WO2015099412A1 - 무/유기 하이브리드 페로브스카이트 화합물 전구물질 - Google Patents

무/유기 하이브리드 페로브스카이트 화합물 전구물질 Download PDF

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WO2015099412A1
WO2015099412A1 PCT/KR2014/012727 KR2014012727W WO2015099412A1 WO 2015099412 A1 WO2015099412 A1 WO 2015099412A1 KR 2014012727 W KR2014012727 W KR 2014012727W WO 2015099412 A1 WO2015099412 A1 WO 2015099412A1
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precursor
organic
perovskite compound
precursor material
ion
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English (en)
French (fr)
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석상일
노준홍
전남중
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Korea Research Institute of Chemical Technology KRICT
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Korea Research Institute of Chemical Technology KRICT
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Priority claimed from KR1020140055845A external-priority patent/KR20150073821A/ko
Application filed by Korea Research Institute of Chemical Technology KRICT filed Critical Korea Research Institute of Chemical Technology KRICT
Priority to KR1020187021016A priority Critical patent/KR101966245B1/ko
Priority to CN201480070171.XA priority patent/CN105830228B/zh
Priority to JP2016538008A priority patent/JP6339203B2/ja
Priority to KR1020167016633A priority patent/KR101893493B1/ko
Priority to US15/102,403 priority patent/US10243141B2/en
Publication of WO2015099412A1 publication Critical patent/WO2015099412A1/ko
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/006—Compounds containing lead, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

  • the present invention relates to precursors of non-organic hybrid perovskite compounds
  • the present invention relates to a light absorber precursor material of a solar cell including an inorganic / organic hybrid perovskite compound as a light absorber.
  • Organic / organic hybrid perovskite compounds also referred to as organometal halide perovskite compounds, consist of organic cations (A), metal cations (M), and halogen anions (X). becomes, "it is a substance represented by the formula medicinal chemistry AMX 3 having a perovskite structure in detail.
  • the inorganic / organic hybrid pe ⁇ skite compound represented by the chemical formula of AMX 3 is a form of A organic cation interposed in a three-dimensional network of MX 6 octahedron.
  • Perovskite compounds have the advantage of self-assembling and self-assembling crystallization, which allows the processing of hot solutions.However, the crystallization rate is very fast and it is difficult to control the self-assembly characteristics. There is a problem that is difficult to manufacture dense thin films with.
  • the problem is that the surface roughness of the perovskite compound film is very large.
  • An object of the present invention is to provide an inorganic / organic hybrid perovskite compound precursor and a membrane thereof capable of producing an inorganic / organic hybrid perovskite compound film by reaction.
  • the purpose of the present invention is thick radish / organic hybrid perovskite
  • the present invention provides an inorganic / organic hybrid perovskite compound precursor capable of producing a compound film, a film of coarse grains, and a film having a dense and smooth surface.
  • Another object of the present invention is to prepare an inorganic / organic hybrid perovskite compound film using an inorganic / organic hybrid perovskite compound precursor.
  • Another object of the present invention is to prepare an inorganic / organic hybrid perovskite compound film prepared using an organic / organic hybrid perovskite compound precursor.
  • the precursors of the inorganic / organic hybrid perovskite compounds according to the present invention contain organic cations, metal cations, halogen anions and guest molecules (GM).
  • the precursor according to one embodiment of the present invention is X-ray diffraction using Cu-? ⁇ rays.
  • diffraction peaks can be detected at diffraction angles 2 ⁇ of 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °.
  • the guest molecule may be a solvent for dissolving the inorganic / organic hybrid perovskite compound.
  • the precursor may be a solvent compound between an inorganic / organic hybrid perovskite compound and a solvent.
  • the guest molecule may be a solvent containing one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine.
  • the guest molecule In the precursor material according to an embodiment of the present invention, the guest molecule
  • One or more may be selected from dimethyl sulfoxide (DMSO) and ⁇ , ⁇ -dimethylformamide (DMF).
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • the precursor material according to the embodiment of the present invention may satisfy the following Formula 1. [18] (Formula 1)
  • A is an organic ammonium ion, an amidinium group ion, or an organic ammonium ion and an amidinium ion . It is a divalent metal ion, X is halogen or silver, and is a real number with 0 ⁇ ⁇ 3.
  • X a and X b are different halogen ions selected from iodine ion (I), chlorine ion (C1-) and bromine ion (Br), and y may be a real number with 0 ⁇ y ⁇ l.
  • the precursor material according to the embodiment of the present invention may be for a solar cell light absorber.
  • the present invention relates to a dispersion or a precursor containing the above precursor.
  • the present invention provides a method for manufacturing a solar cell photoabsorber using the above-described precursors.
  • a method of manufacturing a light absorber comprises the steps of applying or depositing a precursor material on the substrate to form a precursor material layer; and applying energy to the precursor material layer to volatilize guest molecules.
  • Removing may include.
  • the precursor material according to the present invention is a single bulb material, which is free from organic hybrids.
  • Perovskite compounds can be prepared and can be converted into inorganic / organic hybrid perovskite compounds by removal of guest molecules, making it possible to produce inorganic / organic hybrid perovskite compound films with fine and excellent crystallinity. There is this.
  • a dense membrane of high quality inorganic / organic hybrid perovskite compounds can be produced at low cost, and the membrane quality does not change sensitively with the change of process variables. It is very easy to maintain the quality, and has the advantage of making a large-area obligation / dense film of organic hybrid perovskite compound.
  • the light absorber which is a perovskite compound
  • FIG. 2 is an FTIR transmission of a precursor material powder prepared according to one embodiment of the present invention.
  • FIG. 3 is a diagram showing the results of X-ray diffraction according to temperature of precursor material powders prepared according to one embodiment of the present invention.
  • FIG. 4 is a diagram showing the X-ray diffraction results of the precursor material thin film manufactured according to an embodiment of the present invention
  • FIG. 5 is a scanning electron microscope photograph of the perovskite compound thin film prepared from the precursor material thin film manufactured according to the embodiment of the present invention.
  • the present invention relates to a Korean application number 2013-0110020 and a Korean application number.
  • the present applicant is responsible for converting a radiant / organic hybrid perovskite compound into a light absorber.
  • perovskite-based solar cells including inorganic and organic hybrid perovskite compounds.
  • One of the main advantages of the organic / organic hybrid perovskite compound is that it can be applied with a solution coating method.
  • crystallization to an organic / organic hybrid perovskite compound is possible with the solution coating method.
  • the reality is that the speed is very fast, it is difficult to control the self-assembly characteristics, and it is very difficult to manufacture a dense film with a flat surface.
  • the inorganic / organic hybrid perovskite compound contains monovalent organic cations (A), divalent metal cations (M), and halogen anions (X), and has a perovskite structure. It can mean a compound with.
  • the organic / organic hybrid perovskite compound is located at the center of a unit cell in the M-perovskite structure, and X is located at the center of each side of the unit cell, with M being the center.
  • a may be located at each corner (corner) of a unit of Sal. If above it again, ⁇ ⁇
  • the octahedron may be in a corner-shearing three-dimensional network where A organic cations are intercalated.
  • perovskite compound Also referred to as perovskite compound.
  • precursor material the precursor of the inorganic / organic hybrid perovskite compound.
  • the perovskite compound may satisfy the following formula (1).
  • A is a monovalent cation
  • A is an organic ammonium ion
  • Amidinium group ions or organic ammonium ions and amidinium-based ions M is a divalent metal ion
  • X is a halogen ion, wherein the halogen silver is in ⁇ , Br, F- and C1- One or more can be selected.
  • the organic ammonium silver may satisfy the following Chemical Formulas 1-1 to 1-2.
  • R is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl.
  • R 2 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20 aryl, R 3 is hydrogen or C1-C24 alkyl.
  • amidinium-based ions may satisfy the following Formula 1-3.
  • R 4 to R 8 are independently of each other hydrogen, alkyl of C1-C24, cycloalkyl of C3-C20 or aryl of C6-C20.
  • A may be an organic ammonium silver, an amidinium group ion, or an organic ammonium silver or an amidinium ion.
  • A may be an organic ammonium silver, an amidinium group ion, or an organic ammonium silver or an amidinium ion.
  • the charge mobility of the perovskite compound can be significantly improved.
  • A contains both organic ammonium ions and amidinium ions
  • the total molar number of monovalent organic cations is 1, and contains 0.7 to 0.95 amidinium ions and 0.3 to 0.05 organic ammonium ions.
  • A is A x) A
  • a a is an amidinium ion
  • a b is an organic ammonium ion
  • X can be a real number from 0.3 to 0.05.
  • the molar ratio of organoammonium ions i.e., 0.7 to 0.95 moles of amidinium-based ions: 0.3 to 0.05 moles of organic ammonium ions, is capable of absorbing very broad wavelengths of light, This is the range where separation, faster optoelectronics and light holes can be made.
  • R 2 to R 3 of Formula 1-2 and / or R 4 to R S of Formula 1-3 are
  • the perovskite compound i.e., the light absorbing layer of the solar cell.
  • the unit cell size of the perovskite compound is related to the band gap and may have a bandgap energy of 1.5 to 1.1 eV suitable for use as a solar cell in a small unit size.
  • R may be C1-C24 alkyl, specifically C1-C7 alkyl, more specifically methyl.
  • R 2 can be C1-C24 alkyl and R 3 can be hydrogen or C1-C24 alkyl, specifically 3 ⁇ 4 can be C1-C7 alkyl and 3 ⁇ 4 can be hydrogen or C1-C7 alkyl, more specifically 3 ⁇ 4 may be methyl and R 3 may be hydrogen.
  • organic cationic (A) are an example of the use of the perovskite compound film, that is, the application to the light absorbing layer of sunlight, and the design and emission of the wavelength band of the light to be absorbed.
  • the light-emitting layer of the device design of the emission wavelength band in the case of using a semiconductor device of the transistors in consideration of the energy band gap and the threshold voltage (threshold voltage) of formula 1-2, such as of formula 1-1 R 2 ⁇ R 3 And / or 3 ⁇ 4 to 3 ⁇ 4 of formula 1-3 may be appropriately selected.
  • M is a divalent metal ion days.
  • M is M is Cu 2 +, Ni 2+, Co 2+, Fe 2+, Mn 2+, Cr 2+, Pd 2 It may be one or more metal ions selected from + , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ and Yb 2+ .
  • X is a halogen anion.
  • the halogen anion may be selected from one, two or more of I, Br, F, and C1-. Specifically, the halogen anion is iodine (I), chlorine (C1-). ) And bromine ions (Br) may contain one or more selected ions. More specifically, halogen anions may contain iodine ions and bromine ions. Halogen anions contain both iodide and bromine ions. In this case, the crystallinity and moisture resistance of the perovskite compound can be improved.
  • X may be X y) X b y , and X a and X b may be each other.
  • Different halogen ions (different halogen ions selected from iodine ion (1), chlorine ion (C1-) and bromine ion (Br)), and y may be a real number of 0 ⁇ y ⁇ l.
  • X may be X y) X h y
  • X b is bromine ion
  • y may be a real number of 0.05 ⁇ y ⁇ 0.3, specifically 0.1 ⁇ x ⁇ 0.15. Deterioration by moisture can be significantly prevented and the crystallinity of the perovskite compound can be improved.
  • the precursor is a precursor of the perovskite compound described above, and an organic cation, a metal cyanide, a halogen cyanide (X), and a guest molecule (hereinafter, GM).
  • the organic cationic silver, metal ions and halogen anions contained in the precursor are
  • the perovskite compound may be identical to the monovalent organic cations (A), divalent metal ions (M) and halogen anions (X) described above, a detailed description thereof is omitted.
  • the precursor material is amorphous, crystalline, or amorphous and crystalline.
  • the precursor material may be crystalline.
  • the precursor material according to the embodiment of the present invention is diffracted at an X-ray diffraction measurement using Cu-Koc rays, at a refraction angle 2 ⁇ of 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °. Peaks can be detected, where peaks in the range of 5 ° ⁇ 2 ⁇ 40 °
  • Peak strengths of 8.9 to 9.5 ° or 7 to 7.5 ° may be the highest.
  • the precursor material according to one embodiment of the present invention is transferred to a sharp perovskite phase.
  • GM which can prevent conversion, may be in the form of a complex formed by coexistence with A organic cations, M metal cations, and X halogen anions, i.e., the precursors are those in which GM contains A organic cations, M metal cations, and X halogen anions. It may be in the form of a complex formed in combination with a perovskite compound ( ⁇ 3 ).
  • the bond between the perovskite compound and the GM may be a non-covalent bond, and GM is non-covalently bound to one or more selected cations from monovalent organic cations (A) and divalent metal cations (M). It may be a state.
  • the guest molecule may be a solvent that dissolves the perovskite compound.
  • the precursor material may be a perovskite compound and a solvent compound and a solvent compound thereof.
  • Solvent compounds may mean higher order compounds formed between molecules or ions of the solute (perovskite compound) and the molecules or ions of the solvent.
  • the solvent for dissolving the perovskite compound may mean a polar organic solvent, and at 20 ° C 1 atm, solubility of the perovskite compound is 0.5 M or more, specifically, 0.8 M or more. Can mean.
  • the precursor is a solvent compound of the perovskite compound and the solvent that dissolves it, it can be homogeneously and quickly removed at low temperatures and converted into a perovskite compound.
  • the solvent may be a non-covalently bound solvent compound of the skye compound and the GM, and the GM may be a solvent containing one or more elements selected from oxygen, nitrogen, fluorine, chlorine, bromine and iodine containing a non-covalent electron pair.
  • a solvent containing and dissolving a perovskite compound As an example of a solvent containing and dissolving a perovskite compound,
  • DMSO Dimethyl sulfoxide
  • DMF dimethylformamide
  • guest molecules ⁇ , ⁇ -dimethylformamide (DMF; dimethylformamide) or mixtures thereof, i.e. guest molecules
  • One or more may be selected from dimethyl sulfoxide (DMSO) and ⁇ , ⁇ -dimethylformamide (DMF), in which the volume is converted to perovskite compounds upon removal of GM.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • the guest molecule is preferably dimethyl sulfoxide (DMSO).
  • the precursor according to an embodiment of the present invention may satisfy the following formula (2).
  • A is an organic ammonium ion, an amidinium group
  • M is a divalent metal ion
  • X is a halogen ion
  • A, ⁇ , and X are represented by Formula 1. The same as A, ⁇ and X described above.
  • the precursor according to Chemical Formula 2 is removed by GM by external energy, and can be converted into a perovskite compound according to Chemical Formula 1.
  • A is A x) A b x
  • a a is an amidinium-based ion
  • a b is an organic ammonium ion
  • X is 0.
  • X is X y ⁇ X b y
  • X is a different halogen ion selected from iodine chlorine ion (C1-) and bromine ion (Br)
  • y is 0 ⁇
  • X is X y) X b y
  • X a is iodine ion
  • X b is a brine ion
  • y is a real number of 0 ⁇ > 1, specifically, 0.05 It may be a real number ⁇ y ⁇ 0.3, more specifically 0.1 ⁇ y ⁇ 0.15.
  • Perovskite Compounds By the energy applied to the precursor, the guest molecules are removed and converted into crystalline perovskite compounds.
  • the precursor is a complex compound of perovskite compound and GM, it is converted into pure perovskite compound by removing GM by energy application. Can be switched.
  • the precursor material according to one embodiment of the present invention may be for a solar cell light absorber.
  • the present invention relates to a dispersion or a precursor containing the above-mentioned precursor.
  • the dispersions or inks may, of course, contain further known additives so that they may have properties suitable for the application or printing method.
  • the precursor is a non-solvent dripping of a first solution containing an organic cation, a metal cation, a halogen ion and a guest molecule according to the stoichiometric ratio of the perovskite compound; and a solid obtained by the drop.
  • the precursor is a complex of perovskite compound and GM, and the precursor is similar to the perovskite compound in organic solvents (solubility, etc.). Therefore, it can be used as the solvent of the solvent system 1, which dissolves the normal perovskite compound.
  • the solvent that dissolves the precursor material is a solvent that dissolves the perovskite compound and is easily volatile-removable, Can be used.
  • the solvent of the first solution may be a guest molecule, ie, the first solution may be prepared by dissolving an organic cation, a metal cation, and a halogen ion in a solvent that is a guest molecule.
  • the precursor material is similar to the perovskite compound for organic solvents.
  • the nonsolvent can mean an organic solvent that does not dissolve the perovskite compound, meaning that it does not dissolve the perovskite compound at 20 o C 1 atm,
  • An organic solvent having a solubility of perovskite compound of less than 0.1 M, specifically less than 0.01 M, and more specifically less than 0.001 M may be used.
  • An example of a nonsolvent in which the first solution is deposited is a nonpolar organic solvent.
  • Non-polar organic solvents are pentine, nucleene, cyclonuxene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform, ethyl acetate, acetic acid, 1,
  • One or more organic solvents may be selected from 2-dichlorobenzene, tert-butyl alcohol, 2-butanol, isopropanol and methyl ethyl keron, but the present invention is not limited by non-solvents. It is possible to improve the productivity by increasing the concentration of the content of the C solution 1, but the concentration of the first solution may be any concentration so long as the stoichiometric ratio is satisfied within the solubility range of each solute.
  • the recovery of solid phase is sufficient using the method used for normal solid-liquid separation, for example, but not limited to filtering, centrifugation, etc. Drying does not limit the precursors to thermal and safe damage. Range is sufficient. For example, drying It can be performed at room temperature to 50 ° C.
  • the present invention provides a method for manufacturing a solar cell photoabsorber using the above-described precursors.
  • a method of manufacturing a light absorber comprising: applying or depositing a precursor material on a substrate to form a precursor material layer; and applying energy to the precursor material layer to volatilize guest molecules.
  • Removing may include.
  • a dispersion or ink in which a precursor material is dissolved or a perovskite compound precursor material is applied onto a substrate and then dried to form a precursor layer, followed by removing GM from the precursor layer.
  • the layer can be converted to a perovskite compound layer.
  • the precursor when the precursor is a solvent compound, organic cationic, metallic cationic and halogen ions according to the stoichiometric ratio of the perovskite compound or perovskite compound are added to the guest molecule (GM) phosphorus solvent. After dissolving to prepare a solution, the prepared solution is applied onto the substrate and the non-solvent is reapplied to the coating film, whereby a precursor layer containing the precursor can be produced.
  • GM guest molecule
  • the application of the solution, the dispersion or the ink may be screen printing;
  • the energy applied to the precursor layer may include thermal energy, light energy, vibration energy, etc.
  • the amount of energy applied is sufficient to break the bond between the perovskite compound and the GM and to remove the volatilization of the GM.
  • the upper limit of the heat treatment for converting the precursor to the perovskite compound may be such that the substrate to form the perovskite compound is not thermally damaged.
  • the heat treatment can be carried out at 100 to 200 ° C.
  • the heat treatment time is sufficient to allow the precursor to be sufficiently converted to perovskite compound, taking into account the heat treatment temperature.
  • perovskite Dense perovskite compounds that are difficult to control kinetics of crystallization when crystallized from A + M + 3X-> AMX 3 by volatilization of A, M, and X solvents in solution There is a problem that it is difficult to form a membrane.
  • perovskite is not directly formed. It is easy to control perovskite formation kinetics because the perovskite precursor (AM (GM)êtX 3 ) is produced first and then the perovskite is formed by the removal of GM. It is possible to form perovskite films with low surface roughness.
  • the substrate on which the precursor layer is formed is based on its use, and the basic structure necessary for the operation of electronic devices, optical devices, solar cells, or sensors, etc., and other components (structures) other than the perovskite compound film are already present. It can be a formed substrate.
  • the substrate includes a support body substrate; a first electrode positioned on the substrate; and a substrate positioned on the first electrode.
  • the substrate on which the precursor layer is formed is sequentially formed of a substrate, a first electrode, and an electron carrier.
  • It may include stacked laminates.
  • the substrate may be a rigid substrate or a flexible substrate.
  • the substrate may be a rigid substrate or polyethylene comprising a glass substrate.
  • PET Terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • PC Polycarbonate
  • PP polypropylene
  • TAC triacetylsalose
  • It may be a flexible substrate including polyether sulfone (PES) or the like. However, it cannot be limited by the type of substrate of the present invention.
  • PES polyether sulfone
  • the first electrode may be a conductive electrode in ohmic contact with the electron carrier.
  • the first electrode may be a back electrode.
  • the electrode material may be one or more selected from gold, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and a combination thereof.
  • the first electrode is transparent.
  • fluorine-containing tin oxide FTO;
  • Inorganic conductive electrodes such as Fouorine doped Tin Oxide), Indium doped Tin Oxide (ITO), ZnO, CNT (Carbon Nano-Lube), and Graphene, and organic conductive electrodes such as PEDOT: PSS.
  • the first electrode is a transparent electrode, and when the first electrode is an organic conductive electrode, it is better when providing a flexible solar cell or a transparent solar cell.
  • the first electrode may be formed by depositing or applying a substrate electrode material.
  • the first electrode can be formed using the method used to form the front electrode or the back electrode in a conventional solar cell.
  • the electron carrier located on the first electrode may be an electron conductive organic material layer or an inorganic material.
  • Electroconductive organics may be organics used as ⁇ - type semiconductors in conventional organic solar cells. In one specific and non-limiting example, the electroconductive organics are fullerenes (C60, C70, C74, C76, C78, C82). , C95),
  • PCBM ([6,6] -phenyl-C61butyric acid methyl ester)
  • C71-PCBM C84-PCBM
  • PC 70 BM [6,6] -phenyl C 70 -butyric acid methyl ester
  • Electroconductive inorganic materials are commonly used in quantum dot-based solar cells or dye-sensitized solar cells. It may be an electron conductive metal oxide used for the transfer. In one embodiment, the electron conductive metal oxide may be an n-type metal oxide semiconductor.
  • Non-limiting example of n-type metal oxide semiconductor Ti oxide, ⁇ oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide, Yr oxide, La
  • oxides V oxides, A1 oxides, Y oxides, Sc oxides, Sm oxides, Ga oxides, In oxides and SrTi oxides, and their mixtures or composites thereof.
  • the electron transporter can be either a porous layer or a dense layer.
  • the electron transporter may be a film of the above-mentioned electron conductive organic material or a dense film (fihn) of the electron conductive inorganic material.
  • the porous electron transporter may be formed of particles of the above-described electron conductive inorganic material. It can be 50 nm to ⁇ , specifically 50 nm to lOOOnm. If the electron carrier is porous, its specific surface area can be 10 to 100 mVg, and the average particle diameter of the metal oxide particles forming the electron carrier can be 5 to 500 nm.
  • the porosity (apparent porosity) of the porous electron transporter can be 30% to 65%, specifically 40% to 60%.
  • the electron transport film may be further equipped.
  • the electron transport film may play a role of transferring electrons simultaneously with the role of preventing the direct contact between the light absorber and the first electrode.
  • the electron transport film may have a porosity on the energy band diagram.
  • the electron transfer film may be a metal oxide thin film, and the metal oxide of the metal oxide thin film may be a metal of the porous metal oxide.
  • the oxide may be the same material as the oxide.
  • the metal oxide thin film may be formed of Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Ba oxide, Zr oxide, Sr oxide. , Yr oxide, La oxide, V oxide, A1 oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, In oxide, SrTi oxide, a mixture of these stones, and combinations thereof may be one or more selected materials.
  • the electron transporter may be formed by application or deposition. Specifically, the electron transporter may be dried by applying a solution in which the electron transporter material is dissolved or a dispersion (or slurry) in which the electron transporter material is dispersed, or selectively heat-treated the dried product.
  • the deposition can be made using physical vapor deposition or chemical vapor deposition.
  • the porous electron transporter more specifically, the electron transporter
  • Slurry containing metal oxide particles may be applied over the first electrode, dried and heat-treated.
  • the coating of the slurry may be carried out by screen printing; Spin coating; Bar coating; Gravure coating; It can be carried out in one or more selected ways in blade coating; and roll coating.
  • the electron carriers can be formed using a method of forming porous electron carriers of metal oxides known in conventional dye-sensitized positive cells or organic solar cells.
  • a precursor layer is formed and energy is applied to the light absorbing layer of the perovskite compound.
  • the converting step can be performed.
  • [117] Fills the pores of the porous electron transporter, forms a precursor layer in the form of a membrane covering the porous electron transporter, converts it into a perovskite compound, fills the pores of the porous electron transporter, and covers the entire surface of the porous electron transporter.
  • a light absorbing layer having a dense membrane structure can be produced, wherein the thickness of the dense membrane is lmn to
  • the hole transport layer and the second electrode are sequentially disposed on the dense layer of the light absorption layer.
  • the forming step can be performed.
  • the hole transport layer is an organic hole transport material, specifically, monomolecular and high molecular organic.
  • Hole transport material (hole conducting organic material) ⁇ may be included.
  • Organic hole transport material is a conventional non-conductor based solar cell that uses inorganic J semiconductor quantum dots as dyes.
  • Any organic hole transport material used may be used.
  • polymer organic matters in terms of energy matching and stability with a light absorber, a perovskite compound, may be used.
  • [12 is a non-limiting example of a monomolecular to small molecule organic hole transport material.
  • the organic hole transport material is preferably a polymer (hole conducting polymer), which not only ensures stable solar cell operation, but also improves power generation efficiency by energy matching with a light absorber.
  • a polymer hole conducting polymer
  • thiophene-based, paraphenylenevinylene-based, carbazole-based and triphenylamine-based materials may be selected.
  • At least one or more selected from triphenylamines is preferred.
  • P3HT poly [3-hexylthiophene]
  • MDMO-PPV poly [2-methoxy-5- (3 ', 7'-dimethyloctyloxyl)]-1,4-phenylene vinylene
  • MEH-PPV poly [2-methoxy
  • TFB poly (9,9'-dioctylfluorene-co-N- (4-buty lpheny l) diphenyl amine
  • Polyaniline Spiro-MeOTAD ([2,22 ', 7,77'-tetrkis (N, N-di -p-raethoxyphenyl amine) -9,9,9'-spirobi fluorine]
  • PCPDTBT Poly [2, 1,3-benzothiadiazole-4,7-diyl [4,4-bis (2-ethylhexyl-4H-cyclopenta)] [2, 1 -b: 3, 4-b '] dithiophene-2,6-diyl]]
  • Si-PCPDTBT poly [(4,4 , -bis (2-ethylhexyl) dithieno [3,2-b: 2 ', 3'-d] silole) -2,6-diyl-alt- (2, l, 3-benzothiadiazole) -4,7-diyl]
  • PBDTTPD poly ((4,8-diethylhexyloxyl)
  • PFO-DBT poly [2,7-.9,9- (dioctyl-fluorene) -alt-5,5- (4 ', 7'-di-2-.thienyl-2', 1 ',
  • PSiFDTBT poly [(2,7-dioctylsilafluorene) -2,7-diyl-alt- (4,7-bis (2-thienyl) -2, l, 3-benzot hiadiazole) -5,5'-diyl]
  • PSBTBT poly [(4,4'-bis (2-ethylhexyt) dithieno [3,2-b: 2 ', 3'-d] silole) -2,6-diyl-alt- (2, l, 3- b enzothiadiazole) -4,7-diyl]
  • PCDTBT Poly [[9- (l-octylnonyl) -9H-carbazole-2,7-diyl] -2,5-thiophenediyl-2,1,3-benzothiadiazole- 4,7-diyl-2,5-thiophenediyl]),
  • Poly (4-butylphenyl-diphenyl-amine) and their copolymers may include one or more selected materials.
  • the thickness of the hole transport layer may be between l (] nm and 500 mn.
  • the hole transport layer may further include additives commonly used to improve properties such as nonconductor-based solar cells or organic solar cells that use conventional non-conductor quantum dots as dyes to improve conductivity of organic-based hole conductive layers. Yes, of course.
  • the hole carriers are tertiary butyl pyridine (TBP), lithium bis (trifluoro methanesulfonyl) imide (LiTFSI), and
  • One or more additives selected from Tris (2- (lH-pyrazol-l-yl) pyridine) cobalt (III) may further contain additives, and may contain from 0.05 mg to lOOmg additive per lg organic hole transporter.
  • the present invention can not be limited by the presence or absence of additives in the hole transport layer, the type of additives and the content of the additives.
  • the second electrode may be used as long as it is a material commonly used as an electrode material of a front electrode or a back electrode in a solar cell.
  • the second electrode when the second electrode is an electrode material of a back electrode, the second electrode may be used. It may be one or more materials selected from silver, silver, platinum, guaradium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide and combinations thereof.
  • the second electrode may be a transparent electrode.
  • the second electrode may be made of non-mechanical conductivity such as fluorine-containing tin oxide (FTO), indium doped tin oxide (ITO; It may be an electrode, or an organic conductive electrode such as PEDOT: PSS. If you want to provide a transparent solar cell, a flexible solar cell or transparent solar is required if the second electrode is 3 ⁇ 4, which is a transparent electrode, and the second electrode is an organic conductive electrode. Better than when you want to provide a battery.
  • FTO fluorine-containing tin
  • the second electrode may be formed by using deposition or coating.
  • the lower 12 electrodes are used for the front electrode or the back electrode in a conventional solar cell. Of course, it can be formed using the method used to form.
  • the present invention includes a solar cell manufactured by the above-described manufacturing method.
  • a solar cell includes a substrate and a first electrode positioned on the substrate;
  • a porous electron transporter positioned on the first electrode; a light absorbing layer comprising a perovskite art compound, which is a dense film covering the pores of the porous electron transporter and covering the porous electron transporter; a hole transporting layer located on the light absorbing layer; and on the hole transporting layer And a second electrode positioned therein, wherein the perovskite compound may be produced by removing the GM of the precursor material.
  • the dense film of the perovskite compound in the light absorption layer may be lnm to ⁇ .
  • Pbl 2 powder was introduced into a methylsulfoxide (DMSO) solvent and the mixture was stirred at 60 ° C. for 2 hours.
  • DMSO methylsulfoxide
  • the precipitated powder was collected by filter paper and dried for 1 hour at room temperature.
  • CH 3 NH 3 I (hereinafter referred to as MAI) and Pbl 2 powder were introduced into a solvent of dimethyl sulfoxide (DMSO) at a stoichiometric ratio of 1: 1, and stirred at 60 ° C. for 2 hours to give 8 M CH 3.
  • DMSO dimethyl sulfoxide
  • a NH 3 I-PbI 2 -DMSO solution was prepared. The solution was dropped-wise in luene, and then the precipitated powder was collected and separated by filter paper and dried at room temperature for 1 hour.
  • the powder prepared in Comparative Example 1, the precursors MAI, Pbl 2 and the powder obtained in Example 1 were subjected to X-ray diffraction analysis using Cu Ka rays, which are shown in FIG. 1.
  • the powder prepared in Comparative Example 1 is PbI 2 (DMSO) 2 as reported by H. Miyatnae. Chemistry Lett., 9, 663, 1980).
  • the XRD results of this PbI 2 (DMSO) 2 and the XRD results of the powder prepared in Example 1 showed that the powder obtained in Example 1 was different from the PbI 2 (DMSO) 2 phase.
  • the powder obtained in Example 1 exhibited strong diffraction peaks at diffraction angles 2 ⁇ , 6.2 to 6.8 °, 7 to 7.5 °, and 8.9 to 9.5 °.
  • the powder obtained in Example 1 was also found.
  • Example 1 The absorption spectra of each IR are shown and the absorption spectra of the IR show the absorption of S-0, CH, and NH bonds.
  • XRD and FTIR results show that the powder obtained in Example 1 is a MAI-PbI 2 -DMSO mixed crystal.
  • A MA
  • M Pb
  • GM DMSO
  • X I
  • n l in AM (GM) nX 3 presented in Formula 2.
  • XRD analysis was performed according to the heat treatment temperature to examine the transition to the phase and this is shown in FIG. 3. XRD analysis was performed in-situ, and the analysis was performed after maintaining for 1 minute for each temperature section shown. Referring to FIG. 3, at room temperature (RT), pure MAPb (DMSO) was similar to the result of FIG. It can be seen that the I 3 perovskite precursor phase is retained, but as the heat treatment temperature increases, the precursor is converted to the perovskite phase.
  • the XRD spectra at 100 ° C show a weakening of the peaks below the characteristic peak of the precursor, and at the same time a peak near 14 °, a perovskite feature, which is around 100 ° C.
  • a MAI-PbI 2 -DMSO solution was prepared. That is, the volume ratio of GBL'OMSO was 7: 3 and a solution of 0.8 M concentration was prepared based on MAPbI 3 .
  • the prepared MAI-PbI 2 -DMSO solution (total 1 ml) was collectively applied (injected) at the center of rotation on a fused silica substrate, and spin coating was started at 5000 rpm. After 50 seconds, the non-solvent toluene (lmL) was applied to the center of rotation of the porous electrode in the spin state, and then spun coating was further performed for 5 seconds. and dried for a time. Then, the temperature and 25% of 25 0 C and heat treated at a temperature and pressure conditions of 100 ° C for 30 minutes perovskite compound thin film was formed on the phosphorescent light absorber. in the manufacture of a light absorbing thin film surrounding environment The costume humidity was maintained.
  • a thin film was prepared in the same manner as in Example 1, except that 100% gamma-butyrolactone (hereinafter, GBL) was used except for DMSO (MAI-PbI 2 -GBL solution) except for DMSO.
  • GBL gamma-butyrolactone
  • DMSO MAI-PbI 2 -GBL solution
  • the XRD spectrum of the prepared thin film shows that in Example 2, the precursor material-specific pick was observed in the manufactured thin film, but this pick was not observed when pure GBL was used. It can be seen that a membrane of (DMSO) I 3 perovskite precursor was formed.
  • FIG. 5 is a scanning electron micrograph of the perovskite membrane after heat treatment in Example 2 (FIG. 5 (a)) and Comparative Example 2 (FIG. 5 (b)). According to the relationship, the perovskite compound was formed through the precursor phase, and in Comparative Example 2, the perovskite compound was directly formed in the solution. As shown in FIG. 5, the perovskite membrane was formed in the precursor thin film. It can be seen that the perovskite compound is formed in the form of a dense and perfect film when converted to.
  • Pilkington (hereinafter referred to as FTO substrate (first electrode)) was cut to a size of 25 x 25 mm, and the end was etched to partially remove the FTO.
  • a 50 nm thick ⁇ 02 dense film was prepared by spray pyrolysis on a cut and partially etched FTO substrate.
  • the spray pyrolysis was performed using a TAA (Titanium acetylacetonate): EtOH (l: 9 v / v) solution.
  • the thickness was adjusted by repeating the method of spraying for 3 seconds and stopping for 10 seconds on the FTO substrate on the hot plate maintained at 450 ° C.
  • Ethyl cellulose (ethyl cellulose) in 50 nm Ti0 2 powder prepared with an aqueous solution of titanium peroxocomplex dissolved in 1% by weight on a Ti02 basis at 250 ° C for 12 hours. after the 10% by weight with ethyl selreul dissolved in ethyl alcohol, the sum of the agarose solution, a common by adding 5 ml per Ti0 2 powder lg, adding the hotel pinol (terpinol) 5 g per 1 g Ti0 2 powder, ethyl alcohol Ti0 2 paste was prepared by distillation under reduced pressure.
  • Paste weight ratio of 3 (ethanol)) to prepare a 1 ⁇ 0 2 slurry for spin coating.
  • a Ti0 2 thin film on a FTO substrate spin coated with 100 rpm using a spin coating Ti0 2 slurry, followed by heat treatment at 500 ° C for 60 minutes, and then immersing the heat treated substrate in a 30 mM T1C14 aqueous solution at 60 ° C. After leaving for 30 minutes, washed and dried with deionized water and ethanol, and then heat treated at 500 ° C. for 30 minutes to prepare a 300 nm porous Ti0 2 thin film (porous electron transporter). The surface area was 33 m 2 / g and the porosity (apparent porosity) was 50%.
  • Example 2 the fused silica is manufactured and replaced by a porous electron transporter.
  • a hole transport layer was formed by spin coating the solution [15 mg (PTAA) / lmL] at 3000 rpm for 60 seconds, in which 2.31 mg of Lithium Bis (Trifluoro methanesulfonyl) Imide (LiTFSI) and 6.28 mg of TBP (PTB) were added to the PTAA solution.
  • LiTFSI Lithium Bis (Trifluoro methanesulfonyl) Imide
  • a solar cell was manufactured in the same manner as in Example 3, but a fused silica was prepared in Comparative Example 2.
  • a perovskite compound was prepared in the same manner as in Comparative Example 2 on the porous electron carrier.
  • a light absorbing layer was prepared.
  • Example 3 The solar cell prepared in Example 3 and Comparative Example 3 was prepared using AM 1.5 (100 mA / cm 2 ).
  • the photoelectric conversion characteristics were measured under the conditions, and the results are shown in Table 1.
  • the perovskite compound film prepared in Example 3 had a dense thin film covering 100% of the upper surface of the electron transporter. In this case, it was an incomplete film that could not cover the upper surface of the electron transporter to 100%. Thus, in Example 3, it showed better Jsc, Voc, and FF values and excellent photoelectric conversion efficiency.

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Abstract

본발명은 무/유기 하이브리드 페로브스카이트 화합물의 전구물질에 관한 것이며, 본 발명의 일 실시예에 따른 무/유기 하이브리드 페로브스카이트 화합물 전구물질은 유기 양이온, 금속양이온, 할로겐 음이온 및 게스트 분자 (guest molecule, GM)를 함유한다.

Description

명세서
발명의명칭:무 /유기하이브리드페로브스카이트화합물
전구물질
기술분야
[1] 본발명은무 /유기하이브리드페로브스카이트화합물의전구물질에관한
것으로,상세하게，무 /유기하이브리드페로브스카이트화합물을광흡수체로 구비하는태양전지의광흡수체용전구물질에관한것이다.
[2]
배경기술
[3] 오가노메탈할라이드페로브스카이트화합물 (Organometal halide perovskite compound)로도지칭되는무 /유기하이브리드페로브스카이트화합물은유기 양이온 (A),금속양이온 (M)및할로겐음이온 (X)으로이루어지며， ' 페로브스카이트구조를갖는 AMX3의화학식으로대표되는물질이다.상세하게. AMX3의화학식으로대표되는무 /유기하이브리드페 ^브스카이트화합물은 MX6옥타해드론 (octahedron)이코너-쉐어링 (corner-shearing)된 3차원네트워크에 A유기양이온이중간에위치한형태이다.이러한무 /유기하이브리드
페로브스카이트화합물은자기 -조립 (self-assembling)하여결정화되는특징을 가져저온용액공정이가능한장점이있다.그러나，결정화속도가매우빠르고, 자기-조립특성을제어하는것이어려워，실제편평한표면을갖는치밀한 박막을제조하기어려운문제점이있다.
[4] 이러한문제점을해결하기'위해,금속할로겐화물 (MX2)용액을도포하여
금속할로겐화물막올형성하고,금속할로겐화물막상유기할로겐화물 (AX) 용액을도포하여 MX2와 AX가적층된막을형성한후,이두막을반웅시켜 무 /유기하이브리드페로브스카이트화합물막을형성하는순차적적층 방법 (sequential deposition methode)이제안된바있다 (Chem. Mater. 13, 3283 (2001 )).그러나，이러한순차적적층방법은첫째, Pbl2로대표되는 MX2의 용해도가층분히높지못해두꺼운금속할로겐화물막의제조에문제가있으며， 둘째,고온으로 MX2용액을유지해도포하여 200nm이상의두꺼운막올얻었다 하더라도， AX와반응단계에서두께에의해충분히반웅하지못하는문제가 있다.셋째로，기존의순차적적층방법로제작된막의경:우，두막의반웅시큰 부피변화가야기되어，최종적으로수득되는무 /유기하이브리드
페로브스카이트화합물막표면의거칠기가매우크다는문제점이있다.특히， 막표면의거칠기는무 /유기하이브리드페로브스카이트화합물막이
광흡수층으로구비되는태양전지에서,전지의성능지수를떨어뜨리는결정적 요인들이될수있다.
[5] 발명의상세한설명
기술적과제
[6] 본발명의목적은반웅에의해무 /유기하이브리드페로브스카이트화합물 막을제조할수있는무 /유기하이브리드페로브스카이트화합물전구체및이의 막을제공하는것이다.
[7] 상세하게,본발명의목적은두꺼운무 /유기하이브리드페로브스카이트
화합물막의제조가가능하고,조대한결정립의막의제조가가능하며，치밀하고 매끈한표면을갖는막의제조가가능한무 /유기하이브리드페로브스카이트 화합물전구체를제공하는것이다.
[8] 본발명의다른목적은무 /유기하이브리드페로브스카이트화합물전구체를 이용하여무 /유기하이브리드페로브스카이트화합물막을제조하는
제조방법을제공하는것이다.
[9] 본발명의다른목적은무 /유기하이브리드페로브스카이트화합물전구체를 이용하여제조된무 /유기하이브리드페로브스카이트화합물막을
광흡수층으로포함하는태양전지및이의제조방법을제공하는것이다ᅳ
[10]
과제해결수단
[11 ] 본발명에따른무 /유기하이브리드페로브스카이트화합물의전구물질은 유기양이온，금속양이온，할로겐음이온및게스트분자 (guest molecule, GM)를 함유한다.
[12] 본발명의일실시예에따른전구물질은 Cu-Κα선을이용한 X-선회절
측정에서，회절각 2Θ가 6.2 지 6.8°， 7내지 7.5°및 8.9내지 9.5°에서회절 피크가검출될수있다.
[13] 본발명의일실시예에따른전구물질에있어，게스트분자는상기무 /유기 하이브리드페로브스카이트화합물을용해하는용매일수있다.
[14] 본발명의일실시예에따른전구물질은무 /유기하이브리드페로브스카이트 화합물와용매간의용매화합물 (solvate)일수있다.
[15] 본발명의일실시예에따른전구물질에있어，게스트분자는산소,질소，불소， 염소，브롬및요오드에서하나이상선택되는원소를함유하는용매일수있다.
[16] 본발명의일실시예에따른전구물질에있어，상기게스트분자는
Ν,Ν-다이메틸아세트아미드 (Dimethylacetaniid), 1,4-다이옥산 (dioxane), 다이에틸아민 (diethylamine),에틸아세테이트 (ethylacetate),
테트라하이드로퓨란 (tetrahydrofuran),피리딘 (pyridine),메탄올 (methanol), 에탄올 (ethanol),디클로로벤젠 (dichlorobenzene),글리세린 (glycerin),
디메틸술폭시드 (DMSO;dimethyl sulfoxide)및 Ν,Ν-다이메틸포름아미드 (DMF; dimethylformamide )에서하나또는둘이상선택될수있다.
[17] 본발명의일실시예에따른전구물질은하기화학식 1을만족할수있다. [18] (화학식 1)
[19] AM(GM)„X3
[20] A는유기암모늄이온，아미디니움계 (amidinium group)이온또는유기암모늄 이온과아미디니움계이온이며 , Μ은.2가의금속이온이고, X는할로겐 이은이며, 0 < η < 3인실수이다.
[21] 본발명의일실시예에따른전구물질에있어，화학식 1에서, X는 Xvy>Xb y이며,
Xa및 Xb는요오드이온 (I ),클로린이온 (C1-)및브롬이온 (Br)에서선택되는서로 상이한할로겐이온이며， y는 0<y<l인실수일수있다.
[22] 본발명의일실시예에따른전구물질은태양전지광흡수체용일수있다.
[23] 본발명은상술한전구물질을함유하는분산액또는상술한전구물질을
함유하는잉크를포함한다.
[24] 본발명은상술한전구물질을이용한태양전지광흡수체의제조방법을
포함한다.
[25] 본발명의일실시예에따른광흡수체의제조방법은기재상상기전 ΐ물질을 도포또는증착하여전구물질층을형성하는단계;및상기전구물질층에 에너지를인가하여,게스트분자를휘발제거하는단계;를포함할수있다.
[26]
발명의효과
[27] 본발명에따른전구물질은단일전구물질로무 /유기하이브리드
페로브스카이트화합물을제조할수있으며，게스트분자의제거에의해무 /유기 하이브리드페로브스카이트화합물로변환될수있어치밀하고우수한 결정성을갖는무 /유기하이브리드페로브스카이트화합물막의제조가가능한 장점이있다.
[28] 또한,게스트분자를제거하는극히단순한공정으로,무 /유기하이브리드
페로브스카이트화합물의치밀막을제조할수있음에따라，저가의공정으로 고품질의무 /유기하이브리드페로브스카이트화합물의치밀막이제조될수 있고,공정변수의변화에따라민감하게막질이변화되지않음에따라품질 유지가매우용이하고,대면적의무 /유기하이브리드페로브스카이트화합물의 치밀막의제조가가능한장점이있다.
[29] 또한,본발명에따른전구물질을이용하는경우，무 /유기하이브리드
페로브스카이트화합물인광흡수체의완벽한막을형성할수있음에따라, 무 /유기하이브리드페로브스카이트화합물의박막형성제어를용이하게 함으로서박막트랜지스터 (Thin film transistor),발광소자 (Light Emitting diode), 센서，태양전지 (Solar cells)등다양한적용분야에활용될수있다.
[30]
도면의간단한설명
[31] 도 1은본발명의일실시예에따라제조된전구물질분말의 X-선회절결과를 도시한도면이며,
[32] 도 2는본발명의일실시예에따라제조된전구물질분말의 FTIR투과
스펙트럼이며，
[33] 도 3은본발명의일실시예에따라제조된전구물질분말의온도별 X-선회절 결과를도시한도면이며，
[34] 도 4는본발명의일실시예에따라제조된전구물질박막의 X-선회절결과를 도시한도면이며，
[35] 도 5는본발명의일실시예에따라제조된전구물질박막으로부터제조된 페로스카이트화합물박막을관찰한주사전자현미경사진이다.
[36]
발명의실시를위한형태
[37] 이하첨부한도면들을참조하여본발명의전구물질을상세히설명한다. 다음에소개되는도면들은당업자에게본발명의사상이층분히전달될수 있도록하기위해예로서제공되는것이다.따라서，본발명은이하제시되는 도면들에한정되지않고다른형태로구체화될수도있으며,이하제시되는 도면들은본발명의사상을명확히하기위해과장되어도시될수있다.이때， 사용되는기술용어및과학용어에있어서다른정의가없다면,이발명이 속하는기술분야에서통상의지식을가진자가통상적으로이해하고있는 의미를가지며，하기의설명및첨부도면에서본발명의요지를불필요하게 흐릴수있는공지기능및구성에대한설명은생략한다ᅳ
[38] 본발명은대한민국출원번호제 2013-0110020호및대한민국출원번호
제 2013-0110025호의모든내용을포함한다.
[39] 본출원인은무 /유기하이브리드페로브스카이트화합물을광흡수체로
포함하는페로브스카이트계태양전지의효율을향상시키고자많은연구를 수행한결과,무 /유기하이브리드페로브스카이트화합물이다공성
전자전달체의기공을채우며，다공성전자전달체를덮는매끈한표면의 치밀막의형태를가질때，태양전지의광전변환효율이극히현저하게향상됨을 발견하였다.
[40] 무 /유기하이브리드페로브스카이트화합물의주된장점증하나는，용액 도포법을이용할수있다는점이다.그러나，용액도포법을이용하는경우， 무 /유기하이브리드페로브스카이트화합물로의결정화속도가매우빠르고， 자기 -조립특성을제어하는것이어려워，편평한표면을갖는치밀한막으로 제조하기가매우어려운것이현실이다.
[41] 상술한발견을기반으로，용액도포법을이용한무 /유기하이브리드
페로브스카이트화합물막의막질향상의한계를해결하고자각고의연구를 수행한결과,종래무 /유기하이브리드페로브스카이트화합물의공정상의 장점은그대로가질수있으면서도,고품질의치밀막형태로무 /유기하이브리드 페로브스카이트화합물막의제조가가능한전구체를발견하여，본발명을 출원하기에이르렀다.
[42] 본발명을상술함에있어，무 /유기하이브리드페로브스카이트화합물은 1가의 유기양이온 (A), 2가의금속양이온 (M)및할로겐음이온 (X)을함유하며, 페로브스카이트구조를갖는화합물을의미할수있다.
[43] 상세하게，무 /유기하이브리드페로브스카이트화합물은 , Μ이페로브스카이트 구조에서단위셀 (unit cell)의중심에위치하며， X는단위셀의각면중심에 위치하여 M을중심으로옥타헤드론 (octahedron)구조를형성하며， A는단위샐의 각코너 (corner)에위치할수있다.이를다시상술하면， ΜΧή
옥타해드론 (octahedron)이코너-쉐어링 (corner-shearing)된 3차원네트워크에 A 유기양이온이증간에위치한형태일수있다.
[44] 이하의설명에서무 /유기하이브리드페로브스카이트화합물은
페로브스카이트화합물로통칭한다.또한，무 /유기하이브리드페로브스카이트 화합물의전구물질은전구물질로통칭한다.
[45] 페로브스카이트화합물은하기화학식 1을만족할수있다.
[46] (화학식 1)
[47] AMX3
[48] 화학식 1에서 , A는 1가의양이온으로， A는유기암모늄이온,
아미디니움계 (amidinium group)이온또는유기암모늄이온과아미디니움계 이온이며， M은 2가의금속이온이고, X는할로겐이온이다.이때，할로겐이은은 Γ, Br, F-및 C1-에서하나또는둘이상선택될수있다.
[49] 화학식 1에서，유기암모늄이은은하기화학식 1-1내지 1-2를만족할수있다.
[50] (화학식 1-1)
[51] R,-NH3 +
[52] 화학식 1-1에서 R,은 C1-C24의알킬, C3-C20의시클로알킬또는 C6-C20의 아릴이다.
[53] (화학식 1-2)
[54] R2- H3N2 l3
[55] 화학식 1-2에서 R2는 C1-C24의알킬, C3-C20의시클로알킬또는 C6-C20의 아릴이며, R3은수소또는 C1-C24의알킬이다.
[56] 화학식 1에서，아미디니움계이온은하기화학식 1-3을만족할수있다.
[57] -3)
Figure imgf000007_0001
[59] 화학식 1-3에서， R4내지 R8은서로독립적으로，수소, C1-C24의알킬, C3-C20의 시클로알킬또는 C6-C20의아릴이다.
[60] 화학식 1에서， A는유기암모늄이은,아미디니움계 (amidinium group)이온 또는유기암모늄이은과아미디니움계이온일수있다.유기암모늄이온과 아미디니움계이온을모두함유하는경우，페로브스카이트화합물의전하 이동도를현저하게향상시킬수있다.
[61] A가유기암모늄이온과아미디니움계이온을모두함유하는경우， 1가유기 양이온의총몰수를 1로하여， 0.7내지 0.95의아미디니움계이온및 0.3내지 0.05의유기암모늄이온을함유할수있다.즉,화학식 1에서， A는 A x)A 기며 , A a는아미디니움계이온이고, Ab는유기암모늄이온이며， X는 0.3내지 0.05의 실수일수있다.아미디니움계이온과유기암모늄이온간의몰비즉， 0.7내지 0.95몰의아미디니움계이온 : 0.3내지 0.05몰의유기암모늄이온의몰비는매우 넓은파장대역의광을흡수할수있으면서도보다빠른액시톤 (exciton)의이동 및분리，보다빠른광전자및광정공의이동이이루어질수있는범위이다.
[62] 화학식 1-1의 화학식 1-2의 R2~R3및 /또는화학식 1-3의 R4~RS은
페로브스카이트화합물의용도,즉,태양전지의광흡수층등의용도에따라 적절히선택될수있다
[63] 상세하게,페로브스카이트화합물의단위셀의크기가밴드갭과연관되어있고 작은단위샐크기에서태양전지로활용하기에적절한 1.5~1.1 eV의밴드갭 에너지를가질수있다.이에따라，태양전지로활용하기에적절한 1.5~1.1 eV의 밴드갭에너지를고려하는경우，화학식 1-1에서， R,은 C1-C24의알킬, 구체적으로 C1-C7알킬，보다구체적으로메틸일수있다.또한,화학식 1-2에서 R2는 C1-C24의알킬일수있고 R3는수소또는 C1-C24의알킬일수있으며 , 구체적으로 ¾는 C1-C7알킬일수있고 ¾는수소또는 C1-C7알킬일수있으며， 보다구체적으로 ¾는메틸일수있고 R3는수소일수있다.또한，화학식 1-3에서 R4내지 R8은서로독립적으로,수소,아미노또는 C1-C24의알킬，구체적으로， 수소,아미노또는 C1-C7알킬，보다구체적으로수소，아미노또는메틸일수 있으며，보다더구체적으로 R4가수소，아미노또는메틸이고 R5내지 가 수소일수있다.구체적이며비한정적인일예로，아미디니움계이온은 포름아미디니움 (formamidinium, NH2CH=NH2 +)이온，
아세트아미디니움 (acetamidinium, NH2C(CH3)=NH2 +)이온또는
구아미디니움 (Guamidinium, NH2C(NH2)=NH2 +)이온등을들수있다.
[64] 상술한바와같이，유기양이온 (A)의구체적인예들은，페로브스카이트화합물 막의용도，즉，태양광의광흡수층으로의용도를고려한일예이며，흡수하고자 하는광의파장대역의설계,발광소자의발광층으로사용하는경우발광파장 대역의설계，트랜지스터의반도체소자로사용하는경우에너지밴드갭과문턱 전압 (threshold voltage)등을고려하여화학식 1-1의 화학식 1-2의 R2~R3 및 /또는화학식 1-3의 ¾~¾이적절히선택될수있다. [65] 화학식 1에서 , M은 2가의금속이온일수있다.구체적인일예로, M은 M은 Cu 2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+및 Yb2+에서하나또는둘 이상선택된금속이온일수있다.
[66] 화학식 1에서， X는할로겐음이온이다.할로겐음이온은 I , Br, F및 C1-에서 하나또는둘이상선택될수있다.구체적으로,할로겐음이온은요오드이온 (I ), 클로린이온 (C1-)및브롬이온 (Br)에서하나또는둘이상선택된이온을포함할 수있다.보다구체적으로,할로겐음이온은요오드이온및브롬이온을함유할 수있다.할로겐음이온이요오드이온및브롬이온을모두함유하는경우， 페로브스카이트화합물의결정성및내습성을향상시킬수있다.
[67] 구체적인일예로,화학식 1에서， X는 X y)Xb y일수있고， Xa및 Xb는서로
상이한할로겐이온 (요오드이온 (1 )，클로린이온 (C1-)및브롬이온 (Br)에서 선택되는서로상이한할로겐이온)이고, y는 0<y<l인실수일수있다ᅳ보다 구체적으로，화학식 1에서, X는 X y)Xh y일수있고， Xa요오드이온이고， Xb는 브롬이온이며， y는 0.05≤y≤0.3인실수,구체적으로 0.1≤x≤0.15인실수일수 있다.이에의해，수분에의한열화가현저히방지되고페로브스카이트화합물의 결정성이향상될수있다.
[68] 상술한바를기반으로， M을 Pb2+로한，구체적이며비한정적인
페로브스카이트화합물의일예를들면，페로브스카이트화합물은 CH3NH3PbIx Cly(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), CH3NH3PbIxBry(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), CH3NH3PbClxBry(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), CHsNHsPblj O x S인실수, 0≤y≤3인실수및 x+y=3), NH2CH=NH2PbIx Cly(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3),NH2CH=NH2PbIxBry(0≤x≤3인실수ᅳ 0≤y≤3인실수및 x+y=3), NH2CH=NH2PbClxBry(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), NH2CH=NH2PWxFy(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), NH2CH=NH 2(l.x)CH3NH3xPb(I(l.y)Bry)3(x는 0<χ<1인실수이며， y는 0<y<l인실수)， NH2CH=NH 2(1-x)CH3NH3xPb(I(1_y)Bry)3(x는 0.05≤x≤0.3인실수이며， y는 0.05≤y≤().3인실수), NH2
Figure imgf000009_0001
(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3),NH2C(CH3)=NH2PbIxBry(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), NH2C(CH3)=NH2PbClxBry(0≤x≤3인실수， 0≤y≤3인실수 및 x+y=3), NH2C(CH3)=NH2PbIxFy(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), NH2 C(CH3)=NH2(1-x)CH3NH3xPb(I(1-y)Bry)3(x는 0<χ<1인실수이며, y는 0<y<l인실수)， NH2C(CH3)=NH2(l.x)CH3NH3xPb(I(1_y)Bry)3(x는 0.05≤x≤0.3인실수이며， y는
0.05<y<0.3인실수)， NH2C(CH3)=CH2(l-x)CH3NH3xPb(I(l-x)Brx)3(x는 0.05≤x≤0.3인 실수)， NH2C(NH2)=NH2PbIxCly(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3),NH2C(NH2 )=NH2PbIxBry(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), NH2C(NH2)=NH2PbClxBry (0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), NH2C(NH2)=NH2PbIxFy(0≤x≤3인실수， 0<y<3인실수및 x+y=3), NH2C(NH2)=NH2(1_x)CH3NH3xPb(I(1-y)Bry)3(x는。〈；씨인 실수이며， y는 0<y<l인실수), NH2C(NH2)=NH2(l_x)CH3NH3xPb(I(1_y)Bry)3(x는 0.05≤x≤0.3인실수이며， y는 0.05≤y≤0.3인실수)또는 NH2C(NH2)=C 0.X)CH3NH 3xPb(I(1_x)Brx)3(X는 0.05≤x≤0.3인실수)를들수있다.
[69] 본발명에따른일실시예에따른전구물질은상술한페로브스카이트화합물의 전구물질이며，유기양이온，금속양이은,할로겐음이은 (X)및게스트분자 (guest molecule,이하, GM)를함유한다.본발명의일실시예에따른전구물질에서， 전구물질에함유되는유기양이은，금속이온및할로겐음이온은앞서
페로브스카이트화합물에서상술한 1가의유기양이온 (A), 2가의금속이온 (M) 및할로겐음이온 (X)과동일할수있음에따라，이에대한상세한설명은 생략한다.
[70] 결정구조에있어，전구물질은비정질，결정질또는비정질과결정질이
흔재하는물질일수있다.구체적으로,전구물질은결정질일수있다.
[71] 상세하게，본발명의일실시예에따른전구물질은 Cu-Koc선을이용한 X-선 회절측정에서，희절각 2Θ가 6.2내지 6.8°, 7내지 7.5°및 8.9내지 9.5°에서회절 ' 피크가검출될수있다.이때，회절각 5°≤2Θ≤40°의범위에존재하는피크중，
8.9내지 9.5。또는 7내지 7.5°의피크의강도가가장높을수있다.
[72] 본발명의일실시예에따른전구물질은급격한페로브스카이트상으로의
전환을막을수있는 GM이 Α유기양이온, M금속양이온, X할로겐음이온과 공존하여형성된콤플렉스 (Complex)형태일수있다.즉,전구물질은 GM이 A 유기양이온 , Μ금속양이온및 X할로겐음이온을함유하는페로브스카이트 화합물 (ΑΜΧ3)과결합하여형성된콤플렉스 (Complex)형태일수있다.
[73] 구체적으로,페로브스카이트화합물과 GM의결합은비공유결합일수있고， GM은 1가의유기양이온 (A)및 2가의금속양이온 (M)에서하나또는둘이상 선택되는양이온과비공유결합된상태일수있다.
[74] 본발명의일실시예에따른전구물질에있어，게스트분자는페로브스카이트 화합물을용해하는용매일수있다.이에따라,전구물질은페로브스카이트 화합물과이를용해하는용매와의용매화합물 (solvate)일수있다.용매화합물은 용질 (페로브스카이트화합물)의분자또는이온과,용매의분자또는이온 사이에형성되는고차의화합물을의미할수있다.
[75] 이때,페로브스카이트화합물을용해하는용매는극성유기용매를의미할수 있으며 , 20°C 1기압하,페로브스카이트화합물의용해도가 0.5M이상, 구체적으로 0.8 M이상인유기용매를의미할수있다.
[76] 전구물질이페로브스카이트화합물과이를용해하는용매와의용매화합물인 경우,낮은온도에서균질하고빠르게 GM이제거되며페로브스카이트화합물로 변환될수있다.상세하게，전구물질은페로브스카이트화합물과용매인 GM가 비공유결합한용매화합물일수있으며, GM은비공유전자쌍을포함하는산소, 질소,불소，염소,브롬및요오드에서하나이상선택되는원소를함유하는 용매일수있다.
[77] 산소,질소,불소，염소,브롬및요오드에서하나이상선택되는원소를 함유하며，페로브스카이트화합물을용해하는용매의일예로,
Ν,Ν-다이메틸아세트아미드 (Dimethylacetamid), 1,4-다이옥산 (dioxane), 다이에틸아민 (diethylamine),에틸아세테이트 (ethylacetate),
테트라하이드로퓨란 (tetrahydrofuran),피리딘 (pyridine),메탄올 (methanol), 에탄올 (ethanol),디클로로벤젠 (dichlorobenzene),글리세린 (glycerin)및
디메틸술폭시드 (DMSO;dimethyl sulfoxide), Ν,Ν-다이메틸포름아미드 (DMF; dimethylformamide )또는이들이혼합물을들수있다.즉,게스트분자는
Ν,Ν-다이메틸아세트아미드 (Dimethylacetamid), 1 ,4-다이옥산 (dioxane), 다이에틸아민 (diethylamine),에틸아세테이트 (ethylacetate),
테트라하이드로퓨란 (tetrahydrofuran)，피리딘 (pyridine),메탄올 (methanol), 에탄올 (ethanol),디클로로벤젠 (dichlorobenzene),글리세린 (glycerin),
디메틸술폭시드 (DMSO;dimethyl sulfoxide)및 Ν,Ν-다이메틸포름아미드 (DMF; dimethylformamide )에서하나또는둘이상선택될수있다.이때， GM의제거에 따른페로브스카이트화합물로의전환시，부피변화에의한막질손상을 방지하는측면에서,게스트분자는디메틸술폭시드 (DMSO;dimethyl sulfoxide)인 것이좋다.
[78] 본발명의일실시예에따른전구물질은하기화학식 2를만족할수있다.
[79] (화학식 2)
[80] AM(GM)nX3
[81] 화학식 2에서， A는유기암모늄이온,아미디니움계 (amidinium group)이은
또는유기암모늄이온과아미디니움계이온이며， M은 2가의금속이온이고, X는할로겐이온이며, 0 < n < 3인실수이다.이때，화학식 2에서， Α, Μ및 X는 화학식 1을기반으로상술한 A, Μ및 X와동일하다.
[82] 즉，화학식 2에따른전구물질은외부에너지에의해 GM이제거되며,화학식 1에따른페로브스카이트화합물로전환될수있다.
[83] 이때,페로브스카이트화합물에서상술한바와같이,화학식 2에서， Α는 A x)A bx이며, Aa는아미디니움계이온이고, Ab는유기암모늄이온이며， X는 0<χ<1의 실수,구체적으로, 0.05≤x≤0.3의실수일수있다.
[84] 이와독립적으로，화학식 2에서， X는 X yᅳ Xb y이며, X는요오드이온 클로린 이온 (C1-)및브롬이온 (Br)에서선택되는서로상이한할로겐이온이며， y는 0<y<l인실수일수있다.좋게는화학식 2에서， X는 X y)Xb y이며, Xa요오드 이온이고, Xb는브름이온이며， y는 0<> 1의실수，구체적으로, 0.05≤y≤0.3의 실수，보다구체적으로 0.1≤y≤0.15인실수일수있다.
[85] 본발명의일실시예에따른페로브스카이트화합물전구물질에있어,
페로브스카이트화합물전구물질에인가되는에너지에의해,게스트분자가 제거되며결정질의페로브스카이트화합물로변화될수있다.
[86] 즉，전구물질이페로브스카이트화합물과 GM과의콤플렉스화합물임에따라， 에너지인가에의해 GM이제거됨으로서순수한페로브스카이트화합물로 전환될수있다.
[87] 본발명의일실시예에따른전구물질은태양전지광흡수체용일수있다.
[88] 본발명은상술한전구물질을함유하는분산액또는상술한전구물질을
함유하는잉크를포함한다.분산액또는잉크는상술한전구물질및분산매와 함께，도포나인쇄방법에적합한특성을가질수있도록，알려진첨가제들을더 함유할수있음은물론이다.
[89] 전구물질은페로브스카이트화합물의화학양론비에따른유기양이온,금속 양이온,할로겐이온및게스트분자를함유하는제 1용액을비용매에점적하는 단계;및점적에의해수득되는고상을회수하여건조하는단계;를통해제조될 수있다.전구물질이페로브스카이트화합물과 GM의콤플렉스임에따라， 전구물질은유기용매에대해，페로브스카이트화합물과유사내지동일한 특성 (용해도등)을가질수있다.이에따라，통상의페로브스카이트화합물을 용해하는용매가계 1용액의용매로사용될수있다.전구물질을용해하는 용매는페로브스카이트화합물을용해하며용이하게휘발제거가능한 용매이면사용가능하다.구체적인일예로，
감마 -부티로락톤 (Gamma-butyrolactone, GBL),
1-메틸 -2-피롤리돈 (l-Methyl-2-pyrolidinone)등을들수있으나,본발명이이에 의해한정되는것은아니다.
[90] 전구물질이용매화합물인경우，제 1용액의용매가게스트분자일수있다.즉, 제 1용액은유기양이온，금속양이온및할로겐이온을게스트분자인용매에 용해하여제조될수있다.
[91] 이때，전구물질은유기용매에대해，페로브스카이트화합물과유사내지
동일한특성 (용해도등)을가질수있음에따라,비용매는페로브스카이트 화합물을용해하지않는유기용매를의미할수있다.이때，페로브스카이트 화합물을용해하지않는다는의미는 20oC 1기압하,페로브스카이트화합물의 용해도가 0.1 M미만,구체적으로 0.01 M미만，더욱구체적으로 0.001 M미만인 유기용매를의미할수있다.
[92] 제 1용액이점적되는비용매의일예로,비극성유기용매를들수있으며，
비극성유기용매는펜타인,핵센，사이크로핵센, 1,4-다이옥센,벤젠,틀루엔, 트리에틸아민,클로로벤젠,에틸아민,에틸에테르,클로로품，에틸아세테이트， 아세틱액시드， 1,2-다이클로로벤젠， tert-부틸알콜， 2-부탄올,이소프로파놀및 메틸에틸케론에서하나또는둘이상선택되는유기용매를들수있으나，본 발명이비용매에의해한정되는것은아니다.이때,게 1용액내용질의농도를 높여생산성을향상시킬수있으나,제 1용액의농도는각용질의용해도범위 내에서화학양론비를만족하는한어떠한농도여도무방하다.
[93] 고상의회수는통상의고액분리시사용되는방법을이용하면족하다.일예로， 필터링，원심분리등을들수있으나，이에한정되는것은아니다.건조는 전구물질이열적으로안전하게손상되지않는범위이면족하다.일예로，건조는 상온내지 50°C에서수행될수있다.
[94] 본발명은상술한전구물질을이용한태양전지광흡수체의제조방법을
포함한다.
[95] 본발명의일실시예에따른광흡수체의제조방법은기재상상기전구물질을 도포또는증착하여전구물질층을형성하는단계;및상기전구물질층에 에너지를인가하여,게스트분자를휘발제거하는단계;를포함할수있다.
[96] 일예로,전구물질이용해된용액또는페로브스카이트화합물전구물질이 분산된분산액이나잉크를기재상에도포한후건조하여전구층을형성한후, 전구층에서 GM을제거함으로써，전구층을페로브스카이트화합물층으로 전환시킬수있다.
[97] 다른일예로，전구물질이용매화합물인경우，페로브스카이트화합물또는 페로브스카이트화합물의화학양론비에따른유기양이온，금속양이은및 할로겐이온을게스트분자 (GM)인용매에용해하여용액을제조한후,제조된 용액을기재상에도포하고，도포막에비용매를재도포함으로써，전구물질을 함유하는전구층을제조할수있다.
[98] 이때,용액，분산액또는잉크의도포는스크린프린팅 (screen printing);
스핀코팅 (Spin coating); 코팅 (Bar coating);그라비 코팅 (Gravure coating); 불레이드코팅 (Blade coating);및롤 -코팅 (Roll coating);에서하나이상선택된 방법으로수행될수있으나,단시간에대면적을처리하는우수한상업성을 고려할때,스핀코팅으로수행되는것이좋다.
[99] 전구층에인가되는에너지는열에너지,광에너지，진동에너지등을들수 있다.인가되는에너지의크기는페로브스카이트화합물과 GM간의결합이 깨어지며 GM이휘발제거될수있는정도면족하다.일예로，전구물질을 100oC 이상으로가열함으로써，페로브스카이트화합물전구물질을페로브스카이트 화합물로전환시킬수있으며，나아가， 130°C이상으로전구층을가열하는경우, 매우단시간내에페로브스카이트화합물로전환시킬수있다.이때,전구물질을 페로브스카이트화합물로변환시키기위한열처리의상한은페로브스카이트 화합물을형성하고자하는기재가열적으로손상되지않는범위이면족하다.일 예로，열처리는 100내지 200°C에서수행될수있다.열처리시간은열처리 온도를고려하여，전구물질이페로브스카이트화합물로충분히전환될수있는 시간이면족하다 비한정적인일예로，열처리시간은 1분내지 30분일수 있으나，본발명이열처리시간에의해한정될수없음은물론이다.
[100] 이를반응관계로상술하면다음과같다.
[101 ] 반웅관계： A+M+3X+n(GM) -> AM(GM)nX3 (0<n<3인실수) -> AMX3
[102] 용액상의 A, M, X가용매의휘발제거에의해, A+M+3X-> AMX3로결정화되는 경우,결정형성의키네틱스 (kinetics)를제어하기어려워치밀한페로브스카이트 화합물막을형성하기어려운문제가있다.본발명의일실시예에따른 전구물질의반웅관계에서는페로브스카이트가직접형성되는것이아닌 페로브스카이트전구물질 (AM(GM)„X3)이먼저생성되고그다음 GM의제거로 페로브스카이트가형성되기때문에페로브스카이트형성키네틱스 (kinetics)를 제어하기용이해,치밀하고표면거칠기가낮은페로브스카이트막을형성시킬 수있다.
[103] 전구층이형성되는기재는그용도에따라，전자소자,광학소자，태양전지또는 센서등이구동하기위해필수적으로갖는기본구조에서，페로브스카이트 화합물막이외의다른구성 (구조)들이이미형성된기재일수있다.
[104] 이하，태양전지를일예로，상세구조및제조방법을상술한다.
[105] 기재는지지체인기판;기판상위치하는제 1전극;및제 1전극상위치하는
전자전달체;를포함할수있다.
[106] 즉,전구층이형성되는기재는기판,제 1전극및전자전달체가순차적으로
적층된적층체를포함할수있다.
[107] 기판은딱딱한기판또는플렉시블기판일수있 ᅳ.구체적인일예로，기판은 유리기판을포함하는딱딱한 (rigid)기판또는폴리에틸렌
테레프탈레이트 (PET);폴리에틸렌나프탈레이트 (PEN):폴리이미드 (PI);
폴리카보네이트 (PC);폴리프로필렌 (PP);트리아세틸샐를로오스 (TAC);
폴리에테르술폰 (PES)등을포함하는유연한 (flexible)기판일수있다.그러나，본 발명이기판의종류에의해한정될수없음은물론이다.
[108] 제 1전극^전자전달체와오믹접합되는전도성전극이면무방하며,
태양전지에서전면전극또는후면전극의전극물질로통상적으로사용되는 물질이면사용가능하다.비한정적인일예로，제 1전극이후면전극의
전극물질인경우,금，은，백금,팔라듐，구리，알루미늄,탄소，황화코발트, 황화구리，산화니켈및이들의복합물에서하나이상선택된물질일수있다.비 한정적인일예로,제 1전극이투명전극일경우,불소함유산화주석 (FTO;
Fouorine doped Tin Oxide),인듐함유산화주석 (ITO; Indium doped Tin Oxide), ZnO, CNT (카본나노류브)，그래핀 (Graphene)과같은무기계전도성전극일수 있으며， PEDOT:PSS와같은유기계전도성전극일수있다.투명태양전지를 제공하고자하는경우,제 1전극이투명전극인것이좋고,제 1전극이유기계 전도성전극인경우，풀렉시블태양전지나투명태양전지를제공하고자할때 보다좋다ᅳ
[109] 제 1전극은기판상전극물질을증착또는도포하여형성될수있다.증착은
물리적증착 (physical vapor deposition)또는화학적증착 (chemical vapor depositiori)을이용하여형성될수있으며,열증착 (thermal evaporation)에의해 형성될수있다.도포는전극물질의용해액또는전극물질의분산액을기판에 도포한후건조하거나，선택적으로건조된막을열처리함으로써수행될수있다. 그러나,제 1전극이통상의태양전지에서전면전극또는후면전극을형성하는데 사용하는방법을이용하여형성될수있음은물론이다.
[110] 제 1전극상부에위치하는전자전달체는전자전도성유기물층또는무기물 층일수있다.전자전도성유기물은통상의유기태양전지에서 , η형반도체로 사용되는유기물일수있다.구체적이며비한정적인일예로,전자전도성 유기물은풀러렌 (C60, C70, C74, C76, C78, C82, C95),
PCBM([6,6]-phenyl-C61butyric acid methyl ester)), C71-PCBM, C84-PCBM, PC70 BM([6,6]-phenyl C70-butyric acid methyl ester)을포함하는
풀러렌-유도체 (Fulleren-derivative)' PB I(polybenzimidazole) ,
PTCBI(3,4,9,10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ(tetra uorotetracyanoquinodimethane)또는이들의흔합물을포함할수있다.전자전도성 무기물은통상의양자점기반태양전지또는염료감웅형태양전지에서，전자 전달을위해사용되는전자전도성금속산화물일수있다.구체적인일예로, 전자전도성금속산화물은 n-형금속산화물반도체일수있다. n-형금속산화물 반도체의비한정적인일예로， Ti산화물 , Ζη산화물， In산화물， Sn산화물， W산화물, Nb산화물, Mo산화물， Mg산화물, Ba산화물, Zr산화물， Sr산화물， Yr산화물, La산화물, V산화물， A1산화물， Y산화물， Sc산화물, Sm산화물, Ga산화물， In산화물및 SrTi산화물에서하나또는둘이상선택된물질을들수 있으며，이들의흔합물또는이들의복합체 (composite)를들수있다.
[111] 그구조에있어，전자전달체는다공성층이거나치밀층일수있다.치밀한
전자전달체는상술한전자전도성유기물의막또는전자전도성무기물의 치밀막 (fihn)을들수있다.다공성전자전달체는상술한전자전도성무기물의 입자들로이루어진다공막을들수있다.전자전달체의두께는 50nm내지 ΙΟμπι, 구체적으로는 50nm내지 lOOOnm일수있다.전자전달체가다공성인경우그 비표면적은 10내지 lOO mVg일수있으며，전자전달체를이루는금속산화물 입자의평균입경 (diameter)은 5내지 500 nm일수있다.다공성전자전달체의 기공률 (겉보기기공률)은 30%내지 65%,구체적으로 40%내지 60%일수있다.
[112] 전자전달체가다공성구조인경우，제 1전극과전자전달체사이에는
전자전달막이더구비될수있다.전자전달막은광흡수체와제 1전극이직접 접촉하는것을미연에방지하는역할올함과동시에전자를전달하는역할을 수행할수있다.전자전달막은에너지밴드다이어그램상，다공성
금속산화물에서전자전달막을통해제 1전극으로전자가자발적으로이동 가능한물질이면무방하다.비한정적이며구체적인일예로，전자전달막은 금속산화물박막일수있으며，금속산화물박막의금속산화물은다공성 금속산화물의금속산화물과동일내지상이한물질일수있다.상세하게, 금속산화물박막의물질은 Ti산화물， Zn산화물, In산화물, Sn산화물, W산화물， Nb산화물, Mo산화물， Mg산화물， Ba산화물, Zr산화물， Sr산화물， Yr산화물， La산화물， V산화물， A1산화물， Y산화물， Sc산화물， Sm산화물, Ga산화물, In산화물, SrTi산화물，이돌의혼합물및이들의복합물중에서하나이상선택된 물질일수있다.전자전달막의두께는실질적으로 lOrnn이상,보다실질적으로 10nm내지 lOOrnn,보다더실질적으로 50nm내지 lOOnm일수있다. [113] 전자전달체는도포또는증착에의해형성될수있다.구체적으로，전자전달체 물질이용해된용액또는전자전달체물질이분산된분산액 (또는슬러리)을 도포하여건조하거나，선택적으로건조된수득물을열처리하여제조할수있다.. 증작은물리적증작 (physical vapor deposition)또는화학적증작 (chemical vapor deposition)을이용하여형성될수있다.
[114] 다공성전자전달체를일예로,보다구체적으로상술하면，전자전달체는
제 1전극상부에금속산화물입자를함유하는슬러리를도포및건조하고 열처리하여제조될수있다.슬러리의도포는스크린프린팅 (screen printing); 스핀코팅 (Spin coating);바 -코팅 (Bar coating);그라비아 -코팅 (Gravure coating); 블레이드코팅 (Blade coating);및롤 -코팅 (Roll coating);에서하나이상선택된 방법으로수행될수있다.
[115] 그러나，전자전달체가통상의염료감웅형태양전지또는유기태양전지에서 알려진금속산화물의다공성전자전달체형성방법을이용하여형성될수 있음은물론이다ᅳ
[116] 이후,기재의다공성전자전달체상부로상술한바에따라，전구층을형성하고 에너지를인가하여전구층을페로브스카이트화합물의광흡수층으로
변환시키는단계가수행될수있다.
[117] 다공성전자전달체의기공을채우며,다공성전자전달체를덮는막의형태로 전구층을형성시키고，이를페로브스카이트화합물로변환시킴으로써，다공성 전자전달체의기공을채우며다공성전자전달체의표면을모두덮은치밀막의 구조를갖는광흡수층이제조될수있다.이때,치밀막의두께는 lmn내지
ΙΟμτ 일수있다.
[118] 이후,광흡수층의치밀막상부로,정공전달층및제 2전극을순차적으로
형성하는단계가수행될수있다.
[119] 정공전달층은유기정공전달물질，구체적으로단분자내지고분자유기
정공전달물질 (정공전도성유기물)^포함할수있다.유기정공전달물질은무기 J 반도체양자점을염료로사용하는통상의무기반도체기반태양전지에서
사용되는유기정공전달물질이면사용가능하다.그러나，페로브스카이트 화합물인광흡수체와의에너지매칭및안정성측면에서고분자유기
정공전달물질이좋다.
[12이 단분자내지저분자유기정공전달물질의비한정적인일예로，
타센 (pentacene),쿠마린 6(coumarin 6,
3-(2-benzothiazolyl)-7-(diethylamino)coumarin), ZnPC(zinc phthalocyanine), CuPC(copper phthalocyanine), TiOPC(titanium oxide phthalocyanine),
Spiro-MeOTAD(2,2 7J'-tetrakis(N,N-p-dimethoxyphenylamino)-9,9'-spirobifluorene) , F16CuPC(copper(II)
1 ,2,3,4,8,9,10, 1,15, 16,17, l8,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine), SubPc (boron subphthalocyanine chloride)및 N3(cis-di(thiocyanato)-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid)-ruthenium(II))중에서 하나또는둘이상선택되는물질을들수있으나,이에한정되는것은아니다.
[121] 유기정공전달물질은고분자 (정공전도성고분자)인것이좋은데，이를통해 안정적인태양전지의구동이담보될수있을뿐만아니라，광흡수체와의에너지 매칭에의해보다향상된발전효율을가질수있다.구체적으로，정공전도성 고분자로,티오펜계，파라페닐렌비닐렌계，카바졸계및트리페닐아민계에서 하나또는둘이상선택된물질을들수있으며，티오펜계및
트리페닐아민계에서하나또는둘이상선택된것이좋고,보다좋게는
트리페닐아민계일수있다.고분자유기정공전달물질의비한정적인일예로，
P3HT(poly[3-hexylthiophene]), MDMO-PPV(poly[2-methoxy-5-(3',7'- dimethyloctyloxyl)]- 1 ,4-phenylene vinylene), MEH-PPV(poly[2-methoxy
-5-(2"-ethylhexyloxy)-p-phenylene vinylene]), P30T(poly(3-octyl thiophene)), POT( poly(octyl thiophene)), P3DT(poly(3-decyl thiophene)), P3DDT(poly(3-dodecyl thiophene), PPV(poly(p-phenylene vinylene)),
TFB (poly (9 ,9'-dioctylfluorene-co-N- (4-buty lpheny l)diphenyl amine), Polyaniline, Spiro-MeOTAD ([2,22',7,77'-tetrkis (N,N-di-p-raethoxyphenyl amine)-9,9,9'-spirobi fluorine]), PCPDTBT(Poly [2, 1 ,3-benzothiadiazole- 4,7-diyl[4,4-bis(2-ethylhexyl-4H- cyclopenta [2, 1 -b :3 ,4-b'] dithiophene-2,6-diyl]] ,
Si-PCPDTBT(poly[(4,4,-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2, l ,3 - benzothiadiazole) -4,7-diyl]), PBDTTPD(poly((4,8-diethylhexyloxyl)
benzo([l,2-b:4,5-b']dithiophene)-2,6-diyl)-alt-((5-octylthieno[3,4-c]pyrrole-4,6-dione)- l,3-diyl)), PFDTBT(poly[2,7-(9-(2-ethylhexyl)-9-hexyl-fluorene)-alt-5,5-(4', 7, -di-2-thienyl-2',l', 3'-benzothiadiazole)]),
PFO-DBT(poly[2,7-.9,9-(dioctyl-fluorene)-alt-5,5-(4',7'-di-2-.thienyl-2', 1',
3'-benzothiadiazole)]),
PSiFDTBT(poly[(2,7-dioctylsilafluorene)-2,7-diyl-alt-(4,7-bis(2-thienyl)-2,l,3-benzot hiadiazole)-5,5'-diyl]),
PSBTBT(poly[(4,4'-bis(2-ethylhexyt)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,l,3-b enzothiadiazole)-4,7-diyl]), PCDTBT(Poly [[9-(l-octylnonyl)-9H-carbazole-2,7-diyl] -2,5-thiophenediyl -2, 1 ,3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]),
PFB(poly(9,9'-dioctylfluorene-co-bis(N,N'-(4,butylphen^ 1 ,
4-pheny lene)diamine) , F8BT(poly(9,9'-dioctylfluorene-co-benzothiadiazole), PEDOT (poly(3,4-ethylenedioxythiophene)), PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)), PTAA (poly(triarylamine)),
Poly(4-butylphenyl-diphenyl-amine)및이들의공중합체에서하나또는둘이상 선택된물질을들수있다.
[122] 비한정적이며구체적인일예로,정공전달층의두께는 l(] nm내지 500 mn일 수있다. ' [123] 정공전달층은통상의무기반도체양자점을염료로사용하는무기반도체기반 태양전지또는유기태양전지에서유기물기반홀전도층의전도도향상과같은 특성향상을위해통상적으로사용되는첨가제를더포함할수있음은물론이다. 비한정적인일예로，정공전달체는 TBP(tertiary butyl pyridine), LiTFSI(Lithium Bis(Trifluoro methanesulfonyl)Imide)및
Tris(2-(lH-pyrazol-l-yl)pyridine)cobalt(III)에서하나또는들이상선택된 첨가제를더함유할수있으며，유기정공전달물질 lg당 0.05mg내지 lOOmg 첨가제를함유할수있다.그러나,본발명이정공전달층의첨가제유 /무, 첨가제의종류및첨가제의함유량에의해한정될수없음은물론이다.
[124] 제 2전극은태양전지에서전면전극또는후면전극의전극물질로통상적으로 사용되는물질이면사용가능하다.비한정적인일예로，제 2전극이후면전극의 전극물질인경우，제 2전극은금，은,백금，괄라듐,구리,알루미늄，탄소， 황화코발트，황화구리，산화니켈및이들의복합물에서하나이상선택된물질일 수있다.비한정적인일예로，제 2전극이투명전극일경우，제 2전극은불소함유 산화주석 (FTO; Fouorine doped Tin Oxide),인듐함유산화주석 (ITO; Indium doped Tin Oxide), ZnO, CNT (카본나노류브),그래핀 (Graphene)과같은무기계전도성 전극일수있으며, PEDOT:PSS와같은유기계전도성전극일수있다.투명 태양전지를제공하고자하는경우,제 2전극이투명전극인 ¾이좋고,제 2전극이 유기계전도성전극인경우,플렉시블태양전지나투명태양전지를제공하고자 할때보다좋다.
[125] 제 2전극은증착또는도포를이용하여형성될수있다.증착은물리적
증착 (physical vapor deposition)또는화학적증착 (chemical vapor deposition)을 이용하여형성될수있으며,열증착 (thermal evaporation)에의해형성될수있다. 도포는전극물질의용해액또는전극물질의분산액을기판에도포한후 건조하거나，선택적으로건조된막을열처라함으로써수행될수있다.그러나, 저 12전극이통상의태양전지에서전면전극또는후면전극을형성하는데 사용하는방법을이용하여형성될수있음은물론이다.
[126] 본발명은상술한제조방법으로제조된태양전지를포함한다.
[127] 본발명의일실시예.에따른태양전지는기판，기판상위치하는제 1전극;
제 1전극상위치하는다공성전자전달체;다공성전자전달체의기공을채우며 다공성전자전달체를덮는치밀막인페로브스카아트화합물을포함하는 광흡수층;광흡수층상위치하는정공전달층;및정공전달층상에위치하는 제 2전극;을포함하며,페로브스카이트화합물은전구물질의 GM이제거되며 생성된것일수있다.
[128] 광흡수층의페로브스카이트화합물치밀막은 lnm내지 ΙΟμπι일수있다.
[129] 태양전지를상술함에있어，페로브스카이트화합물，정공전달체，전자전달체, 제 1전극,제 2전극,제 1기판및제 2기판등은앞선제조방법에서상술한바와유사 내지동일함에따라，이에대한상세한설명은생략한다ᅳ [130]
[131] (비교예 1)
[132] Pbl2분말을메틸술폭시드 (DMSO)용매에투입하고 60oC에서 2시간동안
교반하여 0.8 M PbI2-DMSO용액을제조하였다.이용액을를루엔에
점적 (drop-wise)한후,침전분말을필터페이퍼로분리수거하여상온에서 1시간 동안건조하였다.
[133]
[134] (실시예 1)
[135] 페로브스카이트전구물질제조
[136] CH3NH3I(이하， MAI)와 Pbl2분말을화학양론비 1:1로디메틸술폭시드 (DMSO) 용매에투입하고， 60oC에서 2시간동안교반하여으8 M CH3NH3I-PbI2-DMSO 용액을제조하였다.이용액을를루엔에점적 (drop-wise)한후，침전분말을필터 페이퍼로분리수거하여상온에서 1시간동안건조하였다.
[137] 비교예 1에서제조된분말,전구체인 MAI, Pbl2및실시예 1에서얻어진분말을 Cu Ka선을이용한 X-선회절분석을실시하였으며,이를도 1에도시하였다.
[138] 도 1에서알수있듯이，실시예 1에서제조된분말 (도 1에서 Pbl2
(MAIXDMSO)로도시)은전구체인 MAI와 Pbl2물질의상이포함되지않았음을 알수있다.또한비교예 1에서제조한분말은 PbI2(DMSO)2로서 H. Miyatnae에 의해보고된물질이다 (Chemistry Lett., 9, 663, 1980).이 PbI2(DMSO)2상의 XRD 결과와실시예 1에서제조된분말의 XRD결과를비교분석해보면실시예 1에서 얻어진분말은 PbI2(DMSO)2상이아님을알수있다.즉,실시예 1에서얻어진 분말은회절각 2Θ, 6.2내지 6.8°， 7내지 7.5°및 8.9내지 9.5°에서강한회절 피크가나타남을알수있다.또한，실시예 1에서얻어진분말은 2Θ가 5내지 40°의영역에서， 7내지 7.5°에위치하는피크가가장회절강도가큰것을알수 있다.이러한 XRD결과는실시예 1에서제조된분말이 MAI, Pbl2, PbI2(DMSO)2 상과전혀다른새로운화합물임을알수있다.
[139] 도 2는실시예 1에서제조된분말의 FTIR(Fourier transform infrared
spectroscopy)결과이다.도 2에각흡수모드를표시하였으며이 IR의투과 스펙트럼올살펴보면 S-0결합과 C-H결합,그리고 N-H결합의흡수가있음을 알수있다.이는실시예 1에서제조된분말이 MAI와 DMSO를모두포함하고 있다는증거라할수있다.또한도 2에서 C=C결합에의한흡수가발생하지 않음을알수있고,이는를루엔이분말에포함되어있지않았음을말해준다. XRD와 FTIR결과를통해실시예 1에서얻어진분말은 MAI-PbI2-DMSO혼합 결정체임을알수있다.
[140] 정확한조성분석을위해원소분석 (Elemental analysis)를실시하였다.분석결과 각원소질량비율이 H=1.6%, C=4.6%, N=2.0%, 0=2.2%, S=3.7%로측정되었으며 이를바탕으로나머지원소의질량비율이 85.9%로추정되었다. CH3NH3I, Pbl2, C 2¾SO(DMSO)의흔합결정을가정하여서로 1:1:1로반웅하였다가정하면 H = 1.7%, C =5.2%, N = 2.0%, O = 2.3%, S = 4.6%, Pb = 29.7%, I = 54.5%이므로 원소분석측정결과와유사한값을보임을알수있다.
[141] 이를통해，실시예 1에서제조된분말은 MAI-PbI2-DMSO가 1:1:1로반응하여 형성된결정으로, MAPb(C2H6SO)I3(=C3H12NSOPbI3)임을알수있다.이는화학식 2에서제시한 AM(GM)nX3에서 A가 MA, M이 Pb, GM이 DMSO, X가 I, n=l인한 예시라볼수있다ᅳ
[142] 이 MAPb(DMSO)I3페로브스카이트전구물질의순수페로브스카이트
상으로의전이를살펴보기위해열처리온도에따른 XRD분석을실시하고이를 도 3에도시하였다. XRD분석은실시간 (in-situ)으로수행되었으며,도시된온도 구간별로 1분간유지한후분석을실시하였다.도 3을보면상온 (room temperaure, RT)에서는도 1의결과와마찬가지로순수한 MAPb(DMSO)I3페로브스카이트 전구물질상을유지함을알수있다.그러나열처리온도가증가함에따라，전구 물질이페로브스카이트상으로전환됨을알수있다. 100°C에서의 XRD 스펙트럼을보면전구물질의특징적픽인 ιο°아래의픽들의강도가약해지면서 동시에페로브스카이트특징픽인 14°부근의픽이나타남을볼수있다.이는 100oC에이르는열에너지에의히 L GM이제거되며페로브스카이트전구물질이 순수한페로브스카이트로전환되고있음을보이는결과이다.또한 130°C에서는 순수한페로브스카이트회절픽만이관찰되며이는전구물질에서순수한 페로브스카이트가형성되었음을말해준다.즉 GM으로존재하던 DMSO가 완전히빠져나가순수한페로브스카이트가형성되었음을알수있다.
[143]
[144] (실시예 2)
[145] 전구물질박막제조
[146] 실시예 1에서제시된방법을이용하되용매로감마부틸로락톤 (GBL)을추가 흔합용매로사용하여 MAI-PbI2-DMSO용액을제조하였다.즉， GBL'OMSO의 부피비율을 7:3으로하고 MAPbI3를기존으로 0.8M농도의용액을제조하였다.
[147] 퓨즈드실리카 (Fused silica)기판상에，제조된 MAI-PbI2-DMSO용액 (총 1ml)을 회전중심에일괄도포 (주입)하고， 5000 rpm으로스핀코팅을시작하였다.스핀 코팅시간이 50초가된시점에스핀중인다공성전극의회전중심에다시 비용매인를루엔 (toluene) lmL를일괄도포 (주입)한후， 5초동안스핀코팅을더 진행하였다.스핀코팅을완료한후,상온에서 1시간동안건조하였다.이후， 100°C의온도및상압조건에서 30분동안열처리하여페로브스카이트화합물 박막인광흡수체를형성하였다.광흡수체박막의제조시주변환경은 250C의 온도및 25%의상대습도를유지하였다.
[148]
[149] (비교예 ¾
[150] 실시예 1과동일하게박막을제조하되용액제조시용매로， DMSO를제외하고 100%감마 -부티로락톤 (이하， GBL)만을사용하였다 (MAI-PbI2-GBL용액). [151]
[152] 도 4는실시예 2(도 4(a))와비교예 2(도 4(b))에서 100oC로열처리되기전
제조된박막의 XRD스펙트럼이다.이결과를보면실시예 2의경우，제조된 박막에서전구물질특정픽이관찰됨을알수있으나，순수 GBL을사용한경우 이픽이관찰되지않았다.즉실시예 2의경우 MAPb(DMSO)I3페로브스카이트 전구물질의막이형성되었음을알수있다.
[153] 도 5는실시예 2(도 5(a))와비교예 2(도 5(b))에서열처리후의페로브스카이트 막을관찰한주사전자현미경사진이다.실시예 2의경우상술한반웅관계에 따라전구물질단계를거쳐페로브스카이트화합물이형성된것이고,비교예 2의경우용액에서직접페로브스카이트화합물이형성된경우이다.도 5에서알 수있듯이,전구물질박막에서페로브스카이트막으로변화되는경우,치밀하고 완벽한막형태로페로브스카이트화합물이형성됨을알수있다.
[154]
[155] (실시예 3)
[156] 다공성 Ti02박막기판제조
[157] 불소함유산화주석이코팅된유리기판 (FTO; F-doped Sn02, 8 ohms/cm2,
Pilkington,이하 FTO기판 (제 1전극))을 25 x 25 mm크기로절단한후,끝부분을 에칭하여부분적으로 FTO를제거하였다.
[158] 절단및부분에칭된 FTO기판위에금속산화물박막으로서 50 nm두께의 ΤΪ02치밀막을분무열분해법으로제조하였다.분무열분해는 TAA (Titanium acetylacetonate):EtOH(l :9 v/v )용액을이용하여수행되었으며 , 450 °C로유지된 열판위에을려진 FTO기판위에 3초간분무하고 10초간정지하는방법을 되풀이하는방법으로두께를조절하였다.
[159] 평균입자크기 (직경 ) 50 nm의 Ti02분말 (Ti02기준으로 1중량 %가용해된 titanium peroxocomplex수용액을 250°C에서 12시간수열처리하여제조)에 ,에틸 샐를로오스 (ethyl cellulose)가 10중량 %로에틸알콜에용해된에틸셀를로오스 용액을, Ti02분말 lg당 5 ml첨가하고，테르피놀 (terpinol)을 Ti02분말 1 g당 5 g 첨가하여흔합한후,에틸알콜을감압증류법으로제거하여 Ti02페이스트를 제조하였다.
[160] 제조된 Ti02분말페이스트에에탄올을첨가 (l(Ti02분말
페이스트): 3(에탄올)의중량비)하여스핀코팅용 1^02슬러리를제조하였다. FTO 기판의 Ti02박막위에，스핀코팅용 Ti02슬러리를이용하여 lOOOrpm으로스핀 코팅하였다.이후， 500 °C에서 60분동안열처리한후， 60 °C의 30 mM T1C14 수용액에열처리된기판을담그고， 30분동안방치한후,탈이온수와에탄올로 세척및건조하고다시 500 °C에서 30분동안열처리하여 300nm두께의다공성 Ti02박막 (다공성전자전달체)을제조하였다.제조된다공성전자전달체의 비표면적은 33m2/g이며，기공률 (겉보기기공률)은 50%이었다.
[161] 실시예 2에서퓨즈드실리카를제조된다공성전자전달체로대체하여 ,다공성 전자전달체상에실시예 2와동일한방법으로페로브스카이트화합물의 광흡수층을제조하였다.이후，광흡수층이상에 PTAA(poly(triarylamine), EM index, Mw=17,500 g/mol)가용해된를루엔용액 [15mg(PTAA)/lmL]을 3000 rpm으로 60초동안스핀코팅하여정공전달층을형성하였다.이때， PTAA 용액에 2.31 mg의 LiTFSI(Lithium Bis(Trifluoro methanesulfonyl)Imide)와 6.28 mg의 TBP(tertiary butyl pyridine)를첨가하였다.이후,정공전달층의상부에 고진공 (5xlO-6 torr이하)의열증착기 (thermal evaporator)로 Au를진공증착하여, 두께가 70 nm인 Au전극 (제 2전극)을형성하여태양전지를제조하였다.
[162]
[163] (비교예 3)
[164] 실시예 3과동일하게태양전지를제조하되，비교예 2에서퓨즈드실리카를 제조된다공성전자전달체로대체하여，다공성전자전달체상에비교예 2와 동일한방법으로페로브스카이트화합물의광흡수층을제조하였다.
[165] 실시예 3과비교예 3에서제조한태양전지를 AM 1.5 (100mA/cm2)의
조건하에서광전변환특성을측정하고，그결과를표 1에나타내었다 ·.실시예 3에서제조한페로브스카이트화합물막은전자전달체의상부표면을 100% 덮는치밀한박막의형태를보이나，비교예 3의경우전자전달체의상부표면을 100%에이르도록덮지못하는불완전한형태의막이었다.따라서실시예 3의 경우에서더우수한 Jsc, Voc, FF값을보이며우수한광전변환효율을보임을알 수있다.
[166] (표 1)실시예 3과비교예 3에서제조한태양전지의성능지수
Figure imgf000022_0001
[168] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는욘발명의보다전반적인이해를돕기위해서제공된것일 뿐，본발명은상기의실시예에한정되는것은아니며,본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[169] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며, 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형ᄋ 있는모든것들은본발명사상의범주에속한다고할것이다.
[170]

Claims

청구범위
[청구항 1] 유기양이은，금속양이온，할로겐음이은및게스트분자 (guest molecule, GM)를함유하는무 /유기하이브리드페로브스카이트 화합물의 전구물질.
[청구항 2] 제 1항에있어서，
상기전구물질은 Cu-Koc선을이용한 X-선회절측정에서，회절각 2Θ가 6.2내지 6.80， 7내지 7.5ᄋ및 8.9내지 9.5°에서회절피크가 검출되는전구물질.
[청구항 3] 제 1항에있어서，
상기게스트분자는상기무 /유기하이브리드페로브스카이트 화합물을용해하는용매인전구물질.
[청구항 4] 제 3항에있어서,
상기전구물질은무 /유기하이브리드페로브스카이트화합물와 용매간의용매화합물 (solvate)인전구물질.
[청구항 5] 제 3항에있어서，
상기게스트분자는산소,질소，불소，염소,브롬및요오드에서 하나이상선택되는원소를함유하는용매인전구물질.
[청구항 6] 제 3항에있어서，
상기게스트분자는
Ν,Ν-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
Ν,Ν-다이메틸포름아미드 (DMF; dimethylformamide)에서하나 또는둘이상선택되는전구물질.
[청구항 7] 제 3항에있어서，
상기전구물질은하기화학식 1을만족하는전구물질.
(화학식 1)
AM(GM)nX3
(A는유기암모늄이온,아미디니움계 (amidinium group)이온또는 유기암모늄이온과아미디니움계이온이며, M은 2가의금속 이온이고， X는할로겐이온이며, 0 < n < 3인실수이다)
[청구항 8] 제 7항에있어서,
상기화학식 1에서, X는 Xa이 y)Xb y 0ᅵ며 , X는요오드이온 (Iᅳ),클로린 이온 (C1-)및브롬이온 (Br)에서선택되는서로상이한할로겐 이온이며， y는 0<y<l인실수인전구물질.
[청구항 9] 제 1항에있어서，
상기전구물질은태양전지광흡수체용인전구물질.
[청구항 10] 제 1항내지제 9항중어느한항에따른전구물질을함유하는 분산액.
[청구항 11] 제 1항내지제 9항중어느한항의전구물질을이용한태양전지 광흡수체의제조방법.
[청구항 12] 제 11항에있어서，
기재상상기전구물질을도포또는증착하여전구물질층을 형성하는단계；및
상기전구물질층에에너지를인가하여，게스트분자를휘발 제거하는단계;
를포함하는태양전지광흡수체의제조방법.
PCT/KR2014/012727 2013-12-23 2014-12-23 무/유기 하이브리드 페로브스카이트 화합물 전구물질 Ceased WO2015099412A1 (ko)

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