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WO2022039522A1 - Film mince de pérovskite comportant un joint de grain cristallin passivé, son procédé de préparation et dispositif électronique le comprenant - Google Patents

Film mince de pérovskite comportant un joint de grain cristallin passivé, son procédé de préparation et dispositif électronique le comprenant Download PDF

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WO2022039522A1
WO2022039522A1 PCT/KR2021/011034 KR2021011034W WO2022039522A1 WO 2022039522 A1 WO2022039522 A1 WO 2022039522A1 KR 2021011034 W KR2021011034 W KR 2021011034W WO 2022039522 A1 WO2022039522 A1 WO 2022039522A1
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perovskite
thin film
grain boundary
lewis base
perovskite thin
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Korean (ko)
Inventor
전남중
신성식
송슬기
김영윤
김범수
박은영
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Korea Research Institute of Chemical Technology KRICT
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
    • H10F77/169—Thin semiconductor films on metallic or insulating substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/20—Electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for manufacturing a perovskite thin film having passivated grain boundaries and an electronic device including the same.
  • the present invention provides a passivation ( passivation) and confirmed that the efficiency of an electronic device including the same can be improved, and the present invention has been completed.
  • the present invention provides a perovskite thin film having a passivated grain boundary and a method for manufacturing the same.
  • the present invention provides an electronic device using the perovskite thin film of the present invention.
  • the present invention provides a perovskite thin film having a passivated grain boundary, the perovskite thin film of the present invention,
  • the Lewis base according to an embodiment of the present invention may be a compound including any one or two or more electron donor elements selected from N, O, and S, and preferably a pKa value of 8 or more.
  • the Lewis base according to an embodiment of the present invention is piperazine, morpholine, 4-dimethylaminopyridine, piperidine, 1-methylpiperidine, pyrrolidine, 1-methylpyrrolidine, diethylamine , triethylamine, tetramethylethylenediamine, and methyl-4-pyridinemethylamine may be any one or two or more selected from, but is not limited thereto.
  • the perovskite thin film according to an embodiment of the present invention may be formed by heat-treating a perovskite precursor solution containing a compound satisfying the following Chemical Formula 1 and a metal halide satisfying the following Chemical Formula 2.
  • A is Cs + or an organocation
  • M is selected from the group consisting of Pb, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, Sn, Ge, and combinations thereof;
  • X is Br - , Cl - or I - .
  • the organocation of A in Formula 1 may be a compound represented by Formula 3 or Formula 4 below.
  • R 1 to R 4 are each independently selected from hydrogen and unsubstituted or substituted (C1-C6)alkyl
  • R 5 to R 8 are each independently selected from hydrogen and unsubstituted or substituted (C1-C20)alkyl or unsubstituted or substituted aryl.
  • the present invention provides a method for manufacturing a perovskite thin film having an immobilized grain boundary of the present invention, the method for manufacturing a perovskite thin film of the present invention is
  • the Lewis base solution according to an embodiment of the present invention may have a pKa value of 8 or more, specifically piperazine, morpholine, 4-dimethylaminopyridine, piperidine, 1-methylpiperidine, pyrrolidine, and 1 -Methylpyrrolidine, diethylamine, triethylamine, tetramethylethylenediamine, and may be any one or two or more selected from methyl-4-pyridinemethylamine, but is not limited thereto.
  • the primary heat treatment according to an embodiment of the present invention may be performed at a temperature of 50 to 300 °C, and the secondary heat treatment may be performed at a temperature of 50 to 150 °C.
  • the present invention provides an electronic device comprising the perovskite thin film of the present invention.
  • the perovskite thin film according to an embodiment of the present invention effectively inhibits the oxidation of metal cations in the perovskite structure by placing Lewis base crystals at the grain boundaries of the perovskite structure crystals, thereby forming the perovskite structure. By making it stable, the efficiency of the electronic device including the same is improved.
  • the method of manufacturing a perovskite thin film according to an embodiment of the present invention is different from the conventionally known method of adding a Lewis base compound to a perovskite precursor solution, after forming a perovskite structure crystal
  • the Lewis base is not only evenly distributed at the perovskite grain boundary, but also stably maintained on the perovskite thin film at high temperature, thereby maintaining the perovskite thin film grain boundary. can maintain the immobilization of
  • the electronic device including the perovskite thin film of the present invention has surprisingly improved properties.
  • Example 1 is a photograph (b) of a thin film after spin-coating DMAP on a crystal (a), a substrate prepared in Preparation Example 1, and heating it at 100° C. for 30 minutes, and a perovskite thin film prepared in Example 1 SEM image of (c) is shown.
  • Figure 2 shows the time-dependent SEM image of the perovskite thin film of Example 1 of the present invention.
  • FIG. 3 shows SEM images of non-annealing and annealing when 4-dimethylaminopyridine is applied.
  • FIG. 5 shows SEM images for each concentration of 4-dimethylaminopyridine of the perovskite thin film.
  • Figure 6 shows the X-ray diffraction pattern for each concentration of 4-dimethylaminopyridine of the perovskite thin film.
  • TCSPC Time-Correlated Single Photon Counting
  • Example 8 is a graph showing the strength of adhesion between the perovskite thin film and the hole transport layer prepared in Example 1 and Comparative Example 1 of the present invention.
  • Example 9 is a graph showing the long-term stability of the perovskite solar cells prepared in Example 1 and Comparative Example 1 of the present invention.
  • DMAP 4-dimethylaminopyridine
  • alkyl refers to a saturated straight-chain or branched non- having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms (when the number of carbon atoms is not particularly limited). It means a cyclic hydrocarbon. "Lower alkyl” means straight-chain or branched alkyl having 1 to 4 carbon atoms.
  • saturated straight chain alkyls are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl and -n- contains decyl
  • saturated branched alkyl is -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, isopentyl, 2-methylhexyl, 3-methylbutyl, 2-methylpentyl, 3- Methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylpentyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-
  • C1-6 alkyl When described as “C1-6" in the present specification, it means that it has 1 to 6 carbon atoms.
  • C 1-6 alkyl means alkyl having 1 to 6 carbon atoms.
  • heterocycle is a cyclic compound containing a heteroatom, including heterocycloalkyl and heteroaryl, and may be a C3-C20, preferably C3-C12, more preferably C3-C8 heterocyclic compound. there is.
  • heterocycloalkyl has 2 to 12, preferably 2 to 10 carbon atoms and 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, for example 1 to 5 refers to a stable 3- to 18-membered saturated or partially unsaturated radical consisting of heteroatoms, 1 to 4 heteroatoms, 1 to 3 heteroatoms, or 1 to 2 heteroatoms.
  • Exemplary heterocyclealkyls include, but are not limited to, stable 3-15 membered saturated or partially unsaturated radicals, stable 3-12 membered saturated or partially unsaturated radicals, stable 3-9 membered saturated or partially unsaturated radicals, stable 8-membered saturated or partially unsaturated radicals, and stable 8-membered saturated or partially unsaturated radicals. radicals, stable 7-membered saturated or partially unsaturated radicals, stable 6-membered saturated or partially unsaturated radicals, or stable 5-membered saturated or partially unsaturated radicals.
  • heteroaryl has at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, and includes 5 to 10 carbon atoms including at least one carbon atom, including mono- and bicyclic ring systems. It is an aromatic heterocycle ring of members.
  • heteroaryls include triazolyl, tetrazolyl, oxadiazolyl, pyridyl, furyl, benzofuranyl, thiophenyl, benzothiophenyl, quinolinyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl ( benzoxazolyl), imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, tria Zinyl, cinnolinyl, phthalazinyl, quinazolinyl, pyrimidyl, oxetanyl, azepinyl, piperazinyl, morpholinyl, dioxanyl, thietanyl and oxazolyl.
  • substituted means that the hydrogen atom of the moiety being substituted (eg, alkyl, aryl, heteroaryl, heterocycle, or cycloalkyl) is replaced by a substituent.
  • each carbon atom of the group being substituted is unsubstituted by more than two substituents.
  • each carbon atom of the group being substituted is unsubstituted by more than one substituent.
  • the two hydrogen atoms are replaced by an oxygen attached to the carbon by a double bond.
  • substituted substituents are hydrogen, halogen, amino, (C1-C10)alkyl, (C1-C10)alkoxy(C1-C10)alkyl, halo(C1-C10)alkyl, (C6-C12)aryl, (C3-C10)heterocycle or (C3-C12)heteroaryl.
  • One aspect of the present invention is a perovskite thin film having a passivated grain boundary.
  • Perovskite thin film according to an embodiment of the present invention is a perovskite structure crystal
  • the presence of a Lewis base at the grain boundary of the perovskite structure crystal can be found through GIWAX measurement of the perovskite thin film.
  • the perovskite thin film according to an embodiment of the present invention a Lewis base is selectively present at the grain boundary of the perovskite structure crystal, thereby preventing defects in the perovskite structure crystal. Therefore, the perovskite thin film of the present invention has excellent properties.
  • the Lewis base present at the grain boundary of the perovskite thin film according to an embodiment of the present invention is selectively distributed at the grain boundary interface of the perovskite thin film unlike conventional surface treatment materials, and the formed Lewis base crystal is The passivation is stably maintained even at a high temperature, specifically 100 °C, which greatly improves the efficiency of the electronic device employing it.
  • the perovskite thin film according to an embodiment of the present invention has a crystal of a Lewis base at the grain boundary of the perovskite structure crystal. Able to know.
  • the electronic device including the perovskite thin film of the present invention has more improved efficiency and durability.
  • the Lewis base according to an embodiment of the present invention may be a compound containing any one or two or more electron donor elements selected from N, O, and S, and specifically, any one or two or more selected from N, O and S It may be a C3-C20 heterocyclic compound containing an electron donor element.
  • the Lewis base according to an embodiment of the present invention may be a monomolecular C3-C20 heterocyclic compound containing any one or two or more electron donor elements selected from N, O, and S, and is preferably selected from N and O. It may be monomolecular C3-C10 heterocycloalkyl or monomolecular C3-C10 heteroaryl containing at least one.
  • the Lewis base according to an embodiment of the present invention may be a mono-molecular C3-C10 heterocycloalkyl or a mono-molecular C3-C10 heteroaryl into which a mono-C1-C10 alkylamino group or a di-C1-C10 alkylamino group is introduced.
  • the Lewis base according to an embodiment of the present invention may be a compound represented by the following Chemical Formula 5 or Chemical Formula 6.
  • R and R' are independently of each other C1-C5 alkyl
  • A is O, S or NR 24 ;
  • R 11 , R 12 and R 21 to R 24 are each independently hydrogen or C 1 -C 5 alkyl
  • n is an integer from 0 to 4
  • m is an integer from 0 to 3.
  • R and R' are each independently C1-C3 alkyl;
  • A is O, S or NR 24 ;
  • R 11 , R 12 , R 21 to R 24 are each independently hydrogen or C 1 -C 3 alkyl;
  • n is an integer from 0 to 2, m may be an integer from 0 to 2,
  • R and R' are each independently C1-C3 alkyl;
  • A is O or NR 24 ;
  • R 11 , R 12 , R 21 to R 24 are each independently hydrogen or C 1 -C 3 alkyl;
  • n may be an integer from 0 to 1
  • m may be an integer from 0 to 1.
  • the Lewis base is piperazine, morpholine, 4-dimethylaminopyridine, piperidine, 1-methylpiperidine, pyrrolidine, 1-methylpyrrolidine, diethylamine, triethylamine, tetramethylethylene. It may be any one or two or more selected from diamine and methyl-4-pyridinemethylamine, and preferably, the Lewis base according to an embodiment of the present invention may have a pKa value of 8 or more.
  • the perovskite structure crystal according to an embodiment of the present invention may be formed by heat-treating a perovskite precursor solution containing a compound satisfying the following Chemical Formula 1 and a metal halide satisfying the following Chemical Formula 2.
  • A is Cs + or an organocation
  • M is selected from the group consisting of Pb, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, Sn, Ge, and combinations thereof;
  • X is Br - , Cl - or I - .
  • the organic cation of A in Formula 1 may be a compound represented by Formula 3 or Formula 4 below.
  • R 1 to R 4 are each independently selected from hydrogen and unsubstituted or substituted (C1-C6)alkyl
  • R 5 to R 8 are each independently selected from hydrogen and unsubstituted or substituted (C1-C20)alkyl or unsubstituted or substituted aryl.
  • the Lewis base employed in the present invention is characterized in that it is a compound containing any one or two or more electron donor elements selected from N, O and S.
  • the Lewis base employed in the present invention is characterized in that the pKa value (which is the pKa value in water) is 8 or more, specifically, the pKa value is 9 or more and 13 or less. If the pKa value is less than 8, the passivation effect of the perovskite grain boundaries may be reduced.
  • the Lewis base is piperazine, morpholine, 4-dimethylaminopyridine, piperidine, 1-methylpiperidine, pyrrolidine, 1-methylpyrrolidine, diethylamine, triethylamine , may be any one or two or more selected from tetramethylethylenediamine and methyl-4-pyridinemethylamine, but is not limited thereto.
  • the Lewis base may be any one or two or more selected from 4-dimethylaminopyridine, 1-methylpiperidine and tetramethylethylenediamine.
  • the compounds represented by Chemical Formulas 5 and 6 are uniformly dispersed in the perovskite grain boundaries and then bound, thereby effectively passivating the perovskite grain boundaries. there is.
  • the perovskite thin film of the present invention is characterized in that a hole transport layer is formed on the perovskite thin film in which Lewis base crystals are formed at grain boundaries.
  • the first step is a step of forming a perovskite structure crystal by applying a perovskite precursor solution to a substrate and performing primary heat treatment.
  • a perovskite precursor solution containing an inorganic or organic halide or a metal halide is applied on a substrate and subjected to a primary heat treatment.
  • the inorganic or organic halide according to an embodiment of the present invention may satisfy the following formula (1).
  • A is Cs + or an organocation
  • X is Br - , Cl - or I - .
  • the metal halide according to an embodiment of the present invention may satisfy the following formula (2).
  • M comprises a metal selected from the group consisting of Pb, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Yb, Sn, Ge, and combinations thereof;
  • X is Br - , Cl - or I - .
  • the organic cation of A in Formula 1 may be represented by Formula 3 or Formula 4 below.
  • R 1 to R 4 are each independently selected from hydrogen and unsubstituted or substituted (C1-C6)alkyl
  • R 5 to R 8 are each independently selected from hydrogen and unsubstituted or substituted (C1-C20)alkyl or unsubstituted or substituted aryl.
  • Chemical Formula 1 may be selected from CH 3 NH 3 I (methylammonium iodide), CH(NH 2 ) 2 I (formamidinium iodide), or CsI (cesium iodide).
  • the perovskite precursor solution may contain 0.8 to 1.2 moles of a metal halide with respect to 1 mole of the inorganic or organic halide.
  • the first heat treatment for annealing the applied perovskite precursor solution is not particularly limited as long as the solution is sufficiently dried and the temperature at which the perovskite structure can be stably maintained, but in one embodiment, the heat treatment is 50 to It may be carried out at a temperature of 300 °C for 10 minutes to 4 hours.
  • the step of forming a metal oxide thin film may be further performed, and the forming step of the metal oxide thin film may be performed by chemical or physical vapor deposition used in a typical semiconductor process, and ,
  • the material of the metal oxide thin film is, for example, Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, It may be at least one material selected from Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, SrTi oxide, and composites thereof, and more preferably, at least one material selected from Ti oxide, Sn oxide, and composites thereof. there is.
  • the second step is a step of forming a Lewis base crystal at the grain boundary of the perovskite structure by applying a Lewis base solution to the crystals of the perovskite structure and performing secondary heat treatment.
  • the Lewis base employed in the present invention may be any one selected from N, O, and S, or a compound containing two or more electron donor elements.
  • the Lewis base employed in the present invention is characterized in that the pKa value is 8 or more, specifically, the pKa value is 9 or more and 13 or less. If the pKa value is less than 8, the passivation effect of the perovskite grain boundaries may be reduced.
  • the Lewis base is piperazine, morpholine, 4-dimethylaminopyridine, piperidine, 1-methylpiperidine, pyrrolidine, 1-methylpyrrolidine, diethylamine, triethylamine , may be any one or two or more selected from tetramethylethylenediamine and methyl-4-pyridinemethylamine, but is not limited thereto.
  • the Lewis base may be any one or two or more selected from 4-dimethylaminopyridine, 1-methylpiperidine and tetramethylethylenediamine.
  • the Lewis base of the present invention may be one or two or more compounds selected from the compounds represented by Chemical Formulas 5 and 6.
  • the solvent for preparing the Lewis base solution may be used without particular limitation as long as it is a solvent that can dissolve the Lewis base and can be easily removed by volatilization during drying.
  • the solvent is chloroform, chlorobenzene, gamma-butyrolactone, formamide, N,N-dimethylformamide, diformamide, acetonitrile, tetrahydrofuran, dimethyl sulfoxide.
  • diethylene glycol, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, acetone, ⁇ -terpineol, ⁇ -terpineol, dihydroterpineol, 2-methoxyethanol , acetylacetone, methanol, ethanol, 2-propanol, butanol, pentanol, hexanol, ketone, diethyl ether, toluene and methyl isobutyl ketone may be any one or two or more selected from.
  • the solvent may be any one or two or more selected from chloroform, chlorobenzene, diethyl ether, toluene and 2-propanol.
  • the heat treatment temperature for the annealing of the Lewis base solution is not particularly limited, but in one embodiment may be performed at a temperature of 50 to 200° C. for 5 minutes to 20 minutes.
  • the annealing of the Lewis base solution may be performed at a temperature of 50 to 150° C., which is a low temperature process, for 5 to 15 minutes.
  • the present invention is different from the conventionally known method of adding a Lewis base to a perovskite precursor solution, after preparing a perovskite structure crystal (structure crystal layer), the Lewis base is placed at the grain boundary of the perovskite structure.
  • the Lewis base is evenly distributed at the grain boundaries of the perovskite structure crystals, and the Lewis base crystals formed at the grain boundaries are at high temperature.
  • the oxidation of metal cations in the perovskite structure is effectively suppressed, and the perovskite structure is stabilized, thereby improving the efficiency of the solar cell.
  • FTO substrate first electrode
  • SnCl 2 ⁇ 2H 2 O was dissolved in IPA at 70 mM, spin-coated at 3000 rpm for 30 seconds, and then heat treated at 150° C. for 30 minutes to control the thickness of the thin film.
  • the perovskite precursor solution was spin-coated on the thin SnO 2 layer prepared in Preparation Example 1 at 1000 rpm for 10 seconds and at 5000 rpm for 50 seconds, and annealed at a temperature of 100° C. for 60 minutes to form a perovskite. A structural crystal layer was formed. At this time, during the second spin coating, 1 ml of diethyl ether was dropped onto the first spin-coated perovskite precursor solution.
  • a chloroform solution containing 3 mmol of 4-dimethylaminopyridine (DMAP, pKa value in water (25° C.): 9.6) was applied on the perovskite structure crystal layer prepared above, which had been cooled after annealing, and was rotated at 5000 rpm. After spin coating for 30 seconds, it was annealed again at 100° C. for 5 minutes to form 4-dimethylaminopyridine crystals at the grain boundaries of the perovskite structure prepared above.
  • DMAP 4-dimethylaminopyridine
  • Bis(trifluoromethane)sulfonimide/acetonitrile (509 mg/ml) and 4-tert butylpyridine were added on the perovskite thin film layer where the Lewis base crystal was formed at the grain boundary of the prepared perovskite structure.
  • a PTAA/chloroform (10.5 mg/ml) solution containing the PTAA/chloroform (10.5 mg/ml) solution was spin-coated at 3000 rpm for 30 seconds to form a hole transport layer.
  • Au was vacuum-deposited on the top of the hole transport layer with a thermal evaporator of high vacuum (5x10 -6 torr or less) to form an Au electrode (second electrode) having a thickness of about 60 nm, and effective active The area (effective active area) was fixed at 0.096 cm2.
  • a photograph of the crystals of the DMAP powder in FIG. 1 is shown in (a), and the image of the evaporated DMAP crystals after heating the DMAP powder at 100° C. for 30 minutes is shown in (b), and the peroves prepared in Example 1 When DMAP was used on the skyte thin film, the SEM image bound through the immobilization of the defect is shown in (c).
  • Figure 2 shows the time SEM image of the perovskite thin film of Example 1
  • Figure 3 shows the SEM image of the case of not annealing (annealing) and annealing (a) when applying 4-dimethylaminopyridine .
  • the Lewis base when the Lewis base is treated without annealing after forming the perovskite structure crystal from FIG. 3 (pdmap w/o annealing, Comparative Example 1, (a)), the Lewis base is entirely at the grain boundary of the perovskite structure crystal. It can be seen that crystallization of the Lewis base occurs selectively at the grain boundary interface of the perovskite structure crystal when the Lewis base is treated (pdmap w annealing) after annealing after forming a perovskite structure crystal after irregular existence. there is.
  • Figure 4 shows the XRD diffraction patterns of DMAP, the perovskite thin film and the perovskite thin film prepared in Example 1.
  • DMAP is present on the perovskite thin film through GIWAX measurement of the perovskite thin film prepared in Example 1 in FIG. 10 .
  • Example 5 All the processes were the same as in Example 1, but in the step of forming a Lewis base crystal at the grain boundary of the prepared perovskite structure, 5 mmol (Example 2), 10 mmol (Example 3), 15 mmol (Example 4), respectively and 20 mmol (Example 5) of 4-dimethylaminopyridine solution were spin-coated and annealed on the perovskite structure crystals respectively prepared to form 4-dimethylaminopyridine crystals at the grain boundaries of the perovskite structure.
  • Example 5 shows SEM images of the perovskite thin films prepared in Example 1 (3 mmol), Example 2 (5 mmol), Example 3 (10 mmol), and Example 4 (15 mmol), It can be seen that a Lewis base crystal was formed at the grain boundary of the lobskite structure crystal.
  • Figure 6 shows the X-ray diffraction pattern for each concentration of 4-dimethylaminopyridine of the perovskite thin film.
  • FIG. 7 is a graph showing the change of TCSPC (Time-Correlated Single Photon Counting) using the perovskite thin film prepared in Examples 2 to 5 of the present invention. It can be seen from Figs. 5 and 6 that a perovskite thin film was formed, and from Fig. 7, as the treatment concentration of DMAP of the present invention increased, defects of the perovskite structure crystal were passivated and the lifespan was increased. there is.
  • TCSPC Time-Correlated Single Photon Counting
  • Example 1 except that the primary heat treatment was not carried out in the step of forming the perovskite structure crystal, in the same manner as in Example 1, except that the perovskite thin film and the same were used.
  • a perovskite solar cell was prepared by carrying out an SEM photograph (pdmap w/o annealing) of the prepared perovskite thin film is shown in FIG. 3 .
  • Example 1 To measure the current-voltage characteristics of the solar cells prepared in Example 1 and Comparative Example 1, an artificial solar device (ORIEL class A solar simulator, Newport, model 91195A) and a source-meter (Kethley, model 2420) ) was used.
  • ORIEL class A solar simulator Newport, model 91195A
  • source-meter Karl Fischer, model 2420
  • the bonding force between the perovskite thin film and the hole transport layer formed on the perovskite thin film of the perovskite solar cell prepared in Example 1 was measured by the double cantilever beam (DCB) test method, and the results are shown in FIG. 8 shown in
  • the adhesion between the perovskite thin film of the present invention and the hole transport layer is compared with the adhesion between the perovskite thin film and the hole transport layer of Comparative Example 1 (indicated by bare)
  • the improvement is remarkable.
  • the DMAP present at the grain boundary of the perovskite structure of the perovskite thin film of the present invention improves the adhesion, and the increase in the adhesion force allows the perovskite electronic device to have excellent durability.

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Abstract

La présente invention concerne un film mince de pérovskite comportant un joint de grain cristallin passivé, son procédé de préparation, et un film mince de pérovskite le comprenant, le film mince de pérovskite comprenant : une structure de pérovskite cristalline ; et une base de Lewis cristalline formée sur le joint de grain de la structure de pérovskite cristalline. Un dispositif électronique utilisant le film mince de pérovskite de la présente invention possède des propriétés étonnamment améliorées.
PCT/KR2021/011034 2020-08-19 2021-08-19 Film mince de pérovskite comportant un joint de grain cristallin passivé, son procédé de préparation et dispositif électronique le comprenant Ceased WO2022039522A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2020-0103712 2020-08-19
KR20200103712 2020-08-19
KR10-2021-0108514 2021-08-18
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CN114665027A (zh) * 2022-03-18 2022-06-24 中山大学 一种基于4-乙炔基哌啶盐酸盐的钙钛矿太阳能电池钝化方法
CN116528599A (zh) * 2023-05-15 2023-08-01 长江三峡集团实业发展(北京)有限公司 一种多齿配体改性的钙钛矿太阳能电池及其制备方法
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CN120826146A (zh) * 2025-09-08 2025-10-21 中矿资源(天津)新材料有限公司 基于吡啶硫醚衍生物钝化的钙钛矿太阳能电池及制备方法

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