WO2015099412A1 - Precursor of inorganic/organic hybrid perovskite compound - Google Patents
Precursor of inorganic/organic hybrid perovskite compound Download PDFInfo
- Publication number
- 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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- WO
- WIPO (PCT)
- Prior art keywords
- precursor
- organic
- perovskite compound
- precursor material
- ion
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 124
- 239000002243 precursor Substances 0.000 title claims abstract description 116
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 27
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 62
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 59
- -1 halogen anion Chemical class 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 150000002892 organic cations Chemical class 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000151 deposition Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
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Classifications
-
- 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, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- 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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