Perovskite optical element and method for manufacturing perovskite optical element

Abstract

The present disclosure provides a perovskite optical element. The perovskite optical element comprises: a first electrode; an electron transport layer formed on the first electrode; a perovskite layer formed on the electron transport layer; a lead halide layer formed on the perovskite layer; an alkylammonium halide layer formed on the lead halide layer; a hole transport layer formed on the alkylammonium halide layer; and a second electrode formed on the hole transport layer.

Description

Perovskite photonic device and method for manufacturing perovskite photonic device

[0001] The present disclosure relates to a perovskite photonic device.

[0002] Perovskite solar cells are solar cells with a specific crystal structure called perovskite, in which the photoactive layer contains organic cations, inorganic cations, and halide anions in a ratio of approximately 1:1:3. In perovskite solar cells, which have a multilayer thin-film structure composed of an electron-transport layer, a light-absorbing layer, and a hole-transport layer, minimizing the physical properties of the perovskite thin film, namely internal defects, is crucial to increasing the efficiency and stability. In other words, passivation of defects is necessary to further improve the efficiency of perovskite solar cells.

[0003] Passivation is a physical and chemical method to correct defects in materials. Polymers, single molecules, and carbon nanotubes are mainly used to correct defects on the surface of perovskite crystals.

[0004] Due to the low-temperature solution process, perovskite layers inevitably form numerous surface and interface defects, and these surface defects significantly affect the photovoltaic properties of perovskite. For example, they can limit crystal growth, induce energy level misalignment at the interface, and affect charge transfer characteristics. Furthermore, defects present in perovskite crystal films can accelerate the degradation of perovskite films when exposed to continuous light and heat. This defect-induced degradation significantly reduces the lifespan of perovskite solar cells.

[0005] To prevent perovskite degradation, various defect-controlling processes are necessary. For example, a defect-controlling material can be applied over prefabricated perovskite.

[0006] Adding Lewis acid molecules to perovskite films can remove lone pairs of electrons present in electron-rich defects by binding to them. Lewis acid additives can be coordinating with halide ions or PbI3. - It forms ions and Lewis adducts, and eliminates corresponding defects by forming coordination or ionic bonds. PbI2, which acts as a Lewis acid, was found to form naturally during the formation of perovskite films, stabilizing surface defects at grain boundaries and reducing the rate of charge recombination. To create the PbI2 phase, an excessive amount of PbI2 is intentionally added to the perovskite precursor solution, allowing it to naturally form at the interface during film formation.

[0007] To date, many papers have reported that the defect characteristics of the perovskite interface layer change significantly depending on the excess PbI2, and that finely controlling the thickness of the PbI2 layer is an important parameter. In addition, Cl - Chemical species such as PbI2 and PbCl2 have also been reported to be generally effective in controlling defects in the perovskite interface layer. However, there is a limitation in that the layering of PbI2, PbCl2, etc. on the perovskite layer is impossible through a solution process due to solubility issues.

[0008] In order to solve the above problems, the present disclosure proposes a method for improving interface characteristics by using a surface defect control material vacuum-deposited between a perovskite layer formed by a solution process and a hole transport layer.

[0009] In order to solve the above problems, the present disclosure aims to significantly improve performance and stability and provide optimal conditions by coating a lead halide layer or an alkyl ammonium halide layer on a perovskite layer formed by a solution process through vacuum deposition.

[0010] According to one embodiment of the present disclosure, a perovskite photonic device includes a first electrode, an electron transport layer formed on the first electrode, a perovskite layer formed on the electron transport layer, a lead halide layer formed on the perovskite layer, an alkyl ammonium halide layer formed on the lead halide layer, a hole transport layer formed on the alkyl ammonium halide layer, and a second electrode formed on the hole transport layer.

[0011] According to one embodiment of the present disclosure, the alkyl ammonium halide layer is formed by vacuum deposition.

[0012] According to one embodiment of the present disclosure, the lead halide layer is formed by vacuum deposition.

[0013] According to one embodiment of the present disclosure, the lead halide layer comprises a PbI2 layer.

[0014] According to one embodiment of the present disclosure, the lead halide layer comprises a PbCl2 layer.

[0015] According to one embodiment of the present disclosure, the lead halide layer comprises a double layer of PbI2 and PbCl2.

[0016] According to one embodiment of the present disclosure, the thickness of the PbI2 layer is greater than 0 nm and less than or equal to 8 nm.

[0017] According to one embodiment of the present disclosure, the thickness of the PbI2 layer is 1.5 nm, and the thickness of the PbCl2 layer is greater than 0 nm and less than or equal to 5 nm.

[0018] According to one embodiment of the present disclosure, the alkylammonium halide layer comprises 4MeO-PEAI (4-Methoxy-Phenethylammonium iodide) or PEAI (Phenethylammonium iodide).

[0019] According to one embodiment of the present disclosure, the thickness of the 4MeO-PEAI layer is 10 nm to 40 nm.

[0020] According to one embodiment of the present disclosure, a method for manufacturing a perovskite photonic device includes the steps of forming a first electrode, forming an electron transport layer on the first electrode, forming a perovskite layer on the electron transport layer by spin coating, forming a lead halide layer on the perovskite layer by vacuum deposition, forming an alkyl ammonium halide layer on the lead halide layer by vacuum deposition, forming a hole transport layer on the alkyl ammonium halide layer, and forming a second electrode on the hole transport layer.

[0021] According to one embodiment of the present disclosure, a lead halide layer or an alkyl ammonium halide layer is coated by vacuum deposition on a perovskite layer formed by a solution process of a perovskite optical device to improve interface characteristics, thereby significantly improving performance and stability compared to existing optical devices.

[0022] In addition, it is possible to provide optimized vacuum deposition thicknesses of the surface treatment layers, PbI2 layer, PbCl2 layer, and 4MeO-PEAI layer.

[0023] The effects of the present disclosure are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by a person having ordinary skill in the art to which the present disclosure belongs (referred to as “one skilled in the art”) from the description of the claims.

[0024] Embodiments of the present disclosure will be described below with reference to the accompanying drawings, wherein like reference numerals represent similar elements, but are not limited thereto.

[0025] Figure 1 is a drawing showing the structure of a vacuum deposition device and a perovskite optical device.

[0026] Figure 2 is a drawing showing a picture of PCE mapped according to the deposition thickness of the 4MeO-PEAI layer and the PbI2 layer.

[0027] Figure 3 is a table showing the JV curve according to the thickness of the 4MeO-PEAI layer and the results of measuring optical device performance evaluation factors according to the thickness of the 4MeO-PEAI layer.

[0028] Figure 4 is a graph and table showing the performance evaluation results according to the thickness of the PbCl2 layer in an optical device surface-treated with PbI2 / PbCl2 / 4MeO-PEAI when the thickness of the 4MeO-PEAI layer is an optimized thickness of 40 nm.

[0029] Figure 5 is a graph of the steady state photoluminescence (PL) spectrum of a surface-treated optical device on a perovskite layer.

[0030] Figures 6 and 7 are tables and graphs showing the performance of perovskite optical devices with various surface treatments.

[0031] Figure 8 is a graph and table showing the MPPT test results of a surface-treated optical element.

[0032] 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 of widely known functions or configurations will be omitted if they may unnecessarily obscure the gist of the present disclosure.

[0033] In the attached drawings, identical or corresponding components are assigned the same reference numerals. Furthermore, in the description of the embodiments below, duplicate descriptions of identical or corresponding components may be omitted. However, even if a description of a component is omitted, it is not intended that such component is not included in any embodiment.

[0034] The advantages and features of the disclosed embodiments, and methods for achieving them, will become clearer with reference to the embodiments described below, along with the accompanying drawings. However, the present disclosure is not limited to the embodiments disclosed below and may be implemented in various different forms. These embodiments are provided solely to ensure the completeness of the disclosure and to fully inform those skilled in the art of the scope of the invention.

[0035] The terms used in this specification will be briefly explained, followed by a detailed description of the disclosed embodiments. The terms used in this specification have been selected from widely used, current terms, taking into account the functions of the present disclosure. However, these terms may vary depending on the intentions of engineers working in the relevant field, precedents, the emergence of new technologies, etc. Furthermore, in certain 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 not be defined simply as names of terms, but rather based on their meanings and the overall content of the present disclosure.

[0036] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise. Furthermore, plural expressions include singular expressions unless the context clearly indicates otherwise. When a part of the specification is said to include a component, this does not exclude other components, but rather implies that other components may be included, unless otherwise specifically stated.

[0037] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0038] The term "about" used throughout this specification is used to encompass the tolerance when there is a tolerance.

[0039] Throughout this specification, references to “A and / or B” mean “A or B, or A and B.”

[0040] Throughout this specification, the term "layer" refers to a layer having a thickness. The layer may be porous or non-porous. Porosity refers to having a void ratio. The layer may have a bulk form as a whole or may correspond to a single crystal thin film, but is not limited thereto.

[0041] Throughout this specification, when a member is said to be located "on" another member, unless otherwise specifically stated, this includes not only cases where the member is in contact with the other member, but also cases where another member exists between the two members.

[0042] Throughout this specification, where efficiency is simply described without further explanation, the efficiency may refer to power conversion efficiency (PCE).

[0043] Throughout this specification, “perovskite” or “PE” means a material having a perovskite crystal structure, which may have various perovskite crystal structures in addition to the ABX3 crystal structure.

[0044] Throughout this specification, a “device” may be a device having a photoelectric conversion function or an electro-optical conversion function, for example, a solar cell.

[0045] Throughout this specification, the term "halide", "halogen", "halide" or "halo" means a material or composition containing a halogen atom belonging to Group 17 of the Periodic Table in the form of a functional group, which may include, for example, chlorine, bromine, fluorine or iodine compounds.

[0046] Throughout this specification, the performance of a solar cell photovoltaic device is measured by power conversion efficiency (PCE), fill factor (FF), and open circuit voltage (V). oc ), which can mean current density.

[0047] An optical device according to one embodiment of the present disclosure may include a first electrode, a first charge transport layer formed on the first electrode, a perovskite layer formed on the first charge transport layer, a second charge transport layer formed on the perovskite layer, and a second electrode formed on the second charge transport layer.

[0048] For example, when the photonic device is used in a solar cell having a nip structure, the photonic device may have a structure in which a first electrode, an electron transport layer (a first charge transport layer), a perovskite layer, a hole transport layer (a second charge transport layer), and a second electrode are sequentially stacked. Or, when the photonic device corresponds to a solar cell having a pin structure, the photonic device may have a structure in which a first electrode, a hole transport layer (a first charge transport layer), a perovskite layer, an electron transport layer (a second charge transport layer), and a second electrode are sequentially stacked.

[0049] For example, the photonic device may have a planar structure, a bilayer structure, or a meso-superstructure structure. Depending on the structure of the photonic device, the shapes of the electrodes, charge transport layer, and perovskite layer may be modified.

[0050] For example, when the photonic 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 composed of a first layer of a TiO2: Perovskite mixed layer in which all of the pores of the porous TiO2 are filled with perovskite, and a second layer of a pure perovskite layer thereon.

[0051] 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. Alternatively, if the first electrode is a cathode, the second electrode may be an anode. For example, the electrode may be a conductive oxide such as indium-tin oxide (ITO), indium-zinc oxide (IZO), flourine-doped tin oxide (FTO), or the like. Alternatively, 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 polyethylene PET (polyethylene terephthalate), PEN (polyethylene naphthelate), PP (polyperopylene), PI (polyimide), PC (polycarbornate), PS (polystylene), POM (polyoxyethylene), etc., in which a conductive material is doped.

[0052] The electrode may correspond to a material commonly used as an electrode material for a front electrode or a back electrode in a photonic 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 a composite 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.

[0053] 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.

[0054] The electron transport layer may correspond to a semiconductor comprising an "n-type material." The "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.

[0055] For example, the electron transport layer may be an electron-conducting organic layer or an electron-conducting inorganic layer. The electron-conducting organic layer may be an organic layer used as an n-type semiconductor in a typical organic solar cell. For example, the electron-conducting organic layer may be a fullerene (C 60 , C70 , C 74 , C 76 , C 78 , C 82 , C 95 ), PCBM([6,6]-phenyl-C 61 butyric acid methyl ester)), and C 71 -PCBM, C 84 -PCBM, PC 70 BM([6,6]-phenyl C 70 -butyric acid methyl ester), polybenzimidazole (PBI), 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI), tetrafluorotetracyanoquinodimethane (F4-TCNQ), or mixtures thereof, but are not limited thereto.

[0056] The electron-conducting inorganic material may be an electron-conducting metal oxide used for electron transport in a typical quantum dot-based solar cell, dye-sensitized solar cell, or perovskite solar cell. 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 a material selected from, but not limited to, one or more of 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.

[0057] 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 electron-conducting organic material described above or a dense film of an electron-conducting inorganic material. The electron transport layer of the porous film may be a porous film composed of particles of the electron-conducting inorganic material described above.

[0058] The hole transport layer may correspond to a semiconductor comprising a "p-type material." The "p-type material" refers to a hole transport material. The hole transport 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 transport material may be an organic hole transport material, an inorganic hole transport material, or a combination thereof.

[0059] The hole transport layer may be manufactured using 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 range from 10 nm to 500 nm, but is not limited thereto.

[0060] The hole transport material may be an organic hole transport material, specifically a single molecule or polymer organic hole transport material (hole conducting organic material). The polymer organic hole transport material may include one or more materials selected from thiophene-based, paraphenylenevinylene-based, carbazole-based, and triphenylamine-based compounds.

[0061] Single-molecule to small-molecule organic hole transport materials include pentacene, coumarin 6 (coumarin 6, 3- (2-benzothiazolyl)-7- (diethylamino)coumarin), zinc phthalocyanine (ZnPC), copper phthalocyanine (CuPC), titanium oxide phthalocyanine (TiOPC), Spiro-MeOTAD (2,2',7,7'-tetrakis(N,Np-dimethoxyphenylamino)- 9,9'-spirobifluorene), F16CuPC (copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro29H,31H-phthalocyanine), and boron subphthalocyanine chloride (SubPc). 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.

[0062] 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 [[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 may include one or more selected from the group consisting of, but is not limited thereto.

[0063] The electron transport layer or hole transport layer may be surface-modified by doping. The electron transport layer or hole transport layer may be formed by applying it to one surface of the 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.

[0064] The perovskite layer can be formed through various processes, including a vapor deposition process or a solution process. The perovskite layer can be formed using a vapor deposition process. The vapor deposition process may correspond to a process in which a material is supplied in a vaporized or plasma state into a vacuum chamber and the material is deposited on a surface of a target object (e.g., a substrate). The perovskite layer can be formed through a coating process during the solution process. The coating process may be selected from the group consisting of, but is not limited to, spin coating, bar coating, nozzle printing, spray coating, slot die coating, gravure printing, inkjet printing, screen printing, electrohydrodynamic jet printing, electrospray, and combinations thereof.

[0065] For example, the perovskite may contain a monovalent organic cation, a divalent metal cation, and a halogen anion. In one embodiment, the perovskite of the present invention may satisfy the following chemical formula:

[0066] [Chemical Formula 1]

[0067] AMX3

[0068] In chemical formula 1, A is a monovalent cation, which may correspond to an organic ammonium ion, an amidinium group ion, or a combination of an organic ammonium ion and an amidinium group ion.

[0069] For example, an organic cation as A has the chemical formula (R1R2R3R4N) + may have. In this case, R1~R4 may correspond to hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

[0070] For example, an organic cation as A has the chemical formula (R5NH3) + , wherein R5 may correspond to hydrogen, or substituted or unsubstituted C1-C20 alkyl.

[0071] For example, an organic cation as A has the chemical formula (R6R7N=CH-NR8R9) + , and in this case, R6~R9 can correspond to hydrogen, methyl, or ethyl.

[0072] M can be a divalent metal ion. For example, M can be 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+ A metal cation selected from the group consisting of, but not limited to, and combinations thereof.

[0073] X may correspond to a halogen ion. For example, the halogen ion is I - , Br - , F - , Cl - and combinations thereof. Including, but not limited to, a halogen ion selected from the group consisting of:

[0074] For example, the perovskite may be one or a mixture of two or more selected from CH3NH3PbI3 (methylammonium lead iodide, MAPbI3) and CH(NH2)2PbI3 (formamidinium lead iodide, FAPbI3).

[0075] According to one embodiment of the present disclosure, a perovskite layer can be formed using spin coating. A thin film can be formed by spin coating a precursor solution in which organic and inorganic materials are mixed in a solvent on a substrate and then heating the solution at a temperature of about 80 to 150° C. (annealing).

[0076] FIG. 1 is a diagram illustrating the structure of a vacuum deposition device and a perovskite photonic device. The nip device structure of a perovskite photonic device (PSC) according to one embodiment of the present disclosure is illustrated in FIG. 1.

[0077] In order to manufacture a device structure according to one embodiment of the present disclosure, a SnO2 layer serving as an electron transport layer is formed by spin coating on an ITO electrode on a glass substrate, a perovskite layer is spin coated thereon, and then transferred to a vacuum chamber, and the chamber is 1x10 -6 After pumping to 10 torr, lead halide and alkyl ammonium halide layers were sequentially evaporated to controlled thicknesses, or only one of the two layers. The alkyl ammonium halide layer was deposited using either 4MeO-PEAI or PEAI.

[0078] A lead halide layer and an alkyl ammonium halide layer can be deposited at a controlled thickness using a vacuum deposition apparatus having a vacuum chamber, multiple precursor sources, and a control unit of FIG. 1.

[0079] Afterwards, Spiro-OMeTAD, which serves as a hole transport layer, is formed by spin coating on the lead halide layer or the alkyl ammonium halide layer, and a gold (Au) electrode is placed on top of it.

[0080] To evaluate the influence of the thickness of the lead halide layer on the surface directly above the perovskite layer according to various embodiments of the present disclosure, a 4MeO-PEAI layer was deposited on the PbI2 layer. The thickness of the 4MeO-PEAI layer was fixed, and the vacuum deposition thickness of the PbI2 layer was varied to 0 nm, 1.5 nm, 4 nm, and 8 nm.

[0081] Fig. 2 is a diagram showing the PCE mapped according to the deposition thickness of the 4MeO-PEAI layer and the PbI2 layer. It can be confirmed that the PCE of the optical device is improved when the PbI2 layer is introduced, but when the thickness increases beyond a certain thickness, the PCE of the optical device decreases. In particular, as shown in the dark-colored part (more than 20.9%) in Fig. 2, the highest PCE is shown under the condition that the PbI2 layer is deposited to a thickness of 1.5 nm, and the PCE tends to decrease as the thickness of the PbI2 layer increases to 4 and 8 nm. In addition, the current density (Jsc) and fill factor (FF) values ​​tend to decrease as the thickness of the PbI2 layer increases to 4 and 8 nm. In summary, it can be seen that the optimal thickness of the PbI2 layer in terms of optical device performance is approximately 1.5 nm.

[0082] When the concentration of long alkyl chains is high, the open circuit voltage (V) of the photodetector oc ) was improved, a 4MeO-PEAI layer was vacuum-deposited on a perovskite layer, and an optical device was fabricated while increasing the thickness of the 4MeO-PEAI layer.

[0083] Fig. 3 is a table showing the JV curve according to the thickness of the 4MeO-PEAI layer and the results of the optical device performance evaluation factor measurement according to the thickness of the 4MeO-PEAI layer. In the JV curve of Fig. 3, when the 4MeO-PEAI layer thickness is 40 nm, the J scIt shows that the V is improved. In the table of Fig. 3, when the 4MeO-PEAI layer thickness is 40 nm, it is higher than when the 4MeO-PEAI layer thickness is 10 nm. oc and the PCE results were significantly larger. Meanwhile, the FF results did not show any significant change depending on the thickness of the 4MeO-PEAI layer.

[0084] Cl - It has been reported that materials such as these are effective in controlling perovskite interface layer defects. Therefore, in order to verify the effect of improving the performance of optical devices by introducing an additional PbCl2 layer, a bilayer of PbI2 / PbCl2 was introduced as a lead halide layer. The thickness of the PbI2 layer was set to the optimal thickness of approximately 1.5 nm as described above, and an optical device was fabricated by controlling the vacuum deposition thickness of the PbCl2 layer.

[0085] Fig. 4 is a graph and table showing the performance evaluation results according to the thickness of the PbCl2 layer in an optical device surface-treated with PbI2 / PbCl2 / 4MeO-PEAI when the thickness of the 4MeO-PEAI layer is the optimal thickness of 40 nm. As can be seen in the table, the performance of the optical device was confirmed to improve when the PbCl2 layer was introduced, but the performance of the optical device was shown to deteriorate when the PbCl2 layer became thicker than a certain thickness. Specifically, the highest performance was shown under the condition where the PbCl2 layer was deposited with a thickness of 0.5 nm, and it can be seen that each parameter (Jsc, Voc, FF, PCE) tended to decrease as the thickness increased to 3 nm and 5 nm.

[0086] To verify the photostability of the thin film solar cell photovoltaic device, various surface treatments were performed on the perovskite layer, and the intensity of the steady-state photoluminescence (PL) spectrum was compared after 1 hour of light soaking (LS) under ambient conditions and AM 1.5 illumination. PL spectroscopy is a non-destructive method for analyzing the optical properties of semiconductors, requiring no electrode attachment to the sample, and allowing the sample to be preserved in its original form.

[0087] LS was performed for 1 hour at about 514 nm where a 2D perovskite phase appears, and steady-state photoluminescence (PL) was measured. The measurement targets are an optical device without surface treatment, an optical device spin-coated with solution-state 4MeO-PEAI as a comparative example of the present disclosure, an optical device vacuum-deposited with a 4MeO-PEAI layer according to an embodiment of the present disclosure, an optical device vacuum-deposited with a 4MeO-PEAI layer on a PbI2 layer according to another embodiment of the present disclosure, and an optical device having a vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI layer according to another embodiment of the present disclosure.

[0088] Figure 5, which shows the measurement results, is a graph of the steady-state PL spectrum of a solar cell optical device surface-treated with a perovskite layer. As shown in Figure 5, the PL intensity was significantly reduced in the optical device spin-coated with 4MeO-PEAI in a solution state, but the rate of decrease in PL intensity was reduced when 4MeO-PEAI was vacuum-deposited.

[0089] In particular, the photonic device with the vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI layer exhibited the smallest change in PL intensity. This suggests that the PbI2 / PbCl2 bilayer enhances the surface passivation capability of 4MeO-PEAI, thereby contributing to the long-term retention of the 2D perovskite phase.

[0090] Figures 6 and 7 are tables and graphs showing the performance of perovskite photonic devices with various surface treatments. Similar parameter values ​​(J) were observed in photonic devices with vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI layers and photonic devices spin-coated with 4MeO-PEAI in solution. sc , V oc , FF, PCE), but the photodetector treated with PbI2 / PbCl2 bilayer shows slightly higher parameter values ​​overall. That is, it can be seen that the photodetector with PbI2 / PbCl2 / 4MeO-PEAI layer has the highest performance.

[0091] The photostability of solar cell photovoltaic devices was measured using the maximum power point tracking (MPPT) method for 7 days under 1-sun illumination in the ambient atmosphere and surface-treated photovoltaic devices as described above.

[0092] Figure 8 is a graph and table showing the results of MPPT tests of surface-treated solar cell photovoltaic devices. In the case of photovoltaic devices with vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI layers, the initial PCE was maintained at 72.95% or more after MPPT tests for more than 7 days, whereas in the case of photovoltaic devices spin-coated with solution-state 4MeO-PEAI (comparative example of the present disclosure), only 53.10% of the initial PCE was maintained after MPPT tests for more than 7 days.

[0093] It can be seen that the reduction ratio compared to the initial PCE after the MPPT test is large in the following order: an optical device spin-coated with solution-state 4MeO-PEAI as a comparative example of the present disclosure, an optical device vacuum-deposited with a 4MeO-PEAI layer according to an embodiment of the present disclosure, an optical device vacuum-deposited with a 4MeO-PEAI layer on a PbI2 layer according to another embodiment of the present disclosure, and an optical device having a vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI layer according to another embodiment of the present disclosure.

[0094] The above results demonstrate that the upper protective layer formed via a vacuum deposition process can suppress moisture and heat-induced damage to the perovskite thin film, thereby enhancing the operational stability of solar cell photovoltaic devices. In particular, the higher the initial PCE after the above test for photovoltaic devices containing a vacuum-deposited PbI2 / PbCl2 bilayer, the higher the photostability of the photovoltaic devices.

[0095] According to one embodiment of the present disclosure, by coating a lead halide layer and an alkyl ammonium halide layer on the perovskite layer of the perovskite optical device by vacuum deposition to improve the interface characteristics, the performance and stability can be significantly improved compared to the existing optical device. In particular, the performance is the highest when the evaporation thickness of the PbI2 layer is about 1.5 nm, the evaporation thickness of the PbCl2 layer is about 0.5 nm, and the deposition thickness of the 4MeO-PEAI is about 40 nm, and based on the fact that the performance and photostability are the highest in the vacuum-deposited PbI2 / PbCl2 / 4MeO-PEAI-based optical device, it was possible to establish an optimal strategy for improving the interface characteristics by vacuum deposition.

[0096] The previous description of the present disclosure is provided to enable any person skilled in the art to make or use the present disclosure. Various modifications to the present disclosure will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to various modifications without departing from the spirit or scope of the present disclosure. Thus, the present disclosure is not intended to be limited to the examples described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

[0097] While the present disclosure has been described in connection with certain embodiments herein, various modifications and variations may be made without departing from the scope of the present disclosure, which would be apparent to those skilled in the art. Furthermore, such modifications and variations are intended to fall within the scope of the claims appended to this specification.

[0098] The above preferred embodiments of the present invention are disclosed for the purpose of illustration, 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 patent claims.

[0099] Anyone having ordinary skill in the art to which the present invention pertains can make various substitutions, modifications, and changes within the scope that does not depart from the technical spirit of the present invention, and therefore the present invention is not limited to the above-described embodiments and the attached drawings.

Claims

1. As a perovskite photonic device, First electrode; An electron transport layer formed on the first electrode; A perovskite layer formed on the electron transport layer; A lead halide layer formed on the perovskite layer; An alkyl ammonium halide layer formed on the lead halide layer; A hole transport layer formed on the above alkyl ammonium halide layer; and A second electrode formed on the above hole transport layer A perovskite photonic device comprising:

2. In paragraph 1, A perovskite optical device in which the above alkyl ammonium halide layer is formed by vacuum deposition.

3. In paragraph 1, A perovskite optical device in which the lead halide layer is formed by vacuum deposition.

4. In paragraph 3, A perovskite optical device, wherein the lead halide layer comprises a PbI2 layer.

5. In paragraph 3, A perovskite optical device, wherein the lead halide layer comprises a PbCl2 layer.

6. In paragraph 3, A perovskite photonic device, wherein the lead halide layer comprises a double layer of PbI2 and PbCl2.

7. In paragraph 4 or paragraph 6, A perovskite optical device, wherein the thickness of the PbI2 layer is greater than 0 nm and less than or equal to 8 nm.

8. In paragraph 6, A perovskite optical device, wherein the thickness of the PbI2 layer is 1.5 nm and the thickness of the PbCl2 layer is greater than 0 nm and less than or equal to 5 nm.

9. In paragraph 1, A perovskite photonic device, wherein the above alkyl ammonium halide layer comprises 4MeO-PEAI (4-Methoxy-Phenethylammonium iodide) or PEAI (Phenethylammonium iodide).

10. In paragraph 9, A perovskite optical device, wherein the thickness of the 4MeO-PEAI layer is 10 nm to 40 nm.

11. A method for manufacturing a perovskite optical device, Step of forming a first electrode; A step of forming an electron transport layer on the first electrode; A step of forming a perovskite layer by spin coating on the electron transport layer; A step of forming a lead halide layer by vacuum deposition on the perovskite layer; A step of forming an alkyl ammonium halide layer by vacuum deposition on the lead halide layer; A step of forming a hole transport layer on the above alkyl ammonium halide layer; and A step of forming a second electrode on the above hole transport layer A method for manufacturing a perovskite optical device, comprising:

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