WO2024225584A1

WO2024225584A1 - Optical device having cross-linked layer

Info

Publication number: WO2024225584A1
Application number: PCT/KR2024/001682
Authority: WO
Inventors: 김영윤; 전남중; 유소민; 김범수; 박은영; 홍순일; 김준석
Original assignee: 한국화학연구원
Priority date: 2023-04-27
Filing date: 2024-02-06
Publication date: 2024-10-31

Abstract

The present disclosure relates to an optical device having a cross-linked layer. The optical device having a crosslinked layer comprises: a first electrode; an electron transport layer formed on the first electrode; a cross-linked layer formed on the electron transport layer; a perovskite layer formed on the cross-linked layer; a hole transport layer formed on the perovskite layer; and a second electrode formed on the hole transport layer, wherein the cross-linked layer is formed by cross-linking of glycidyltrimethylammonium chloride (GTMACl).

Description

Optical device having a cross-linked layer

The present disclosure relates to an optical device having a cross-linked layer, and more particularly, to an optical device in which a cross-linked layer is formed by GTMACl.

The need for developing environmentally friendly and sustainable energy technologies that can respond to climate change is increasing. Photovoltaic devices include both photoelectric conversion devices and electro-optical conversion devices. Among photoelectric conversion devices, solar cells are receiving attention as a solution that can actively respond to future energy demands as a sustainable energy technology. Solar cells are semiconductor devices that convert solar energy into electrical energy and utilize the photovoltaic effect.

However, since today's solar cell technology does not show an efficiency level that can replace future energy demands, technological innovation that goes beyond the current level of technology is needed. Accordingly, technologies based on innovative materials such as dye-sensitized solar cells, organic solar cells, quantum dot solar cells, and perovskite solar cells (PSC) have been developed as next-generation solar cells.

Among them, perovskite solar cells have emerged as one of the thin-film solar cells that will replace conventional silicon solar cells. Perovskite solar cells, which include hole transport materials, light absorbing materials, and electron transport materials, exhibit remarkably high photovoltaic effects by using perovskite materials as light absorbing materials. However, perovskite solar cells have problems in that the charge transport ability is reduced due to defects in the charge transport layer that occur during the manufacturing process, and the stability of the solar cell is also reduced.

The present disclosure aims to provide an optical device having improved stability and efficiency by including a cross-linking layer.

An optical device having a cross-linked layer according to one embodiment of the present disclosure, comprising: a first electrode, an electron transport layer formed on the first electrode, a cross-linked layer formed on the electron transport layer, a perovskite layer formed on the cross-linked layer, a hole transport layer formed on the perovskite layer, and a second electrode formed on the hole transport layer, wherein the cross-linked layer is formed by cross-linking of GTMACl (Glycidyltrimethylammonium chloride).

In one embodiment of the present disclosure, crosslinks of GTMACl are formed by annealing.

An optical module is provided, manufactured by combining a plurality of optical elements according to one embodiment of the present disclosure.

A method for manufacturing an optical device having a cross-linked layer according to one embodiment of the present disclosure, comprising: a step of forming an electrode; a step of forming an electron transport layer on the electrode; and a step of forming a cross-linked layer on the electron transport layer.

In one embodiment of the present disclosure, the step of forming a cross-linking layer includes the step of introducing GTMACl onto the electron transport layer and the step of annealing the GTMACl at 100 degrees Celsius.

By using various embodiments of the present disclosure, the electron transport ability of the electron transport layer can be improved by suppressing defects in the electron transport layer by introducing a cross-linking layer.

By using various embodiments of the present disclosure, the blocking effect of the electrode for minority carriers can be improved.

By utilizing various embodiments of the present disclosure, the efficiency and stability of optical devices can be improved.

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 (hereinafter referred to as “ordinary skilled in the art”) from the description of the claims.

FIG. 1 is a drawing showing the structure of an optical device according to one embodiment of the present disclosure.

FIG. 2 is a diagram showing a cyclic voltammetry (CV) graph of an optical device according to one embodiment of the present disclosure.

FIG. 3 is a diagram showing a TCSPC (Time-Correlated Single Photon Counting) spectrum of an optical device according to one embodiment of the present disclosure.

FIG. 4 is a diagram showing the current density and efficiency of an optical device according to one embodiment of the present disclosure.

FIG. 5 is a diagram showing the current density of an optical module manufactured by combining a plurality of optical elements according to one embodiment of the present disclosure.

FIGS. 6 to 8 are drawings showing electrical characteristics of an optical device according to one embodiment of the present disclosure.

FIG. 9 is a diagram showing an FT-IR spectrum of a cross-linked layer according to one embodiment of the present disclosure.

FIG. 10 is a diagram showing capacitance when light is irradiated on an optical device according to one embodiment of the present disclosure.

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 there is a risk of unnecessarily obscuring the gist of the present disclosure.

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.

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

Throughout this specification, the term "at least one" included in a Markush format expression means including one or more selected from the group consisting of elements described in the Markush format expression.

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

The term "about" or the like used in this disclosure is used to encompass the tolerance when there is a tolerance.

In this disclosure, the term "at least one" included in a Markush format expression means including one or more selected from the group consisting of components described in the Markush format expression.

In the present disclosure, “perovskite” or “PE” means a material having a perovskite crystal structure, and may have various perovskite crystal structures in addition to the crystal structure of ABX ₃ .

In the present disclosure, the term "optical device" is used to mean both a photoelectric conversion device and an electro-optical conversion device. For example, the optical device includes, but is not limited to, a solar cell, a light emitting diode (LED), a photodetector, an X-ray detector, and a laser.

As used herein, the term “halide”, “halogen”, “halogenide” 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.

Throughout this specification, the term "layer" means a layer having a thickness. The layer may be porous or non-porous. Porosity means 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.

Throughout this specification, when an element is said to be located "on" another element, unless otherwise specifically stated, this includes not only cases where an element is in contact with another element, but also cases where another element exists between the two elements.

Throughout this specification, where efficiency is simply described without any further explanation, the efficiency may mean Power Conversion Efficiency (PCE).

The advantages and features of the disclosed embodiments, and the methods for achieving them, will become apparent with reference to the embodiments described below together with the accompanying drawings. However, the present disclosure is not limited to the embodiments disclosed below, but may be implemented in various different forms, and these embodiments are provided only to make the present disclosure complete, and to fully inform those skilled in the art of the scope of the invention.

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

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.

For example, when the photonic device is used in a solar cell having an n-i-p 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 p-i-n 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.

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 electrode, charge transport layer, and perovskite layer may be modified.

For example, when the photonic device has a Bi-Layer structure, the perovskite layer may have a bi-layer structure formed by filling perovskite into porous TiO ₂ to form a layer. The bi-layer may mean a structure composed of a first layer of a TiO ₂ : Perovskite mixed layer in which all of the pores of the porous TiO ₂ are filled with perovskite, and a second layer of a pure perovskite layer thereon.

The electrode comprises a first electrode and/or a second electrode, and can be an anode or a cathode. The electrode can be an anode or a cathode. When the first electrode is an anode, the second electrode can be a cathode. Alternatively, when the first electrode is a cathode, the second electrode can be an anode. For example, the electrode can 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 can 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 terephthalate (PET), polyethylene naphthelate (PEN), polyperopylene (PP), polyimide (PI), polycarbornate (PC), polystylene (PS), or polyoxyethylene (POM), doped with a conductive material.

The electrode may correspond to a material typically 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 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.

As a charge transport layer, an electron transport layer (ETL) or a hole transport layer (HTL) may be formed on the first electrode. When the first charge transport layer is an electron transport layer, the second charge transport layer may correspond to a hole transport layer. Alternatively, when the first charge transport layer is a hole transport layer, the second charge transport layer may correspond to an electron transport layer.

The electron transport layer may correspond to a semiconductor comprising an "n-type material." The "n-type material" means 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 may be doped with one or more dopant elements.

For example, the electron transport layer can be an electron conductive organic layer or an electron conductive inorganic layer. The electron conductive organic layer can be an organic layer used as an n-type semiconductor in a typical organic solar cell. For example, the electron conductive organic layer can include, but is not limited to, fullerene (C60, C70, C74, C76, C78, C82, C95), PCBM ([6,6]-phenyl-C61butyric 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 (tetrafluorotetracyanoquinodimethane) or mixtures thereof.

The electron-conducting inorganic material can be an electron-conducting metal oxide used for electron transport in conventional quantum dot-based solar cells, dye-sensitized solar cells or perovskite-based solar cells. In one embodiment, the electron-conducting metal oxide can be an n-type metal oxide semiconductor. For example, the n-type metal oxide semiconductor can 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.

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 above-described electron-conducting organic material or a dense film of the above-described electron-conducting inorganic material. The electron transport layer of the porous film may be a porous film formed of particles of the above-described electron-conducting inorganic material.

The hole transport layer may correspond to a semiconductor comprising a "p-type material". The "p-type material" means a hole transporting material. The hole transporting material may be a single hole transporting compound or elemental material, or a mixture of two or more hole transporting compounds or elemental materials. The hole transporting 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.

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, but is not limited to, 10 nm to 500 nm.

The hole transport material may correspond to 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 series, paraphenylene vinylene series, carbazole series, and triphenylamine series.

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,N-p-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 contain 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.

Polymeric organic hole transport materials include 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-octyl thiophene)) -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 their The copolymer may include, but is not limited to, one or more selected materials.

The electron transport layer or hole transport layer can be surface modified by doping. The electron transport layer or hole transport layer can be formed by applying it to one surface of the electrode or coating it in the form of a film by 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.

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 of supplying a material in a vaporized state or a plasma state into a vacuum chamber and depositing the material 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 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.

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:

[Chemical Formula 1]

AMX ₃

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.

For example, an organic cation as A can have the chemical formula (R ₁ R ₂ R ₃ R ₄ N) ⁺ . In this case, R ₁ to R ₄ can correspond to hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

For example, an organic cation as A may have the chemical formula (R ₅ NH ₃ ) ⁺ , where R ₅ may correspond to hydrogen, or a substituted or unsubstituted C1-C20 alkyl.

For example, an organic cation such as A has the chemical formula (R ₆ R ₇ N=CH-NR ₈ R ₉ ) ⁺ , where R ₆ to R ₉ can correspond to hydrogen, methyl, or ethyl.

M can be a divalent metal ion. For example, M includes a metal cation selected from the group consisting of 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⁺ and combinations thereof, but is not limited thereto.

X may correspond to a halogen ion. For example, the halogen ion includes, but is not limited to, a halogen ion selected from the group consisting of I ^- , Br ^- , F ^- , Cl ^{- ,} and combinations thereof.

For example, the perovskite can be one or a mixture of two or more selected from CH ₃ NH ₃ PbI ₃ (methylammonium lead iodide, MAPbI ₃ ) and CH(NH ₂ ) ₂ PbI ₃ (formamidinium lead iodide, FAPbI ₃ ).

FIG. 1 is a drawing showing the structure of an optical device according to one embodiment of the present disclosure. In one embodiment, the first electrode and the second electrode may be composed of FTO (Fluorine doped Tin Oxide) and Au, respectively.

In one embodiment, the electron transport layer may include tin oxide. For example, the electron transport layer may be composed of a bilayer structure of a sol-gel based SnO ₂ layer and a SnO ₂ nanoparticle layer, but is not limited thereto.

In one embodiment, a cross-linked layer is formed between the electron transport layer and the perovskite layer to suppress defects in the electron transport layer and enhance the blocking effect for minority carriers of the electrode. Through this configuration, the electron transport ability of the electron transport layer can be enhanced, and the efficiency and stability of the optical device can be improved. At this time, the cross-linked layer can be formed as a uniform thin film (uniform/conformal coating) over the entire area on the electron transport layer.

In one embodiment, the cross-linking layer disposed between the electron transport layer and the perovskite layer can be formed by cross-linking of GTMACl (Glycidyltrimethylammonium chloride). Specifically, the cross-linking layer can be generated by cross-linking between GTMACl molecules through annealing after GTMACl is coated on the electron transport layer. At this time, the annealing can be performed at 100 degrees Celsius.

In one embodiment, the hole transport layer can include Spiro-OMeTAD. Holes generated in the perovskite layer can travel to the electrode through the hole transport layer.

In one embodiment, a diffusion barrier layer (not shown in the drawing) is disposed between the hole transport layer and the electrode to suppress diffusion of the electrode, thereby improving the stability of the optical device. According to one embodiment, the diffusion barrier layer may be disposed between the hole transport layer and the electrode Au.

Performance comparison

The performance of the optical device was evaluated according to the presence or absence of a cross-linking layer using GTMACl using the following method using a perovskite optical device, and the results of the test on the optical device structure below are shown in Table 1 below.

Photonic device structure: Glass / FTO / Sol-gel SnO ₂ / SnO ₂ NPs / Cross-linked layer by GTMACl / (FAPbI ₃ ) _0.95 (MAPbBr ₃ ) _0.05 Perovskite / Spiro-OMeTAD / MoO ₃ / ITO / Au

1) Current-voltage characteristics: Using an artificial sun simulator (ORIEL class A solar simulator, Newport, model 91195A) and a source meter (Kethley, model 2420), light of the AM1.5G spectrum was irradiated through the artificial sun simulator with an irradiance of 1,000 W/㎡. The voltage was applied in both directions (Reverse/Forward) and the current was measured, through which the open circuit voltage (VOC), short-circuit current density (JSC), and fill factor (FF) were measured.

2) Power conversion efficiency (PCE): The final power conversion efficiency was obtained by multiplying the values of open circuit voltage, short-circuit current density, and fill factor calculated from the current-voltage characteristics.

3) Stability: Stability was evaluated by substituting the measured PCE value into the following calculation formula.

Calculation formula = (η ₁ / η ₀ ) x 100

In the calculation formula, η ₀ represents the initial photoelectric conversion efficiency of the perovskite photonic device immediately after the stability test begins, and η ₁ represents the photoelectric conversion efficiency measured after a certain period of time after continuously irradiating the same perovskite photonic device with the AM1.5G spectrum and 1 Sun light intensity of an artificial solar device.

4) Maximum power point tracking (MPPT): In the case of light irradiance stability results, the voltage indicating the maximum output is continuously detected and tracked, thereby indicating the relative maximum output value that changes over time.

	ReverseReverse				ForwardForward
	V _OC (V) V _OC (V)	J _SC (mA/cm²) J _SC (mA/cm ² )	FFFF	PCE (%)PCE (%)	V _OC (V) V _OC (V)	J _SC (mA/cm²) J _SC (mA/cm ² )	FFFF	PCE (%)PCE (%)
ReferenceReference	1.14 (1.12)1.14 (1.12)	24.41 (24.20)24.41 (24.20)	0.81 (0.78)0.81 (0.78)	22.69 (21.11)22.69 (21.11)	1.14 (1.13)1.14 (1.13)	24.40 (24.34)24.40 (24.34)	0.80 (0.76)0.80 (0.76)	22.48 (20.98)22.48 (20.98)
가교결합층 도입Introduction of cross-linked layer	1.16 (1.14)1.16 (1.14)	24.85 (24.65)24.85 (24.65)	0.82 (0.80)0.82 (0.80)	23.39 (22.46)23.39 (22.46)	1.15 (1.14)1.15 (1.14)	24.83 (24.57)24.83 (24.57)	0.80 (0.79)0.80 (0.79)	22.92 (22.07)22.92 (22.07)

In Table 1, it can be confirmed that the efficiency of the optical device increases with the introduction of the cross-linking layer by GTMACl. FIG. 2 is a diagram showing a cyclic voltammetry (CV) graph of the optical device according to an embodiment of the present disclosure. FIG. 2 shows the degree to which the redox reaction of the Fe(CN) ₆ ^3-/4- couple is blocked on bare FTO. In FIG. 2, it can be confirmed that the blocking ability in FTO is improved as a uniform cross-linking layer is formed by GTMACl compared to the case where only SnO ₂ is present without a cross-linking layer, thereby effectively suppressing the accumulation of unwanted holes and non-luminescent recombination of electrons and holes.

In a photonic device with an n-i-p structure, electrons with a (-) charge must be accepted on the n-type side, and holes with a (+) charge must be collected on the opposite electrode (p-type side). The blocking effect refers to the process of accepting electrons as they are but preventing them from coming into direct contact with holes and inducing recombination with electrons.

FIG. 3 is a diagram showing a TCSPC (Time-Correlated Single Photon Counting) spectrum of a photonic device according to one embodiment of the present disclosure. As illustrated in FIG. 3, by introducing a cross-linking layer using GTMACl, the carrier lifetime generated through defect passivation can be increased. That is, it can be confirmed that the non-luminous recombination of electrons and holes is suppressed and maintained for a longer period of time by suppressing and compensating for defects in the electron transport layer.

FIG. 4 is a diagram showing the current density and efficiency of an optical device according to one embodiment of the present disclosure. In FIG. 4, it can be confirmed that, compared to an optical device to which a cross-linking layer is not introduced, the current density and efficiency of an optical device in which defects are suppressed by introducing a cross-linking layer using GTMACl are improved, and the deviation of the measured efficiency is reduced and the reproducibility is increased.

FIG. 5 is a diagram showing the current density of an optical module manufactured by combining a plurality of optical elements according to one embodiment of the present disclosure. Although FIG. 5 illustrates that five optical elements are combined, the present invention is not limited thereto and an optical module may be manufactured by combining any number of optical elements. A cross-linking layer using GTMACl according to one embodiment described above may be disposed on each of the optical elements included in the optical module illustrated in FIG. 5.

In Fig. 5, it can be confirmed that the current density of the optical module manufactured by combining optical elements formed with a cross-linked layer by GTMACl is further improved. That is, it can be confirmed that defects within the optical element are suppressed and efficiency is improved by introducing a uniform cross-linked layer even in a large-area module.

FIGS. 6 to 8 are diagrams showing electrical characteristics of an optical device according to an embodiment of the present disclosure. FIG. 6 shows the results of measuring the transient photocurrent (TPC) of the optical device. It can be confirmed that by introducing a cross-linking layer into the optical device, the transport of electrons generated by optical excitation (optical pumping) is smooth, thereby reducing the lifetime of the generated carriers. FIG. 7 shows the results of measuring the transient photovoltage (TPV) of the optical device. It can be confirmed that by introducing a cross-linking layer into the optical device, defects in the electron transport layer are suppressed, thereby maintaining the photovoltage for a longer period of time. FIG. 8 shows the results of measuring the light irradiation stability of the optical device over time. It can be confirmed that by introducing a uniform cross-linking layer, electron transport is improved, defects in the electron transport layer are suppressed, thereby improving the stability of the optical device.

FIG. 9 is a diagram showing an FT-IR spectrum of a cross-linked layer according to one embodiment of the present disclosure. In FIG. 9, it can be confirmed that the peak (epoxy peak) near 1100 cm ^-1 is reduced. That is, it can be confirmed that the epoxy structure of GTMACl is broken and cross-linked bonds are formed by annealing.

Fig. 10 is a diagram showing the capacitance when light is irradiated on an optical device according to one embodiment of the present disclosure. It can be confirmed that the capacitance in the low frequency band decreases with the introduction of the cross-linking layer. That is, it can be confirmed that the stability of the optical device is improved by suppressing ion migration with the introduction of the cross-linking layer.

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.

Although the present disclosure has been described in connection with some embodiments herein, it should be understood that various modifications and changes may be made therein without departing from the scope of the present disclosure as understood by those skilled in the art to which the present disclosure pertains. Furthermore, such modifications and changes should be considered to fall within the scope of the claims appended hereto.

Claims

As an optical device having a cross-linked layer,

First electrode;

An electron transport layer formed on the first electrode;

Cross-linked layer formed on the above electron transport layer

A perovskite layer formed on the above cross-linked layer;

A hole transport layer formed on the perovskite layer; and

A second electrode formed on the above hole transport layer

Including,

The above cross-linked layer is an optical element formed by cross-linking of GTMACl (Glycidyltrimethylammonium chloride).
In the first paragraph,

The cross-linking of the above GTMACl is formed by annealing, which is an optical element.
An optical module manufactured by combining a plurality of optical elements according to claim 1 or 2.
A method for manufacturing an optical device having a cross-linked layer,

Step of forming an electrode;

A step of forming an electron transport layer on the above electrode; and

A method for manufacturing an optical device, comprising the step of forming a cross-linking layer on the electron transport layer.
In paragraph 4,

The step of forming the above cross-linked layer is:

A step of introducing GTMACl onto the electron transport layer; and

A method for manufacturing an optical device, comprising the step of annealing the above GTMACl at 100 degrees Celsius.