyl group; Aromatic ring groups; Or include all aliphatic ring groups, which may be monocyclic or polycyclic, and include all rings condensed by combining one or two or more.
  • the heterocycle formed herein means that at least one carbon atom of the hydrocarbon ring is substituted with a hetero atom, and may be an aliphatic ring or an aromatic ring, and may be monocyclic or polycyclic.
  • the charge transport material further includes an ionic group.
  • the charge transport material further includes an ionic group, and the ionic group is intercalated with the center of the charge transport material represented by Chemical Formula 1. That is, an ionic group is provided in the empty space of the center of a crown type compound, and chemically bonds.
  • an ionic group is provided in the empty space of the center of a crown type compound, and chemically bonds.
  • in the binding of ions not only a single molecule of the crown compound but two or more molecules may form a three-dimensional structure to participate in the binding.
  • heat treatment or UV treatment may be used to crosslink a plurality of crown-type compounds.
  • the number of ions of the metal to be inserted and the type of the metal may be selected by controlling the size of the crown-type charge transport material by adjusting the number of repetitions of n.
  • the ionic group as described above, the light absorption through redistribution of incident light increases, and due to the increase of the interfacial dipole, the barrier of charge is adjustable. In addition, high efficiency solar cells can be expected due to increased conductivity.
  • the ionic group may be a cationic group or an anionic group.
  • the ionic group may include one molecule, and includes two or more molecules forming a three-dimensional structure to bind.
  • the ionic group is titanium (Ti), zirconium (Zr), strontium (Sr), zinc (Zn), indium (In), lanthanum (La), vanadium (V), mol Libdenum (Mo), Tungsten (W), Tin (Sn), Niobium (Nb), Magnesium (Mg), Calcium (Ca), Barium (Ba), Aluminum (Al), Yttrium (Y), Scandium (Sc Cation of a metal selected from the group consisting of (a), samarium (Sm) gallium (Ga), potassium (K), cobalt (Co), copper (Cu), silver (Ag), sodium (Na) and lead (Pb); Ammonium ions selected from the group consisting of NH 4 + and CH 3 NH 3 + ; Or N 3 -, CH 3 CO 2 -, CN -, Br -, Cl -, I -, F -, SCN -, ClO 4 -, NO
  • the photoactive layer and the charge transport layer are provided in contact with each other. What is provided in contact does not limit physical bonding or chemical bonding.
  • the charge transport layer is provided on one surface close to the first electrode of the photoactive layer. In another embodiment, the charge transport layer is provided on one surface close to the second electrode of the photoactive layer.
  • the charge transport layer serves as a buffer layer.
  • the charge transport layer may play a role of smoothing electron transfer between the photoactive layer and the charge transport layer.
  • the thickness of the charge transport layer is 1 nm to 70 nm. In one embodiment, it is 1 nm to 20 nm. When the thickness of the charge transport layer is within the above range, there is an effect of increasing the charge mobility and increasing the recombination.
  • the thickness of the photoactive layer is 30 nm to 600 nm. In another embodiment, it is 80 nm to 500 nm.
  • the solar cell has a normal structure in which the first electrode is an anode and the second electrode is a cathode, and the charge transport layer is provided between the photoactive layer and the second electrode.
  • the normal structure may mean that an anode is formed on a substrate.
  • the first electrode formed on the substrate may be an anode.
  • Figure 1 illustrates an example of a solar cell according to an exemplary embodiment of the present specification.
  • Figure 1 shows a solar cell of a normal structure.
  • 1 includes ITO as an anode on a substrate and a buffer layer on the anode.
  • a photoactive layer was provided on the buffer layer, and a charge transport layer including the crown type charge transport material was formed on the photoactive layer.
  • a cathode was formed using Al.
  • the solar cell according to the exemplary embodiment of the present specification is not limited to the structure and the material of FIG. 1, an additional layer may be provided, and each layer may be configured using various materials.
  • the solar cell has an inverted structure in which the first electrode is a cathode and the second electrode is an anode, and the charge transport layer is provided between the photoactive layer and the first electrode.
  • the inverted structure may mean that a cathode is formed on a substrate.
  • the first electrode formed on the substrate may be a cathode.
  • FIG. 2 illustrates an example of a solar cell according to an exemplary embodiment of the present specification. Specifically, Figure 2 shows a solar cell of the inverted structure.
  • FIG. 2 is provided with ITO as a cathode on a substrate, and a charge transport layer including the aforementioned crown-type charge transport material is formed on the cathode. Further, a photoactive layer was provided on the charge transport layer, a buffer layer was provided on the photoactive layer, and MoO 3 / Al was formed as an anode.
  • crown-type charge transport material and the ionic group of the cation or anion may be further included on the cathode.
  • the solar cell according to the exemplary embodiment of the present specification is not limited to the structure and the material of FIG. 2, and additional layers may be provided, and each layer may be configured using various materials.
  • the buffer layer herein may be a cathode buffer layer or an anode buffer layer.
  • the charge transport layer further includes one or two materials selected from the group consisting of metal oxides, carbon compounds, metal carbide dielectric materials, and quantum dot compounds. .
  • a second charge transport layer including one or two materials selected from the group consisting of metal oxides, carbon compounds, metal carbide dielectric materials, and quantum dot compounds Include.
  • the metal oxide includes, but is not limited to, titanium oxide (TiO x ), zinc oxide (ZnO), vanadium oxide (V 2 O 5 ), nickel oxide (NiO x ), or ruthenium oxide (RuO x ). .
  • the carbon compound includes graphene and carbon nanotubes (CNT), but is not limited thereto.
  • the dielectric material may be polyethyleneimine (PEI), ethoxylated polyethyleneimine (PEIE), PFN ⁇ Poly [(9,9-bis (3'-dimethylamino) propyl) -2,7-fluorene) -alt-2 , 7- (9,9-diotylfluorene)]), and the like.
  • PEI polyethyleneimine
  • PEIE ethoxylated polyethyleneimine
  • PFN Poly [(9,9-bis (3'-dimethylamino) propyl) -2,7-fluorene) -alt-2 , 7- (9,9-diotylfluorene)]
  • the metal carbide includes cesium carbonate and the like, but is not limited thereto.
  • the quantum dot compound may include Cds, Pds, CdTe, or a mixture thereof, but is not limited thereto.
  • the charge transport material represented by Formula 1 is doped in the second charge transport layer.
  • the concentration of the charge transport material represented by Formula 1 is one selected from the group consisting of the metal oxide, carbon compound, metal carbide dielectric material, and quantum dot compound Or 0.1 wt% to 10 wt% with respect to the mass of the two materials (the second charge transport material).
  • the doping concentration of the charge transport material represented by Formula 1 is 0.1wt% to 1wt% based on the mass of the second charge transport material.
  • Figure 3 illustrates an example of a solar cell according to an exemplary embodiment of the present specification.
  • Figure 1 shows a solar cell of the inverted structure. 1 shows ITO as a cathode on a substrate, and a second charge transport layer on the cathode.
  • a first charge transport layer including a charge transport material represented by Formula 1 was formed on the second charge transport layer.
  • a photoactive layer was formed on the first charge transport layer, and MoO 3 / Al was formed as an anode.
  • the second charge transport layer may include ZnO.
  • the second charge transport layer may include a dielectric material.
  • the dielectric material is a conjugated polymer electrolyte, PFN ⁇ Poly ((9,9-bis (3'-dimethylamino) propyl) -2,7-fluorene) -alt-2,7- (9,9-diotylfluorene)]) It may include, and as a non-conjugated polymer electrolyte, may include PEI (polyethyleneimine) and / or PEIE (ethoxylated polyethyleneimine).
  • FIG. 4 illustrates an example of a solar cell according to an exemplary embodiment of the present specification. Specifically, Figure 4 shows a solar cell of the inverted structure.
  • FIG. 4 is provided with ITO as a cathode on a substrate, and a second charge transport layer doped with a charge transport material represented by Formula 1 is formed on the cathode. Further, a photoactive layer was provided on the charge transport layer, and MoO 3 / Al was formed on the photoactive layer.
  • the solar cell includes a first charge transport layer including a charge transport material represented by Chemical Formula 1, and a metal oxide, a carbon compound, a metal carbide dielectric material, and a quantum dot compound. And a second charge transport layer comprising one or two materials selected from the group.
  • first charge transport layer and the second charge transport layer are provided in contact with each other.
  • first charge transport layer including the charge transport material represented by Formula 1 is provided between the photoactive layer and the second charge transport layer.
  • the charge transport layer means a layer for transporting “holes” or “electrons”, and may be an electron transport layer or a hole transport layer.
  • the charge transport layer is an electron transport layer.
  • the electron transport layer of the present specification may be a cathode buffer layer.
  • the first electrode may be a cathode. In another embodiment, the first electrode may be an anode.
  • the second electrode may be an anode.
  • the first electrode may be a cathode.
  • the first electrode of the present specification may be a cathode electrode, and may be a transparent conductive oxide layer or a metal electrode.
  • the first electrode When the first electrode is a transparent electrode, the first electrode may be a conductive oxide such as tin indium oxide (ITO) or zinc indium oxide (IZO). Furthermore, the first electrode may be a translucent electrode. When the first electrode is a translucent electrode, it may be made of a translucent metal such as Ag, Au, Mg, Ca or an alloy thereof. When the translucent metal is used as the first electrode, the solar cell may have a microcavity structure.
  • the electrode of the present specification is a transparent conductive oxide layer
  • the electrode may be made of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), PC (polycarbornate), PS ( conductive on flexible and transparent materials such as polystylene, POM (polyoxymethylene), AS resin (acrylonitrile styrene copolymer), ABS resin (acrylonitrile butadiene styrene copolymer) and plastics including TAC (Triacetyl cellulose), PAR (polyarylate), etc. Doped materials may be used.
  • ITO indium tin oxide
  • FTO fluorine doped tin oxide
  • AZO aluminum doped zinc oxide
  • IZO indium zinc oxide
  • ZnO-Ga 2 O 3 ZnO-Al 2 O 3 and antimony tin oxide (ATO)
  • ATO antimony tin oxide
  • the second electrode may be an anode, and the second electrode may be a metal electrode.
  • the metal electrode includes silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd). It may include one or two or more selected from the group consisting of. More specifically, the metal electrode may be silver (Ag).
  • the forming of the first electrode and / or the second electrode may be performed by sequentially cleaning the patterned ITO substrate with a detergent, acetone, and isopropanol (IPA), and then removing the 100 from the heating plate to remove moisture. After drying for 1 minute to 30 minutes at 250 ° C., specifically for 10 minutes at 250 ° C., the substrate surface may be hydrophilically modified when the substrate is thoroughly cleaned. Pretreatment techniques for this are a) surface oxidation using parallel planar discharge, b) oxidation of the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) oxygen radicals generated by plasma. To oxidize.
  • the bonding surface potential can be maintained at a level suitable for the surface potential of the hole injection layer, the formation of the polymer thin film on the ITO substrate can be facilitated, and the quality of the thin film can be improved.
  • One of the above methods is selected according to the state of the substrate. In any of these methods, the effective effect of pretreatment can be expected by preventing oxygen escape from the surface of the substrate and restraining the remaining of moisture and organic matter as much as possible.
  • the surface modification method of the patterned ITO substrate in this invention does not need to specifically limit, Any method may be used as long as it is a method of oxidizing a substrate.
  • the solar cell includes one or more organic material layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generating layer, an electron blocking layer, an electron injection layer, and an electron transport layer. It includes more.
  • the solar cell has an inverted structure in which the first electrode is a cathode and the second electrode is an anode, and a cathode buffer layer is provided between the first electrode and the photoactive layer. An anode buffer layer is provided between the second electrode and the photoactive layer.
  • anode buffer layer and the cathode buffer layer may further include another organic material layer.
  • only one of the anode buffer layer and the cathode buffer layer may be included, and may not include the buffer layer.
  • the solar cell has a normal structure in which the first electrode is an anode and the second electrode is a cathode, and between the first electrode and the photoactive layer.
  • An anode buffer layer is provided, and a cathode buffer layer is provided between the second electrode and the photoactive layer.
  • the cathode buffer layer may be an electron transport layer.
  • the anode buffer layer may be a hole transport layer.
  • the solar cell is an organic solar cell or an organic-inorganic hybrid solar cell.
  • the organic solar cell or the organic-inorganic hybrid solar cell may select the material of the photoactive layer according to the needs of those skilled in the art.
  • the photoactive layer in the organic solar cell includes an electron donor material and an electron acceptor material as a photoactive material.
  • the photoactive material may mean the electron donor material and the electron acceptor material.
  • the electron donor material is at least one electron donor; Or a polymer of at least one kind of electron acceptor and at least one kind of electron donor.
  • the electron donor may include at least one kind of electron donor.
  • the electron donor includes a polymer of at least one kind of electron acceptor and at least one kind of electron donor.
  • the electron donor material is thiophene-based, fluorene-based, carbazole-based, etc. starting with MEH-PPV (poly [2-methoxy-5- (2′-ethyl-hexyloxy) -1,4-phenylene vinylene]) It can be a variety of high molecular and monomolecular materials.
  • the monomolecular substance is copper (II) phthalocyanine, zinc phthalocyanine, tris [4- (5-dicynomethylidemethyl-2-thienyl) phenyl] Amine (tris [4- (5-dicyanomethylidenemethyl-2-thienyl) phenyl] amine), 2,4-bis [4- (N, N-dibenzylamino) -2,6-dihydroxyphenyl] squalane (2,4-bis [4- (N, N-dibenzylamino) -2,6-dihydroxyphenyl] squaraine), benz [b] anthracene, and pentacene It may include one or more materials.
  • the polymer material is poly 3-hexyl thiophene (P3HT: poly 3-hexyl thiophene), PCDTBT (poly [N-9'-heptadecanyl-2,7-carbazole-alt-5,5- (4'-) 7'-di-2-thienyl-2 ', 1', 3'-benzothiadiazole)]), 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)]), PFO-DBT (poly [2,7- (9,9-dioctyl-fluorene) ) -alt-5,5- (4,7-di 2-thienyl-2,1,3-benzothiadiazole)]), PTB7 (Poly [[4,8-bis [(2-a)
  • the electron acceptor material may be a fullerene derivative or a nonfullerene derivative.
  • the fullerene derivative may be a C 60 to C 120 fullerene derivative and can be selected by those skilled in the art as needed.
  • the fullerene derivative may be substituted or unsubstituted by selecting from the above-described substituents as necessary.
  • the fullerene derivative has an ability to separate electron-hole pairs (exciton, electron-hole pair) and charge mobility compared to the non-fullerene derivative, which is advantageous for efficiency characteristics.
  • the photoactive layer may be a bulk heterojunction structure or a double layer junction structure.
  • the bulk heterojunction structure may be a bulk heterojunction (BHJ) junction type
  • the bilayer junction structure may be a bi-layer junction type.
  • the photoactive materials are dissolved in an organic solvent and then the solution is introduced into the photoactive layer in a thickness ranging from 50 nm to 280 nm by spin coating or the like.
  • the photoactive layer may be applied to a method such as dip coating, screen printing, spray coating, doctor blade, brush painting.
  • the photoactive layer in the organic-inorganic hybrid solar cell is a quantum dot solar cell using a quantum dot (quantum dot), a silicon solar cell using a silicon layer or a perovskite using a compound of the perovskite structure
  • Photoactive layer materials such as a skytight solar cell, can be selected according to the needs of those skilled in the art.
  • the conductive oxide of the electron transport layer may be electron-extracting metal oxides, specifically, titanium oxide (TiO x ); Zinc oxide (ZnO); And cesium carbonate (Cs 2 CO 3 ) It may include one or more selected from the group consisting of.
  • the metal may include a core shell including metal oxides such as silver nanoparticles (Ag nanoparticles), gold nanoparticles (Au nanoparticles), Ag-SiO 2 , Ag-TiO 2 , Au-TiO 2, and the like. core shell) material.
  • the core shell material includes a metal as a core, and includes metal oxides such as Ag-SiO 2 , Ag-TiO 2 , Au-TiO 2 , as shells.
  • the electron transport layer may be formed by being applied to one surface of the first electrode or coated in a film form using sputtering, E-Beam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blade or gravure printing.
  • the hole transport layer may be introduced on top of the pretreated photoactive layer by spin coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, gravure coating, brush painting, thermal deposition, and the like.
  • poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate) [PEDOT: PSS] is mainly used as a conductive polymer solution, and is used as a hole-extracting metal oxides material.
  • Molybdenum oxide (MoO x ), vanadium oxide (V 2 O 5 ), nickel oxide (NiO), tungsten oxide (WO x ) and the like can be used.
  • the hole transport layer may be formed to a thickness of 5 nm ⁇ 10 nm through the MoO 3 thermal deposition system.
  • the solar cell may further include a substrate.
  • the substrate may be provided under the first electrode.
  • the substrate may use a substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness.
  • a glass substrate, a thin film glass substrate, or a transparent plastic substrate may be used.
  • the plastic substrate may include a film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone (PEEK), and polyimide (PI) in the form of a single layer or a multilayer.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PEEK polyether ether ketone
  • PI polyimide
  • the substrate is not limited thereto, and a substrate commonly used in solar cells may be used.
  • the solar cell may have a wound structure.
  • the solar cell can be manufactured in the form of a flexible film, it can be rolled into a cylindrical shape can be made into a hollow solar cell structure.
  • the solar cell When the solar cell is a wound structure, it can be installed by placing it on the ground. In this case, while the sun at the position where the solar cell is installed is moved from east to west, it is possible to secure a portion where the incident angle of light is maximum. Therefore, there is an advantage to increase the efficiency by absorbing as much light as possible while the sun is floating.
  • the present specification comprises the steps of preparing a substrate; Forming a first electrode on the substrate; Forming at least two organic material layers including at least two organic material layers including a photoactive layer and a charge transport layer on the first electrode; And forming a second electrode on the organic material layer.
  • a method of manufacturing the solar cell may use a method generally used except for including the aforementioned charge transport layer.
  • the forming of the first electrode may include modifying the surface to be hydrophilic after cleaning.
  • the manufacturing of the single layer solar cell may further include forming a hole transport layer and forming an electron transport layer.
  • the solar cell further includes the step of heat treatment or UV treatment after forming the organic material layer.
  • the charge transport material according to an exemplary embodiment of the present specification includes a charge transport material in which an ionic group is inserted in the middle of a crown compound represented by Chemical Formula 1.
  • the compounds represented by Formula 1 may be bonded to each other to form a single chemically bonded fullerene layer. In this case, there is an effect of increasing the thermal stability.
  • the substrate, the first electrode, the photoactive layer, the charge transport layer and the second electrode are the same as described above.
  • a film was formed after heat treatment after spin coating a charge transport layer containing 0.1 wt% of a crown derivative having the following crosslinkable substituent in a solution of 1: 1 mixing ethyl acetate and methanol on an ITO glass as a first electrode.
  • a photoactive layer was formed on the charge transport layer with P3HT: PC 60 BM.
  • a second electrode was formed of Ag on the buffer layer to prepare an organic solar cell having an inverted structure.
  • An organic solar cell was manufactured by the same method as Experimental Example 1, except for using a material including potassium ions (K + ) in the center of 18-crown-6 in Experimental Example 1.
  • An organic solar cell was manufactured by the same method as Experimental Example 1, except that ZnO instead of cross linkable [18-crown-6] as the charge transport layer in Experimental Example 1.
  • An organic solar cell was manufactured by the same method as Experimental Example 1, except that the following crown derivative was used in Experimental Example 1.
  • An organic solar cell was manufactured by the same method as Experimental Example 1, except for using a material including potassium ions (K + ) in the center of 18-crown-6 in Experimental Example 1.
  • An organic solar cell was manufactured by the same method as Experimental Example 3, except that Hexacyclen was used in Experimental Example 1.
  • ITO / Hexacyclen / P3HT PC 60 BM / MoO 3 / Ag
  • Hexacyclen showed better thermal stability than ZnO even without cross linking due to its high dielectric constant and melting point, and higher open voltage, current density and charge compared to 18-crown-6. As a result, more than 50% efficiency was obtained.

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Abstract

La présente invention concerne une cellule solaire et un procédé de fabrication de cette dernière, et fournit une cellule solaire comprenant : une première électrode ; une seconde électrode disposée à l'opposé de la première électrode ; une couche photoactive disposée entre la première électrode et la seconde électrode ; et une couche de transport de charge comprenant un matériau de transport de charge représenté par la formule 1 entre la couche photoactive et la première électrode ou la seconde électrode.
PCT/KR2015/004406 2014-04-30 2015-04-30 Cellule solaire et son procédé de fabrication Ceased WO2015167285A1 (fr)

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WO2026046134A1 (fr) * 2024-09-02 2026-03-05 宁德时代新能源科技股份有限公司 Cellule photovoltaïque à pérovskites et son procédé de fabrication, module photovoltaïque, dispositif de production d'énergie et dispositif électrique

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KR20170070721A (ko) * 2015-12-14 2017-06-22 주식회사 엘지화학 원통형 페로브스카이트 태양 전지
EP3451399B1 (fr) 2016-06-03 2020-04-29 LG Chem, Ltd. Élément électronique organique et procédé de fabrication de celui-ci
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KR102447198B1 (ko) * 2020-09-18 2022-09-26 성균관대학교산학협력단 광안정성이 향상된 양자점 태양전지 및 이의 제조방법
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WO2026046134A1 (fr) * 2024-09-02 2026-03-05 宁德时代新能源科技股份有限公司 Cellule photovoltaïque à pérovskites et son procédé de fabrication, module photovoltaïque, dispositif de production d'énergie et dispositif électrique

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