Perovskite optical device and manufacturing method therefor

Abstract

A perovskite optical device according to one embodiment of the present invention comprises a perovskite layer and a self-assembled monolayer formed on the perovskite layer, wherein the self-assembled monolayer includes a self-assembling material and a blending polymer, the self-assembling material including an anchor group, a linker group and a terminal functional group, wherein the anchor group includes silane, a carboxylic acid, a phosphoric acid group or a combination thereof, the linker group includes an alkyl chain, the terminal functional group includes an amino group, a carbonyl group, a sulfhydryl group or a combination thereof, and the blending polymer can include PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F or a combination thereof.

Description

Perovskite optical device and method for manufacturing the same

[0001] The present disclosure relates to a perovskite optical device and a method for manufacturing the same.

[0002] There is a growing need to develop eco-friendly and sustainable energy technologies capable of addressing climate change. Optical devices encompass both photovoltaic and electro-photovoltaic devices; solar cells, a type of photovoltaic device, are gaining attention as a sustainable energy technology and a solution capable of actively responding to future energy demands. Solar cells are the most basic unit of photovoltaic power generation and are semiconductor devices that convert solar energy into electrical energy, utilizing the photovoltaic effect.

[0003] However, since current solar cell technology does not demonstrate the efficiency required to meet future energy demands, technological innovation that surpasses the current level is necessary. Accordingly, technologies based on innovative materials such as dye-sensitized solar cells, organic solar cells, quantum dot solar cells, and perovskite solar cells (PSCs) have been developed as next-generation solar cells.

[0004] Among these, perovskite solar cells have emerged as a key pillar of thin-film solar cells capable of replacing conventional silicon solar cells. Perovskite solar cells, which contain hole transport materials, light-absorbing materials, and electron transport materials, utilize perovskite materials as light-absorbing materials to exhibit a significantly high photovoltaic effect. In this regard, the self-assembled monolayer (SAM) in the perovskite photodetector constituting the perovskite solar cell can improve charge transfer characteristics by modifying the interface between the perovskite photodetector and the electrode. However, due to the hydrophobicity of the self-assembled monolayer, large-area coating is not easy, limiting its application to small devices.

[0005] Accordingly, research has been conducted to improve device performance by surface treating the self-assembled monolayer or forming a separate passivation layer, but this leads to additional problems such as device stability and cell reproducibility, resulting in performance limitations in large-area perovskite optoelectronic devices.

[0006] The present disclosure aims to provide a perovskite optical device and a method for manufacturing perovskite to solve the above-mentioned problems.

[0007] Some embodiments of the present disclosure can improve perovskite deposition and lead to improved performance in large-area perovskite photodetectors by fabricating a self-assembled monolayer by blending a polymer containing PFN into a Me-4PACz solution for perovskite photodetectors.

[0008] However, the technical problems that the present invention aims to solve are not limited to those described above, and other unmentioned problems can be clearly understood by those skilled in the art from the description of the invention below.

[0009] A perovskite optical device according to one embodiment of the present disclosure for solving technical problems comprises a perovskite layer and a self-assembled monolayer formed on the perovskite layer, wherein the self-assembled monolayer comprises a self-assembled material and a blending polymer, wherein the self-assembled material comprises an anchor group, a linker group and a terminal functional group, wherein the anchor group comprises a silane, a carbonyl acid, a phosphate group or a combination thereof, the linker group comprises an alkyl chain, the terminal functional group comprises an amino group, a carbonyl group, a sulfhydryl group or a combination thereof, and the blending polymer may comprise PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F or a combination thereof.

[0010] According to one embodiment of the present disclosure, the self-assembling material may include Me-4PACz, Me-SB, MSBP, MeO-PEAI, Me-DMAI, or a combination thereof.

[0011] A perovskite optical device according to one embodiment of the present disclosure further comprises a hole transport layer (HTL), and a self-assembled monolayer may be interposed between the perovskite layer and the hole transport layer.

[0012] According to one embodiment of the present disclosure, the hole transport layer is Nickel Oxide (NiO₂). x It may include Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate (PEDOT:PSS), Copper Thiocyanate (CuSCN), Copper Iodide (CuI), or a combination thereof.

[0013] A perovskite optical device according to one embodiment of the present disclosure further comprises an electron transport layer (ETL), and the electron transport layer may be opposite to a self-assembled monolayer with respect to the perovskite layer.

[0014] According to one embodiment of the present disclosure, the electron transport layer is PCBM ([6,6]-Phenyl-C61-butyric acid methyl ester), C 60 It may include (Fullerene), SnO2 (Tin dioxide), or a combination thereof.

[0015] According to one embodiment of the present disclosure, the band gap of the perovskite layer may be 1.60 eV to 2.5 eV.

[0016] A method for manufacturing a perovskite optical device according to one embodiment of the present disclosure for solving technical problems comprises the steps of forming a self-assembled monolayer and forming a perovskite layer on the self-assembled monolayer, wherein the self-assembled monolayer comprises a self-assembled material and a blending polymer, wherein the self-assembled material comprises an anchor group, a linker group and a terminal functional group, wherein the anchor group comprises a silane, a carbonyl acid, a phosphate group or a combination thereof, the linker group comprises an alkyl chain, the terminal functional group comprises an amino group, a carbonyl group, a sulfhydryl group or a combination thereof, and the blending polymer may comprise PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F or a combination thereof.

[0017] According to one embodiment of the present disclosure, the step of forming a self-assembled monolayer may include the step of dissolving a self-assembled material, the step of dissolving a blending polymer, and the step of adding a solution in which the blending polymer is dissolved to a solution in which the self-assembled material is dissolved.

[0018] A perovskite tandem cell according to one embodiment of the present disclosure for solving technical problems may include a first layer comprising a perovskite photodetector according to the present disclosure and a second layer comprising a photodetector having a bandgap different from that of the perovskite photodetector.

[0019] According to various embodiments of the present disclosure, the blended self-assembled monolayer can improve perovskite deposition to form a highly crystalline perovskite thin film and can improve the efficiency and stability of the perovskite optical device.

[0020] The effects of the present disclosure are not limited to those mentioned above, and other unmentioned effects will be clearly understood by those skilled in the art from the description in the claims.

[0021] Embodiments of the present disclosure will be described with reference to the accompanying drawings described below, wherein similar reference numerals indicate similar elements, but are not limited thereto.

[0022] Figure 1 is a process diagram for forming a self-assembled monolayer (SAM) in a method for manufacturing a perovskite optical device.

[0023] Figure 2 is a photograph showing the perovskite deposition coverage for pure SAM and SAM blended with various amounts of PFN.

[0024] Figure 3 is a diagram for analyzing the contact angle between a PFN blending solution and a perovskite precursor depending on the presence or absence of SAM and PFN blending on a transparent electrode substrate.

[0025] Figure 4 is a graph showing SEM images and perovskite particle size distribution to analyze the size of perovskite particles deposited on SAM depending on the presence or absence of PFN blending.

[0026] Figure 5 illustrates the steady-state luminescence and time-resolved photoluminescence spectrum analysis of a perovskite film deposited on a blend of pure SAM and PFN SAM.

[0027] Figure 6 is a graph showing the JV data and external quantum efficiency (EQE) (right) data of a 1.80 eV bandgap perovskite solar cell fabricated with pure SAM and PFN blended SAM.

[0028] Figure 7 is a graph showing the stability data of a 1.80 eV bandgap perovskite solar cell fabricated with pure SAM and SAM blended with PFN.

[0029] Figure 8 is a diagram illustrating the photovoltaic performance of a large-area perovskite solar cell fabricated with a SAM blended with PFN.

[0030] Figure 9 is a summary table showing the reported module efficiency and area of ​​a 1.80 eV wide bandgap perovskite compared with the present invention.

[0031] Hereinafter, specific details for implementing the present disclosure will be described in detail with reference to the attached drawings. However, in the following description, specific descriptions regarding well-known functions or configurations will be omitted if there is a risk that the gist of the present disclosure may be unnecessarily obscured.

[0032] The terms used in this disclosure will be briefly explained, and the disclosed embodiments will be described in detail. The terms used in this specification have been selected to be as generally used as possible, taking into account their functions in this disclosure; however, these terms may vary depending on the intent of those skilled in the art, case law, the emergence of new technologies, etc. Additionally, in specific cases, terms may be arbitrarily selected by the applicant, and in such cases, their meanings will be described in detail in the relevant description of the invention. Therefore, the terms used in this disclosure should be defined not merely by their names, but based on their meanings and the content throughout this disclosure.

[0033] In the present disclosure, singular expressions include plural expressions unless the context clearly specifies them to be singular. Additionally, plural expressions include singular expressions unless the context clearly specifies them to be plural.

[0034] In the present disclosure, when a part is described as including a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0035] In this specification, the description "A and / or B" means A, or B, or A and B.

[0036] Throughout this specification, terms such as "approximately" are used to encompass tolerances when tolerances exist.

[0037] Throughout this specification, the term “at least one” included in a Markush-format expression means that it includes one or more selected from the group consisting of components described in the Markush-format expression.

[0038] Throughout this specification, "perovskite," "PE," or "perovskite compound" refers to a material having a perovskite crystal structure, and may have various perovskite crystal structures in addition to the ABX3 crystal structure.

[0039] Throughout this specification, the term "optical device" is used to include both photoelectric conversion devices and electro-optical conversion devices. For example, optical devices include, but are not limited to, LEDs (Light Emitting Diodes), solar cells, photodetectors, X-ray detectors, and lasers.

[0040] Throughout this specification, the terms “halide,” “halogen,” “halogenate,” or “halo” refer to a material or composition in which a halogen atom belonging to Group 17 of the periodic table is included in the form of a functional group, and may include, for example, chlorine, bromine, fluorine, or iodine compounds.

[0041] Throughout this specification, "precursor" to "precursor" may refer to a precursor or reactive agent used to manufacture perovskite, and is not limited to a specific material.

[0042] Throughout this specification, the term “layer” refers to a layer having thickness. The layer may be porous or non-porous. Porosity means having porosity. The layer may be in a bulk form or may be a single crystal thin film, but is not limited thereto.

[0043] Throughout this specification, when a component is described as being located "on" another component, unless specifically stated otherwise, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components.

[0044] Throughout this specification, where "efficiency" is described simply without further explanation, it refers to Power Conversion Efficiency (PCE).

[0045]

[0046] Perovskite optoelectronic device

[0047] A perovskite optical device according to one embodiment of the present disclosure for solving technical problems may include a perovskite layer and a self-assembled monolayer (SAM) formed on the perovskite layer. Here, the self-assembled monolayer may include a self-assembled material and a blending polymer.

[0048] In one embodiment, the self-assembling material comprises an anchor group, a linker group, and a terminal functional group, wherein the anchor group comprises a silane, a carbonyl acid, a phosphate group, or a combination thereof, the linker group comprises an alkyl chain, and the terminal functional group may comprise an amino group, a carbonyl group, a sulfhydryl group, or a combination thereof.

[0049] Specifically, the self-assembling material may include Me-4PACz ([4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid), Me-SB (3-(Dimethylamino)propylsulfonic acid betaine), MSBP (3-[Dimethyl(4-sulfobutyl)ammonio]propane-1-sulfonate), MeO-PEAI (2-Methoxyethylammonium iodide), Me-DMAI (N1-methylethane-1,2-diammonium iodide), or a combination thereof.

[0050] PFN(Poly(9,9-bis(3'-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide, 100-100 ml of PFN(Poly(9,9-bis(3′-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide), PFN-E (Poly(9,9-bis(3′-(N,N-diethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide), PFN-P (Poly(9,9-bis(3′-(N,N-dimethyl)-N-propylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide), PFN-H (Poly(9,9-bis(3'-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dihexylfluorene))dibromide), PFN-M (Poly(9,9-bis(3'-(N,N-dimethyl)-N-methylammonium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide) PFN-B (Poly(9,9-bis(4′-(N,N-dimethyl)-N-ethylammoinium-butyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene))dibromide), PFN-F (Poly(9,9-bis(3'-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-bis(2-ethylhexyl)fluorene))dibromide) 이외에 다양한 이이온의 조합을 포함할 수 있다.

[0051] A perovskite optical device according to one embodiment of the present disclosure may further include a hole transport layer (HTL) or an electron transport layer (ETL). Specifically, an optical device according to one embodiment may include a first electrode, a first charge transport layer, a perovskite layer, a second charge transport layer, and a second electrode.

[0052] For example, if the optical device is used in a solar cell with a nip structure, the optical device may have a structure in which a first electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a second electrode are sequentially stacked. Alternatively, if the optical device corresponds to a solar cell with a pin structure, the solar cell may have a structure in which a first electrode, a hole transport layer, a perovskite layer, an electron transport layer, and a second electrode are sequentially stacked.

[0053] For example, the optical device may have a planar structure, a bi-layer structure, or a meso-superstructure structure. Depending on the structure of the optical device, the shapes of the electrode, charge transport layer, and perovskite layer may be modified. For example, if the optical device has a bi-layer structure, the perovskite layer may have a bi-layer structure formed by filling porous TiO2 with perovskite to form a layer. The bi-layer may refer to a structure consisting of a first layer of a TiO2:perovskite mixed layer in which the pores of porous TiO2 are completely filled with perovskite, and a second layer of a pure perovskite layer above it.

[0054] According to one embodiment, the hole transport layer is Nickel Oxide (NiO₂). xIt may include Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate (PEDOT:PSS), Copper Thiocyanate (CuSCN), Copper Iodide (CuI), or a combination thereof. The electron transport layer may be opposite to the self-assembled monolayer based on the perovskite layer.

[0055] According to one embodiment, the electron transport layer is PCBM ([6,6]-Phenyl-C61-butyric acid methyl ester), C 60 It may include (Fullerene), SnO2 (Tin dioxide), or a combination thereof. The self-assembled monolayer of the perovskite photodetector may be interposed between the perovskite layer and the hole transport layer.

[0056] The electrode comprises a first electrode and / or a second electrode and may be an anode or a cathode. The electrode may be an anode or a cathode. If the first electrode is an anode, the second electrode may be a cathode. For example, the electrode may be a conductive oxide such as indium-tin oxide (ITO) or indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), etc. Or, the electrode may comprise a material selected from the group consisting of silver (Ag), gold (Au), magnesium (Mg), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), nickel (Ni), palladium (Pd), chromium (Cr), calcium (Ca), samarium (Sm), and lithium (Li), and combinations thereof. Alternatively, the electrode may correspond to a flexible and transparent material such as plastic, such as PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbonate), PS (polystyrene), POM (polyoxyethylene), etc., on which a conductive material is doped.

[0057] The electrode may correspond to a material commonly used as an electrode material for the front electrode or back electrode in an optical device. The electrode may be a material selected from one or more of gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and composites thereof, but is not limited thereto. For example, the electrode may be one or more inorganic conductive electrodes selected from fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), ZnO, carbon nanotubes (CNT), and graphene, or may correspond to an organic conductive electrode such as PEDOT:PSS, but is not limited thereto.

[0058] As a charge transport layer, an electron transport layer (ETL) or a hole transport layer (HTL) may be formed on the first electrode. If the first charge transport layer is an electron transport layer, the second charge transport layer may correspond to a hole transport layer. Alternatively, if the first charge transport layer is a hole transport layer, the second charge transport layer may correspond to an electron transport layer.

[0059] The electron transport layer may correspond to a semiconductor containing an "n-type material." An "n-type material" refers to an electron transport material. The electron transport material may be a single electron transport compound or elemental material, or a mixture of two or more electron transport compounds or elemental materials. The electron transport compound or elemental material may be undoped or doped with one or more dopant elements.

[0060] For example, the electron transport layer may be an electron-conducting organic layer or an electron-conducting inorganic layer. The electron-conducting organic material may be an organic material used as an n-type semiconductor in a conventional organic solar cell. For example, the electron-conducting organic material may include, but is not limited to, fullerene (C60, C70, C74, C76, C78, ​​C82, C95), PCBM ([6,6]-phenyl-C61-butyric acid methyl ester), and fullerene-derivatives including C71-PCBM, C84-PCBM, PC70BM ([6,6]-phenyl C70-butyric acid methyl ester), PBI (polybenzimidazole), PTCBI (3,4,9,10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ (tetra-uorotetracyanoquinodimethane), and mixtures thereof.

[0061] The electron-conducting inorganic material may be an electron-conducting metal oxide used for electron transfer in conventional quantum dot-based solar cells, dye-sensitized solar cells, or perovskite-based solar cells. In one embodiment, the electron-conducting metal oxide may be an n-type metal oxide semiconductor. For example, the n-type metal oxide semiconductor may be one or more materials selected from Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, and SrTi oxide, a mixture thereof, or a composite thereof, but is not limited thereto.

[0062] The electron transport layer may be a dense layer (dense film) or a porous layer (porous film). The dense electron transport layer may be a film of the aforementioned electron-conducting organic material or a dense film of the aforementioned electron-conducting inorganic material. The electron transport layer of the porous film may be a porous film composed of particles of the aforementioned electron-conducting inorganic material.

[0063] The hole transport layer may correspond to a semiconductor containing a "p-type material." A "p-type material" refers to a hole transporting material. The hole transporting material may be a single hole transport compound or elemental material, or a mixture of two or more hole transport compounds or elemental materials. The hole transport compound or elemental material may be undoped or doped with one or more dopant elements. The hole transporting material may be an organic hole transporting material, an inorganic hole transporting material, or a combination thereof.

[0064] The hole transport layer may be manufactured by a solution process. The hole transport layer may be a thin film of an organic hole transport material. The thickness of the hole transport layer thin film may be 10 nm to 500 nm, but is not limited thereto.

[0065] The hole transport material may correspond to an organic hole transport material, specifically a monomeric to polymeric organic hole transport material (hole-conducting organic material). As a polymeric organic hole transport material, it may include one or more materials selected from thiophene-based, paraphenylene-vinylene-based, carbazole-based, and triphenylamine-based materials.

[0066] Single-molecule to low-molecular-weight organic hole transporters include pentacene, coumarin 6 (coumarin 6, 3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC (zinc phthalocyanine), CuPC (copper phthalocyanine), TiOPC (titanium oxide phthalocyanine), 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-hexadecafluoro29H,31H-phthalocyanine), SubPc (boron subphthalocyanine chloride), and It may include one or more substances selected from N3(cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II)), but is not limited thereto.

[0067] 고분자 유기 정공 수송물질은, P3HT(poly[3-hexylthiophene]), MDMO-PPV(poly[2-methoxy-5-(3',7'- dimethyloctyloxyl)]-1,4-phenylene vinylene), MEH-PPV(poly[2-methoxy -5-(2''-ethylhexyloxy)-p-phenylene vinylene]), P3OT(poly(3-octyl thiophene)), POT( poly(octyl thiophene)), P3DT(poly(3-decyl thiophene)), P3DDT(poly(3-dodecyl thiophene), PPV(poly(p-phenylene vinylene)), TFB(poly(9,9'-dioctylfluorene-co-N-(4-butylphenyl)diphenyl amine), Polyaniline, SpiroMeOTAD ([2,22′,7,77′-tetrkis (N,N-di-p-methoxyphenyl amine)-9,9,9′-spirobi fluorine]), PCPDTBT(Poly[2,1,3-benzothiadiazole- 4,7-diyl[4,4-bis(2-ethylhexyl-4H- cyclopenta [2,1-b:3,4- b']dithiophene-2,6-diyl]], Si-PCPDTBT(poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)- 2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl) benzo([1,2- b:4,5-b']dithiophene)-2,6-diyl)-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl)), PFDTBT(poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene)-alt-5,5-(4', 7, -di-2-thienyl-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)]), PSiFDTBT(poly[(2,7-dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl]), PSBTBT(poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)- 2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl]), PCDTBT(Poly It may include one or more substances selected from [[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]), PFB(poly(9,9′-dioctylfluorene-co-bis(N,N′-(4,butylphenyl))bis(N,N′-phenyl-1,4-phenylene)diamine), F8BT(poly(9,9′-dioctylfluorene-co-benzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)), PTAA (poly(triarylamine)), Poly(4-butylphenyldiphenyl-amine) and copolymers thereof, but is not limited thereto.

[0068] The electron transport layer or hole transport layer may correspond to a buffer layer or may include a buffer layer. The surface of the electron transport layer or hole transport layer may be modified using doping. The electron transport layer or hole transport layer may be formed by applying it to one surface of an electrode or coating it in the form of a film through spin coating, dip coating, inkjet printing, gravure printing, spray coating, bar coating, gravure coating, brush painting, thermal evaporation, sputtering, E-Beam, screen printing, blade process, etc.

[0069] The perovskite layer may be formed to be in direct contact with the first electrode. Alternatively, the perovskite layer may be formed to be in direct contact with the electron transport layer or the hole transport layer. The perovskite layer comprises a perovskite to be described later.

[0070] A perovskite layer can be formed through various processes, including vapor deposition processes or solution processes. A perovskite layer can be formed using a vapor deposition process. A vapor deposition process may correspond to a process of supplying a material into a vacuum chamber in a vaporized or plasma state to deposit the material on the surface of a target object (e.g., a substrate). A perovskite layer can be formed through a coating process during a solution process. The coating process may be selected from the group consisting of spin coating, bar coating, nozzle printing, spray coating, slot die coating, gravure printing, inkjet printing, screen printing, electrohydrodynamic jet printing, electrospray, and combinations thereof, but is not limited thereto.

[0071]

[0072] perovskite

[0073] Perovskites may contain monovalent organic cations, divalent metal cations, and halogen anions. A perovskite or perovskite compound according to one embodiment of the present disclosure may satisfy the following chemical formula 1.

[0074]

[0075] [Chemical Formula 1]

[0076] AMX3

[0077]

[0078] In Chemical Formula 1, A is a monovalent cation and may be an organic ammonium ion, an amidinium group ion, or a combination of an organic ammonium ion and an amidinium group ion.

[0079] In Chemical Formula 1, the organic ammonium ion can satisfy Chemical Formula 1-1 or 1-2 below.

[0080]

[0081] [Chemical Formula 1-1]

[0082] R1-NH3 +

[0083]

[0084] In chemical formula 1-1, R1 is a C1-C24 alkyl, a C3-C20 cycloalkyl, or a C6-C20 aryl.

[0085]

[0086] [Chemical Formula 1-2]

[0087] R2-C3H3N2 + -R3

[0088]

[0089] In chemical formula 1-2, R2 is a C1-C24 alkyl, a C3-C20 cycloalkyl, or a C6-C20 aryl, and R3 is hydrogen or a C1-C24 alkyl.

[0090] In Chemical Formula 1, the amidinium-based ion can satisfy Chemical Formula 1-3 below.

[0091]

[0092] [Chemical Formula 1-3]

[0093]

[0094]

[0095] In chemical formula 1-3, R4 to R8 are independently hydrogen, a C1-C24 alkyl, a C3-C20 cycloalkyl, or a C6-C20 aryl.

[0096] In Chemical Formula 1, A may correspond to an organic ammonium ion, an amidinium group ion, or a combination of an organic ammonium ion and an amidinium group ion. When both organic ammonium ions and amidinium group ions are present, the charge mobility of the perovskite can be significantly improved.

[0097] R1 of Formula 1-1, R2 to R3 of Formula 1-2 and / or R4 to R8 of Formula 1-3 can be appropriately selected depending on the use of the perovskite, i.e., the use of the optical device.

[0098] For example, the size of the unit cell of a perovskite is related to the band gap, and it can have a band gap energy of 1.2 eV to 2.5 eV, which is suitable for use as a solar cell in small unit cell sizes. Accordingly, when considering a band gap energy of 1.2 eV to 2.5 eV suitable for use as a solar cell, in Chemical Formula 1-1, R1 can be a C1-C24 alkyl, specifically a C1-C7 alkyl, more specifically a methyl. Also, in Chemical Formula 1-2, R2 can be a C1-C24 alkyl and R3 can be hydrogen or a C1-C24 alkyl; specifically, R2 can be a C1-C7 alkyl and R3 can be hydrogen or a C1-C7 alkyl; more specifically, R2 can be methyl and R3 can be hydrogen. Additionally, in Chemical Formula 1-3, R4 to R8 may independently be hydrogen, amino, or C1-C24 alkyl, specifically hydrogen, amino, or C1-C7 alkyl, more specifically hydrogen, amino, or methyl, and even more specifically R4 may be hydrogen, amino, or methyl and R5 to R8 may be hydrogen. As a specific and non-limiting example, the amidinium-based ion is formamidinium (formamidinium, NH2CH=NH2 + ) ion, acetamidinium (acetamidinium, NH2C(CH3)=NH2 + ) ion or guamidinium (Guamidinium, NH2C(NH2)=NH2 + Examples include ions, etc.

[0099] As described above, specific examples of organic cations (A) are examples considering the use of perovskite films, that is, as light absorption layers for sunlight, and R1 of Formula 1-1, R2~R3 of Formula 1-2 and / or R4~R8 of Formula 1-3 can be appropriately selected by considering the design of the wavelength band of light to be absorbed, the design of the emission wavelength band when used as a light-emitting layer of a light-emitting device, and the energy band gap and threshold voltage when used as a semiconductor device of a transistor.

[0100] In Chemical Formula 1, M can be a divalent metal ion. As a specific example, M is Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ and Yb 2+ It may be one or more selected metal ions.

[0101] In Chemical Formula 1, X is a halogen anion. Specifically, the halogen ion is I - , Br - , F - , Cl - It includes, but is not limited to, a halogen ion selected from the group consisting of combinations thereof. For example, X may correspond to an oxygen ion.

[0102] More specifically, the halogen anion may contain iodide ions and bromide ions. If the halogen anion contains both iodide ions and bromide ions, the crystallinity and moisture resistance of the perovskite can be improved.

[0103] As a specific example, in Chemical Formula 1, X is X a (1-y) Xb y It could be, X a and X b are different halogen ions (iodide ions (I - ), chlorine ion (Cl - ) and bromide ions (Br - Different halogen ions selected from ) and y can be a real number such that 0 < y < 1.

[0104]

[0105] Perovskite tandem cell

[0106] A perovskite tandem cell according to one embodiment of the present disclosure for solving technical problems may include a first layer comprising a perovskite photodetector according to the present disclosure and a second layer comprising a photodetector having a bandgap different from that of the perovskite photodetector.

[0107]

[0108] Examples

[0109] Figure 1 is a process diagram for forming a self-assembled monolayer (SAM) in a method for manufacturing a perovskite optical device.

[0110] A method for manufacturing a perovskite optical device according to one embodiment of the present disclosure for solving technical problems may include the steps of forming a self-assembled monolayer and forming a perovskite layer on the self-assembled monolayer. Here, the self-assembled monolayer may include a self-assembled material and a blending polymer.

[0111] Referring to FIG. 1, the step of forming a self-assembled monolayer may be initiated by dissolving a self-assembled material. Subsequently, a blending polymer may be dissolved. In one embodiment, the self-assembled material may include a zwitterion containing a methyl side chain.

[0112] Afterward, the solution in which the blending polymer is dissolved can be added to the solution in which the self-assembling material is dissolved. In one embodiment, the blending polymer may include PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F, or a combination thereof.

[0113] Through this process, self-assembled monolayer thin films with added blending polymers can be fabricated.

[0114] Figure 2 is a photograph showing the perovskite deposition coverage for pure SAM and SAM blended with various amounts of PFN.

[0115] Referring to FIG. 2, from left to right in FIG. 2, a pure SAM layer without PFN blending, a SAM layer with 0.05 mg / mL of PFN dissolved in a blending polymer, a SAM layer with 0.10 mg / mL of PFN dissolved in a blending polymer, a SAM layer with 0.30 mg / mL of PFN dissolved in a blending polymer, a SAM layer with 0.50 mg / mL of PFN dissolved in a blending polymer, and a SAM layer with 1.00 mg / mL of PFN dissolved in a blending polymer were fabricated, and a comparative example and an example are shown in which perovskite was deposited on each SAM layer. In the comparative example, almost no perovskite thin film was formed in the pure SAM layer, but in the example, a perovskite thin film was formed without defects in the SAM layer with PFN dissolved in a blending polymer.

[0116] Figure 3 is a diagram for analyzing the contact angle with a solution of a perovskite precursor depending on whether SAM and PFN are blended on a transparent electrode substrate.

[0117] Referring to Fig. 3, in the case of a transparent electrode substrate in its pure form, the contact angle with the perovskite precursor solution is approximately 57 degrees, but when a SAM layer is present, it increases to approximately 80 degrees, confirming that the SAM layer has hydrophobic characteristics. On the other hand, the contact angle of the SAM layer blended with PFN decreases to approximately 50 degrees, showing that it exhibits higher hydrophobic characteristics than the transparent electrode substrate in its pure form. This suggests that the SAM layer blended with PFN is advantageous for forming large-area perovskite thin films.

[0118] Figure 4 is a graph showing SEM images and perovskite particle size distribution to analyze the size of perovskite particles deposited on SAM depending on the presence or absence of PFN blending.

[0119] Referring to the SEM image in Fig. 4, it can be confirmed that when perovskite is deposited on a SAM layer blended with PFN, larger grains are formed compared to when perovskite is deposited on a SAM layer in a pure form, and the perovskite layer has high crystallinity. In particular, referring to the graph in Fig. 4, it can be seen that the distribution of perovskite grain size shifts to the right in the example using a SAM layer blended with PFN compared to the comparative example using a SAM layer in a pure form.

[0120] Figure 5 illustrates the steady-state luminescence and time-resolved photoluminescence spectrum analysis of perovskite films deposited on pure SAM and PFN-blended SAM. Through Figure 5, it can be seen that faster hole collection characteristics are exhibited in the example using a PFN-blended SAM layer compared to the comparative example using a pure form SAM layer.

[0121] Figure 6 is a graph showing the JV data and external quantum efficiency (EQE) (right) data of a 1.80 eV bandgap perovskite solar cell fabricated with pure SAM and PFN blended SAM.

[0122] Referring to FIG. 6, it can be seen that a perovskite solar cell with a bandgap of 1.80 eV fabricated with a SAM blended with PFN has a PCE of 19% or higher. In particular, when blended without changing the bandgap of the perovskite layer through EQE measurement, it can have fast charge collection characteristics with high EQE characteristics in the long wavelength region. According to one embodiment of the present disclosure, the bandgap of the perovskite layer may be 1.60 eV to 2.50 eV, 1.65 eV to 2.10 eV, or 1.70 eV to 1.90 eV.

[0123] Figure 7 is a graph showing stability data of a 1.80 eV bandgap perovskite solar cell fabricated with pure SAM and SAM blended with PFN. Specifically, Figure 7 shows the results of stability experiments conducted on a 1.80 eV bandgap perovskite solar cell according to a comparative example and an embodiment at a temperature of 85 degrees Celsius and a relative humidity of 85%. Referring to Figure 7, it can be seen that in the comparative example using a pure form of SAM layer, the efficiency (PCE) decreased rapidly after about 200 hours, whereas in the embodiment using a SAM layer blended with PFN, the efficiency remained at 80% even after 1000 hours.

[0124] Figure 8 is a diagram illustrating the photovoltaic performance of a large-area perovskite solar cell fabricated with a SAM blended with PFN.

[0125] Referring to Fig. 8, a perovskite solar cell with a bandgap of 1.80 eV fabricated with a PFN-blended SAM has a module area of ​​24.5 cm² 2 Based on the standard, an efficiency of over 17% can be confirmed.

[0126] Figure 9 is a summary table showing the reported module efficiency and area of ​​a 1.80 eV wide bandgap perovskite compared with the present invention.

[0127] Referring to FIG. 9, it can be seen that the perovskite module according to the present invention exhibits a high efficiency of 17.09% in the largest area compared to the module efficiency previously reported for a 1.80 eV wide bandgap perovskite.

[0128]

[0129] Preparation Example

[0130] Example 1: Preparation of self-assembled monolayer precursor solution

[0131] A Me-4PACz self-assembled monolayer precursor solution was prepared at a concentration of 1 mmol / mL, and the precursor was dissolved in ethanol and filtered through a 0.2 μm PTFE filter.

[0132]

[0133] Example 2: Preparation of PFN precursor solution

[0134] A PFN precursor solution was prepared to a concentration of 0.1 mg / mL, completely dissolved in methanol, and then filtered through a 0.2 μm PTFE filter.

[0135]

[0136] Example 3: Preparation and Use of Self-Assembled Monolayer Blended Precursor Solution

[0137] SAM blending solutions were prepared by mixing filtered Me-4PACz self-assembled monolayer and PFN precursor solutions in various volume ratios, and the blending precursors were stirred for at least 2 hours before use.

[0138]

[0139] Comparative Example: Preparation and Use of Perovskite Precursor Solution Without Reducing Agent

[0140] A self-assembled monolayer precursor solution was prepared in the same manner as in Example 1, and then a self-assembled monolayer was prepared without blending it with the PFN precursor solution of Example 2.

[0141]

[0142] The preferred embodiments of the present invention described above are disclosed for illustrative purposes only, and those skilled in the art with ordinary knowledge of the present invention will be able to make various modifications, changes, and additions within the spirit and scope of the present invention, and such modifications, changes, and additions should be considered to fall within the scope of the claims.

[0143] Since various substitutions, modifications, and changes are possible within the scope of the technical concept of the present invention for those skilled in the art to which the present invention pertains, the present invention is not limited by the aforementioned embodiments and attached drawings.

Claims

1. Self-assembled monolayer; and It includes a perovskite layer formed on the self-assembled monolayer, and The above self-assembled monolayer Includes self-assembling materials and blending polymers, The above self-assembled material comprises an anchor group, a linker group, and a terminal functional group, and The above Anchor group comprises a silane, a carbonyl acid, a phosphate group, or a combination thereof, and The above linker group includes an alkyl chain, and The above terminal functional group comprises an amino group, a carbonyl group, a sulfhydryl group, or a combination thereof, and The above blending polymer comprises PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F, or a combination thereof, perovskite photodetector 2. In Paragraph 1, The above self-assembled material comprises Me-4PACz, Me-SB, MSBP, MeO-PEAI, Me-DMAI, or a combination thereof, a perovskite photodetector.

3. In Paragraph 1, It further includes a hole transport layer (HTL), and The above self-assembled monolayer is interposed between the above perovskite layer and the above hole transport layer, forming a perovskite optical device.

4. In Paragraph 3, The hole transport layer mentioned above is Nickel Oxide (NiO₂). x A perovskite photovoltaic device comprising Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate (PEDOT:PSS), Copper Thiocyanate (CuSCN), Copper Iodide (CuI), or a combination thereof.

5. In Paragraph 3, It further includes an electron transport layer (ETL), and The above electron transport layer is a perovskite optical device that is opposite to the self-assembled monolayer with respect to the perovskite layer.

6. In Paragraph 5, A perovskite photodetector, wherein the electron transport layer comprises PCBM ([6,6]-Phenyl-C61-butyric acid methyl ester), C60 (Fullerene), SnO2 (Tin dioxide), or a combination thereof.

7. In Paragraph 1, A perovskite optical device having a band gap of 1.6 eV to 2.5 eV of the perovskite layer.

8. Step of forming a self-assembled monolayer; The method includes the step of forming a perovskite layer on the self-assembled monolayer, and The above self-assembled monolayer Includes self-assembling materials and blending polymers, The above self-assembled material comprises an anchor group, a linker group, and a terminal functional group, and The above Anchor group comprises a silane, a carbonyl acid, a phosphate group, or a combination thereof, and The above linker group includes an alkyl chain, and A method for manufacturing a perovskite photodetector, wherein the terminal functional group comprises an amino group, a carbonyl group, a sulfhydryl group, or a combination thereof, and the blending polymer comprises PFN, PFN-E, PFN-P, PFN-H, PFN-M, PFN-B, PFN-F, or a combination thereof.

9. In Paragraph 8, The step of forming the self-assembled monolayer above A step of dissolving the above self-assembling material; A step of dissolving the above blending polymer; and A step of adding the solution in which the blending polymer is dissolved to the solution in which the self-assembling material is dissolved; A method for manufacturing a perovskite photodetector, comprising 10. A first layer comprising a perovskite optical element according to claim 1; and A second layer comprising an optical element having a bandgap different from that of the perovskite optical element; A perovskite tandem cell comprising

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