WO2022270878A1 - Perovskite composite - Google Patents
Perovskite composite Download PDFInfo
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- WO2022270878A1 WO2022270878A1 PCT/KR2022/008809 KR2022008809W WO2022270878A1 WO 2022270878 A1 WO2022270878 A1 WO 2022270878A1 KR 2022008809 W KR2022008809 W KR 2022008809W WO 2022270878 A1 WO2022270878 A1 WO 2022270878A1
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- Prior art keywords
- perovskite
- perovskite composite
- composite
- corresponds
- ion
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- 239000002131 composite material Substances 0.000 title claims abstract description 71
- -1 halogen anion Chemical class 0.000 claims abstract description 58
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 150000002892 organic cations Chemical class 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 26
- 239000000460 chlorine Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 6
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- 239000000843 powder Substances 0.000 claims description 6
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- 150000002500 ions Chemical class 0.000 description 11
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- 239000001257 hydrogen Substances 0.000 description 10
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000000909 amidinium group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
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- 239000012071 phase Substances 0.000 description 5
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
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- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/24—Lead compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present disclosure relates to a perovskite composite, and more particularly, to a perovskite composite having a Br composition ratio below a certain value.
- Optical devices include both photoelectric conversion devices and electro-optical conversion devices, and a solar cell, one of the photoelectric conversion devices, is attracting attention as a sustainable energy technology as a solution that can actively respond to future energy demand.
- a solar cell is the most basic unit of photovoltaic power generation and a semiconductor device that converts solar energy into electrical energy, and uses a photovoltaic effect.
- perovskite solar cells have taken off as one axis of thin-film solar cells to replace conventional silicon solar cells.
- a perovskite solar cell including a hole transporting material, a light absorbing material, and an electron transporting material exhibits a remarkably high photovoltaic effect by using the perovskite material as a light absorbing material.
- Embodiments disclosed herein provide a perovskite composite having high photoelectric conversion efficiency by adjusting the composition ratio of Br to a certain value or less in the perovskite composition.
- the perovskite composite according to an embodiment of the present disclosure is a perovskite containing an organic cation (A), a metal cation (M), and a halogen anion (X) (AMX 3 ), and MACl (methylammonium salt cargo, CH 3 NH 3 Cl), X includes Br - and halide anions other than Br - , and stoichiometrically, Br - corresponds to 1% or less of halide anions other than Br - .
- the perovskite composite further includes a guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine.
- GM guest molecule
- the perovskite composite corresponds to a crystalline solid powder.
- the organic cation (A) corresponds to an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion
- the metal cation (M) is a divalent metal cation corresponds to
- the perovskite composite according to an embodiment of the present disclosure includes perovskite and MACl (methylammonium chloride, CH 3 NH 3 Cl), and the perovskite composite satisfies the following chemical formula.
- FA formamidinium
- CH NH 2 +
- methylammonium CH 3 NH 3 +
- x corresponds to a real number satisfying 0 ⁇ x ⁇ 1
- n corresponds to a real number satisfying 0 ⁇ n ⁇ 1
- x has a value less than or equal to 0.01.
- the perovskite composite further includes a guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine.
- GM guest molecule
- the perovskite composite corresponds to a crystalline solid powder.
- the perovskite composite is for a light absorber of a solar cell.
- the power conversion efficiency of an optical device may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
- the phase stability of the perovskite thin film may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
- the mobility of the perovskite thin film may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
- the band gap of the perovskite is adjusted, the grain size is increased, , can increase the mobility and diffusion length in the perovskite thin film.
- FIG. 2 shows the ultraviolet-visible light (UV-VIS) absorption spectrum measurement results according to the wavelength of the perovskite thin film using the perovskite composite according to an embodiment of the present disclosure.
- UV-VIS ultraviolet-visible light
- TRPL time-resolved photoluminescence
- references to "A and/or B" herein means A, or B, or A and B.
- the term "at least one" included in the expression of the Markush form means including one or more selected from the group consisting of elements described in the expression of the Markush form.
- perovskite or “PE” or “perovskite compound” means a material having a perovskite crystal structure, and in addition to the crystal structure of ABX 3 , various perovskite crystal structures can have
- optical device is used to include both photoelectric conversion devices and electro-optical conversion devices.
- optical elements include, but are not limited to, light emitting diodes (LEDs), solar cells, photodetectors, X-ray detectors, and lasers.
- halide refers 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, for example, It may contain chlorine, bromine, fluorine or iodine compounds.
- precursor may mean a precursor or reactant used to prepare perovskite, and is not limited to a specific material.
- the term "layer” means a layer form having a thickness.
- a layer may correspond to porous or non-porous.
- Porosity means having porosity.
- the layer may have a bulk form or correspond to a single crystal thin film, but is not limited thereto.
- the efficiency means power conversion efficiency (PCE).
- the perovskite or perovskite compound according to an embodiment of the present disclosure may satisfy Formula 1 below.
- 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.
- the organic ammonium ion may satisfy Chemical Formula 1-1 or 1-2 below.
- R 1 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.
- R 2 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, and R 3 is hydrogen or C1-C24 alkyl.
- the amidinium-based ion may satisfy Chemical Formulas 1-3 below.
- R 4 to R 8 are each independently hydrogen, C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.
- 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.
- the charge mobility of perovskite can be remarkably improved.
- R 1 in Formula 1-1, R 2 to R 3 in Formula 1-2, and/or R 4 to R 8 in Formula 1-3 may be appropriately selected depending on the use of the perovskite, that is, the use of the optical device. there is.
- the size of the perovskite unit cell is related to the band gap, and may have a band gap energy of 1.5 to 1.1 eV suitable for use as a solar cell in a small unit cell size.
- R 1 is C1-C24 alkyl, specifically C1-C7 alkyl, more specifically methylyl
- R 2 may be C1-C24 alkyl
- R 3 may be hydrogen or C1-C24 alkyl
- R 2 may be C1-C7 alkyl
- R 3 may be hydrogen or C1 -C7 alkyl, more specifically R 2 can be methyl and R 3 can be hydrogen.
- R 4 to R 8 in Formula 1-3 may be each independently hydrogen, amino or C1-C24 alkyl, specifically hydrogen, amino or C1-C7 alkyl, more specifically hydrogen, amino or methyl, , even more specifically R 4 may be hydrogen, amino or methyl and R 5 to R 8 may be hydrogen.
- organic cation (A) are examples considering the use of the perovskite film, that is, the use as a light absorbing layer of sunlight, and design of the wavelength band of light to be absorbed, the light emitting layer of the light emitting device
- R 1 in Formula 1-1, R 2 ⁇ R 3 in Formula 1-2 and/or R 4 to R 8 of Formula 1-3 may be appropriately selected.
- M may be a divalent metal ion.
- 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 It may be one or more metal ions selected from Yb 2+ .
- X is a halogen anion.
- 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.
- X may correspond to an oxygen ion.
- the halide anion may contain iodine ions and bromine ions.
- the halide anion contains both iodine ions and bromine ions, the crystallinity and moisture resistance of the perovskite can be improved.
- X may be X a (1-y) X b y
- X a and X b are different halogen ions (iodine ion (I - ), chlorine ion (Cl - ) and bromine ions (Br ⁇ )
- y may be a real number such that 0 ⁇ y ⁇ 1.
- a perovskite composite according to an embodiment of the present disclosure may satisfy Formula 2 below.
- A may be an organic cation.
- 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.
- the charge mobility of perovskite can be remarkably improved.
- M may be a metal cation or a divalent metal cation.
- M may be a Pb 2+ metal ion.
- X may be a halogen anion.
- the halogen anion may include a halogen anion selected from the group consisting of I - , Br - , F - , Cl - and combinations thereof.
- MA corresponds to methylammonium ion.
- n may be a real number satisfying 0 ⁇ n ⁇ 1.
- AMX 3 may correspond to the material described above with respect to Formula 1.
- the perovskite composite according to an embodiment of the present disclosure contains an organic cation (A), a metal cation (M), a halogen anion (X), and MACl.
- Organic cations, metal ions and halide anions contained in the perovskite complex are monovalent organic cations (A), divalent metal ions (M) and halide anions (X ), a detailed description thereof will be omitted.
- the perovskite composite according to an embodiment of the present disclosure may correspond to a precursor of perovskite.
- the precursor may be amorphous, crystalline, or a mixture of amorphous and crystalline materials.
- the precursor according to an embodiment of the present disclosure may correspond to crystalline and may have a perovskite phase.
- MACl contained in the perovskite composite according to an embodiment of the present disclosure corresponds to a compound containing MA (Methylammonium, CH 3 NH 3 + ) and Cl - .
- the perovskite composite according to an embodiment of the present disclosure may be in the form of a complex formed by the coexistence of AMX 3 and MA. That is, the perovskite complex may be in the form of a complex formed by combining MA with perovskite (AMX 3 ) containing A organic cation, M metal cation, and X halide anion.
- the bond between the perovskite and MACl may be a non-covalent bond
- the MACl may be a non-covalent bond between a monovalent organic cation (MA) and Cl - .
- MA monovalent organic cation
- the non-perovskite phase that FAPbI 3 may have can be remarkably removed.
- ⁇ -FAPbI 3 perovskite phase
- X may be X a (1-y) X b y
- X a is any one of halogen anions other than bromine ion
- X b is bromine ion
- y is 0 ⁇ It may be a real number with y ⁇ 0.01.
- bromine ions are 1% or less compared to halogen anions other than bromine, for example, 1% or less compared to iodine ions, the band gap decreases compared to the case where it exceeds 1%.
- a of the perovskite composite according to an embodiment contains both an organic ammonium ion and an amidinium-based ion
- a in Formula 2 is A a (1-x) A b x
- a a is an amidi A nium-based ion
- a b is an organic ammonium ion
- x may be a real number satisfying 0 ⁇ x ⁇ 1.
- X may be X a (1-y) X b y
- X a and X b are different halogen anions (iodine ion (I - ), chlorine ion (Cl - ) and bromine ion ( Br - )
- y may be a real number such that 0 ⁇ y ⁇ 1.
- the perovskite composite may satisfy Formula 3 below.
- MA is methylammonium (methylammonium, CH 3 NH 3 + )
- x can be a real number with 0 ⁇ x ⁇ 1 there is.
- Chemical Formula 3 when the halogen anion of the perovskite composite contains both iodine ion and bromine ion, crystallinity and moisture resistance may be improved.
- a perovskite composite according to an embodiment of the present disclosure may satisfy Formula 4 below.
- GM corresponds to a guest molecule. Guest molecules can prevent rapid conversion to the perovskite phase.
- A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion
- M is a divalent metal ion
- X is a halogen ion, 0 ⁇ m ⁇ 3 It's a mistake.
- A, M, X, MACl, and n are the same as those described above based on formula (2).
- GM may have a complex form formed by the coexistence of A organic cation, M metal cation, and X halogen anion. That is, the perovskite complex may be in the form of a complex formed by combining GM with perovskite (AMX 3 ) containing A organic cation, M metal cation, and X halide anion.
- Chemical Formula 4 is different from Chemical Formula 2 in that GM is additionally contained, and the above description in relation to Chemical Formula 2 can be applied to the remaining composition other than GM in Chemical Formula 4.
- the bond between perovskite and GM may be a non-covalent bond, and GM may be in a non-covalent bond with one or two or more cations selected from monovalent organic cations (A) and divalent metal cations (M). there is.
- the perovskite composite may be a solvate of perovskite and a solvent dissolving the perovskite.
- a solvate may refer to a higher order compound formed between molecules or ions of a solute (perovskite) and molecules or ions of a solvent.
- the solvent dissolving the perovskite may mean a polar organic solvent, and may mean an organic solvent having a solubility of perovskite of 0.5M or more, specifically, 0.8M or more under 20 ° C. and 1 atmosphere.
- the perovskite composite When the perovskite composite is a solvate of perovskite and a solvent dissolving the perovskite, the GM is removed homogeneously and rapidly at a low temperature and can be converted into perovskite.
- the perovskite composite may be a solvate in which perovskite and GM, a solvent, are non-covalently bonded, and GM is an element selected from oxygen, nitrogen, fluorine, chlorine, bromine, and iodine containing non-covalent electron pairs. It may be a solvent containing.
- a solvent containing at least one element selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine and dissolving perovskite N, N-dimethylacetamide, 1,4-dioxane (dioxane), diethylamine, ethyl acetate, tetrahydrofuran, pyridine, methanol, ethanol, dichlorobenzene, glycerin and dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), or a mixture thereof.
- the guest molecule is N,N-dimethylacetamid, 1,4-dioxane, diethylamine, ethylacetate, tetrahydrofuran, pyridine , methanol, ethanol, dichlorobenzene, glycerin, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF), one or more can be chosen
- GM can be removed by external energy.
- guest molecules are removed by external energy and can be changed into crystalline perovskite.
- the perovskite composite is a complex compound of perovskite and GM, it can be converted into pure perovskite by removing GM by applying energy.
- the perovskite composite according to an embodiment of the present disclosure may be used as a light absorber for a solar cell.
- the perovskite composite according to an embodiment of the present disclosure includes a dispersion containing the perovskite composite or an ink containing the above-described perovskite composite.
- the dispersion or ink may further contain known additives so as to have properties suitable for coating or printing methods, together with the above-described perovskite composite and dispersion medium.
- the perovskite complex is obtained by dropping a first solution containing organic cations, metal cations, halogen ions, and guest molecules according to the stoichiometric ratio of perovskite into a non-solvent, and recovering the solid phase obtained by the dropping It can be prepared through the step of drying.
- the obtained solid phase may correspond to a crystalline solid powder.
- the perovskite composite is a complex of perovskite and GM, the perovskite composite may have properties (solubility, etc.) similar to those of perovskite in organic solvents. Accordingly, a common perovskite-dissolving solvent may be used as a solvent for the first solution.
- Any solvent that dissolves the perovskite composite can be used as long as it dissolves the perovskite and can be easily volatilized.
- Specific examples include gamma-butyrolactone (GBL) and 1-methyl-2-pyrrolidone, but the present invention is not limited thereto. .
- the solvent of the first solution may be a guest molecule. That is, the first solution may be prepared by dissolving organic cations, metal cations, and halogen ions in a solvent serving as guest molecules.
- the non-solvent may mean an organic solvent that does not dissolve the perovskite.
- the meaning of not dissolving perovskite may mean an organic solvent having a solubility of perovskite of less than 0.1M, specifically less than 0.01M, and more specifically less than 0.001M, at 20° C. and 1 atm.
- a non-polar organic solvent may be used, and the non-polar organic solvent may include pentane, hexene, cyclohexene, 1,4-dioxene, benzene, toluene, triethyl amine, chlorobenzene , ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1,2-dichlorobenzene, tert-butyl alcohol, 2-butanol, one or more organic solvents selected from isopropanol and methyl ethyl ketone
- the present invention is not limited by the non-solvent. At this time, productivity can be improved by increasing the concentration of the solute in the first solution, but the concentration of the first solution may be any concentration as long as the stoichiometric ratio is satisfied within the solubility range of each solute.
- the recovery of the solid phase is sufficient by using a method used in normal solid-liquid separation.
- filtering, centrifugation, etc. may be mentioned, but is not limited thereto. Drying is sufficient as long as the perovskite composite is not thermally and safely damaged. For example, drying may be performed at room temperature to 50°C.
- the present invention includes a method for manufacturing a light absorber for a solar cell using the above-described perovskite composite.
- a method for manufacturing a light absorber includes forming a perovskite composite layer by coating or depositing the perovskite composite on a substrate, and applying energy to the perovskite composite layer. Thus, a step of volatilizing and removing the guest molecules may be included.
- a solution in which the perovskite composite is dissolved or a dispersion or ink in which the perovskite composite is dispersed is coated on a substrate, dried to form a precursor layer, and then GM is removed from the precursor layer to form a precursor layer. can be converted into a perovskite layer.
- a solution is prepared by dissolving organic cations, metal cations, and halogen ions according to the stoichiometric ratio of the perovskite in a solvent that is a guest molecule (GM),
- GM guest molecule
- a precursor layer containing a perovskite composite can be prepared by applying the prepared solution on a substrate and re-applying a non-solvent to the coating film.
- the application of the solution, dispersion or ink is screen printing, spin coating, bar-coating, gravure-coating, blade coating, and roll-coating. It may be performed by one or more selected methods in roll coating, but considering the excellent commercial properties of treating a large area in a short time, it is preferable to perform spin coating.
- Energy applied to the precursor layer may include thermal energy, light energy, vibration energy, and the like.
- the amount of energy applied is sufficient to break the bond between the perovskite and GM and volatilize the GM.
- GM can be removed to obtain crystalline perovskite, and furthermore, when the precursor layer is heated to 130 ° C or higher, crystalline perovskite can be obtained in a very short time. You can get lobsite.
- the upper limit of the heat treatment for converting the perovskite composite into perovskite is sufficient as long as the base material to form the perovskite is not thermally damaged.
- heat treatment may be performed at 100 to 200 °C.
- the heat treatment time is sufficient as long as the perovskite composite can be sufficiently converted into perovskite.
- the heat treatment time may be 1 minute to 30 minutes, but the present invention cannot be limited by the heat treatment time, of course.
- a thin film is fabricated by spin-coating the perovskite composite solution described above.
- the optical device finally fabricated as described above has a structure of FTO / SnO 2 / Perovskite / Spiro-OMeTAD / Au.
- the performance of the optical device was evaluated through the following method using the perovskite optical device manufactured through the above Examples and Comparative Examples 1 to 3, and the results are shown in Table 1 below.
- FIG. 1 shows a SEM image of a perovskite thin film using a perovskite composite according to an embodiment of the present disclosure.
- the grain size of the perovskite varies according to the concentration (%) of MAPbBr 3 .
- the grain size of the perovskite prepared in Example is larger than the grain size in Comparative Examples 1 to 3.
- Figure 2 shows the result of measuring the light absorption spectrum according to the wavelength of the perovskite thin film using the perovskite composite according to an embodiment of the present disclosure. As shown, it can be seen that as the concentration of MAPbBr 3 decreases, the absorption spectrum shows a behavior shifting to a longer wavelength and the band gap decreases.
- TRPL time-resolved photoluminescence
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Abstract
A perovskite composite, according to one embodiment of the present disclosure, comprises: perovskite (AMX3) containing an organic cation (A), a metal cation (M), and a halogen anion (X); and methylammonium chloride (MACl) (CH3NH3Cl), wherein X includes Br- and halogen anions other than the Br-, and stoichiometrically, the Br- is less than 1% compared to the halogen anions other than the Br-.
Description
본 개시는 페로브스카이트 복합체에 관한 것으로, 보다 구체적으로는 일정 수치 이하의 Br 조성 비율을 갖는 페로브스카이트 복합체에 관한 것이다.The present disclosure relates to a perovskite composite, and more particularly, to a perovskite composite having a Br composition ratio below a certain value.
기후변화에 대응할 수 있는 환경 친화적이고 지속 가능한 에너지 기술 개발의 필요성이 증가하고 있다. 광소자는 광전변환소자 및 전광변환소자를 모두 포괄하는데, 광전변환소자 중 하나인 태양전지는 지속 가능한 에너지 기술로서 미래의 에너지 수요에 능동적으로 대응할 수 있는 해결책으로 각광받고 있다. 태양전지는 태양광발전의 가장 기본단위이자 태양광에너지를 전기에너지로 변환시켜주는 반도체 소자로서, 광기전력효과(Photovoltaic Effect)를 이용한다.The need to develop environmentally friendly and sustainable energy technologies that can respond to climate change is increasing. Optical devices include both photoelectric conversion devices and electro-optical conversion devices, and a solar cell, one of the photoelectric conversion devices, is attracting attention as a sustainable energy technology as a solution that can actively respond to future energy demand. A solar cell is the most basic unit of photovoltaic power generation and a semiconductor device that converts solar energy into electrical energy, and uses a photovoltaic effect.
하지만 오늘날 태양전지 기술은 미래의 에너지 수요를 대체할 정도의 효율을 보이지 못하기 때문에, 현재의 기술 수준을 뛰어넘는 기술 혁신이 필요한 상황이다. 이에 차세대 태양전지로서 염료감응 태양전지, 유기물 태양전지, 양자점 태양전지, 페로브스카이트 태양전지(Perovskite Solar Cell, PSC)와 같은 혁신적 소재를 바탕으로 한 기술들이 개발되어 왔다.However, since today's solar cell technology is not efficient enough to replace future energy demand, technological innovation beyond the current technology level is required. 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.
그 중에서도 페로브스카이트 태양전지는 종래 실리콘 태양전지를 대체할 박막 태양전지의 한 축으로 도약하였다. 정공 수송물질, 광흡수물질, 및 전자 수송물질을 포함하는 페로브스카이트 태양전지는 페로브스카이트 물질을 광흡수물질로 이용하여 현저히 높은 광기전 효과를 나타낸다.Among them, perovskite solar cells have taken off as one axis of thin-film solar cells to replace conventional silicon solar cells. A perovskite solar cell including a hole transporting material, a light absorbing material, and an electron transporting material exhibits a remarkably high photovoltaic effect by using the perovskite material as a light absorbing material.
본 명세서에서 개시되는 실시예들은, 페로브스카이트 조성에서 Br의 조성 비율을 일정 수치 이하로 조정함으로써 높은 광전변환효율을 갖는 페로브스카이트 복합체를 제공한다.Embodiments disclosed herein provide a perovskite composite having high photoelectric conversion efficiency by adjusting the composition ratio of Br to a certain value or less in the perovskite composition.
본 개시의 일 실시예에 따른 페로브스카이트 복합체는, 유기 양이온(A), 금속 양이온(M), 및 할로겐 음이온(X)을 함유하는 페로브스카이트(AMX3), 및 MACl(메틸암모늄염화물, CH3NH3Cl)을 포함하고, X는 Br- 및 Br- 이외의 할로겐 음이온을 포함하고, 화학정량적으로 Br-은 Br- 이외의 할로겐 음이온 대비 1% 이하에 해당한다.The perovskite composite according to an embodiment of the present disclosure is a perovskite containing an organic cation (A), a metal cation (M), and a halogen anion (X) (AMX 3 ), and MACl (methylammonium salt cargo, CH 3 NH 3 Cl), X includes Br - and halide anions other than Br - , and stoichiometrically, Br - corresponds to 1% or less of halide anions other than Br - .
일 실시예에 따르면, 페로브스카이트 복합체는 산소, 질소, 염소, 브롬 및 요오드 중 적어도 하나 이상의 원소를 포함하는 용매에 해당하는 게스트 분자(GM)를 더 포함한다.According to one embodiment, the perovskite composite further includes a guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine.
일 실시예에 따르면, 페로브스카이트 복합체는 결정질의 고체 파우더에 해당한다.According to one embodiment, the perovskite composite corresponds to a crystalline solid powder.
일 실시예에 따르면, 유기 양이온(A)은 유기 암모늄 이온, 아미디니움계(amidinium group) 이온, 또는 유기 암모늄 이온 및 아미디니움계 이온에 해당하고, 금속 양이온(M)은 2가의 금속 양이온에 해당한다.According to one embodiment, the organic cation (A) corresponds to an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion, and the metal cation (M) is a divalent metal cation corresponds to
본 개시의 일 실시예에 따른 페로브스카이트 복합체는, 페로브스카이트 및 MACl(메틸암모늄염화물, CH3NH3Cl)을 포함하고, 페로브스카이트 복합체는 하기 화학식을 만족한다.The perovskite composite according to an embodiment of the present disclosure includes perovskite and MACl (methylammonium chloride, CH 3 NH 3 Cl), and the perovskite composite satisfies the following chemical formula.
(FAPbI3)1-x(MACl)n(MAPbBr3)x
(FAPbI 3 ) 1-x (MACl) n (MAPbBr 3 ) x
(FA는 포름아미디니움(formamidinium, NH2CH=NH2
+)에 해당하고, 메틸암모늄(methylammonium, CH3NH3
+)에 해당하며, x는 0<x<1을 만족하는 실수에 해당하고, n은 0<n<1을 만족하는 실수에 해당)(FA corresponds to formamidinium (NH 2 CH=NH 2 + ), corresponds to methylammonium (CH 3 NH 3 + ), and x corresponds to a real number satisfying 0<x<1 and n corresponds to a real number satisfying 0<n<1)
일 실시예에 따르면, x는 0.01 이하의 값을 갖는다.According to one embodiment, x has a value less than or equal to 0.01.
일 실시예에 따르면, 페로브스카이트 복합체는 산소, 질소, 염소, 브롬 및 요오드 중 적어도 하나 이상의 원소를 포함하는 용매에 해당하는 게스트 분자(GM)를 더 포함한다.According to one embodiment, the perovskite composite further includes a guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine.
일 실시예에 따르면, 페로브스카이트 복합체는 결정질의 고체 파우더에 해당한다.According to one embodiment, the perovskite composite corresponds to a crystalline solid powder.
일 실시예에 따르면, 페로브스카이트 복합체는 태양전지의 광흡수체용이다.According to one embodiment, the perovskite composite is for a light absorber of a solar cell.
본 개시의 다양한 실시예들에 따르면, 페로브스카이트 복합체에서 Br의 조성 비율을 일정 수치 이하로 조정함으로써 광소자의 전력 변환 효율을 향상시킬 수 있다.According to various embodiments of the present disclosure, the power conversion efficiency of an optical device may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
또한, 본 개시의 다양한 실시예들에 따르면, 페로브스카이트 복합체에서 Br의 조성 비율을 일정 수치 이하로 조정함으로써 페로브스카이트 박막의 상 안정성을 향상시킬 수 있다.In addition, according to various embodiments of the present disclosure, the phase stability of the perovskite thin film may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
또한, 본 개시의 다양한 실시예들에 따르면, 페로브스카이트 복합체에서 Br의 조성 비율을 일정 수치 이하로 조정함으로써 페로브스카이트 박막의 이동도를 향상시킬 수 있다.In addition, according to various embodiments of the present disclosure, the mobility of the perovskite thin film may be improved by adjusting the composition ratio of Br to a predetermined value or less in the perovskite composite.
또한, 본 개시의 다양한 실시예들에 따르면, 페로브스카이트 복합체에서 Br의 조성 비율을 일정 수치 이하로 조정함으로써, 페로브스카이트의 밴드갭을 조절하고, 그레인 사이즈(grain size)를 증대시키며, 페로브스카이트 박막에서의 이동도(mobility) 및 확산거리(diffusion length)를 증가시킬 수 있다.In addition, according to various embodiments of the present disclosure, by adjusting the composition ratio of Br to a certain value or less in the perovskite composite, the band gap of the perovskite is adjusted, the grain size is increased, , can increase the mobility and diffusion length in the perovskite thin film.
본 개시의 효과는 이상에서 언급한 효과로 제한되지 않으며, 언급되지 않은 다른 효과들은 청구범위의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.Effects of the present disclosure are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.
본 개시의 효과는 이상에서 언급한 효과로 제한되지 않으며, 언급되지 않은 다른 효과들은 청구범위의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.Effects of the present disclosure are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.
도 1은 본 개시의 일 실시예에 따른 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 SEM 이미지(bar scale = 500nm)를 나타낸다.1 shows an SEM image (bar scale = 500 nm) of a perovskite thin film using a perovskite composite according to an embodiment of the present disclosure.
도 2는 본 개시의 일 실시예에 따른 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 파장에 따른 자외선-가시광선(UV-VIS) 흡수 스펙트럼 측정 결과를 나타낸다.Figure 2 shows the ultraviolet-visible light (UV-VIS) absorption spectrum measurement results according to the wavelength of the perovskite thin film using the perovskite composite according to an embodiment of the present disclosure.
도 3은 실시예 및 비교예 1 내지 3에서 제조된 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 TRPL(time-resolved photoluminescence) 특성을 나타낸다.3 shows time-resolved photoluminescence (TRPL) characteristics of perovskite thin films using the perovskite composites prepared in Examples and Comparative Examples 1 to 3.
도 4는 MAPbBr3의 농도(%)에 따른 페로브스카이트 박막에서의 이동도와 확산거리(diffusion length)를 나타낸다.4 shows the mobility and diffusion length in the perovskite thin film according to the concentration (%) of MAPbBr 3 .
도 5는 실시예 및 비교예 1 내지 3에서 제조된 광소자의 외부 양자 효율(External Quantum Efficiency, EQE) 스펙트럼을 나타낸다.5 shows External Quantum Efficiency (EQE) spectra of optical devices manufactured in Examples and Comparative Examples 1 to 3.
이하, 본 개시의 실시를 위한 구체적인 내용을 첨부된 도면을 참조하여 상세히 설명한다. 다만, 이하의 설명에서는 본 개시의 요지를 불필요하게 흐릴 우려가 있는 경우, 널리 알려진 기능이나 구성에 관한 구체적 설명은 생략하기로 한다.Hereinafter, specific details for the implementation of the present disclosure will be described in detail with reference to the accompanying drawings. However, in the following description, if there is a risk of unnecessarily obscuring the gist of the present disclosure, detailed descriptions of well-known functions or configurations will be omitted.
본 개시에서 사용되는 용어에 대해 간략히 설명하고, 개시된 실시예에 대해 구체적으로 설명하기로 한다. 본 명세서에서 사용되는 용어는 본 개시에서의 기능을 고려하면서 가능한 현재 널리 사용되는 일반적인 용어들을 선택하였으나, 이는 관련 분야에 종사하는 기술자의 의도 또는 판례, 새로운 기술의 출현 등에 따라 달라질 수 있다. 또한, 특정한 경우는 출원인이 임의로 선정한 용어도 있으며, 이 경우 해당되는 발명의 설명 부분에서 상세히 그 의미를 기재할 것이다. 따라서, 본 개시에서 사용되는 용어는 단순한 용어의 명칭이 아닌, 그 용어가 가지는 의미와 본 개시의 전반에 걸친 내용을 토대로 정의되어야 한다.Terms used in this disclosure will be briefly described, and the disclosed embodiments will be described in detail. The terms used in this specification have been selected from general terms that are currently widely used as much as possible while considering the functions in the present disclosure, but they may vary according to the intention of a person skilled in the related field, a precedent, or the emergence of new technologies. In addition, in a specific case, there is also a term arbitrarily selected by the applicant, and in this case, the meaning will be described in detail in the description of the invention. Therefore, the terms used in the present disclosure should be defined based on the meaning of the terms and the general content of the present disclosure, not simply the names of the terms.
본 개시에서, 단수의 표현은 문맥상 명백하게 단수인 것으로 특정하지 않는 한, 복수의 표현을 포함한다. 또한, 복수의 표현은 문맥상 명백하게 복수인 것으로 특정하지 않는 한, 단수의 표현을 포함한다.In this disclosure, expressions in the singular number include plural expressions unless the context clearly dictates that they are singular. Also, plural expressions include singular expressions unless the context clearly specifies that they are plural.
본 개시에서, 어떤 부분이 어떤 구성요소를 포함한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있음을 의미한다.In the present disclosure, when a part includes a certain component, this means that it may further include other components without excluding other components unless otherwise stated.
본 명세서에서 "A 및/또는 B"의 기재는 A, 또는 B, 또는 A 및 B를 의미한다.Reference to "A and/or B" herein means A, or B, or A and B.
본 명세서 전체에서 사용되는 정도의 용어 "약" 등은 허용오차가 존재할 때 허용오차를 포괄하는 의미로 사용된 것이다.As used throughout this specification, the term "about" and the like is intended to encompass tolerances when tolerances exist.
본 명세서 전체에서, 마쿠쉬 형식의 표현에 포함된 "적어도 어느 하나"의 용어는 마쿠쉬 형식의 표현에 기재된 구성 요소들로 이루어진 군에서 선택되는 하나 이상을 포함하는 것을 의미한다.Throughout this specification, the term "at least one" included in the expression of the Markush form means including one or more selected from the group consisting of elements described in the expression of the Markush form.
본 명세서 전체에서, "페로브스카이트" 또는 "PE" 또는 "페로브스카이트 화합물"은 페로브스카이트 결정구조를 가지는 물질을 의미하며, ABX3의 결정구조 외에도 다양한 페로브스카이트 결정구조를 가질 수 있다.Throughout this specification, "perovskite" or "PE" or "perovskite compound" means a material having a perovskite crystal structure, and in addition to the crystal structure of ABX 3 , various perovskite crystal structures can have
본 명세서 전체에서, "광소자"는 광전변환 소자와 전광변환 소자를 모두 포함하는 의미로 사용된다. 예컨대, 광소자는 LED(Light Emitting Diode), 태양광 전지(Solar Cell), 광검출기(Photodetector), X-선 검출기(X-ray detector), 레이저(Laser)를 포함하며, 이에 제한되는 것은 아니다.Throughout this specification, "optical device" is used to include both photoelectric conversion devices and electro-optical conversion devices. For example, optical elements include, but are not limited to, light emitting diodes (LEDs), solar cells, photodetectors, X-ray detectors, and lasers.
본 명세서 전체에서, 용어 "할라이드", "할로겐", "할로겐화물" 또는 "할로"는 주기율표의 17 족에 속하는 할로겐 원자가 작용기의 형태로 포함되어 있는 재질 또는 조성물을 의미하는 것으로서, 예를 들어, 염소, 브롬, 불소 또는 요오드 화합물을 포함할 수 있다.Throughout this specification, the term "halide", "halogen", "halogenide" or "halo" refers 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, for example, It may contain chlorine, bromine, fluorine or iodine compounds.
본 명세서 전체에서, "전구물질"은, 페로브스카이트를 제조하는데 사용되는 프리커서(precursor) 또는 반응체를 의미할 수 있으며, 특정 물질로 제한되지 않는다.Throughout this specification, "precursor" may mean a precursor or reactant used to prepare perovskite, and is not limited to a specific material.
본 명세서 전체에서, 용어 "층"은 두께를 가지는 레이어(layer) 형태를 의미한다. 층은 다공성에 해당하거나 비-다공성에 해당할 수 있다. 다공성은 공극률을 가지는 것을 의미한다. 층은 벌크(bulk) 형태를 가지거나 또는 단결정 박막(single crystal thin film)에 해당할 수 있으며, 이에 제한되는 것은 아니다.Throughout this specification, the term "layer" means a layer form having a thickness. A layer may correspond to porous or non-porous. Porosity means having porosity. The layer may have a bulk form or correspond to a single crystal thin film, but is not limited thereto.
본 명세서 전체에서, 어떤 부재가 다른 부재 "상"에 위치하고 있다고 할 때, 이는 특별히 반대되는 기재가 없는 한 어떤 부재가 다른 부재에 접해 있는 경우 뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.Throughout this specification, when a member is said to be located “on” another member, this applies not only to the case where a member is in contact with another member, but also to the case where another member exists between the two members, unless otherwise stated. include
본 명세서 전체에서, 별다른 추가 설명 없이 단순히 효율로만 기재되어 있는 경우, 해당 효율은 전력 변환 효율(Power Conversion Efficiency, PCE)을 의미한다.Throughout this specification, when simply described as efficiency without any additional explanation, the efficiency means power conversion efficiency (PCE).
개시된 실시예의 이점 및 특징, 그리고 그것들을 달성하는 방법은 첨부되는 도면과 함께 후술되어 있는 실시예들을 참조하면 명확해질 것이다. 그러나, 본 개시는 이하에서 개시되는 실시예들에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있으며, 단지 본 실시예들은 본 개시가 완전하도록 하고, 본 개시가 통상의 기술자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것일 뿐이다.Advantages and features of the disclosed embodiments, and methods of achieving them, will become apparent with reference to the following embodiments in conjunction with the accompanying drawings. However, the present disclosure is not limited to the embodiments disclosed below and may be implemented in various different forms, but only the present embodiments make the present disclosure complete, and the present disclosure does not extend the scope of the invention to those skilled in the art. It is provided only for complete information.
첨부된 도면에서, 동일하거나 대응하는 구성요소에는 동일한 참조부호가 부여되어 있다. 또한, 이하의 실시예들의 설명에 있어서, 동일하거나 대응되는 구성요소를 중복하여 기술하는 것이 생략될 수 있다. 그러나, 구성요소에 관한 기술이 생략되어도, 그러한 구성요소가 어떤 실시예에 포함되지 않는 것으로 의도되지는 않는다.In the accompanying drawings, identical or corresponding elements are given the same reference numerals. In addition, in the description of the following embodiments, overlapping descriptions of the same or corresponding components may be omitted. However, omission of a description of a component does not intend that such a component is not included in an embodiment.
페로브스카이트perovskite
본 개시의 일 실시예에 따른 페로브스카이트 또는 페로브스카이트 화합물은 하기 화학식 1을 만족할 수 있다.The perovskite or perovskite compound according to an embodiment of the present disclosure may satisfy Formula 1 below.
[화학식 1][Formula 1]
AMX3
AMX 3
화학식 1에서, A는 1가의 양이온으로, 유기 암모늄 이온, 아미디니움계(amidinium group) 이온, 또는 유기 암모늄 이온 및 아미디니움계 이온의 조합일 수 있다.In 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.
화학식 1에서, 유기 암모늄 이온은 하기 화학식 1-1 또는 1-2를 만족할 수 있다.In Chemical Formula 1, the organic ammonium ion may satisfy Chemical Formula 1-1 or 1-2 below.
[화학식 1-1][Formula 1-1]
R1-NH3
+
R 1 -NH 3 +
화학식 1-1에서 R1은 C1-C24의 알킬, C3-C20의 시클로알킬 또는 C6-C20의 아릴이다.In Formula 1-1, R 1 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.
[화학식 1-2][Formula 1-2]
R2-C3H3N2
+-R3
R 2 -C 3 H 3 N 2 + -R 3
화학식 1-2에서 R2는 C1-C24의 알킬, C3-C20의 시클로알킬 또는 C6-C20의 아릴 이며, R3은 수소 또는 C1-C24의 알킬이다.In Formula 1-2, R 2 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, and R 3 is hydrogen or C1-C24 alkyl.
화학식 1에서, 아미디니움계 이온은 하기 화학식 1-3을 만족할 수 있다.In Chemical Formula 1, the amidinium-based ion may satisfy Chemical Formulas 1-3 below.
[화학식 1-3][Formula 1-3]
화학식 1-3에서, R4 내지 R8은 서로 독립적으로, 수소, C1-C24의 알킬, C3-C20의 시클로알킬 또는 C6-C20의 아릴이다.In Formula 1-3, R 4 to R 8 are each independently hydrogen, C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.
화학식 1에서, A는 유기 암모늄 이온, 아미디니움계(amidinium group) 이온 또는 유기 암모늄 이온과 아미디니움계 이온의 조합에 해당할 수 있다. 유기 암모늄 이온과 아미디니움계 이온을 모두 함유하는 경우, 페로브스카이트의 전하 이동도를 현저하게 향상시킬 수 있다.In 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. In the case of containing both organic ammonium ions and amidinium-based ions, the charge mobility of perovskite can be remarkably improved.
화학식 1-1의 R1, 화학식 1-2의 R2~R3 및/또는 화학식 1-3의 R4~R8은 페로브스카이트의 용도, 즉, 광소자의 용도에 따라 적절히 선택될 수 있다.R 1 in Formula 1-1, R 2 to R 3 in Formula 1-2, and/or R 4 to R 8 in Formula 1-3 may be appropriately selected depending on the use of the perovskite, that is, the use of the optical device. there is.
예컨대, 페로브스카이트의 단위셀의 크기가 밴드갭과 연관되어 있고 작은 단위셀 크기에서 태양전지로 활용하기에 적절한 1.5~1.1 eV의 밴드갭 에너지를 가질 수 있다. 이에 따라, 태양전지로 활용하기에 적절한 1.5~1.1 eV의 밴드갭 에너지를 고려하는 경우, 화학식 1-1에서, R1은 C1-C24의 알킬, 구체적으로 C1-C7 알킬, 보다 구체적으로 메틸일 수 있다. 또한, 화학식 1-2에서 R2는 C1-C24의 알킬일 수 있고 R3는 수소 또는 C1-C24의 알킬일 수 있으며, 구체적으로 R2는 C1-C7 알킬일 수 있고 R3는 수소 또는 C1-C7 알킬일 수 있으며, 보다 구체적으로 R2는 메틸일 수 있고 R3는 수소일 수 있다. 또한, 화학식 1-3에서 R4 내지 R8은 서로 독립적으로, 수소, 아미노 또는 C1-C24의 알킬, 구체적으로, 수소, 아미노 또는 C1-C7 알킬, 보다 구체적으로 수소, 아미노 또는 메틸일 수 있으며, 보다 더 구체적으로 R4가 수소, 아미노 또는 메틸이고 R5 내지 R8가 수소일 수 있다. 구체적이며 비 한정적인 일 예로, 아미디니움계 이온은 포름아미디니움(formamidinium, NH2CH=NH2
+) 이온, 아세트아미디니움(acetamidinium, NH2C(CH3)=NH2
+) 이온 또는 구아미디니움(Guamidinium, NH2C(NH2)=NH2
+) 이온 등을 들 수 있다.For example, the size of the perovskite unit cell is related to the band gap, and may have a band gap energy of 1.5 to 1.1 eV suitable for use as a solar cell in a small unit cell size. Accordingly, when considering a band gap energy of 1.5 to 1.1 eV suitable for use as a solar cell, in Formula 1-1, R 1 is C1-C24 alkyl, specifically C1-C7 alkyl, more specifically methylyl can In Formula 1-2, R 2 may be C1-C24 alkyl, R 3 may be hydrogen or C1-C24 alkyl, specifically, R 2 may be C1-C7 alkyl, and R 3 may be hydrogen or C1 -C7 alkyl, more specifically R 2 can be methyl and R 3 can be hydrogen. In addition, R 4 to R 8 in Formula 1-3 may be each independently hydrogen, amino or C1-C24 alkyl, specifically hydrogen, amino or C1-C7 alkyl, more specifically hydrogen, amino or methyl, , even more specifically R 4 may be hydrogen, amino or methyl and R 5 to R 8 may be hydrogen. As a specific and non-limiting example, the amidinium-based ion is formamidinium (NH 2 CH=NH 2 + ) ion, acetamidinium (NH 2 C(CH 3 )=NH 2 + ) and ions or guamidinium (NH 2 C(NH 2 )=NH 2 + ) ions.
상술한 바와 같이, 유기 양이온(A)의 구체적인 예들은, 페로브스카이트 막의 용도, 즉, 태양광의 광흡수층으로의 용도를 고려한 일 예이며, 흡수하고자 하는 광의 파장 대역의 설계, 발광소자의 발광층으로 사용하는 경우 발광 파장 대역의 설계, 트랜지스터의 반도체 소자로 사용하는 경우 에너지 밴드갭과 문턱 전압(threshold voltage)등을 고려하여 화학식 1-1의 R1, 화학식 1-2의 R2~R3 및/또는 화학식 1-3의 R4~R8이 적절히 선택될 수 있다.As described above, specific examples of the organic cation (A) are examples considering the use of the perovskite film, that is, the use as a light absorbing layer of sunlight, and design of the wavelength band of light to be absorbed, the light emitting layer of the light emitting device When used as a light emission wavelength band design, when used as a semiconductor device of a transistor, considering the energy band gap and threshold voltage, R 1 in Formula 1-1, R 2 ~ R 3 in Formula 1-2 and/or R 4 to R 8 of Formula 1-3 may be appropriately selected.
화학식 1에서, M은 2가의 금속 이온일 수 있다. 구체적인 일 예로, M은 Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+ 및 Yb2+에서 하나 또는 둘 이상 선택된 금속 이온일 수 있다.In Chemical Formula 1, M may 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 It may be one or more metal ions selected from Yb 2+ .
화학식 1에서, X는 할로겐 음이온이다. 구체적으로, 할로겐 이온은 I-, Br-, F-, Cl- 및 이들의 조합들로 이루어진 군으로부터 선택되는 할로겐 이온을 포함하는 것이나, 이에 제한되는 것은 아니다. 예를 들어, X는 산소 이온에 해당할 수 있다.In Formula 1, X is a halogen anion. Specifically, 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, X may correspond to an oxygen ion.
보다 구체적으로, 할로겐 음이온은 요오드 이온 및 브롬 이온을 함유할 수 있다. 할로겐 음이온이 요오드 이온 및 브롬 이온을 모두 함유하는 경우, 페로브스카이트의 결정성 및 내습성을 향상시킬 수 있다.More specifically, the halide anion may contain iodine ions and bromine ions. When the halide anion contains both iodine ions and bromine ions, the crystallinity and moisture resistance of the perovskite can be improved.
구체적인 일 예로, 화학식 1에서, X는 Xa
(1-y)Xb
y 일 수 있고, Xa 및 Xb는 서로 상이한 할로겐 이온(요오드 이온(I-), 클로린 이온(Cl-) 및 브롬 이온(Br-)에서 선택되는 서로 상이한 할로겐 이온)이고, y는 0＜y＜1인 실수일 수 있다. As a specific example, in Formula 1, X may be X a (1-y) X b y , and X a and X b are different halogen ions (iodine ion (I - ), chlorine ion (Cl - ) and bromine ions (Br − ), and y may be a real number such that 0<y<1.
페로브스카이트 복합체perovskite complex
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 하기 화학식 2를 만족할 수 있다.A perovskite composite according to an embodiment of the present disclosure may satisfy Formula 2 below.
[화학식 2][Formula 2]
AM(MACl)nX3
AM(MACl) n X 3
화학식 2에서, A는 유기 양이온일 수 있다. 예를 들어, A는 유기 암모늄 이온, 아미디니움계(amidinium group) 이온 또는 유기 암모늄 이온과 아미디니움계 이온의 조합에 해당할 수 있다. 유기 암모늄 이온과 아미디니움계 이온을 모두 함유하는 경우, 페로브스카이트의 전하 이동도를 현저하게 향상시킬 수 있다.In Formula 2, A may be an organic cation. For example, 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. In the case of containing both organic ammonium ions and amidinium-based ions, the charge mobility of perovskite can be remarkably improved.
화학식 2에서, M은 금속 양이온일 수 있고, 2가의 금속 양이온일 수 있다. 예를 들어, M은 Pb2+ 금속 이온일 수 있다.In Formula 2, M may be a metal cation or a divalent metal cation. For example, M may be a Pb 2+ metal ion.
화학식 2에서, X는 할로겐 음이온일 수 있다. 구체적으로, 할로겐 음이온은 I-, Br-, F-, Cl- 및 이들의 조합들로 이루어진 군으로부터 선택되는 할로겐 음이온을 포함할 수 있다.In Formula 2, X may be a halogen anion. Specifically, the halogen anion may include a halogen anion selected from the group consisting of I - , Br - , F - , Cl - and combinations thereof.
화학식 2에서, MA는 메틸암모늄(methylammonium) 이온에 해당한다.In Formula 2, MA corresponds to methylammonium ion.
화학식 2에서, n은 0<n<1을 만족하는 실수일 수 있다.In Chemical Formula 2, n may be a real number satisfying 0<n<1.
화학식 2에서 AMX3는 화학식 1과 관련해서 상술한 물질과 대응될 수 있다.In Formula 2, AMX 3 may correspond to the material described above with respect to Formula 1.
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 유기 양이온(A), 금속 양이온(M), 할로겐 음이온(X) 및 MACl을 함유한다. 페로브스카이트 복합체에 함유되는 유기 양이온, 금속 이온 및 할로겐 음이온은 앞서 화학식 1의 페로브스카이트와 관련해서 상술한 1가의 유기 양이온(A), 2가의 금속 이온(M) 및 할로겐 음이온(X)과 동일할 수 있음에 따라, 이에 대한 상세한 설명은 생략한다.The perovskite composite according to an embodiment of the present disclosure contains an organic cation (A), a metal cation (M), a halogen anion (X), and MACl. Organic cations, metal ions and halide anions contained in the perovskite complex are monovalent organic cations (A), divalent metal ions (M) and halide anions (X ), a detailed description thereof will be omitted.
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 페로브스카이트의 전구물질에 해당할 수 있다.The perovskite composite according to an embodiment of the present disclosure may correspond to a precursor of perovskite.
결정구조에 있어, 전구물질은 비정질, 결정질 또는 비정질과 결정질이 혼재하는 물질일 수 있다. 구체적으로, 본 개시의 일 실시예에 따른 전구물질은 결정질에 해당할 수 있고, 페로브스카이트 상을 가질 수 있다.In terms of crystal structure, the precursor may be amorphous, crystalline, or a mixture of amorphous and crystalline materials. Specifically, the precursor according to an embodiment of the present disclosure may correspond to crystalline and may have a perovskite phase.
본 개시의 일 실시예에 따른 페로브스카이트 복합체에 함유된 MACl은 MA(Methylammonium, CH3NH3
+)와 Cl-을 함유한 화합물에 해당한다.MACl contained in the perovskite composite according to an embodiment of the present disclosure corresponds to a compound containing MA (Methylammonium, CH 3 NH 3 + ) and Cl - .
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 AMX3와 MA가 공존하여 형성된 콤플렉스(Complex) 형태일 수 있다. 즉, 페로브스카이트 복합체는 MA가 A 유기 양이온, M 금속 양이온 및 X 할로겐 음이온을 함유하는 페로브스카이트(AMX3)와 결합하여 형성된 콤플렉스(Complex) 형태일 수 있다.The perovskite composite according to an embodiment of the present disclosure may be in the form of a complex formed by the coexistence of AMX 3 and MA. That is, the perovskite complex may be in the form of a complex formed by combining MA with perovskite (AMX 3 ) containing A organic cation, M metal cation, and X halide anion.
구체적으로, 페로브스카이트와 MACl 간의 결합은 비공유결합일 수 있고, MACl은 1가의 유기 양이온(MA)과 Cl- 간의 비공유 결합된 상태일 수 있다. MACl을 함유함으로써 FAPbI3가 가질 수 있는 비페로브스카이트상을 현저히 제거할 수 있다. 예컨대, MACl을 이용할 경우, 검정색 파우더로 침전되는 α-FAPbI3(페로브스카이트 상)를 제조할 수 있다.Specifically, the bond between the perovskite and MACl may be a non-covalent bond, and the MACl may be a non-covalent bond between a monovalent organic cation (MA) and Cl - . By containing MACl, the non-perovskite phase that FAPbI 3 may have can be remarkably removed. For example, when using MACl, it is possible to prepare α-FAPbI 3 (perovskite phase) which precipitates as a black powder.
일 실시예에 따르면, 화학식 2에서 X는 Xa
(1-y)Xb
y 일 수 있고, Xa는 브롬 이온을 제외한 할로겐 음이온 중 어느 하나이고, Xb는 브롬 이온이며, y는 0<y≤0.01인 실수일 수 있다. 화학정량적으로 브롬 이온이 브롬 이외의 할로겐 음이온 대비 1% 이하, 예컨대 요오드 이온 대비 1% 이하인 경우, 1%를 초과하는 경우와 대비해서 밴드갭이 감소한다. 또한, 화학정량적으로 브롬 이온이 브롬 이외의 할로겐 음이온 대비 1% 이하인 경우, 그레인 사이즈(grain size)가 커지는 등 결정성이 향상되며, 페로브스카이트 박막의 이동도(mobility) 및 확산 거리(diffusion length)가 증가한다.According to an embodiment, in Formula 2, X may be X a (1-y) X b y , X a is any one of halogen anions other than bromine ion, X b is bromine ion, and y is 0< It may be a real number with y≤0.01. When stoichiometrically, bromine ions are 1% or less compared to halogen anions other than bromine, for example, 1% or less compared to iodine ions, the band gap decreases compared to the case where it exceeds 1%. In addition, stoichiometrically, when bromine ions are 1% or less compared to halide anions other than bromine, crystallinity is improved such as grain size increases, and mobility and diffusion distance of perovskite thin films are improved. length) increases.
일 실시예에 따른 페로브스카이트 복합체의 A가 유기 암모늄 이온과 아미디니움계 이온을 모두 함유하는 경우, 화학식 2에서 A는 Aa
(1-x)Ab
x이며, Aa는 아미디니움계 이온이고, Ab는 유기 암모늄 이온이며, x는 0<x<1을 만족하는 실수일 수 있다. 이 경우, 화학식 2에서 X는 Xa
(1-y)Xb
y 일 수 있고, Xa 및 Xb는 서로 상이한 할로겐 음이온(요오드 이온(I-), 클로린 이온(Cl-) 및 브롬 이온(Br-)에서 선택되는 서로 상이한 할로겐 음이온)이고, y는 0＜y＜1인 실수일 수 있다. 이 때에도, 화학정량적으로 브롬 이온이 브롬 이외의 할로겐 음이온 대비 1% 이하인 경우, 1%를 초과하는 경우와 대비해서 밴드갭이 작아지고, 그레인 사이즈(grain size)가 커지는 등 결정성이 향상되며, 페로브스카이트 박막에서의 이동도(mobility) 및 확산거리(diffusion length)가 증가할 수 있다.When A of the perovskite composite according to an embodiment contains both an organic ammonium ion and an amidinium-based ion, A in Formula 2 is A a (1-x) A b x , and A a is an amidi A nium-based ion, A b is an organic ammonium ion, and x may be a real number satisfying 0<x<1. In this case, in Formula 2, X may be X a (1-y) X b y , and X a and X b are different halogen anions (iodine ion (I - ), chlorine ion (Cl - ) and bromine ion ( Br - ), and y may be a real number such that 0 < y < 1. Even at this time, when the bromine ion is 1% or less relative to the halogen anion other than bromine in terms of stoichiometric ratio, the band gap is reduced and the grain size is increased compared to the case where the bromine ion exceeds 1%. Crystallinity is improved, such as, Mobility and diffusion length in the perovskite thin film can be increased.
예컨대, 페로브스카이트 복합체는 하기 화학식 3을 만족할 수 있다.For example, the perovskite composite may satisfy Formula 3 below.
[화학식 3][Formula 3]
(FAPbI3)1-x(MACl)n(MAPbBr3)x
(FAPbI 3 ) 1-x (MACl) n (MAPbBr 3 ) x
상기 화학식 3에서, FA는 포름아미디니움(formamidinium, NH2CH=NH2
+)이고, MA는 메틸암모늄(methylammonium, CH3NH3
+)이며, x는 0<x<1인 실수일 수 있다. 화학식 3과 같이, 페로브스카이트 복합체의 할로겐 음이온이 요오드 이온 및 브롬 이온을 모두 함유하는 경우, 결정성 및 내습성이 향상될 수 있다.In Formula 3, FA is formamidinium (NH 2 CH=NH 2 + ), MA is methylammonium (methylammonium, CH 3 NH 3 + ), and x can be a real number with 0 <x <1 there is. As shown in Chemical Formula 3, when the halogen anion of the perovskite composite contains both iodine ion and bromine ion, crystallinity and moisture resistance may be improved.
GM 함유 페로브스카이트 복합체GM-containing perovskite composites
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 하기 화학식 4를 만족할 수 있다.A perovskite composite according to an embodiment of the present disclosure may satisfy Formula 4 below.
[화학식 4][Formula 4]
AM(GM)m(MACl)nX3
AM(GM) m (MACl) n X 3
상기 화학식 4에서 GM은 게스트 분자(Guest Molecule)에 해당한다. 게스트 분자는 급격한 페로브스카이트 상으로의 전환을 막을 수 있다. 상기 화학식에서 A는 유기 암모늄 이온, 아미디니움계(amidinium group) 이온 또는 유기 암모늄 이온과 아미디니움계 이온이며, M은 2가의 금속 이온이고, X는 할로겐 이온이며, 0＜m＜3인 실수이다. A, M, X, MACl, 및 n은 화학식 2를 기반으로 상술한 것과 동일하다.In Chemical Formula 4, GM corresponds to a guest molecule. Guest molecules can prevent rapid conversion to the perovskite phase. In the above formula, A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion, M is a divalent metal ion, X is a halogen ion, 0 <m <3 It's a mistake. A, M, X, MACl, and n are the same as those described above based on formula (2).
GM은 A 유기 양이온, M 금속 양이온, X 할로겐 음이온과 공존하여 형성된 콤플렉스(Complex) 형태를 가질 수 있다. 즉, 페로브스카이트 복합체는 GM이 A 유기 양이온, M 금속 양이온 및 X 할로겐 음이온을 함유하는 페로브스카이트(AMX3)와 결합하여 형성된 콤플렉스(Complex) 형태일 수 있다.GM may have a complex form formed by the coexistence of A organic cation, M metal cation, and X halogen anion. That is, the perovskite complex may be in the form of a complex formed by combining GM with perovskite (AMX 3 ) containing A organic cation, M metal cation, and X halide anion.
화학식 4는 화학식 2와 비교할 때 GM이 추가로 함유되었다는 점에서 차이가 있으며, 화학식 4에서 GM 이외의 나머지 조성에 대해서는 화학식 2와 관련해서 상술한 설명이 적용될 수 있다. Chemical Formula 4 is different from Chemical Formula 2 in that GM is additionally contained, and the above description in relation to Chemical Formula 2 can be applied to the remaining composition other than GM in Chemical Formula 4.
구체적으로, 페로브스카이트와 GM의 결합은 비공유결합일 수 있고, GM은 1가의 유기 양이온(A) 및 2가의 금속 양이온(M)에서 하나 또는 둘 이상 선택되는 양이온과 비공유 결합된 상태일 수 있다.Specifically, the bond between perovskite and GM may be a non-covalent bond, and GM may be in a non-covalent bond with one or two or more cations selected from monovalent organic cations (A) and divalent metal cations (M). there is.
게스트 분자는 페로브스카이트를 용해하는 용매일 수 있다. 이에 따라, 페로브스카이트 복합체는 페로브스카이트와 이를 용해하는 용매와의 용매화합물(solvate)일 수 있다.Guest molecules can be solvents that dissolve the perovskite. Accordingly, the perovskite composite may be a solvate of perovskite and a solvent dissolving the perovskite.
용매화합물은 용질(페로브스카이트)의 분자 또는 이온과, 용매의 분자 또는 이온 사이에 형성되는 고차의 화합물을 의미할 수 있다.A solvate may refer to a higher order compound formed between molecules or ions of a solute (perovskite) and molecules or ions of a solvent.
페로브스카이트를 용해하는 용매는 극성 유기 용매를 의미할 수 있으며, 20℃ 1기압 하, 페로브스카이트의 용해도가 0.5M 이상, 구체적으로 0.8M 이상인 유기용매를 의미할 수 있다.The solvent dissolving the perovskite may mean a polar organic solvent, and may mean an organic solvent having a solubility of perovskite of 0.5M or more, specifically, 0.8M or more under 20 ° C. and 1 atmosphere.
페로브스카이트 복합체가 페로브스카이트와 이를 용해하는 용매와의 용매화합물인 경우, 낮은 온도에서 균질하고 빠르게 GM이 제거되며 페로브스카이트로 변환될 수 있다. 상세하게, 페로브스카이트 복합체는 페로브스카이트와 용매인 GM이 비공유 결합한 용매화합물일 수 있으며, GM은 비공유 전자쌍을 포함하는 산소, 질소, 불소, 염소, 브롬 및 요오드에서 하나 이상 선택되는 원소를 함유하는 용매일 수 있다.When the perovskite composite is a solvate of perovskite and a solvent dissolving the perovskite, the GM is removed homogeneously and rapidly at a low temperature and can be converted into perovskite. In detail, the perovskite composite may be a solvate in which perovskite and GM, a solvent, are non-covalently bonded, and GM is an element selected from oxygen, nitrogen, fluorine, chlorine, bromine, and iodine containing non-covalent electron pairs. It may be a solvent containing.
산소, 질소, 불소, 염소, 브롬 및 요오드에서 하나 이상 선택되는 원소를 함유하며, 페로브스카이트를 용해하는 용매의 일 예로, N,N-다이메틸아세트아미드(Dimethylacetamid), 1,4-다이옥산(dioxane), 다이에틸아민(diethylamine), 에틸 아세테이트(ethylacetate), 테트라하이드로퓨란(tetrahydrofuran), 피리딘(pyridine), 메탄올(methanol), 에탄올(ethanol), 디클로로벤젠(dichlorobenzene), 글리세린(glycerin) 및 디메틸술폭시드(DMSO, dimethyl sulfoxide), N,N-다이메틸포름아미드(DMF, dimethylformamide) 또는 이들이 혼합물을 들 수 있다. 즉, 게스트 분자는 N,N-다이메틸아세트아미드(Dimethylacetamid), 1,4-다이옥산(dioxane), 다이에틸아민(diethylamine), 에틸 아세테이트(ethylacetate), 테트라하이드로퓨란(tetrahydrofuran), 피리딘(pyridine), 메탄올(methanol), 에탄올(ethanol), 디클로로벤젠(dichlorobenzene), 글리세린(glycerin), 디메틸술폭시드(DMSO, dimethyl sulfoxide) 및 N,N-다이메틸포름아미드(DMF, dimethylformamide)에서 하나 또는 둘 이상 선택될 수 있다.An example of a solvent containing at least one element selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine and dissolving perovskite, N, N-dimethylacetamide, 1,4-dioxane (dioxane), diethylamine, ethyl acetate, tetrahydrofuran, pyridine, methanol, ethanol, dichlorobenzene, glycerin and dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), or a mixture thereof. That is, the guest molecule is N,N-dimethylacetamid, 1,4-dioxane, diethylamine, ethylacetate, tetrahydrofuran, pyridine , methanol, ethanol, dichlorobenzene, glycerin, dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF), one or more can be chosen
외부 에너지에 의해 GM이 제거될 수 있다. 본 개시의 일 실시예에 따르면, 외부 에너지에 의해 게스트 분자가 제거되며 결정질의 페로브스카이트로 변화될 수 있다.GM can be removed by external energy. According to one embodiment of the present disclosure, guest molecules are removed by external energy and can be changed into crystalline perovskite.
즉, 페로브스카이트 복합체가 페로브스카이트와 GM과의 콤플렉스 화합물임에 따라, 에너지 인가에 의해 GM이 제거됨으로서 순수한 페로브스카이트로 전환될 수 있다.That is, since the perovskite composite is a complex compound of perovskite and GM, it can be converted into pure perovskite by removing GM by applying energy.
본 개시의 일 실시예에 따른 페로브스카이트 복합체는 태양전지 광흡수체용일 수 있다.The perovskite composite according to an embodiment of the present disclosure may be used as a light absorber for a solar cell.
본 개시의 일 실시예에 따른 페로브스카이트 복합체는, 페로브스카이트 복합체를 함유하는 분산액 또는 상술한 페로브스카이트 복합체을 함유하는 잉크를 포함한다. 분산액 또는 잉크는 상술한 페로브스카이트 복합체 및 분산매와 함께, 도포나 인쇄 방법에 적합한 특성을 가질 수 있도록, 알려진 첨가제들을 더 함유할 수 있음은 물론이다.The perovskite composite according to an embodiment of the present disclosure includes a dispersion containing the perovskite composite or an ink containing the above-described perovskite composite. Of course, the dispersion or ink may further contain known additives so as to have properties suitable for coating or printing methods, together with the above-described perovskite composite and dispersion medium.
페로브스카이트 복합체는 페로브스카이트의 화학양론비에 따른 유기 양이온, 금속 양이온, 할로겐 이온 및 게스트 분자를 함유하는 제1 용액을 비용매에 점적하는 단계, 및 점적에 의해 수득되는 고상을 회수하여 건조하는 단계를 통해 제조될 수 있다. 여기서, 수득되는 고상은 결정질의 고체 파우더에 해당할 수 있다. 페로브스카이트 복합체가 페로브스카이트와 GM의 콤플렉스임에 따라, 페로브스카이트 복합체는 유기 용매에 대해, 페로브스카이트와 유사 내지 동일한 특성(용해도 등)을 가질 수 있다. 이에 따라, 통상의 페로브스카이트를 용해하는 용매가 제1 용액의 용매로 사용될 수 있다. 페로브스카이트 복합체를 용해하는 용매는 페로브스카이트를 용해하며 용이하게 휘발 제거 가능한 용매이면 사용 가능하다. 구체적인 일 예로, 감마-부티로락톤(Gamma-butyrolactone, GBL), 1-메틸-2-피롤리돈(1-Methyl-2-pyrolidinone) 등을 들 수 있으나, 본 발명이 이에 의해 한정되는 것은 아니다.The perovskite complex is obtained by dropping a first solution containing organic cations, metal cations, halogen ions, and guest molecules according to the stoichiometric ratio of perovskite into a non-solvent, and recovering the solid phase obtained by the dropping It can be prepared through the step of drying. Here, the obtained solid phase may correspond to a crystalline solid powder. As the perovskite composite is a complex of perovskite and GM, the perovskite composite may have properties (solubility, etc.) similar to those of perovskite in organic solvents. Accordingly, a common perovskite-dissolving solvent may be used as a solvent for the first solution. Any solvent that dissolves the perovskite composite can be used as long as it dissolves the perovskite and can be easily volatilized. Specific examples include gamma-butyrolactone (GBL) and 1-methyl-2-pyrrolidone, but the present invention is not limited thereto. .
페로브스카이트 복합체가 용매화합물인 경우, 제1 용액의 용매가 게스트 분자일 수 있다. 즉, 제1 용액은 유기 양이온, 금속 양이온 및 할로겐 이온을 게스트 분자인 용매에 용해하여 제조될 수 있다.When the perovskite composite is a solvate, the solvent of the first solution may be a guest molecule. That is, the first solution may be prepared by dissolving organic cations, metal cations, and halogen ions in a solvent serving as guest molecules.
이때, 페로브스카이트 복합체는 유기 용매에 대해, 페로브스카이트와 유사 내지 동일한 특성(용해도 등)을 가질 수 있음에 따라, 비용매는 페로브스카이트를 용해하지 않는 유기 용매를 의미할 수 있다. 이때, 페로브스카이트를 용해하지 않는다는 의미는 20℃ 1기압 하, 페로브스카이트의 용해도가 0.1M 미만, 구체적으로 0.01M 미만, 더욱 구체적으로 0.001M 미만인 유기용매를 의미할 수 있다.At this time, as the perovskite composite may have properties (solubility, etc.) similar to or identical to those of the perovskite in organic solvents, the non-solvent may mean an organic solvent that does not dissolve the perovskite. . At this time, the meaning of not dissolving perovskite may mean an organic solvent having a solubility of perovskite of less than 0.1M, specifically less than 0.01M, and more specifically less than 0.001M, at 20° C. and 1 atm.
제1 용액이 점적되는 비용매의 일 예로, 비극성 유기 용매를 들 수 있으며, 비극성 유기 용매는 펜타인, 헥센, 사이크로헥센, 1,4-다이옥센, 벤젠, 톨루엔, 트리에틸 아민, 클로로벤젠, 에틸아민, 에틸에테르, 클로로폼, 에틸아세테이트, 아세틱엑시드, 1,2-다이클로로벤젠, tert-부틸알콜, 2-부탄올, 이소프로파놀 및 메틸에틸케톤에서 하나 또는 둘 이상 선택되는 유기 용매를 들 수 있으나, 본 발명이 비용매에 의해 한정되는 것은 아니다. 이때, 제1 용액 내 용질의 농도를 높여 생산성을 향상시킬 수 있으나, 제1 용액의 농도는 각 용질의 용해도 범위 내에서 화학양론비를 만족하는 한 어떠한 농도여도 무방하다.As an example of the non-solvent in which the first solution is dripped, a non-polar organic solvent may be used, and the non-polar organic solvent may include pentane, hexene, cyclohexene, 1,4-dioxene, benzene, toluene, triethyl amine, chlorobenzene , ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1,2-dichlorobenzene, tert-butyl alcohol, 2-butanol, one or more organic solvents selected from isopropanol and methyl ethyl ketone However, the present invention is not limited by the non-solvent. At this time, productivity can be improved by increasing the concentration of the solute in the first solution, but the concentration of the first solution may be any concentration as long as the stoichiometric ratio is satisfied within the solubility range of each solute.
고상의 회수는 통상의 고액 분리 시 사용되는 방법을 이용하면 족하다. 일 예로, 필터링, 원심분리 등을 들 수 있으나, 이에 한정되는 것은 아니다. 건조는 페로브스카이트 복합체가 열적으로 안전하게 손상되지 않는 범위이면 족하다. 일 예로, 건조는 상온 내지 50℃에서 수행될 수 있다.The recovery of the solid phase is sufficient by using a method used in normal solid-liquid separation. As an example, filtering, centrifugation, etc. may be mentioned, but is not limited thereto. Drying is sufficient as long as the perovskite composite is not thermally and safely damaged. For example, drying may be performed at room temperature to 50°C.
본 발명은 상술한 페로브스카이트 복합체를 이용한 태양전지 광흡수체의 제조방법을 포함한다.The present invention includes a method for manufacturing a light absorber for a solar cell using the above-described perovskite composite.
본 개시의 일 실시예에 따른 광흡수체의 제조방법은 기재 상 상기 페로브스카이트 복합체를 도포 또는 증착하여 페로브스카이트 복합체층을 형성하는 단계, 및 상기 페로브스카이트 복합체층에 에너지를 인가하여, 게스트 분자를 휘발 제거하는 단계를 포함할 수 있다.A method for manufacturing a light absorber according to an embodiment of the present disclosure includes forming a perovskite composite layer by coating or depositing the perovskite composite on a substrate, and applying energy to the perovskite composite layer. Thus, a step of volatilizing and removing the guest molecules may be included.
일 예로, 페로브스카이트 복합체가 용해된 용액 또는 페로브스카이트 복합체가 분산된 분산액이나 잉크를 기재상에 도포한 후 건조하여 전구층을 형성한 후, 전구층에서 GM을 제거함으로써, 전구층을 페로브스카이트층으로 전환시킬 수 있다.For example, a solution in which the perovskite composite is dissolved or a dispersion or ink in which the perovskite composite is dispersed is coated on a substrate, dried to form a precursor layer, and then GM is removed from the precursor layer to form a precursor layer. can be converted into a perovskite layer.
다른 일 예로, 페로브스카이트 복합체가 용매화합물인 경우, 페로브스카이트의 화학양론비에 따른 유기 양이온, 금속 양이온 및 할로겐 이온을 게스트 분자(GM)인 용매에 용해하여 용액을 제조한 후, 제조된 용액을 기재 상에 도포하고, 도포막에 비용매를 재도포함으로써, 페로브스카이트 복합체를 함유하는 전구층을 제조할 수 있다.As another example, when the perovskite complex is a solvate, a solution is prepared by dissolving organic cations, metal cations, and halogen ions according to the stoichiometric ratio of the perovskite in a solvent that is a guest molecule (GM), A precursor layer containing a perovskite composite can be prepared by applying the prepared solution on a substrate and re-applying a non-solvent to the coating film.
이때, 용액, 분산액 또는 잉크의 도포는 스크린 프린팅(screen printing), 스핀코팅(Spin coating), 바-코팅(Bar coating), 그라비아-코팅(Gravure coating), 블레이드 코팅(Blade coating), 및 롤-코팅(Roll coating)에서 하나 이상 선택된 방법으로 수행될 수 있으나, 단시간에 대면적을 처리하는 우수한 상업성을 고려할 때, 스핀코팅으로 수행되는 것이 바람직하다.At this time, the application of the solution, dispersion or ink is screen printing, spin coating, bar-coating, gravure-coating, blade coating, and roll-coating. It may be performed by one or more selected methods in roll coating, but considering the excellent commercial properties of treating a large area in a short time, it is preferable to perform spin coating.
전구층에 인가되는 에너지는 열 에너지, 광 에너지, 진동 에너지 등을 들 수 있다. 인가되는 에너지의 크기는 페로브스카이트와 GM간의 결합이 깨어지며 GM이 휘발 제거될 수 있는 정도면 족하다. 일 예로, 페로브스카이트 복합체를 100℃이상으로 가열함으로써, GM을 제거하여 결정질의 페로브스카이트를 수득할 수 있으며, 나아가 130℃이상으로 전구층을 가열하는 경우, 매우 단시간 내에 결정질의 페로브스카이트를 수득할 수 있다. 이때, 페로브스카이트 복합체를 페로브스카이트로 변환시키기 위한 열처리의 상한은 페로브스카이트를 형성하고자 하는 기재가 열적으로 손상되지 않는 범위이면 족하다. 일 예로, 열처리는 100 내지 200℃에서 수행될 수 있다. 열처리 시간은 열처리 온도를 고려하여, 페로브스카이트 복합체가 페로브스카이트로 충분히 전환될 수 있는 시간이면 족하다. 비한정적인 일 예로, 열처리 시간은 1분 내지 30분일 수 있으나, 본 발명이 열처리 시간에 의해 한정될 수 없음은 물론이다.Energy applied to the precursor layer may include thermal energy, light energy, vibration energy, and the like. The amount of energy applied is sufficient to break the bond between the perovskite and GM and volatilize the GM. For example, by heating the perovskite composite to 100 ° C or higher, GM can be removed to obtain crystalline perovskite, and furthermore, when the precursor layer is heated to 130 ° C or higher, crystalline perovskite can be obtained in a very short time. You can get lobsite. At this time, the upper limit of the heat treatment for converting the perovskite composite into perovskite is sufficient as long as the base material to form the perovskite is not thermally damaged. For example, heat treatment may be performed at 100 to 200 °C. Considering the heat treatment temperature, the heat treatment time is sufficient as long as the perovskite composite can be sufficiently converted into perovskite. As a non-limiting example, the heat treatment time may be 1 minute to 30 minutes, but the present invention cannot be limited by the heat treatment time, of course.
(FAPbI3)1-x(MACl)(MAPbBr3)x 합성 방법(FAPbI 3 ) 1-x (MACl)(MAPbBr 3 ) x Synthesis method
1. (FAPbI3)1-x(MACl)(MAPbBr3)x (Formamidinium-methyl-ammonium lead iodide bromide) 용액을 제조한다. 이 경우, 실시예 및 비교예에 따른 페로브스카이트 복합체의 조성은 다음과 같다.1. Prepare a (FAPbI 3 ) 1-x (MACl)(MAPbBr 3 ) x (Formamidinium-methyl-ammonium lead iodide bromide) solution. In this case, the composition of the perovskite composite according to Examples and Comparative Examples is as follows.
- 실시예: (FAPbI3)0.992(MACl)(MAPbBr3)0.008 Complex- Example: (FAPbI 3 ) 0.992 (MACl)(MAPbBr 3 ) 0.008 Complex
- 비교예 1: (FAPbI3)(MACl) Complex- Comparative Example 1: (FAPbI 3 ) (MACl) Complex
- 비교예 2: (FAPbI3)0.975(MACl)(MAPbBr3)0.025 Complex- Comparative Example 2: (FAPbI 3 ) 0.975 (MACl) (MAPbBr 3 ) 0.025 Complex
- 비교예 3: (FAPbI3)0.9(MACl)(MAPbBr3)0.1 Complex- Comparative Example 3: (FAPbI 3 ) 0.9 (MACl) (MAPbBr 3 ) 0.1 Complex
우선, FAPbI3, MACl, MAPbBr3의 정량을 각각 용매(DMF 0.8ml: DMSO 0.1ml)에 녹인다. FAPbI3 0.8g, MACl 0.035g에 대해 MAPbBr3를 0g, 0.0055g, 0.0172g, 0.0858g 첨가함으로써 실시예 및 비교예 1 내지 3을 각각 제조한다. 이 경우, 실시예는 MAPbBr3 0.8 mol%, 비교예 1 내지 3은 각각 MAPbBr3 0 mol%, 2.5 mol%, 10 mol%에 해당한다. 상술한 용매는 예시로서, 본 발명은 상술한 용매의 비율 및 종류에 제한되지 않는다.First, quantitative amounts of FAPbI 3 , MACl, and MAPbBr 3 are dissolved in a solvent (DMF 0.8ml: DMSO 0.1ml), respectively. Examples and Comparative Examples 1 to 3 were prepared by adding 0 g, 0.0055 g, 0.0172 g, and 0.0858 g of MAPbBr 3 to 0.8 g of FAPbI 3 and 0.035 g of MACl, respectively. In this case, Examples correspond to 0.8 mol% of MAPbBr 3 , and Comparative Examples 1 to 3 correspond to 0 mol%, 2.5 mol%, and 10 mol% of MAPbBr 3 , respectively. The above-mentioned solvent is an example, and the present invention is not limited to the ratio and type of the above-mentioned solvent.
2. 상술한 페로브스카이트 복합체 용액을 스핀코팅하여 박막을 제작한다.2. A thin film is fabricated by spin-coating the perovskite composite solution described above.
3. 상술한 바에 따라 최종 제작된 광소자는 FTO / SnO2 / Perovskite / Spiro-OMeTAD / Au 구조를 갖는다.3. The optical device finally fabricated as described above has a structure of FTO / SnO 2 / Perovskite / Spiro-OMeTAD / Au.
성능 비교Performance Comparison
상기 실시예 및 비교예 1 내지 3을 통해 제조된 페로브스카이트 광소자를 이용하여 하기 방법을 통해 광소자의 성능을 평가하였으며, 그 결과를 하기 표 1에 표기하였다.The performance of the optical device was evaluated through the following method using the perovskite optical device manufactured through the above Examples and Comparative Examples 1 to 3, and the results are shown in Table 1 below.
1,000 W/㎡의 일조 강도와 온도 85℃및 습도 85%의 항온 항습 조건에서 실시예 및 비교예 1 내지 3을 통해 제조된 페로브스카이트 광소자를 280 내지 2500 ㎚ 파장의 광원에 노출시켜 광전변환효율(power conversion efficiency, PCE) 값을 측정하였다.Photoelectric conversion by exposing the perovskite optical device prepared in Examples and Comparative Examples 1 to 3 to a light source with a wavelength of 280 to 2500 nm under a constant temperature and humidity condition of 1,000 W / ㎡ of sunlight intensity, temperature of 85 ° C and humidity of 85% Efficiency (power conversion efficiency, PCE) values were measured.
|
조건 (FAPbI3 +MACl 30mol%)condition (FAPbI 3 +MACl 30 mol%) |
효율efficiency | |||
| Voc [V]V oc [V] | Jsc [mA/cm2]J sc [mA/cm 2 ] | FFFF | PCE [%]PCE [%] | |
|
실시예 MAPbBr3 0.8 mol%Example MAPbBr 3 0.8 mol % |
1.171.17 | 2525 | 84.184.1 | 24.624.6 |
|
비교예 1MAPbBr3 0 mol% |
1.161.16 | 25.125.1 | 81.181.1 | 23.623.6 |
| 비교예 2MAPbBr3 2.5 mol%Comparative Example 2MAPbBr 3 2.5 mol% | 1.181.18 | 24.524.5 | 80.580.5 | 23.323.3 |
|
비교예 3MAPbBr3 10 mol% |
1.191.19 | 24.124.1 | 79.679.6 | 22.822.8 |
표 1에 따르면, 실시예에 따른 광소자가 비교예 1 내지 3보다 더 높은 전력 변환 효율을 나타냄을 확인할 수 있다.According to Table 1, it can be confirmed that the optical device according to the embodiment exhibits higher power conversion efficiency than Comparative Examples 1 to 3.
한편, 도 1은 본 개시의 일 실시예에 따른 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 SEM 이미지를 나타낸다. 도시된 바와 같이, MAPbBr3의 농도(%)에 따라 페로브스카이트의 그레인 사이즈(grain size)가 달라짐을 확인할 수 있다. 이 경우, 실시예에서 제조된 페로브스카이트의 그레인 사이즈가 비교예 1 내지 3에서의 그레인 사이즈보다 크기가 더 큼을 확인할 수 있다.Meanwhile, FIG. 1 shows a SEM image of a perovskite thin film using a perovskite composite according to an embodiment of the present disclosure. As shown, it can be confirmed that the grain size of the perovskite varies according to the concentration (%) of MAPbBr 3 . In this case, it can be confirmed that the grain size of the perovskite prepared in Example is larger than the grain size in Comparative Examples 1 to 3.
도 2는 본 개시의 일 실시예에 따른 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 파장에 따른 광흡수 스펙트럼 측정 결과를 나타낸다. 도시된 바와 같이, MAPbBr3의 농도가 감소할수록 흡수 스펙트럼이 장파장으로 이동하는 거동을 보이며 밴드갭이 감소함을 확인할 수 있다.Figure 2 shows the result of measuring the light absorption spectrum according to the wavelength of the perovskite thin film using the perovskite composite according to an embodiment of the present disclosure. As shown, it can be seen that as the concentration of MAPbBr 3 decreases, the absorption spectrum shows a behavior shifting to a longer wavelength and the band gap decreases.
도 3은 실시예 및 비교예 1 내지 3에서 제조된 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 TRPL(time-resolved photoluminescence) 특성을 나타낸다. 도시된 바와 같이, 비교예 1 내지 3과 비교하여 실시예서 제조된 페로브스카이트 복합체를 이용한 페로브스카이트 박막의 PL 수명이 증가한 것을 확인할 수 있다.3 shows time-resolved photoluminescence (TRPL) characteristics of perovskite thin films using the perovskite composites prepared in Examples and Comparative Examples 1 to 3. As shown, it can be seen that the PL lifetime of the perovskite thin film using the perovskite composite prepared in Example increased compared to Comparative Examples 1 to 3.
도 4는 MAPbBr3의 농도(%)에 따른 이동도(Mobility)와 확산거리(diffusion length)를 나타낸다. 도시된 바와 같이, 이동도는 실시예에서 비교예 2 다음으로 높게 나타났고, 확산거리는 실시예에서 가장 높게 나타났다.4 shows mobility and diffusion length according to the concentration (%) of MAPbBr 3 . As shown, the mobility was the highest in the examples next to Comparative Example 2, and the diffusion distance was the highest in the examples.
도 5는 실시예 및 비교예 1 내지 3에서 제조된 광소자의 외부 양자 효율(External Quantum Efficiency, EQE) 스펙트럼을 나타낸다. 도시된 바와 같이, MAPbBr3의 농도(%)가 증가할수록 스펙트럼이 청색편이 되어 Jsc가 감소하였다. 또한, 실시예의 경우 비교예 1과 비교하여 스펙트럼의 차이가 크지 않음을 확인할 수 있다. 이는 표 1의 Jsc에서도 확인할 수 있다.5 shows External Quantum Efficiency (EQE) spectra of optical devices manufactured in Examples and Comparative Examples 1 to 3. As shown, as the concentration (%) of MAPbBr 3 increases, the spectrum becomes blue-shifted and J sc decreases. In addition, in the case of Example, it can be confirmed that the difference in spectrum is not large compared to Comparative Example 1. This can also be confirmed from J sc in Table 1.
상기한 본 발명의 바람직한 실시예는 예시의 목적으로 개시된 것이고, 본 발명에 대해 통상의 지식을 가진 당업자라면 본 발명의 사상과 범위 안에서 다양한 수정, 변경 및 부가가 가능할 것이며, 이러한 수정, 변경 및 부가는 특허청구 범위에 속하는 것으로 보아야 할 것이다.The preferred embodiments of the present invention described above have been disclosed for illustrative purposes, 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 regarded as falling within the scope of the claims.
본 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서, 여러 가지 치환, 변형 및 변경이 가능하므로, 본 발명은 전술한 실시예 및 첨부된 도면에 의해 한정되는 것이 아니다.Those skilled in the art to which the present invention pertains can make various substitutions, modifications, and changes without departing from the technical spirit of the present invention. is not limited by
Claims (9)
- 페로브스카이트 복합체로서,As a perovskite complex,유기 양이온(A), 금속 양이온(M), 및 할로겐 음이온(X)을 함유하는 페로브스카이트(AMX3); 및a perovskite containing an organic cation (A), a metal cation (M), and a halogen anion (X) (AMX 3 ); andMACl(메틸암모늄염화물, CH3NH3Cl)MACl (Methylammonium Chloride, CH 3 NH 3 Cl)을 포함하고,including,X는 Br- 및 Br- 이외의 할로겐 음이온을 포함하고,X contains a halogen anion other than Br - and Br - ,화학정량적으로 Br-은 Br- 이외의 할로겐 음이온 대비 1% 이하에 해당하는, 페로브스카이트 복합체.Stoichiometrically, Br - is a perovskite composite that corresponds to 1% or less of halide anions other than Br - .
- 제1항에 있어서,According to claim 1,산소, 질소, 염소, 브롬 및 요오드 중 적어도 하나 이상의 원소를 포함하는 용매에 해당하는 게스트 분자(GM)Guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine를 더 포함하는, 페로브스카이트 복합체.Further comprising a perovskite composite.
- 제2항에 있어서, According to claim 2,상기 페로브스카이트 복합체는 결정질의 고체 파우더에 해당하는, 페로브스카이트 복합체.The perovskite composite corresponds to a crystalline solid powder, the perovskite composite.
- 제1항에 있어서,According to claim 1,상기 유기 양이온(A)은 유기 암모늄 이온, 아미디니움계(amidinium group) 이온, 또는 유기 암모늄 이온 및 아미디니움계 이온에 해당하고,The organic cation (A) corresponds to an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium group ion,상기 금속 양이온(M)은 2가의 금속 양이온에 해당하는, 페로브스카이트 복합체.The metal cation (M) corresponds to a divalent metal cation, perovskite composite.
- 페로브스카이트 복합체로서,As a perovskite complex,페로브스카이트; 및perovskite; andMACl(메틸암모늄염화물, CH3NH3Cl)MACl (Methylammonium Chloride, CH 3 NH 3 Cl)을 포함하고,including,상기 페로브스카이트 복합체는 하기 화학식을 만족하는, 페로브스카이트 복합체.The perovskite complex satisfies the following chemical formula, perovskite complex.[화학식][chemical formula](FAPbI3)1-x(MACl)n(MAPbBr3)x (FAPbI 3 ) 1-x (MACl) n (MAPbBr 3 ) x(FA는 포름아미디니움(formamidinium, NH2CH=NH2 +)에 해당하고, MA는 메틸암모늄(methylammonium, CH3NH3 +)에 해당하며, x는 0<x<1을 만족하는 실수에 해당하고, n은 0<n<1을 만족하는 실수에 해당)(FA corresponds to formamidinium (NH 2 CH=NH 2 + ), MA corresponds to methylammonium (CH 3 NH 3 + ), and x is a real number satisfying 0<x<1 , and n corresponds to a real number satisfying 0<n<1)
- 제5항에 있어서,According to claim 5,상기 x는 0.01 이하의 값을 갖는, 페로브스카이트 복합체.Wherein x has a value of 0.01 or less, the perovskite composite.
- 제6항에 있어서,According to claim 6,산소, 질소, 염소, 브롬 및 요오드 중 적어도 하나 이상의 원소를 포함하는 용매에 해당하는 게스트 분자(GM)Guest molecule (GM) corresponding to a solvent containing at least one element of oxygen, nitrogen, chlorine, bromine, and iodine를 더 포함하는, 페로브스카이트 복합체.Further comprising a perovskite composite.
- 제7항에 따른 페로브스카이트 복합체는 결정질의 고체 파우더에 해당하는, 페로브스카이트 복합체.The perovskite composite according to claim 7 corresponds to a crystalline solid powder.
- 제1항 또는 제5항에 따른 페로브스카이트 복합체는 태양전지의 광흡수체용인, 페로브스카이트 복합체.The perovskite composite according to claim 1 or 5 is for a light absorber of a solar cell, a perovskite composite.
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| KR20170098307A (en) * | 2014-12-23 | 2017-08-29 | 에이에스엠엘 네델란즈 비.브이. | A lithography patterning process and a resist used in the process |
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Non-Patent Citations (2)
| Title |
|---|
| KAWANO YU; CHANTANA JAKAPAN; NISHIMURA TAKAHITO; MINEMOTO TAKASHI: "Influence of halogen content in mixed halide perovskite solar cells on cell performances through device simulation", SOLAR ENERGY MATERIALS AND SOLAR CELLS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, vol. 205, 12 November 2019 (2019-11-12), NL , XP085935569, ISSN: 0927-0248, DOI: 10.1016/j.solmat.2019.110252 * |
| KIM MINJIN, KIM GI-HWAN, LEE TAE KYUNG, CHOI IN WOO, CHOI HYE WON, JO YIMHYUN, YOON YUNG JIN, KIM JAE WON, LEE JIYUN, HUH DAIHONG,: "Methylammonium Chloride Induces Intermediate Phase Stabilization for Efficient Perovskite Solar Cells", JOULE, CELL PRESS, vol. 3, no. 9, 1 September 2019 (2019-09-01), pages 2179 - 2192, XP055885360, ISSN: 2542-4351, DOI: 10.1016/j.joule.2019.06.014 * |
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