WO2017176053A1 - 무/유기 하이브리드 페로브스카이트 화합물 막 및 이의 제조방법 - Google Patents

무/유기 하이브리드 페로브스카이트 화합물 막 및 이의 제조방법 Download PDF

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WO2017176053A1
WO2017176053A1 PCT/KR2017/003743 KR2017003743W WO2017176053A1 WO 2017176053 A1 WO2017176053 A1 WO 2017176053A1 KR 2017003743 W KR2017003743 W KR 2017003743W WO 2017176053 A1 WO2017176053 A1 WO 2017176053A1
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perovskite compound
organic
compound film
scattering
film
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French (fr)
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서장원
노준홍
전남중
석상일
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Korea Research Institute of Chemical Technology KRICT
UNIST Academy Industry Research Corp
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Korea Research Institute of Chemical Technology KRICT
UNIST Academy Industry Research Corp
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Priority to US16/091,057 priority Critical patent/US10796857B2/en
Priority to EP17779353.6A priority patent/EP3441432A4/en
Publication of WO2017176053A1 publication Critical patent/WO2017176053A1/ko
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H10K10/488—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
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    • H10K50/00—Organic light-emitting devices
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an inorganic / organic hybrid perovskite compound film and a method for producing the same, in detail, an organic / organic hybrid perovskite compound film and a solution having excellent crystallinity and orientation and exhibiting single crystal-like properties. It relates to a method for preparing the same based on the application method.
  • 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). ,
  • the swarovski compound has a very low material price
  • Self-assembling crystallization allows low cost solution process and low cost process, and it can be manufactured with low cost raw materials, so it is excellent in commerciality and various light emitting devices, memory devices, sensors, photovoltaic devices, etc. Active research is being done in the field.
  • perovskite compound a solid state solar cell based on a perovskite compound (hereinafter referred to as a perovskite compound).
  • the present applicant has a new structure of perovskite having a significantly higher power generation efficiency through Korean Patent Publication No. 2014-0035284.
  • Perovskite which has been staying at less than 10% by proposing a new structure of perovskite solar cells.
  • the efficiency of the solar cell has been improved to 21%, the efficiency of the crystalline silicon-based solar cell and the efficiency of about 20%, which is comparable to that of the crystalline silicon-based solar cell, must be improved along with these structural changes. Need.
  • non-radiative recombination and scattering of photocharges should be minimized.
  • Such non-radiative recombination and scattering should be minimized. It is caused by trap sites of grain boundaries present in the perovskite compound film itself and defects in the perovskite compound crystals. Accordingly, similar crystallinity is required to prevent the disappearance of photocharges.
  • the perovskite compound is a single crystal, it has been reported to have a hole diffusion length of 175 ⁇ due to high charge mobility, long axtone life time and low trap concentration (H. Jinsong et. Al., Science 2015 , 347, 967-970), and trap concentrations of single-crystal perovskite compounds are similar to high-purity silicon and trap concentrations (0. M. Bakr et al. Science 2015, 347, 519). It has been. However, the production of devices having various structures using the perovskite compound of the single crystal itself is difficult to be practically realized, and the commerciality is very low.
  • perovskite compounds are those using a phosphate process, the crystallinity is highly crystalline and its orientation is controlled to give a grain structure similar to a single crystal and extremely coarse grains.
  • the technology for producing a perovskite compound film is a key technology that can dramatically improve the performance of perovskite compound-based devices including solar cells while maintaining the commerce of low cost and simple process and mass production.
  • An object of the present invention is to provide a film having a controlled orientation of perovskite compound, which is composed of finely coarse grains with fine crystallinity and excellent orientation. It is to provide a sky compound film.
  • Another object of the present invention is to provide a method for producing an orientation-controlled perovskite compound film using a low cost, simple process solution coating method, and in detail, has excellent crystallinity and extremely coarse grain. It is to provide a method for producing a perovskite compound film which is composed of grains and whose orientation is controlled.
  • Another object of the present invention is to provide a film of perovskite compound with controlled orientation.
  • the inorganic / organic hybrid perovskite compound film is polycrystalline and has a fine angle of incidence angle of X-rays using 1.0688 human X-ray wavelengths.
  • GIWAXS Grazing Incidence Wide Angle X-ray Scattering
  • organic / organic hybrid In one embodiment according to the first aspect of the present invention, organic / organic hybrid
  • the perovskite compound film may have 3 to 15 peaks in the scattering vector (q, A ′′ 1 ) on the (100) plane.
  • the scattering spectrum is the intensity distribution of the scattering vector component qz on the y-axis and the scattering vector component q xy on the X-axis.
  • the scattering spectrum may satisfy the following equation (1). [14] (Relationship 1)
  • the non-organic hybrid perovskite compound film according to the second aspect of the present invention is a polycrystal and has a steep angle incident wide-angle X-ray using an X-ray wavelength of 1.0688A.
  • the scattering intensity of the (100) plane according to the azimuth has a continuous scattering intensity in the range of 10 to 170 ⁇ .
  • the defined orientation satisfies Equation 3 below.
  • PO (IOO) means the orientation of the (100) plane parallel to the film, where 1 90 is
  • I ave Based on scattering intensity of (100) plane according to azimuth, strength at 90 ° azimuth angle, I ave is based on scattering intensity of (100) plane along same azimuth angle, average scattering intensity in a range of 10 to 170 ° to be.
  • organic / organic hybrid In one embodiment according to the second aspect of the present invention, organic / organic hybrid
  • the perovskite compound film can satisfy the following equation (5), which is defined by the following equation (4).
  • UF is a uniformity
  • I ave is the mean scattering intensity in the range of azimuth from 10 to 170 ° based on the scattering intensity of the (100) plane according to azimuth
  • ⁇ is the scattering in the range of 10 to 170 °.
  • the inorganic / organic hybrid perovskite compound membrane duty / organic hybrid perovskite compound is represented by the following formula (1), (2) or (3). Can be satisfied.
  • A is a monovalent cation
  • A is an organic ammonium ion
  • ACM ⁇ NJXa [35]
  • A is a monovalent cation
  • A is an organic ammonium ion, an amidinium group silver or an organic ammonium ion and an amidinium-based ion
  • M is a divalent metal ion
  • N Is a doped metal ion selected from at least one of monovalent and trivalent metal ions, a being a real number with 0 ⁇ a ⁇ 0.1 and X being halogen or silver.
  • A is a monovalent cation
  • A is an organic ammonium ion
  • Amidinium group silver or organic ammonium ion and amidinium-based ion
  • ⁇ ' is a monovalent metal ion
  • ⁇ 2 is a trivalent metal ion
  • b is
  • the production method of the inorganic / organic hybrid perovskite compound film according to the present invention is coated with a perovskite compound solution containing an additive which is a substrate-based / organic hybrid perovskite compound and an organic halide. And contacting the prepared perovskite compound solution with the non-solvent of the perovskite compound to form an organic / organic hybrid perovskite compound film, the additive content in the perovskite compound solution, That is, the crystal orientation of the organic / organic hybrid perovskite compound film is controlled by controlling the molar ratio of the perovskite compound: additive in the perovskite compound solution.
  • the inorganic / organic hybrid ferrite according to the present invention is controlled by controlling the molar ratio of the perovskite compound: additive in the perovskite compound solution.
  • the method for producing a lobite compound film is a perovskite containing an additive which is a substrate business / organic hybrid perovskite compound and an organic halide. Applying a kite compound solution, and contacting the perovskite compound solution applied on the substrate with the non-solvent of the perovskite compound, followed by annealing. The additive content in the perovskite compound solution is determined. By controlling the crystal orientation of the organic / organic hybrid perovskite compound film.
  • the additive is
  • It may be methyl ammonium halide.
  • the perovskite compound solution may contain 0.2 to 0.7 mole of additive based on 1 mole of inorganic / organic hybrid perovskite compound.
  • the perovskite compound solution may contain 0.75 to 1.5 moles of additive based on 1 mole of organic / organic hybrid perovskite compound.
  • the application of the perovskite solution and the contact with the nonsolvent may be performed by the sequential application of the perovskite solution and the nonsolvent using spin coating.
  • the present invention is a radish / organic hybrid according to the first or second aspect described above.
  • a device comprising a perovskite compound film is included.
  • the device according to the embodiment of the present invention may be an electronic device, a light emitting device, a memory device, a photovoltaic device, an optical sensor, or a thermoelectric device.
  • the perovskite compound film according to the present invention has an extremely good orientation and has the advantage of having a highly crystalline film composed of coarse grains of several ⁇ order.
  • the production method according to the present invention can produce a perovskite compound film with controlled orientation using simple solution coating, and has coarse grains with controlled crystallinity and excellent crystallinity. There is an advantage that can be made of perovskite compound membranes.
  • Example 1 is a view showing a GIWAXS spectrum according to the additive content of the perovskite compound film prepared in Example 1,
  • FIG. 2 is a diagram showing a GIWAXS spectrum of a 1: 1 sample in FIG.
  • FIG. 3 is a diagram showing (100) plane diffraction intensity of 1: 0.25 sample according to azimuth angle in FIG.
  • FIG. 6 is a scanning electron micrograph of the surface of the perovskite compound film of 1: 0.5 sample in FIG. 1;
  • FIG. 7 shows the surface of a perovskite compound film of 1: 1 sample in FIG.
  • FIG. 8 is a diagram showing an X-ray diffraction pattern of the perovskite compound film prepared in Example 1.
  • FIG. 8 is a diagram showing an X-ray diffraction pattern of the perovskite compound film prepared in Example 1.
  • the present invention relates to an organic / organic hybrid perovskite compound film, a method for producing the same, and an element including the organic / organic hybrid perovskite compound film.
  • the organic / organic hybrid perovskite compound is an organometal.
  • organic / organic hybrid perovskite compounds include organic cations (A), metal cations (M) and Halogenated silver (X)
  • Perovskite compounds are MX 6 octahedron
  • Corner-sharing-A is in the form of organic cations in the three-dimensional network of (S corner aring h e) is located in the middle.
  • the present invention provides a perovskite compound film in which the perovskite compound grains forming the perovskite compound film are highly oriented in a specific direction.
  • the film (hereinafter referred to as the perovskite compound film) is polycrystalline and has a Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) spectrum, which is discrete (100) using an X-ray wavelength of 1.0688 human. It has scattering intensity of) plane.
  • GIWAXS Grazing Incidence Wide Angle X-ray Scattering
  • Dispersion strength of the (100) plane is discontinuous, which means that diffraction of the (100) plane on the GIWAXS spectrum does not occur omnidirectionally, so that the diffraction peak appears only at a specific azimuth. This means a spot diffraction pattern or appearance of the (100) plane on the GIWAXS spectrum.
  • the scattering intensity of the (100) plane is discontinuous, which means that there is an area of zero diffraction intensity by the (100) plane diffraction in the azimuth angle range of 0 to 180 ° on the GIWAXS spectrum.
  • the case where the diffraction intensity is 0 includes the case where the intensity of the noise level is detected.
  • the scattering intensity of the (100) plane is discontinuous, GIWAXS
  • the diffraction peak of (100) plane is present (diffraction by plane (100) plane) only in the azimuth angle range of 85 to 95 ° in the azimuth angle range of 60 to 120 °, more specifically 60 to 120 A single diffraction peak with the center of the (100) plane diffraction peak at an azimuth angle of 85 to 95 0 in the azimuth angle range of °
  • perovskite compound grains that form the film are oriented in only a few specific directions where diffraction peaks exist.
  • the scattering vector (q, A- 1 ) on the (100) plane of the GIWAXS spectrum there may be 3 to 15 peaks on the scattering vector (q, A- 1 ) on the (100) plane of the GIWAXS spectrum.
  • the scattering vector on the (100) planes has the largest relative strength.
  • the number of peaks with intensity above 10% can be three to five.
  • the (100) crystal plane can correspond to the number of directions oriented, i.e. the presence of three to fifteen diffraction peaks by diffraction of the (100) plane is found in the crystals forming the perovskite compound film (100). Means that the crystal plane is oriented in only 3 to 15 specific directions
  • the number of peaks having a strength of 10% or more based on the highest peak strength is 3 to 5, in the crystals forming the perovskite compound film. It means to exist in five directions.
  • Discontinuous GIWAXS spectra of non-arc spot shape and 3 to 15, substantially 3 to 5 peaks are indicative of the extremely good orientation of the perovskite compound film according to the first aspect of the present invention. .
  • the diffraction peaks due to diffraction of the (100) plane in the azimuth angle range of 0 to 180 ° are 3 to 8 ⁇ , 40 to 45 °, 85 to 95 ° and 170 to 178 °.
  • a more specific and non-limiting example, based on the strength of the largest peak, can be four peaks with an intensity greater than 10%, four peaks ranging from 3 to 8 0 , 40 to 45 0. It can be located at azimuth angles of 85 to 95 ° and 170 to 178 °.
  • the scattering spectrum of the perovskite compound film may be an intensity distribution of the scattering vector component 3 ⁇ 4 on the y axis and the scattering vector component q xy on the X axis.
  • the peak of the (100) plane with the highest strength can be located.
  • the crystals forming the perovskite compound film are oriented so that the (100) crystal plane is located in some specific direction, and most of the crystals are arranged parallel to the film.
  • the degree of preferred orientation of the (100) crystal plane in a particular direction can be defined as the diffraction strength on the GIWAXS spectrum. Specifically, in the 0 to 180 ° azimuth region, the (100) plane The diffraction peak can satisfy the following relation
  • Equation 1 I f is the intensity of the relatively largest peak of the (100) plane, and 1 5 is the strength of the second largest peak of the diffraction peak of the (100) plane.
  • the perovskite compound film according to the embodiment of the present invention may have an I f / I s of 2.5 or more, and 1 may be substantially 10 or less.
  • [79] is 2.0, more specifically 2.5 or more, which means that a large number of the grains forming the perovskite compound film are oriented parallel to the (100) plane film.
  • the perovskite compound film is based on the diffraction intensity of the (100) plane according to an azimuth angle of 0 to 180 °, the azimuth angle of 85 to 95 °, more specifically.
  • the half-width (FWHM) of the diffraction angle of the diffraction peak, located between 88 and 92 ° and practically 90 °, may be less than 5.5 °, and more specifically, less than 4.5 °. This narrow half-width allows many grains to be very precise ( 100) means that the plane is oriented parallel to the film and has a well-defined preferential orientation.
  • the (100) plane corresponds to the dense plane in the perovskite structure, and the perovskite compound film having a high orientation in which these dense planes are oriented parallel to the film can have excellent charge mobility. It can have significantly lower tram concentrations and significantly reduce the scattering of charge.
  • the perovskite compound film may be composed of extremely coarse grains having an average grain size of 1 to 5 mu m. Perovskite compound films having the above orientation and extremely coarse grains can exhibit very similar properties to single crystals.
  • a perovskite compound membrane in which the perovskite compound grains forming the perovskite compound film are randomly oriented.
  • the surface energy which is the energy between the compound crystal and the atmosphere (environmental device), the grain boundary energy between the crystal and the crystal, and the interfacial energy between the heterogeneous material and the perovskite compound crystal located under the perovskite compound film
  • This driving force causes the polycrystalline perovskite compound film to exhibit a preferred orientation with more random orientation in a particular direction with the random arrangement of the grains, i.e., scattering.
  • the intensity is detected continuously regardless of the orientation of the scattering vector above the specific plane (eg, (100) plane).
  • the second aspect of the present invention provides a perovskite compound film having substantially perfect randomly arranged grains by suppressing the preferred orientation with such random orientation. do.
  • the present invention provides a perovskite compound film having a preferential orientation in which the (100) plane is arranged in parallel with the surface of the film, with random orientation, in two aspects. As described above, when the (100) plane, which is a dense film, is arranged parallel to the film, it may have better charge mobility than other preferred orientations, and may have a significantly lower tram concentration.
  • the inorganic / organic hybrid perovskite compound film according to the second aspect of the present invention is polycrystalline and has a fine angle of incidence angle of incidence using an X-ray wavelength of 1.0688A.
  • GIWAXS Grazing Incidence Wide Angle X-ray Scattering
  • PO (IOO) means the orientation of the (100) plane parallel to the film, where 1 90 is
  • I ave Based on scattering intensity of (100) plane according to azimuth, strength at 90 ° azimuth, I ave is based on scattering intensity of (100) plane along same azimuth angle, average scattering intensity in a range of 10 to 170 ° to be.
  • PO (IOO) forms a perovskite compound film.
  • orientation of grains it means the degree to which (100) grains are oriented parallel to the perovskite compound film.
  • the preferred orientation where the face is parallel to the film does not appear substantially or appears very weak, and more than 5 ⁇ (100) has the preferred orientation with the (100) face film parallel to the random film.
  • PO (IOO) of 15 to 25 can mean that a large amount of grains have preferential orientation with the (100) plane parallel to the film.
  • the present invention is an embodiment according to the second aspect, which has an extremely random orientation.
  • the perovskite compound film which provides a perovskite compound film and has a random orientation, is an organic / organic hybrid perovskite compound film, which is a polycrystal, and has a fine angle of incidence angle of X-ray scattering using 1.0688 human X-ray wavelengths.
  • GIWAXS Grazing Incidence Wide Angle X-ray Scattering
  • the scattering intensity of the (100) plane according to the azimuth, and the scattering intensity in the range of 10 to 170 ° are defined as The uniformity of the equations can satisfy the following relation. [94] (Relationship 4)
  • UF is a uniformity
  • I ave is the average scattering intensity in the range of azimuth from 10 to 170 ° based on the scattering intensity of the (100) plane according to azimuth
  • ⁇ is the scattering in the range of 10 to 170 °.
  • the uniformity of 0.1 to 0.4 means that the perovskite compound grains forming the perovskite compound film are extremely randomly arranged. It means.
  • the PO (IOO) according to relation 2 described above may be 1.0 to 2.0.
  • the uniformity of 0.1 to 0.4 is a uniformity that has not been realized in the method of forming a perovskite compound film of a conventional polycrystalline polymorph, including the solution coating method.
  • a perovskite compound film having a random orientation and simultaneously having a preferential orientation parallel to the (100) plane film.
  • the resulting organic / organic hybrid perovskite compound film having a random orientation and simultaneously having a preferential orientation parallel to the (100) plane film.
  • the PO (IOO) can be 5 to 25, substantially 5 to 15, and substantially 5 to 10.
  • the perovskite compound film having a PO (IOO) of 5 to 25, substantially 5 to 15, and substantially 5 to 10 has a random orientation in which omnidirectional diffraction occurs, and at the same time, the (100) plane Priority orientation parallel to the membrane can also have an advanced structure.
  • the perovskite compound film may be composed of coarse grains having an average grain size of 500 nm to 3 ⁇ .
  • the perovskite compound may satisfy the following formula (1), (2) or (3).
  • A is a monovalent cation
  • A is an organic ammonium ion
  • Amidinium group ions or organic ammonium ions are silver and amidinium-based silver, ⁇ is a divalent metal ion and X is a halogen ion, wherein the halogen ions are I-, Br, F- and C1-. One or more can be selected from.
  • 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
  • N is a doped metal ion selected from at least one of monovalent and trivalent metal ions
  • a is a real number with 0 ⁇ a ⁇ 0.1
  • X is a halogen ion, wherein one or more halogen ions can be selected from I-, Br, F- and C1-.
  • the monovalent metal silver silver metal ion as the doping metal ion may be selected from Li + , Na +, K +, Rb +, Cs + , In 1+ , Cu 1+ and Ag ions. .
  • trivalent metal ions of which the doped metal is silver are Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Sc 3+ , , 3+ , La 3+ , Ce 3+ , Fe 3
  • One or more may be selected from + , Ru 3+ , Cr 3+ , V 3+ , Ti 3+ , Sb 3+ , Bi 3+ and As 3+ ions.
  • the electrical properties of the perovskite compound may be controlled to n- type or p-type.
  • the monovalent metal may be doped with silver so that the perovskite compound may have a p-type.
  • the perovskite compound may have n-type oligomers. It is similar to that of an acceptor doped in a conventional silicon semiconductor, and trivalent metal ions are similar to those doped by ordinary silicon semiconductors, where both monovalent and trivalent metal ions may be doped.
  • the electrical properties of the perovskite compound can be controlled.
  • M may be a divalent metal ion.
  • M is M 2 Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ and
  • One or more selected metal ions in Yb 2+ may be present.
  • A is a monovalent cation
  • A is an organic ammonium ion
  • ⁇ is a monovalent metal silver
  • ⁇ 2 is a trivalent metal ion
  • b is
  • the monovalent metal ion is a bandgap suitable for solar absorption and small holes
  • one or more may be selected from In 1+ , Cu ' + and Ag 1+ .
  • the trivalent metal is silver Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Sc 3+ , ⁇ 3+ , La 3+ , Ce 3+ , Fe 3+ ,
  • One or more of Ru 3+ , Cr 3+ , V 3+ , Ti 3+ , Sb 3+ , Bi 3+ and As 3+ can be selected, and the bandgap suitable for solar absorption, in terms of small electron effective mass
  • One or more may be selected from Sb 3+ , BP + , Ga 3+ , and In 3+.
  • a monovalent metal ion-a trivalent metal silver pair is a direct transition band gap.
  • It has a structure, having a suitable band gap energy of the solar radiation absorbing and may be to the to having a significantly smaller effective mass of a hole and an electron effective mass of the 10 second order i) to V).
  • the double perovskite structure has monovalent metal ions (N 1 ) and trivalent at the M-site of the single perovskite structure.
  • metal ions (N 2) are regularly arranged in a crystal lattice structure, ⁇ 2 ⁇ ' ⁇ 2 ⁇ 6 medicinal chemistry can have sikol as is known, double perovskite structure (double-layered perovskite structure) is N!
  • the X 3 octahead and the N 2 X 3 octahead are regularly alternating with each other, with organic cations in the corner-shearing three-dimensional network.
  • This double perovskite structure is cubic. It can belong to the F m m space group of the crystal system.
  • Formula 1 Formula 2 or Formula 3, the organic ammonium ion may satisfy the following Formulas 4-5.
  • R is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20
  • R 2 is C1-C24 alkyl, C3-C20 cycloalkyl or C6-C20
  • Aryl, 3 ⁇ 4 is hydrogen or alkyl of C1-C24.
  • R 4 to R 8 are independently of each other hydrogen, alkyl of C1-C24, cycloalkyl of C3-C20 or aryl of C6-C20.
  • Formula 1 In Formula 1, Formula 2 or Formula 3, A is an organic ammonium ion,
  • Amidinium groups can be silver or organic ammonium ions and amidinium ions. When both organic ammonium ions and amidinium ions are contained, the charge mobility of the perovskite compound is significantly improved. You can do it.
  • A contains both organic ammonium ions and amidinium ions
  • the total molar number of monovalent organic cations is 1, so that the ammonium ions of 7 to 0.95 and the organic ammonium of 0.3 to 0.05
  • A may be A x) A b x , where A a is an amidinium ions, is an organic ammonium ion, and X is 0.3 to 05.
  • the molar ratio between amidinium ions and organic ammonium ions, i.e., 0.7 to 0.95 moles of amidinium ions: 0.3 to 0.05 moles of organic ammonium, is capable of absorbing light in a very wide wavelength range. This is the range in which faster exciton transfer and separation and faster photoelectron and light hole movement can be achieved.
  • the unit cell size of the perovskite compound is perovskite.
  • the band gap of the compound is influenced. Accordingly, the perovskite compound film such as the semiconductor channel layer, the light emitting layer, the semiconductor layer, the light absorbing layer, and the charge storage layer is considered, so that the applicable band gap can have a suitable band gap.
  • R H and the formula (5) it is of the R 2 ⁇ R 3 and / or formula (6) be appropriately adjusted in, which is well known for employees semiconductor device related element nagwang.
  • a bandgap energy of 1.5-1.1 eV suitable for use as a solar cell that absorbs sunlight in a small unit cell size.
  • a band of 1.5-U eV suitable for use as a solar cell may be C1-C24 alkyl, specifically C1-C7 alkyl, more specifically methyl.
  • R 2 may be C1-C24 alkyl
  • R 3 may be hydrogen or C1-C24 alkyl
  • specifically 3 ⁇ 4 may be C1-C7 alkyl
  • R 3 may be hydrogen or C1-C7 alkyl
  • More specifically, R 2 may be methyl and R 3 may be hydrogen.
  • hydrogen, amino or C1-C24 It may be alkyl, specifically, hydrogen, amino or C1-C7 alkyl, more specifically hydrogen, amino or methyl, more specifically R 4 hydrogen, amino or methyl and R 5 to 3 ⁇ 4 hydrogen.
  • organic cation (A) are examples of the use of the perovskite compound film, that is, the application to the light absorption layer of sunlight, and the design and emission of the wavelength band of the light to be absorbed.
  • the design of the emission wavelength band when used as the semiconductor device of the transistor, the energy band gap and threshold voltage fluctuating in consideration of the characteristics required for the application, R 2 to R 3 and / or Formula 6 may be appropriately selected.
  • M may be a divalent metal ion.
  • M may be Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+. It may be one or more selected metal ions from Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ and Yb 2+ .
  • Chemical Formula 1 Chemical Formula 2 or Chemical Formula 3, X is a halogen anion.
  • Anions may be selected from one or more of I-, Br, F and CI-.
  • halogen anions are one or more of iodine (1-), chlorine (C1-) and bromine (Br).
  • the selected silver may contain silver. More specifically, the halogen anion may contain iodine silver and bromine ions. When the halogen anion contains both iodide and bromine ions, the crystallinity and moisture resistance of the perovskite compound are enhanced. I can make it
  • X in Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, X may be X y) X b y , and X a and X b may be different halogen halides (iodine ion (1-), chlorine ion (C1). -) And bromine ions (Br) are different halogen ions), and y may be a real number of 0 ⁇ y ⁇ l. More specifically, in Formula 1, X may be X y) X b y and X a iodine ion, X b is bromine ion, y may be a real number of 0.05 ⁇ y ⁇ 0.3, specifically 0.1 ⁇ y ⁇ 0.15, i.e.
  • the total molar number of the negative silver can be 1, and the iodine ion of 0.7 to 0.95 and bromine of 0.3 to 0.05 can be contained. .
  • y is 0.05 ⁇ y ⁇ 0.3 real number
  • NH 2 C (NH 2 ) CH 2 (1-X) CH 3 NH 3 x Pb (V x) Br x ) 3 ( x may be 0.05? x? 0.3.
  • the thickness of the perovskite compound film may be appropriately adjusted in consideration of its use, but may be, for example, 10 nm to ⁇ . In view of the solar cell application, the thickness of the perovskite compound film may be 100 to 800 nm. .
  • the present invention provides a method for producing a perovskite compound film having controlled crystal orientation.
  • the present applicant controls the protrusion structure of the light absorbing structure by varying the molar ratio of organic halides and metal halides in the light absorber solution when forming the perovskite compound Technology has been provided.
  • the light absorbing structure of the perovskite compound in the form of a low surface roughness and a dense film is disclosed through the present patent application No. 2014-0035285, No. 2014-0035284 or No. 2014-0035286.
  • the perovskite compound can add organic halides to the solution dissolved in the solvent. It was found that the orientation of the perovskite compound film can be controlled by the content of the organic halide phosphate additive when the solution is coated and the non-solvent is brought into contact with the applied solution.
  • the additive is preferably methyl ammonium halide.
  • Methylammonium halides are methylammonium chloride, methylammonium bromide, methylammonium iodide, methylammonium fluoride or their May include a mixture, more preferably methylammonium chloride.
  • the substrate may be appropriately designed in consideration of the use of the perovskite compound film.
  • the substrate may be a rigid substrate or a flexible substrate and, independently of it, may be a transparent or opaque substrate.
  • the substrate may be a monocrystalline L polycrystalline or amorphous, or a mixed phase in which a crystalline phase and an amorphous phase are mixed.
  • the substrate may be a laminated layer of semiconductors, ceramics, metals, polymers, or two or more materials selected from them, each layer being a non-limiting example of a semiconductor substrate, such as silicon (Si), germanium (Ge), or silicon.
  • Group 4-6 semiconductors including lead sulfide (PbS), or two or more materials selected from them, can be layered and stacked on top of each other.
  • Ceramic substrates include semiconductor oxides, semiconductor nitrides, and semiconductor carbides.
  • a metal oxide, a metal carbide, a metal nitride, or a laminate of two or more materials selected from each other may be laminated.
  • a semiconductor of semiconductor oxide, semiconductor nitride, or semiconductor carbide may be a group 4 semiconductor, group 3-5.
  • Non-limiting examples of metal substrates include transition metals, precious metals, or combinations thereof.
  • Examples of polymer substrates include polyethylene terephthalate (PET), polyethylene naphthalate (PEN),
  • Triacetyl Cellulose TAC
  • PES Polyethersulfone
  • PDMS Polydimethylsiloxane
  • substrates comprising amorphous oxide substrates such as glass or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), and polycarbonate (PC).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • PC polycarbonate
  • PP Polypropylene
  • Triacetylcellose TAC
  • PES polyethersulfone
  • Flexible polymer substrates such as polydimethylsiloxane (PDMS) and the like.
  • the organic / inorganic hybrid perovskite compound film is provided, the lower part of the perovskite compound film Sub-components may be appropriately modified in design, i.e., the substrate may be a pre-formed component under the perovskite compound film of the device to be manufactured, based on a known device structure.
  • the perovskite compound solution is a monovalent organic cationic (A), metal cation (M) and halogen anion (X) to satisfy the above formulas (1) to (3).
  • Perovskite compound itself may be dissolved in the solvent, together with the additive, in addition to the solvent dissolving organic cations (A), divalent metal cations (M), and halogen anions (X). May contain
  • the molar concentration of the perovskite compound in the perovskite compound solution may be 0.4M to 1.8M, specifically 0.8M to 1.1M, but is not limited thereto.
  • the solvent of the perovskite compound solution can be used as long as it is a polar organic solvent that dissolves the perovskite compound and the additive.
  • the solvent is gamma-butyrolactone, formamide, die Methyl formamide,
  • One or more may be selected from acetylacetone, methanol, ethanol, propanol, ketone and methyl isobutyl ketone.
  • the solution of perovskite compound is one mole of perovskite compound in solution.
  • the perovskite compound solution may contain 2 to 0.7 moles, preferably 0.2 to 0.55 moles of methyl ammonium halide, based on 1 mole of the perovskite compound in the solution.
  • the non-solvent is brought into contact after the application of the sky compound solution to the substrate, the perovskite compound film according to the above two aspects can be produced.
  • perovskite compound film having an extremely random orientation can be prepared.
  • 0.35 to 55 moles, specifically 0.45 to 0.55 moles of methyl per mole of perovskite compound contained in the perovskite compound solution perovskite compound membranes can be prepared with a random orientation but with a preferred preferential orientation parallel to the surface of the membrane.
  • the perovskite compound solution may contain 0.75 to 1.5 moles, preferably 0.9 to 1.5 moles, of additives based on 1 mole of the perovskite compound in the solution.
  • the solution may contain from 75 to 1.5 moles, preferably from 0.9 to 1.5 moles of methylammonium halide, per mole of perovskite compound in the solution.
  • the perovskite compound film according to the first aspect described above can be produced.
  • the application of the perovskite compound solution is sufficient to apply the liquid phase, which is commonly used to form a film.
  • the liquid phase which is commonly used to form a film.
  • the orientation of the film of the perovskite compound can be controlled.
  • the nonsolvent may be an organic solvent that does not dissolve perovskite compounds, and may be a nonpolar organic solvent. Specifically, the nonsolvent has a dielectric constant ( ⁇ ; relative dielectric constant) of 20 or less and a nonpolar solvent having a dielectric constant of 1 to 20.
  • the non-solvent may be pentine, nuxene, cyclonuxene, 1,4-dioxene, benzene, toluene, triethylamine, chlorobenzene, ethylamine, ethyl ether, chloroform ⁇ ethyl acetate, acetone.
  • One or more may be selected from, but are not limited to, ticacids, 1,2-dichlorobenzene, tert-butyl alcohol, 2-butanol, isopropanol and methyl ethyl ketone.
  • the coated light absorber solution after application of the perovskite compound solution and before the solvent of the perovskite compound solution in the substrate is volatilized, ie, by applying a non-solvent to the dried substrate. And non-solvent contact can be made.
  • the coating of the perovskite compound solution and the non-solvent coating are carried out independently of each other, or the non-solvent during application of the perovskite compound solution.
  • Non-solvent coating is also preferred for spin coating in terms of uniform coating, large-area processing, and fast processing time. In practical example, the coating of the light absorber solution and the coating of the non-solvent are all spin coating.
  • the non-solvent is applied by injecting a non-solvent into the rotation center of the spin coating, or after injecting the perovskite compound solution into the rotation center, the injected light absorber solution This can be done by injecting a nonsolvent into the center of rotation, which rotates the substrate to evenly distribute the substrate.
  • the time interval between the completion of the surface layer preparation solution and the time of introduction of the nonsolvent may be properly adjusted at the center of rotation of the spin coating.
  • a nonsolvent may be introduced 1 to 100 seconds immediately after completion of the perovskite compound solution.
  • a two-step process of application of a more detailed perovskite compound solution and contact of the nonsolvent For the coating process, reference may be made to Patent Application No. 2014-0035285, Patent Application No. 2014-0035284 or Patent Application No. 2014-0035286 of the present applicant, and the present invention discloses Patent Application No. 2014-0035285 of the present applicant. It includes the contents described in 2014-0035284 or published patent 2014-0035286.
  • Annealing can be carried out to volatilize the solvent or nonsolvent of the remaining perovskite compound solution, while simultaneously removing the additive.
  • Annealing can be performed at temperatures of 100 to 150 ° C, preferably 130 to 150 ° C.
  • the annealing time may be as long as the additive is reliably removed, and in particular, it may be performed for 1 to 10 minutes, but is not limited to this.
  • the present invention relates to a perovskite compound film (first or second aspect) described above.
  • It includes an electronic device, an optical device, a memory device, a thermoelectric device or a sensor.
  • the electronic device includes a transistor, and the optical device includes a light emitting device including a light emitting diode or a laser, a photodetecting device (optical sensor), or a photovoltaic device (solar cell), and the memory device is a volatile or nonvolatile memory device.
  • the sensor includes a detection sensor for detecting an organic compound or a biochemical.
  • the present invention is the basic structure of a light emitting diode is one electrode-n type
  • the present invention provides a basic structure of a resistance change type memory.
  • the metal strips may be spaced apart from each other, and the system electrode may be metal strips arranged in another direction so as to be orthogonal to the metal strips of the first electrode.
  • the present invention provides a gate positioned at the top or the bottom of a semiconductor channel with a semiconductor channel and an insulating film (gate insulating film) positioned between the source and drain and the source and the drain facing each other, which are the basic structures of the transistor.
  • a gate positioned at the top or the bottom of a semiconductor channel with a semiconductor channel and an insulating film (gate insulating film) positioned between the source and drain and the source and the drain facing each other, which are the basic structures of the transistor. of It includes a transistor based on the structure, but having a semiconductor channel containing the above-described perovskite-based compound film.
  • perovskite compounds in commercially important solar cells is described in more detail.
  • the present invention provides a light absorbing layer containing the above-described perovskite compound film.
  • It includes a solar cell.
  • a solar cell includes a light absorber and a light absorber phase including a first electrode, a first charge carrier disposed on the first electrode, and a perovskite compound film disposed on the first charge carrier.
  • the second charge carrier may be positioned, and the second electrode may be positioned on the second charge carrier.
  • the first electrode may be positioned on a substrate, and the substrate may be a rigid substrate or
  • the substrate may be a rigid substrate or a polyethylene terephthalate (PET) including a glass substrate;
  • PET polyethylene terephthalate
  • PEN Polyethylene naphthalate
  • PI polyimide
  • PC polycarbonate
  • It may be a flexible substrate including polypropylene (PP); triacetylcellose (TAC); polyethersulfone (PES) and the like.
  • PP polypropylene
  • TAC triacetylcellose
  • PES polyethersulfone
  • the present invention may not be limited by the type of substrate.
  • the first electrode may be a conductive electrode that is ohmic-bonded with a crab 1 electric charge carrier.
  • any material commonly used as an electrode material of a front electrode or a back electrode may be used.
  • the first electrode 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 fluorine-containing tin oxide (FTO), indium doped tin oxide (ITO; indium doped tin oxide), ZnO, carbon nanocarbon (CNT), graphene
  • FTO fluorine-containing tin oxide
  • ITO indium doped tin oxide
  • ZnO carbon nanocarbon
  • CNT carbon nanocarbon
  • graphene It may be a non-mechanical conductive electrode such as Graphene, etc., or an organic conductive electrode such as PEDOT: PSS.
  • both the electrode (the first electrode and the second electrode) and the substrate are transparent and transparent substrates.
  • the electrode (first electrode or second electrode) is an organic conductive electrode, it is better to provide a flexible solar cell or a transparent solar cell.
  • the first charge carrier located on the first electrode prevents direct contact between the first electrode and the light absorber and may serve to provide a movement path through which charges of photoelectrons or holes generated in the light absorber move.
  • the first charge carrier and low 12 The charge carriers can shift complementary charges.
  • the first charge carrier can shift complementary charges.
  • the two charge carriers may be hole transporters. If the first charge carrier is a hole transporter, the two charge carriers may be electron transporters.
  • the first charge carrier is an electron carrier, but when the first charge carrier is a hole carrier, the first charge carrier may be related to the second charge carrier described below.
  • the first charge carrier may be related to the second charge carrier described below.
  • the electron transporter may be an electron conductive organic layer or an inorganic layer.
  • the electron conductive organic material may be an organic material used as an n-type semiconductor in a conventional organic solar cell.
  • the electron conductive organic material is fullerene (C60, C70, C74, C76, C78, C82, C95), PCBM ([6,6] -phenyl-C61butyric acid methyl ester)) and
  • PBI polybenzimidazole
  • C71-PCBM C84-PCBM
  • PC 70 BM [6,6] -phenyl C 70 -butyric acid methyl ester
  • It may include PTCBI (3,4,9, 10-perylenetetracarboxylic bisbenzimidazole), tetrauorotetracyanoquinodimethane (F4-TCNQ) or a combination thereof.
  • Electromagnetically conductive minerals are usually quantum dot-based solar cells or dye-sensitized
  • the electron conductive metal oxide may be an electron conductive metal oxide used for electron transfer.
  • the electron conductive metal oxide may be an n-type metal oxide semiconductor.
  • 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 Oxide, V oxide, A1 oxide, Y oxide, Sc oxide,
  • One or more materials selected from Sm oxide, Ga oxide, In oxide, and SrTi oxide may be mentioned, and their mixtures or composites thereof may be mentioned.
  • the electron transporter may be a porous layer (porous membrane) or a dense layer (dense membrane).
  • the dense electron transporter may be a film of an electron conductive organic material or an electron conductive inorganic film. Can be.
  • Porous electron transport consists of particles of the above-mentioned electron conductive inorganic
  • the thickness of the electron transporter can range from 50 nm to ⁇ , specifically from 50 nm to 100 m. If the electron carrier is porous, its specific surface area can be between 10 and 100 mVg, and the average of the electron-conducting inorganic particles that make up the electron carrier. The particle diameter 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 carrier has a porous structure, there is a gap between the first electrode and the electron carrier.
  • the electron transport film may be further equipped.
  • the electron transport film may serve to prevent direct contact between the light absorber and the first electrode, and at the same time, to transport electrons.
  • the electron transport film may be formed on an energy band diagram or in a porous manner.
  • the electron transfer film may be a metal oxide thin film, and the metal oxide of the metal oxide thin film may be the same as or different from the metal oxide of the porous metal oxide.
  • Materials include 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,
  • the material may be one or more selected from among Sc oxides, Sm oxides, Ga oxides, In oxides, SrTi oxides, ZnSn oxides, their mixtures, and their complexes.
  • the thickness of the electron transport film is substantially lOnm and substantially more lOnm to lOOnm. More practically, 50 nm to 100 nm.
  • the perovskite compound film is formed according to the above-described method for producing a perovskite compound film on the electron transporter after forming the first electrode and the electron transporter.
  • the light absorber of the perovskite compound can be produced in the form of a membrane filling the pores of the electron carrier and covering the upper portion of the electron carrier.
  • the perovskite compound film is manufactured according to the above-described method for producing the perovskite compound film on the electron carrier.
  • Light absorber can be manufactured.
  • the second charge carrier may be a hole transporter, and the hole transporter may be an organic hole transporter, an inorganic hole transporter, or a stack thereof.
  • the hole carrier comprises an inorganic hole carrier
  • the inorganic hole carrier is a hole
  • It may be a conductivity type, i.e., a p-type semiconductor, an oxide semiconductor, a sulfide semiconductor, a halide semiconductor or a combination thereof.
  • oxide semiconductors include NiO, CuO, CuA10 2 , CuGa0 2
  • sulfide semiconductors include PbS and halogenated semiconductors such as Pbl 2 . It is not limited by the hole transport material.
  • the hole transporter may be a dense layer (dense membrane).
  • the dense hole transporter is p-type described above.
  • An inorganic hole transport material has a thickness of 50nm to ⁇ ⁇ , in particular number of days is lOnm to lOOOnm, 50nm to lOOOnm in detail.
  • the organic hole transporter is organic.
  • Hole transport materials specifically monomolecular and may contain molecular organic hole transport materials (hole conduction, organic matter).
  • Organic hole transport materials are organic organic materials used in conventional non-conductor-based solar cells that use non-conductive quantum dots as dyes.
  • the hole transporter may be a thin film of organic hole transporter, the thickness of which is It can be 10 nm to 500 nm.
  • Organic hole carriers may, of course, further include additives commonly used to improve the conductivity of organic-based hole conducting layers in inorganic conductor-based solar cells using conventional non-conductive quantum dots as dyes.
  • the hole transporter is one of tertiary butyl pyridine (TBP), Lithium Bis (Trifluoro methanesulfonyl) Imide (LiTFSI) and Tris (2- (lH-pyrazol-l-yl) pyndine) cobalt (III).
  • TBP tertiary butyl pyridine
  • LiTFSI Lithium Bis (Trifluoro methanesulfonyl) Imide
  • two or more selected additives may be added and may contain from 0.05 mg to lOOmg additive per lg organic hole transporter.
  • the present invention is limited by the presence or absence of an additive in the hole carrier, the type
  • the second electrode may be a conductive electrode that is ohmic-conjugated with a hole carrier.
  • Any material commonly used as an electrode material of a front electrode or a back electrode in a solar cell may be used.
  • the second electrode may be one or more selected from silver, silver, platinum, palladium, copper, aluminum, carbon, cobalt sulfide, copper sulfide, nickel oxide, and combinations thereof.
  • the second electrode when the second electrode is a transparent electrode, the second electrode is fluorine-containing tin oxide (FTO; Fouorine doped Tin Oxide), indium doped tin oxide ( ⁇ ; Indium doped Tin Oxide), ZnO, CNT (carbon nanotube) It may be an inorganic conductive electrode such as graphene, or an organic conductive electrode such as PEDOT: PSS.
  • the second electrode may be a transparent electrode, and the second electrode may be an organic conductive electrode. For electrodes, it is better than to provide flexible solar cells or transparent solar cells.
  • Pilkington (hereinafter referred to as an 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 Ti0 2 dense film was prepared by spray pyrolysis on a cut and partially etched FTO substrate.
  • the spray pyrolysis was performed using TAA (Titanium acetylacetonate): EtOH (1: 9 v / v%) solution.
  • the thickness was adjusted by repeating the method of spraying for 3 seconds and stopping for 10 seconds on an FTO substrate placed on a hot plate maintained at 450 ° C.
  • Titanium peroxocomplex aqueous solution was prepared by hydrothermal treatment at 250 ° C. for 12 hours), ethyl cellulose dissolved in ethyl alcohol with 10% by weight of ethyl cellulose.
  • the solution was added 5 ml per lg Ti0 2 powder, terpinol was added by adding 5 g per 1 g Ti0 2 powder, and then ethyl alcohol was removed by distillation under reduced pressure to prepare Ti0 2 paste.
  • Ethanol was added to the Ti0 2 powder prepared paste (l (Ti0 2 powder paste): 5 (ethanol), by weight) to prepare a Ti0 2 slurry for spin coating.
  • l (Ti0 2 powder paste): 5 (ethanol), by weight was added to the Ti0 2 powder prepared paste (l (Ti0 2 powder paste): 5 (ethanol), by weight) to prepare a Ti0 2 slurry for spin coating.
  • porous Ti0 2 thin film was fabricated by heat treatment at C for 30 minutes, wherein the thickness of the porous Ti0 2 thin film (porous electron transporter) was 100 nm and the specific surface area of the prepared porous electron transporter was 33 m 2 /. g, and the porosity (apparent porosity) was 50%.
  • Methyl ammonium chloride was added to prepare a perovskite compound solution.
  • the prepared perovskite compound solution is applied (injected) at the center of rotation on the porous electron transporter, and after 60 seconds at 1500 rpm, the spin coating is performed at 5000 rpm. At the time when the spin coating time reached 50 seconds, 1 mL of toluene was uncoated (injected) again at the center of rotation of the porous electron transporter in spin, and then spin coated for 60 seconds.
  • the perovskite compound film After spin coating, annealing was performed for 10 minutes at a temperature of 150 ° C. and atmospheric pressure to form a perovskite compound film.
  • the perovskite compound is filled with pores of the porous electron transporter and the porous electron transporter is prepared. It was confirmed that it was manufactured in the form of a covering dense film (thickness of about 250 nm).
  • the main conversion mirror In preparing the perovskite compound film, the main conversion mirror maintained a temperature of 25 ° C and a relative humidity of 25%.
  • X-ray with (FWHM) was carried out under the incident angle of 0.3 ° and the bending magnet light source 6D UNIST-PAL beamline of the Pohang Accelerator Laboratory was used. Scattered images were collected using a two-dimensional domain detector (manufacturer: Rayonix, model name MX225-HS), and the detector was taken from a sample.
  • the measurement area of the sample was 0.15 mm x 1 mm (vertical length in the normal direction X length in the beam direction).
  • Example 1 is a diagram showing GIWAXS spectrum according to the additive content of the perovskite compound film prepared in Example 1. The closer to white in the drawing, the larger the diffraction intensity was detected, and the closer to black. Small diffraction intensity was detected.
  • 1: 0 is the same as that of Example 1 without adding an additive.
  • FT (yri0 2 ref is a diagram showing the GIWAXS spectrum of the substrate on which the porous electron transporter is formed before the perovskite compound film is formed.
  • perovskite compound film when no additive is added, a perovskite compound film is produced in which a coarse orientation and a preferential orientation coexist, but the orientation in which the (100) plane is placed in parallel with the film (substrate) is preferable.
  • Perovskite compound When the additive ratio is 1: 0.2, it is understood that the perovskite compound film having an extremely random orientation, which does not exhibit a specific orientation, is completely disappeared when the additive orientation is not added.
  • perovskite compounds when the ratio of the additive is within 0.5, a new preferential orientation with random orientation, i.e., orientation or other appearance of (100) faces parallel to the surface of the substrate (substrate) have.
  • FIG. 3 shows the (100) diffraction intensity of a 1: 0.25 sample according to the azimuth angle in FIG. 1
  • FIG. 4 shows the (100) diffraction intensity of the 1: 0 sample according to the azimuth angle in FIG. It is shown.
  • the average intensity in the azimuth angle range from 170 ° to 170 °
  • the second largest peak (I f ) at a 90 ° azimuth angle (I f ) is 2.67, indicating that most of the grains of the perovskite compound are oriented so that the (100) crystal plane is parallel to the film.
  • a peak peak at a 90 ° azimuth angle (FWHM) is sharp at 4.1 °, and a 1: 0.75 sample is also shown at 5.2 ° as a half peak width (FWHM) of a peak at 90 ° azimuth.
  • FWHM half peak width
  • Fig. 7 is a scanning electron micrograph of the surface of the 1: 1 sample of the perovskite compound film.
  • the additive content controls the orientation of the perovskite compound film, and at the same time, a significant coarsening of the perovskite compound grains occurs.
  • the average grain size is 3 to 5 ⁇ , and a perovskite compound film is formed of highly coarse grains with high orientation.
  • the pattern (using the Cu-Kot line) is shown. 1: 0.25, 1: 0.5, 1: 0.75, and 1: 1 are 0.25 mol, 0.5 mol, 0.75 based on 1 mol of perovskite compound. X-ray diffraction results of the sample added with mole or 1 mole of additive.

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Abstract

본 발명은 무/유기 하이브리드 페로브스카이트 화합물 막에 관한 것으로, 본 발명에 따른 무/유기 하이브리드 페로브스카이트 화합물 막은 다결정체이며, 1.0688Å의 X-선 파장을 이용한 스침각 입사 광각 X-선 산란(GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼 상, 불연속적인 (100)면의 산란 강도를 갖는를 갖는다.

Description

명세서
발명의명칭:무 /유기하이브리드페로브스카이트화합물막및 이의제조방법
기술분야
[1] 본발명은무 /유기하이브리드페로브스카이트화합물막및이의제조방법에 관한것으로，상세하게,결정성과배향성이우수하여단결정유사특성을보이는 무 /유기하이브리드페로브스카이트화합물막및용액도포법에기반한이의 제조방법에관한것이다.
배경기술
[2] 오가노메탈할라이드페로브스카이트화합물 (Organometal halide perovskite compound)로도지칭되는무 /유기하이브리드페로브스카이트화합물은유기 양이온 (A),금속양이온 (M)및할로겐음이온 (X)으로이루어지며，
페로브스카이트구조를갖는물질이다.이러한무 /유기하이브리드
꿰로브스카이트화합물은소재가격이매우낮고，
자기 -조립 (self-assembling)하여결정화되는특성에의해저가의용액공정및 저은공정이가능하며，저가의원료로제조가능함에따라상업성이우수하여 , 발광소자,메모리소자,센서,광발전소자등다양한분야에서활발한연구가 이루어지고있다.
[3] 페로브스카이트태양전지는광흡수물질이무 /유기하이브리드
페로브스카이트화합물 (이하，페로브스카이트화합물)에기반한고체상 태양전지를의미한다.본출원인은대한민국공개특허제 2014-0035284호를 통해,현저하게높은발전효율을갖는신규한구조의페로브스카이트 태양전지를제안한바있으며，발전효율이 21%에 이르는페로브스카이트 태양전지를개발한바있다.새로운구조의페로브스카이트태양전지를 제안함으로써，종래 10%안깎에머물고있던페로브스카이트태양전지의 효율을 21%에 이르도록향상시켰으나，결정질실리콘기반태양전지의효율과 버금가는 20%중반대의효율을갖기위해서는，이러한구조변경과함께 페로브스카이트화합물자체의물성을향상시켜야할필요가있다.
[4] 페로브스카이트태양전지의발전효율을보다더향상시키기위해서는, 광전하의비-방사재결합 (non-radiative recombination)및스캐터링에의한감소를 최소화하여야한다.이러한비-방사재결합및스캐터링은페로브스카이트 화합물막자체에존재하는입계 (grain boundary)의트랩장소 (trap site)와 페로브스카이트화합물결정 (crystal)내의결함 (defect)에의해주로발생한다. 이에따라，광전하의소멸을방지하기위해서는단결정과유사한결정성이 요구된다.
[5] 잘알려진바와같이，대표적인물질인 CH3NH3PbI3를포함하여 페로브스카이트화합물이단결정인경우，높은전하이동도와긴액시톤라이프 타임및낮은트랩농도에의해 175μπι에이르는정공확산길이 (diffusion length)를가짐이보고 (H. Jinsong et. al., Science 2015, 347, 967-970)된바있으며 , 단결정체의페로브스카이트화합물의트랩 (trap)농도는고순도실리콘과트랩 농도와유사하다고보고 (0. M. Bakr et al. Science 2015, 347, 519)된바있다. 그러나,단결정체의페로브스카이트화합물자체를이용하여다양한구조의 소자를제조하는것은실질적으로구현되기어려우며，상업성이매우떨어진다.
[6] 이에따라,페로브스카이트화합물의가장큰장점인용액공정을이용하여， 고결정성을갖고，그배향성이조절되어단결정과유사한그레인 (grain)구조를 가지며，극히조대한결정립 (grain)들로이루어진페로브스카이트화합물막을 제조하는기술은,저가의단순공정및대량생산이라는상업성을유지하면서도 태양전지를비롯한페로브스카이트화합물기반소자들의성능을비약적으로 향상시킬수있는핵심기술이라할수있다.
발명의상세한설명
기술적과제
[7] 본발명의목적은，배향성이제어된페로브스카이트화합물막을제공하는 것이며，상세하게,우수한결정성을갖고극히조대한그레인 (grain)들로 이루어지며,그배향성이제어된페로브스카이트화합물막을제공하는것이다.
[8] 본발명의다른목적은,저가의단순공정인용액도포법을이용하여배향성이 제어된페로브스카이트화합물막의제조방법을제공하는것이며，상세하게， 우수한결정성을갖고극히조대한그레인 (grain)들로이루어지며，그배향성이 제어된페로브스카이트화합물막의제조방법을제공하는것이다.
[9] 본발명의또다른목적은배향성이제어된페로브스카이트화합물막을
포함하는소자를제공하는것이다.
과제해결수단
[10] 본발명의계 1양태에따른무 /유기하이브리드페로브스카이트화합물막은 다결정체이며, 1.0688人의 X-선파장올이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼상, 불연속적인 (100)면의산란강도를갖는다.
[11] 본발명의제 1양태에따른일실시예에 있어，무 /유기하이브리드
페로브스카이트화합물막은 (100)면의산란백터 (q, A"1)에서， 3내지 15개의 피크 (peak)가존재할수있다.
[12] 본발명의제 1양태에따른일실시예에 있어，산란스펙트럼은산란백터성분 q z를 y축으로，산란백터성분 qxy를 X축으로한강도분포이며， (100)면의 피크 (peak)증 qxy=0에상대적으로가장강도가큰피크가위치할수있다.
[13] 본발명의제 1양태에따른일실시예에 있어,산란스펙트럼은하기관계식 1을 만족할수있다. [14] (관계식 1)
[15] 2.0 < If/Is
[16] 관계식 1에서， If는 (100)면의피크 (peak)중상대적으로가장큰피크의
강도이며， 는 (100)면의피크중상대적으로두번째큰피크의강도이다.
[17] 본발명의제 2양태에따른무 /유기하이브리드페로브스카이트화합물막은 다결정체이며, 1.0688A의 X-선파장을이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼에서， 방위각 (azimuth)에따른 (100)면의산란강도기준, 10내지 170ο의방위각 범위에서연속적인산란강도를가지며 ,하기관계식 2로규정되는배향성이 하기관계식 3을만족한다.
[18] (관계식 2)
[19] PO(100) = I90/Iave
[20] PO(IOO)은 (100)면이막에평행하게배향된배향성을의미하며， 190은
방위각 (azimuth)에따른 (100)면의산란강도기준, 90°방위각에서의강도이며， I ave는동일한방위각에따른 (100)면의산란강도기준, 10내지 170°의방위각 범위의평균산란강도이다.
[21] (관계식 3)
[22] 1.0 < PO(100) < 25
[23] 본발명의제 2양태에따른일실시예에 있어,무 /유기하이브리드
페로브스카이트화합물막은하기관계식 4로규정되는균일도가하기관계식 5를만족할수있다.
[24] (관계식 4)
[25] UF = o/Iave
[26] UF는균일도로， Iave는방위각 (azimuth)에따른 (100)면의산란강도기준， 10 내지 170°의방위각범위의평균산란강도이며， σ는 10내지 170°의방위각 범위의산란강도표준편차이다.
[27] (관계식 5)
[28] 0.1 < UF < 0.4
[29] 본발명의제 1양태또는제 2양태에따른일실시예에있어，무 /유기하이브리드 페로브스카이트화합물막의무 /유기하이브리드페로브스카이트화합물은 하기화학식 1，화학식 2또는화학식 3을만족할수있다.
[30] (화학식 1)
[31] AMX3
[32] 화학식 1에서 , A는 1가의양이온으로 , A는유기암모늄이온,
아미디니움계 (amidinium group)이온또는유기암모늄이온과아미디니움계 이온이며 , Μ은 2가의금속이온이며, X는할로겐이온이다.
[33] (화학식 2)
[34] ACM^NJXa [35] 화학식 2에서， A는 1가의양이온으로， A는유기암모늄이온， 아미디니움계 (amidinium group)이은또는유기암모늄이온과아미디니움계 이온이며， M은 2가의금속이온이고， N은 1가의금속이온및 3가의금속이온중 하나이상선택되는도핑금속이온이며， a는 0<a≤0.1인실수이며, X는할로겐 이은이다.
[36] (화학식 3)
[37] A(N .bN )X3
[38] 화학식 3에서 , A는 1가의양이온으로, A는유기암모늄이온,
아미디니움계 (amidinium group)이은또는유기암모늄이온과아미디니움계 이온이며 , Ν'은 1가의금속이온이고， Ν2는 3가의금속이온이며， b는
0.4≤b≤0.6인실수이며, X는할로겐이온이다.
[39] 본발명에따른무 /유기하이브리드페로브스카이트화합물막의제조방법은 기재상무 /유기하이브리드페로브스카이트화합물및유기할로겐화물인 첨가제를함유하는페로브스카이트화합물용액을도포하고,도포된 페로브스카이트화합물용액과페로브스카이트화합물의비용매를접촉시킨후 어닐링하여무 /유기하이브리드페로브스카이트화합물막을제조하는단계;를 포함하며 ,페로브스카이트화합물용액내의첨가제함량，즉,페로브스카이트 화합물용액에함유된페로브스카이트화합물：첨가제의몰비를조절하여 무 /유기하이브리드페로브스카이트화합물막의결정배향성을제어한다.즉， 본발명에따른무 /유기하이브리드페로브스카이트화합물막의제조방법은， 기재상무 /유기하이브리드페로브스카이트화합물및유기할로겐화물인 첨가제를함유하는페로브스카이트화합물용액을도포하는단계,및기재상 도포된페로브스카이트화합물용액과페로브스카이트화합물의비용매를 접촉시킨후어닐링하는단계;를포함하며，페로브스카이트화합물용액내의 첨가제함량을조절하여무 /유기하이브리드페로브스카이트화합물막의결정 배향성을제어한다.
[40] 본발명의일실시예에따른제조방법에있어，첨가제는
메틸암모늄할로겐화물일수있다.
[41] 본발명의일실시예에따른제조방법에있어,페로브스카이트화합물용액은 무 /유기하이브리드페로브스카이트화합물 1몰기준 0.2내지 0.7몰의첨가제를 함유할수있다.
[42] 본발명의일실시예에따른제조방법에있어,페로브스카이트화합물용액은 무 /유기하이브리드페로브스카이트화합물 1몰기준 0.75내지 1.5몰의 첨가제를함유할수있다ᅳ
[43] 본발명의일실시예에따른제조방법에있어，페로브스카이트용액의도포및 비용매와의접촉은스핀코팅을이용한페로브스카이트용액및비용매의 순차적도포에의해수행될수있다.
[44] 본발명은상술한제 1양태또는제 2양태에따른무 /유기하이브리드 페로브스카이트화합물막을포함하는소자를포함한다.
[45] 본발명의 일실시예에따른소자는전자소자，발광소자,메모리소자,광발전 소자，광센서또는열전소자일수있다.
발명의효과
[46] 본발명에따른페로브스카이트화합물막은극히우수한배향성을가지며，수 μπι오더 (order)의조대한그레인 (grain)들로이루어진고결정성막인장점이 있다.
[47] 본발명에따른제조방법은단순한용액도포를이용하여，배향성이제어된 페로브스카이트화합물막을제조할수있으며，제어된배향성을가지면서도， 우수한결정성올갖는조대한그레인 (grain)들로이루어진페로브스카이트 화합물막올제조할수있는장점이 있다.
도면의간단한설명
[48] 도 1은실시예 1에서제조된페로브스카이트화합물막의 첨가제함량에따른 GIWAXS스펙트럼을도시한도면이며，
[49] 도 2는도 1에서， 1： 1샘플의 GIWAXS스펙트럼을도시한도면이며，
[50] 도 3은도 1에서, 1： 0.25샘플의 (100)면회절강도를방위각에따라도시한 도면이며,
[51] 도 4는도 1에서, 1： 0샘플의 (100)면회절강도를방위각에따라도시한
도면이며,
[52] 도 5는도 1에서， 1： 1샘플의 (100)면회절강도를방위각에따라도시한
도면이며,
[53] 도 6은도 1에서 1:0.5샘플의페로브스카이트화합물막의표면을관찰한 주사전자현미경사진이며，
[54] 도 7은도 1에서 1:1샘플의페로브스카이트화합물막의표면을관찰한
주사전자현미경사진이며，
[55] 도 8은실시예 1에서제조된페로브스카이트화합물막의 X-선회절패턴을 도시한도면이다.
[56]
발명의실시를위한형태
[57] 이하첨부한도면들을참조하여본발명올상세히설명한다.다음에소개되는 도면들은당업자에게본발명의사상이충분히전달될수있도록하기위해 예로서제공되는것이다.따라서，본발명은이하제시되는도면들에한정되지 않고다른형태로구체화될수도있으며，이하제시되는도면들은본발명의 사상을명확히하기위해과장되어도시될수있다.이때，사용되는기술용어및 과학용어에 있어서다른정의가없다면，이발명이속하는기술분야에서 통상의지식을가진자가통상적으로이해하고있는의미를가지며，하기의설명 및첨부도면에서본발명의요지를불필요하게흐릴수있는공지기능및 구성에 대한설명은생략한다.
[58] 본발명은무 /유기하이브리드페로브스카이트화합물막,이의제조방법및 무 /유기하이브리드페로브스카이트화합물막을포함하는소자에관한것이다.
[59] 본발명에서，무 /유기하이브리드페로브스카이트화합물은，오가노메탈
할라이드페로브스?] "이트화합물 (Organometal halide perovskite compound)로도 통칭된다.무 /유기하이브리드페로브스카이트화합물 (이하，페로브스카이트 화합물)은유기 양이온 (A),금속양이온 (M)및할로겐음이은 (X)으로
이루어지며,페로브스카이트구조를갖는화합물이다.상세하게，
페로브스카이트화합물은 MX6옥타헤드론 (octahedron)이
코너-쉐어링 (corner-Shearing)된 3차원네트워크에 A유기양이온이중간에 위치한형태이다.
[60] 본발명은제 1양태로,페로브스카이트화합물막을이루는페로브스카이트 화합물결정립 (grain)들이특정한방향으로고도하게배향된페로브스카이트 화합물막을제공한다.
[61] 본발명의제 1양태에따른무 /유기하이브리드페로브스카이트화합물
막 (이하,페로브스카이트화합물막)은다결정체이며， 1.0688人의 X-선파장을 이용한스침각입사광각 X-선산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼상，불연속적인 (100)면의산란강도를갖는다.
[62] (100)면의산란강도가불연속적이다함은, GIWAXS스펙트럼상 (100)면의 회절이전방위적으로발생하지않아,특정방위각 (azimuth)에서만회절피크가 나타남을의미하는것이다.즉， GIWAXS스펙트럼상 (100)면의스팟형태의 회절패턴이나타남을의미하는것이다.
[63] 구체적으로, (100)면의산란강도가불연속적이다함은， GIWAXS스펙트럼상 0내지 180°의방위각범위에서 (100)면의회절에의한회절강도가 0인영역이 존재함을의미하는것이다.이때회절강도가 0인경우는노이즈 (noise)레벨의 강도가검출되는경우를포함함은물론이다.
[64] 보다구체적으로 (100)면의산란강도가불연속적이다함은， GIWAXS
스펙트럼상 60내지 120°의방위각범위에서 85내지 95°의방위각에서만 (100)면의회절피크가존재 ((100)면에의한회절이검출됨)함을의미하는 것이며，보다구체적으로 60내지 120°의방위각범위에서 85내지 950의 방위각에 (100)면의회절피크의중심이위치하는단일한회절피크가
존재 ((100)면에의한회절이검출됨)함을의미하는것이다.
[65] 이러한불연속적산란패턴은페로브스카이트화합물막이우수한결정
배향성을가짐을의미하며，막을이루는페로브스카이트화합물결정 (grain)들이 회절피크가존재하는몇몇특정방향으로만배향되어 있음을의미한다ᅳ
[66] 나아가, GIWAXS스펙트럼상 60내지 120°의방위각범위에서 85내지 95°의 방위각에만회절피크가존재 (피크의중심이존재)한다는것은，페로브스카이트 화합물막을이루는결정들에서， (100)결정면이임의로틸트 (tilt)되어 있지않고 많은결정들의 (100)결정면이막에평행하게배향되어 있는것을의미한다.
[67] 구체적으로,본발명의게 1양태에따른일실시예에 있어， GIWAXS스펙트럼 상 (100)면의산란백터 (q, A-1)상, 3내지 15개의피크 (peak)가존재할수있다.즉, 0내지 180°의방위각범위에서 (100)면의회절에의한회절피크가 3내지 15개 존재할수있다.실질적으로， (100)면의산란백터상상대적으로가장큰피크의 강도를기준으로， 10%이상의강도를갖는피크의수는 3내지 5개일수있다.
[68] 이러한회절피크의수는페로브스카이트화합물막을이루는결정들에서，
(100)결정면이배향된방향의수에대응할수있다.즉， (100)면의회절에의한 회절피크가 3내지 15개존재하는것은，페로브스카이트화합물막을이루는 결정들에서， (100)결정면이 3내지 15개의특정방향으로만배향되어존재하는 것을의미한다
[69] 또한，가장큰피크의강도를기준으로 10%이상의강도를갖는피크의수가 3 내지 5개인것은，페로브스카이트화합물막을이루는결정들에서,거의 대부분의결정들이 (100)결정면이 3내지 5개의방향으로배향되어존재함을 의미한다.
[70] 원호형상이아닌스팟형상의불연속적인 GIWAXS스펙트럼및 3내지 15개, 실질적으로 3내지 5개의피크는，본발명의제 1양태에따른페로브스카이트 화합물막의극히우수한배향성을나타내는지표이다.
[71] 구체적이며비한정적인일예로， 0내지 180°의방위각범위에서 (100)면의 회절에의한회절피크는 3내지 8ο, 40내지 45°, 85내지 95°및 170내지 178°의 방위각에위치할수있다.보다구체적이며비한정적인일예로，가장큰피크의 강도를기준으로， 10%이상의강도를갖는피크는 4개일수있으며， 4개의피크는 3내지 80， 40내지 450， 85내지 95°및 170내지 178°의방위각에위치할수있다.
[72] 본발명의제 1양태에따른일실시예에 있어，페로브스카이트화합물막의산란 스펙트럼은산란백터성분 ¾를 y축으로，산란백터성분 qxy를 X축으로한강도 분포일수있으며， (100)면의피크 (peak)중 qxy=0에상대적으로가장강도가큰 피크가위치할수있다.달리상술하면， 0내지 180°방위각 (azimuth)영역에서， 90°방위각 (azimuth)에상대적으로가장강도가큰 (100)면의피크가위치할수 있다.
[73] 이는페로브스카이트화합물막을이루는결정들이몇몇특정방향으로 (100) 결정면이위치하도록배향되되，대부분의결정들이 (100)결정면이막과 평행하게배열되어 있음을의미한다.
[74] (100)결정면의특정방향으로의우선적배향 (preferred orientation)의정도는 GIWAXS스펙트럼상의회절강도로규정될수있다.상세하게， 0내지 180° 방위각 (azimuth)영역에서, (100)면의회절피크는하기관계식 1을만족할수 있다ᅳ
[75] (관계식 1)
[76] 2.0 <If/Is [77] 관계식 1에서, If는 (100)면의회절피크 (peak)중상대적으로가장큰피크의 강도이며， 15는 (100)면의회절피크중상대적으로두번째큰피크의강도이다.
[78] 보다특징적으로，본발명의게 1양태에따른페로브스카이트화합물막은 If/Is 가 2.5이상일수있으며, 1 는실질적으로 10이하일수있다.
[79] 가 2.0,보다특징적으로는 2.5이상은,페로브스카이트화합물막을이루는 결정립들중극히많은결정립들이 (100)면이막과평행한방향으로배향되어 있음을의미한다.
[80] 본발명의제 1양태에따른일실시예에있어,페로브스카이트화합물막은, 0 내지 180°의방위각에따른 (100)면의회절강도기준,방위각 85내지 95°,보다 구체적으로는 88내지 92°,실질적으로는 90°에위치하는회절피크의방위각의 반치폭 (FWHM)이 5.5°이하，보다특징적으로는 4.5°이하일수있다.이러한 좁은반치폭은，많은결정립들이매우엄밀하게 (100)면이막과평행한방향으로 배향되어있음을의미하며，잘규정된우선적배향성을가짐을의미한다.
[81] (100)면은페로브스카이트구조에서치밀면에해당하며,이러한치밀면들이 막과평행한방향으로배향된고배향성을갖는페로브스카이트화합물막은, 우수한전하이동도를가질수있으며，현저하게낮은트램농도를가질수있고， 전하의스캐터링을현저하게감소시킬수있다.
[82] 본발명의제 1양태에따른일실시예에있어 ,페로브스카이트화합물막은평균 결정립의크기가 1내지 5μηι인극히조대한결정립들로이루어질수있다. 상술한배향성을가지면서극히조대한결정립올갖는페로브스카이트화합물 막은단결정과매우유사한특성을나타낼수있다.
[83] 본발명은제 2양태로，페로브스카이트화합물막을이루는페로브스카이트 화합물결정립 (grain)들이랜덤하게배향된페로브스카이트화합물막올 제공한다.
[84] 다결정체의페로브스카이트화합물막올제조하는경우，페로브스카이트
화합물결정과대기 (분위기기체)간의에너지인표면에너지 (surface energy), 결정과결정간의입계에너지,페로브스카이트화합물막하부에위치하는이종 물질과페로브스카이트화합물결정간의계면에너지등을최소화시키려는 구동력이존재한다.이러한구동력에의해，다결정체의페로브스카이트화합물 막은결정립의랜덤한배열과함께특정방향으로보다많이배향되어있는 우선적배향 (preferred orientation)성을동시에나타내게된다.즉，산란백터성분 를 y축으로，산란백터성분 qxy를 X축으로한강도분포인 GIWAXS 스펙트럼에서,특정면 (일예로, (100)면)에해당하는산란백터상방위와 무관하게연속적으로강도가검출되어산란패턴이원호를이루나，그원호중 일부분들의산란강도가다른부분들보다상대적으로강한패턴을나타내게 된다.그러나，이러한상대적으로강한패턴은게 1양태에서상술한바람직한 (100)의배향성，즉, (100)면이막 (또는기재)표면과평행하게위치하는배향성을 갖지못해，전기적특성이저하되는문제점이있다. [85] 본발명은제 2양태로,이러한랜덤한배향성 (random orientation)과함께 나타나는우선적배향성 (preferred orientation)이 억제되어，실질적으로거의 완벽하게결정립들이 랜덤하게배열된페로브스카이트화합물막을제공한다. 또한，본발명은게 2양태로，랜덤한배향성과함께， (100)면이막의표면에 평행하게배열된우선적배향성을갖는페로브스카이트화합물막을제공한다. 상술한바와같이，치밀막인 (100)면이막에평행하게배열된경우,다른우선적 배향보다도우수한전하이동도를가질수있으며,현저하게낮은트램농도도를 가질수있다.
[86] 본발명의제 2양태에따른무 /유기하이브리드페로브스카이트화합물막은 다결정체이며， 1.0688A의 X-선파장을이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼에서, 방위각 (azimuth)에따른 (100)면의산란강도기준， 10내지 170ο의방위각 범위에서 연속적인산란강도를가지며，하기관계식 2로규정되는배향성이 하기관계식 3을만족한다.
[87] (관계식 2)
[88] ΡΟ(100) = I90/Iave
[89] PO(IOO)은 (100)면이막에평행하게배향된배향성을의미하며， 190은
방위각 (azimuth)에따른 (100)면의산란강도기준, 90°방위각에서의강도이며, I ave는동일한방위각에따른 (100)면의산란강도기준， 10내지 170°의방위각 범위의평균산란강도이다.
[90] (관계식 3)
[91] 1.0 < PO(100) < 25
[92] 상술한관계식 2에서 PO(IOO)은페로브스카이트화합물막을이루는
결정립들의배향에서， (100)결정립이페로브스카이트화합물막과평행하게 배향된정도를의미한다.관계식 3에서 PO(IOO)가 1.0이상임은,랜덤한배향성이 주를이루되 , (100)면이막에평행하게배향된우선적배향성이실질적으로 나타나지않거나,매우미약하게나타남을의미하며， 5이상의 ΡΟ(100)은랜덤한 배향성과함께 (100)면이막에평행하게배향된우선적배향성이뚜렷이 나타남을의미한다.나아가, 15내지 25의 PO(IOO)은다량의결정립이 (100)면이 막에평행하게배향된우선적배향성을가짐을의미할수있다.
[93] 본발명은제 2양태에따른일실시예로,극히 랜덤한배향을갖는
페로브스카이트화합물막을제공하며，랜덤한배향을갖는페로브스카이트 화합물막은무 /유기하이브리드페로브스카이트화합물막은다결정체이며, 1.0688人의 X-선파장올이용한스침각입사광각 X-선산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼에서 ,방위각 (azimuth)에따른 (100)면의산란강도기준, 10내지 170°의방위각범위에서연속적인산란 강도를가지며,하기관계식 4로규정되는균일도가하기관계식 5를만족할수 있다. [94] (관계식 4)
[95] UF = o/Iave
[96] UF는균일도로， Iave는방위각 (azimuth)에따른 (100)면의산란강도기준， 10 내지 170°의방위각범위의평균산란강도이며 , σ는 10내지 170°의방위각 범위의산란강도표준편차이다.
[97] (관계식 5)
[98] 0.1 < UF < 0.4
[99] 관계식 4로규정되는균일도가 0.1내지 0.4，보다구체적으로는균일도가 0.1 내지 0.3이라함은，페로브스카이트화합물막을이루는페로브스카이트화합물 결정립 (grain)들이극히 랜덤하게배열된다결정체막임을의미한다.
페로브스카이트화합물막이관계식 4및관계식 5를만족할때,상술한관계식 2에따른 PO(IOO)은 1.0내지 2.0일수있다. 0.1내지 0.4의균일도는용액 도포법을포함하여종래기재상다결정체의페로브스카이트화합물막을 형성하는방법에서는구현되지못했던균일도이다.
[100] 본발명은계 2양태에따른일실시예로,랜덤한배향을갖되， (100)면이막에 평행한우선적배향성을동시에갖는페로브스카이트화합물막을제공한다. 이에따른무 /유기하이브리드페로브스카이트화합물막은
다결정체이며 ,1.0688 A의 X-선파장을이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼에서, 방위각 (azimuth)에따른 (100)면의산란강도기준, 10내지 170ο의방위각 범위에서연속적인산란강도를가지며，관계식 3으로규정되는 PO(IOO)이 5 내지 25，실질적으로 5내지 15，보다실질적으로 5내지 10을만족할수있다. PO(IOO)가 5내지 25，실질적으로 5내지 15,보다실질적으로 5내지 10을 만족하는페로브스카이트화합물막은전방위적회절이발생하는ᅳ랜덤한 배향성을가짐과동시에， (100)면이막과평행하게배향된우선적배향성또한 발달한구조를가질수있다.
[101] 본발명의계 2양태에따른일실시예에 있어，페로브스카이트화합물막은평균 결정립의크기가 500nm내지 3μηι인조대한결정립들로이루어질수있다.
[102] 이하，제 1양태및제 2양태에따른페로브스카이트화합물막의세부구성을 상술하며,이하특정양태를명시하며한정하지않는한，상술하는내용은 제 1양태에따른페로브스카이트화합물막및제 2양태에따른페로브스카이트 화합물막모두에해당한다.
[103] 본발명의 일실시예에따른페로브스카이트화합물막에 있어，
페로브스카이트화합물막의 GIWAXS스펙트럼은 λ = 1.0688人 (11.6keV),빔 크기 150;Mn(h)xl20 (v) (FWHM:반가폭)을갖는 X-선을이용하여 입사각 =0.3° 조건에서측정된것일수있으며， 2차원영역검출기를이용하여회절패턴을 캡춰한것일수있고，검출기는 GIWAXS측정을위한샘플로부터 246.4118mm에 위치된것일수있으며，샘플의측정면적은 0.1mm2내지 20mm2일수있다. [104] 본발명의일실시예에따른페로브스카이트화합물막에있어, 페로브스카이트화합물은하기화학식 1，화학식 2또는화학식 3을만족할수 있다.
[105] (화학식 1)
[106] AMX3
[107] 화학식 1에서， A는 1가의양이온으로， A는유기암모늄이온,
아미디니움계 (amidinium group)이온또는유기암모늄이은과아미디니움계 이은이며 , Μ은 2가의금속이온이고, X는할로겐이온이다.이때，할로겐이온은 I-, Br, F-및 C1-에서하나또는둘이상선택될수있다.
[108] (화학식 2)
[109] A(M1-aNa)X3
[110] 화학식 2에서 , A는 1가의양이온으로, A는유기암모늄이온,
아미디니움계 (amidinium group)이온또는유기암모늄이온과아미디니움계 이온이며， M은 2가의금속이온이고， N은 1가의금속이온및 3가의금속이온중 하나이상선택되는도핑금속이온이며， a는 0<a≤0.1인실수이며， X는할로겐 이온이다.이때，할로겐이온은 I-, Br, F-및 C1-에서하나또는둘이상선택될수 있다.
[111] 화학식 2에서，도핑금속이온인 1가의금속이은은금속이온은 Li+, Na+, K+, Rb +， Cs+,In1+, Cu1+및 Ag 이온에서하나또는둘이상선택될수있다.
[112] 화학식 2에서，도핑금속이은인 3가의금속이온은 Al3+, Ga3+, In3+, Tl3+, Sc3+, Υ3+ ， La3+, Ce3+, Fe3+, Ru3+, Cr3+, V3+, Ti3+, Sb3+, Bi3+및 As3+이온에서하나또는둘이상 선택될수있다.
[113] 화학식 2와같이, 1가의금속이온및 /또는 3가의금속이온이도핑된경우， 페로브스카이트화합물의전기적특성이 n형또는 p형으로조절될수있다. 상세하게, 1가의금속이은으로도핑되어페로브스카이트화합물이 p형을가질 수있다.또한， 3가의금속이온으로도핑되어페로브스카이트화합물이 n형올 가질수있다.즉, 1가의금속이온은통상의실리콘반도체에서어셉터가도핑된 것과유사하며， 3가의금속이온은통상의실리콘반도체에서도너가도핑된 것과유사하다.이때， 1가의금속이온과 3가의금속이온모두가도핑될수 있으며，보다다량으로함유된종류의금속이은에의해전체적인
페로브스카이트화합물의전기적특성이조절될수있음은물론이다.
[114] 화학식 1또는화학식 2에서 , M은 2가의금속이온일수있다.구체적인일
예로， M은 M은 Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+및 Yb2+ 에서하나또는둘이상선택된금속이온일수있다.
[115] (화학식 3)
[116] A(N'1.bN2 b)X3
[117] 화학식 3에서， A는 1가의양이온으로， A는유기암모늄이온，
아미디니움계 (amidinium group)이온또는유기암모늄이온과아미디니움계 이온이며 , ΙΨ은 1가의금속이은이고 , Ν2는 3가의금속이온이며， b는
0.4≤b≤0.6인실수이며， X는할로겐이온이다.
[118] 화학식 3에서， 1가의금속이온은태양광흡수에적합한밴드갭，작은정공
유효질량측면에서， In1+, Cu'+및 Ag1+에서하나또는둘이상선택될수있다.
[119] 화학식 3에서, 3가의금속이은은 Al3+, Ga3+, In3+, Tl3+, Sc3+, Υ3+, La3+, Ce3+, Fe3+,
Ru3+, Cr3+, V3+, Ti3+, Sb3+, Bi3+및 As3+에서하나또는둘이상선택될수있으며， 태양광흡수에적합한밴드갭，작은전자유효질량측면에서 Sb3+, BP+, Ga3+,및 In 3+에서하나또는둘이상선택될수있다.
[120] 보다좋게는， 1가의금속이온 -3가의금속이은쌍은,직접천이형밴드갭
구조를가지고,태양광흡수에적합한밴드갭에너지를가지며， 10-2오더의 현저하게작은정공유효질량과전자유효질량을갖는하기의하기 i)내지 V)일 수있다.
[121] i)In1+-Sb3+
[122] ii)In1+-Bi3+
[123] iii)Cu1+-In3+
[124] iv)Ag1+-In3+
[125] v)Ag1+-Ga3+
[126] 이때, b=().5일수있으며,이러한경우,페로브스카이트화합물은단순
페로브스카이트구조가아닌,이중페로브스카이트구조를가질수있다.이중 페로브스카이트구조는단일페로브스카이트구조의 M-자리 (site)에 1가의금속 이온 (N1)과 3가의금속이온 (N2)이규칙적으로배열된결정격자구조로서， Α2Ν' Ν2Χ6의화학식올가질수있다.알려진바와같이，이중페로브스카이트 구조 (double-layered perovskite structure)는 N!X3옥타헤드론과 N2X3옥타헤드론이 서로규칙적으로교번되며코너-쉐어링 (corner-shearing)된 3차원네트워크에 유기양이온이증간에위치한형태이다.이러한이중페로브스카이트구조는 큐빅결정계 (crystal system)의 Fm m공간군 (space group)에속할수있다.
[127] 화학식 1，화학식 2또는화학식 3에서,유기암모늄이온은하기화학식 4내지 5를만족할수있다ᅳ
[128] (화학식 4)
[129] R,-NH3 +
[130] 화학식 4에서 R,은 C1-C24의알킬, C3-C20의시클로알킬또는 C6-C20의
아릴이다.
[131] (화학식 5)
[132] R2-C3H3N2 +-R3
[133] 화학식 5에서 R2는 C1-C24의알킬， C3-C20의시클로알킬또는 C6-C20의
아릴이며 , ¾은수소또는 C1-C24의알킬이다.
[134] 화학식 1,화학식 2또는화학식 3에서,아미디니움계이온은하기화학식 6을 만족할수있다. [135] (화학식 6)
Figure imgf000015_0001
[137] 화학식 6에서, R4내지 R8은서로독립적으로，수소， C1-C24의 알킬， C3-C20의 시클로알킬또는 C6-C20의아릴이다.
[138] 화학식 1,화학식 2또는화학식 3에서， A는유기암모늄이온,
아미디니움계 (amidinium group)이은또는유기암모늄이온과아미디니움계 이온일수있다.유기암모늄이온과아미디니움계이온올모두함유하는경우， 페로브스카이트화합물의전하이동도를현저하게향상시킬수있다.
[139] A가유기암모늄이온과아미디니움계이온을모두함유하는경우， 1가유기 양이온의총몰수를 1로하여 ,으7내지 0.95의아미디니움계이온및 0.3내지 0.05의유기암모늄이은을함유할수있다.즉，화학식 1,화학식 2또는화학식 3에서, A는 A x)Ab x일수있으며 ,이때， Aa는아미디니움계이온이고， 는유기 암모늄이온이며， X는 0.3내지으 05의실수일수있다.아미디니움계이온과 유기암모늄이온간의몰비즉， 0.7내지 0.95몰의아미디니움계이온： 0.3내지 0.05몰의유기암모늄이은의몰비는매우넓은파장대역의광을흡수할수 있으면서도보다빠른엑시톤 (exciton)의 이동및분리，보다빠른광전자및 광정공의 이동이이루어질수있는범위이다.
[140] 화학식 4의 화학식 5의 R广 R3및 /또는화학식 6의 은페로브스카이트 화합물의용도에따라적절히선택될수있다.
[141] 상세하게,페로브스카이트화합물의단위셀의크기는페로브스카이트
화합물의밴드갭에 영향올미친다.이에따라，반도체채널층，발광층，반도체층， 광흡수층，전하저장층과같은페로브스카이트화합물막의용도를고려하여， 해당용도가적합한밴드갭을가질수있도록화학식 4의 RH화학식 5의 R2~R3 및 /또는화학식 6의 이적절히조절될수있으며，이는반도체소자나광 소자관련종사자에게는주지의사실이다.
[142] 구체예로，작은단위셀크기에서 태양광을흡수하는태양전지로활용하기에 적절한 1.5-1.1 eV의밴드갭에너지를가질수있다.이에따라,태양전지로 활용하기에적절한 1.5-U eV의밴드갭에너지를고려하는경우，화학식 4에서, 은 C1-C24의알킬，구체적으로 C1-C7알킬，보다구체적으로메틸일수있다. 또한，화학식 5에서 R2는 C1-C24의알킬일수있고 R3는수소또는 C1-C24의 알킬일수있으며，구체적으로 ¾는 C1-C7알킬일수있고 R3는수소또는 C1-C7 알킬일수있으며，보다구체적으로 R2는메틸일수있고 R3는수소일수있다. 또한，화학식 6에서 R4내지 R8은서로독립적으로,수소，아미노또는 C1-C24의 알킬，구체적으로，수소,아미노또는 C1-C7알킬,보다구체적으로수소，아미노 또는메틸일수있으며，보다더구체적으로 R4가수소,아미노또는메틸이고 R5 내지 ¾가수소일수있다.구체적이며비한정적인일예로，아미디니움계 이온은포름아미디니움 (formamidinium, NH2CH=NH2 +)이온，
아세트아미디니움 (acetamidinium, NH2C(CH3)=NH2 +)또는
구아미디니움 (Guamidinium, NH2C(NH2)=NH2 +)등을들수있다.
[143] 상술한바와같이，유기양이온 (A)의구체적인예들은，페로브스카이트화합물 막의용도,즉,태양광의광흡수층으로의용도를고려한일예이며,흡수하고자 하는광의파장대역의설계,발광소자의발광층으로사용하는경우발광파장 대역의설계,트랜지스터의반도체소자로사용하는경우에너지밴드갭과문턱 전압 (threshold voltage)둥을해당용도에요구되는특성을고려하여화학식 4의 R „화학식 5의 R2~R3및 /또는화학식 6의 이적절히선택될수있다.
[144] 화학식 1또는화학식 2에서， M은 2가의금속이온일수있다.구체적인일 예로， M은 M은 Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+및 Yb2+ 에서하나또는둘이상선택된금속이온일수있다.
[145] 화학식 1,화학식 2또는화학식 3에서， X는할로겐음이온이다.할로겐
음이온은 I-, Br, F및 CI-에서하나또는둘이상선택될수있다.구체적으로, 할로겐음이온은요오드이온 (1-)，클로린이온 (C1-)및브롬이온 (Br)에서하나 또는둘이상선택된이은을포함할수있다.보다구체적으로，할로겐음이온은 요오드이은및브롬이온을함유할수있다.할로겐음이온이요오드이온및 브롬이온을모두함유하는경우,페로브스카이트화합물의결정성및내습성올 향상시킬수있다ᅳ
[146] 구체예로，화학식 1,화학식 2또는화학식 3에서， X는 X y)Xb y일수있고, Xa 및 Xb는서로상이한할로겐이온 (요오드이온 (1-)，클로린이온 (C1-)및브롬 이온 (Br)에서선택되는서로상이한할로겐이온)이고, y는 0<y<l인실수일수 있다.보다구체적으로，화학식 1에서， X는 X y)Xb y일수있고, Xa요오드 이온이고, Xb는브롬이온이며， y는 0.05≤y≤0.3인실수,구체적으로 0.1≤y≤0.15인 실수일수있다.즉，수분에의한열화가현저히방지되고 100°C이하의저온 공정에서도우수한결정성을갖기위해,할로겐음이온이요오드이온및브롬 이온을모두함유하는경우,음이은의총몰수를 1로하여， 0.7내지 0.95의 요오드이온및 0.3내지 0.05의브롬이은을함유할수있다.
[147] 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), CH3NH3PbIxFy(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), NH2CH=NH2PbIx Cly(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3),NH2CH=NH2PbIxBry(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), NH2CH=NH2PbClxBry(0≤x≤3인실수， 0≤y≤3인실수및 x+y=3), NH2CH=NH2PbIxFy(0≤x≤3인실수, 0≤y≤3인실수및 x+y=3), NH2CH=NH wCHsNH PbadDBryMx는 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≤0.3인실수), NH2 CH=CH2(1.x)CH3NH3xPb(I(1-x)Brx)3(x는 0.05<x<0.3인실수)， N¾C(CH3)=NH2PbIxCly (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(1_x)CH3NH3xPb(I(1_y)Bry)3(x는 0.05≤x≤0.3인실수이며， y는
0.05<y<0.3인실수)， NH2C(CH3)=CH2(1.x)CH3NH3xPb(I(1-x)Brx)3(x는 ().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 0<χ<1인 실수이며 , y는 0<y<l인실수)， NH2C(NH2)=NH2(1-x)CH3NH3xPb(I(1_y)Bry)3(x는
0.05≤x≤0.3인실수이며, y는 0.05≤y≤0.3인실수)또는 NH2C(NH2)=CH2(1-X)CH3NH 3xPb(Vx)Brx)3(x는 0.05≤x≤0.3인실수)를들수있다.
[148] 본발명의일실시예에따른페로브스카이트화합물막에있어,
페로브스카이트화합물막의두께는그용도를고려하여적절히조절될수 있으나，구체적인일예로, 10nm내지 Ιμπι일수있다.태양전지의용도를 고려하는경우,페로브스카이트화합물막의두께는 100내지 800nm일수있다.
[149] 본발명은결정배향성이제어된페로브스카이트화합물막의제조방법을
제공한다.
[150] 본출원인은대한민국공개특허제 2014-0091489호를통해，페로브스카이트 화합물형성시，광흡수체용액내유기할로겐화물과금속할로겐화물의몰비를 달리함으로써，광흡수구조체의돌출구조를제어하는기술을제공한바있다. 또한，본출원인의공개특허제 2014-0035285호,공개특허제 2014-0035284호또는 공개특허제 2014-0035286호를통해，표면거칠기가낮으며치밀한막형상으로 페로브스카이트화합물의광흡수구조체를제조하는기술을제공한바있다. 이러한연구와연장되어,전지효율올보다증가시키기위해페로브스카이트 화합물자체의물성을개선하고자각고의노력을기을인결과，놀랍게도 페로브스카이트화합물이용매에용해된용액에유기할로겐화물을첨가제로 첨가한후，용액올도포하고도포된용액에비용매를접촉시키는경우， 유기할로겐화물인첨가제의함량에의해，페로브스카이트화합물막의 배향성이제어될수있음을발견하였다ᅳ
[151] 또한,다양한유기할로겐화물을첨가제로하여,막의배향성에미치는영향을 검토한결과，어떤유기할로겐화물보다도，메틸암모늄할로겐화물을첨가제로 사용하는경우，단지첨가제의양을조절하는것만으로，극히랜덤한배열에서 고도로특정된배향성까지막의배향성이놀랍도록제어되며，그제어가 안정적이고재현성있게이루어지는것을발견하였다.
[152] 이러한발견에기반한본발명에따른제조방법은기재상무 /유기하이브리드 페로브스카이트화합물및유기할로겐화물인첨가제를함유하는
페로브스카이트화합물용액을도포하고，도포된페로브스카이트화합물 용액과페로브스카이트화합물의비용매를접촉시킨후어닐링하여무 /유기 하이브리드페로브스카이트화합물막을제조하는단계;를포함하며， 페로브스카이트화합물용액내의첨가제함량을조절하여무 /유기하이브리드 페로브스카이트화합물막의결정배향성올제어하는특징이있다.
[153] 이때，첨가제는메틸암모늄할로겐화물인것이좋다.어떤
유기할로겐화물보다도，메틸암모늄할로겐화물을첨가제로사용하는경우，단지 첨가제의양，즉，페로브스카이트화합물용액에함유된페로브스카이트화합물 대비첨가제의몰비를조절하는것만으로，극히랜덤한배열에서고도로특정된 배향성까지막의배향성이놀랍도록제어되며，그제어가안정적이고재현성 있게이루어질수있다.메틸암모늄할로겐화물은메틸암모늄클로라이드, 메틸암모늄브로마이드，메틸암모늄아요다이드，메틸암모늄플루오라이드또는 이들의흔합물을포함할수있으며，보다좋게는메틸암모늄클로라이드일수 있다.
[154] 기재는페로브스카이트화합물막의용도를고려하여적절히설계될수있다. 구체적으로，기재는리지드기재또는플렉서블기재일수있으며 ,이와 독립적으로，투명또는불투명기재일수있다.결정학적으로，기재는단결정처 L 다결정체또는비정질체이거나，결정상과비정질상이혼재된흔합상일수있다. 일예로，기재는반도체,세라믹，금속，고분자또는이들에서선택된둘이상의 물질이각층을이루며적층된적층체일수있다ᅳ반도체기재의비한정적인일 예로,실리콘 (Si),게르마늄 (Ge)또는실리콘게르마늄 (SiGe)을포함하는 4족 반도체갈륨비소 (GaAs),인듐인 (InP)또는갈륨인 (GaP)을포함하는 3-5족반도체 황화카드뮴 (CdS)또는텔루르화아연 (ZnTe)올포함하는 2-6족반도체
황화납 (PbS)을포함하는 4-6족반도체또는이들에서선택된둘이상의물질이 각층을이루며적층된적층체를들수있다.세라믹기재의비한정적인일예로， 반도체산화물，반도체질화물,반도체탄화물,금속산화물，금속탄화물, 금속질화물또는이들에서선택된둘이상의물질이각층을이루며적층된 적층체를들수있다.이때,반도체산화물,반도체질화물또는반도체탄화물의 반도체는 4족반도체， 3-5족반도체, 2-6족반도체， 4-6족반도체또는이들의 흔합물을포함할수있다.금속기재의비한정적인일예로，귀금속을포함하는 전이금속，금속또는이들의흔합물을들수있다.고분자기재의일예로， 폴리에틸렌테레프탈레이트 (PET),폴리에틸렌나프탈레이트 (PEN),
폴리이미드 (PI),폴리카보네이트 (PC),폴리프로필렌 (PP),
트리아세틸셀를로오스 (TAC),폴리에테르술폰 (PES),폴리디메틸실록산 (PDMS) 또는이들의흔합물을들수있다ᅳ
[155] 태양전지로의용도를고려한기재의구체예로，기재는유리와같은비정질 산화물기판또는폴리에틸렌테레프탈레이트 (PET),폴리에틸렌나프탈레이트 (PEN),폴리이미드 (PI),폴리카보네이트 (PC),폴리프로필렌 (PP),
트리아세틸셀를로오스 (TAC)，플리에테르술폰 (PES)또는
폴리디메틸실록산 (PDMS)과같은플렉시블고분자기판등일수있다.
[156] 이때，트랜지스터와같은전자소자，발광다이오드나레이저와같이광을
발생하는발광소자，메모리소자,열전소자,광발전용소자 (태양전지),광센서 등,유 /무기하이브리드페로브스카이트화합물막이구비되는소자의기본 구조에따라,페로브스카이트화합물막하부의하부구성요소가적절히설계 변경될수있다.즉，기재는，기알려진소자구조를기반으로,제조하고자하는 소자의페로브스카이트화합물막하부에위치하는구성요소가기형성된것일 수있다.
[157] 본발명의일실시예에따른제조방법에있어,페로브스카이트화합물용액은 상술한화학식 1내지 3을만족하도록 1가의유기양이온 (A),금속양이온 (M)및 할로겐음이온 (X)을함유할수있으며,이와독립적으로첨가제와함께 페로브스카이트화합물자체가용매에용해된것일수있다.유기양이온 (A), 2가의금속양이온 (M)및할로겐음이온 (X)을용해하는용매를함유할수있다.
[158] 페로브스카이트화합물용액내페로브스카이트화합물의몰농도는 0.4M내지 1.8M,구체적으로 0.8M내지 1.1M일수있으나，이에한정되는것은아니다.
[159] 페로브스카이트화합물용액의용매는페로브스카이트화합물및첨가제를 용해하는극성유기용매이면사용가능하다.구체적이며비한정적인일예로， 용매는감마-부티로락톤，포름아마이드，다이메틸포름아마이드,
다이포름아마이드，아세토나이트릴，테트라하이드로퓨란，다이메틸설폭사이드， 다이에틸렌글리콜， 1-메틸 -2-피를리돈 , Ν,Ν-다이메틸아세트아미드，아세톤， ex-터피네올， β-터피네올，다이하이드로터피네올， 2-메특시에탄올,
아세틸아세톤，메탄올,에탄올，프로판올,케톤，메틸이소부틸케톤등에서하나 또는둘이상선택될수있다.
[160] 페로브스카이트화합물용액은용액에함유된페로브스카이트화합물 1몰
기준 0.2내지 0/7몰，실질적으로 0.2내지 0.55몰의첨가제를함유할수있다. 좋게는,페로브스카이트화합물용액은용액에함유된페로브스카이트화합물 1몰기준으2내지 0.7몰，좋게는 0.2내지 0.55몰의메틸암모늄할로겐화물을 함유할수있다.이러한함량을갖는페로브스카이트화합물용액을기재에 도포한후，비용매를접촉시키는경우,상술한게 2양태에따른페로브스카이트 화합물막을제조할수있다.
[161] 나아가，페로브스카이트화합물용액이용액에함유된페로브스카이트화합물 1몰기준 0.2내지 0.3몰의메틸암모늄할로겐화물，좋게는
메틸암모늄할로겐화물을함유하는경우，우선적배향성이현저하게억제되어 극히랜덤한배향을갖는페로브스카이트화합물막을제조할수있다.또한， 페로브스카이트화합물용액이용액에함유된페로브스카이트화합물 1몰기준 0.35내지으55몰,구체적으로 0.45내지 0.55몰의메틸암모늄할로겐화물，좋게는 메틸암모늄할로겐화물을함유하는경우，랜덤한배향을가지면서도 (100) 결정면이막의표면과평행한바람직한우선배향성을갖는페로브스카이트 화합물막올제조할수있다.
[162] 페로브스카이트화합물용액은용액에함유된페로브스카이트화합물 1몰 기준 0.75내지 1.5몰,좋게는 0.9내지 1.5몰의첨가제를함유할수있다.좋게는， 페로브스카이트화합물용액은용액에함유된페로브스카이트화합물 1몰기준 으 75내지 1.5몰,좋게는 0.9내지 1.5몰의메틸암모늄할로겐화물을함유할수 있다.이러한함량을갖는페로브스카이트화합물용액을기재에도포한후, 비용매를접촉시키는경우，상술한제 1양태에따른페로브스카이트화합물막을 제조할수있다.
[163] 페로브스카이트화합물용액의도포는액상을도포하여막을형성하는데 통상적으로사용하는도포방법이면족하다.다만,다양한도포방법중，균일한 액의도포，대면적처리및빠른공정시간측면에서스핀코팅을이용하는것이 보다유리하다.
[164] 상술한바와같이，첨가제를함유하는페로브스카이트화합물용액을
도포하되,도포된페로브스카이트화합물용액을비용매 (페로브스카이트 화합물의비용매)와접촉시킴으로써,비로소페로브스카이트화합물막의 배향성이제어될수있다.
[165] 비용매는페로브스카이트화합물을용해하지않는유기용매일수있으며， 비극성유기용매일수있다.구체적으로비용매는유전율 (ε;상대유전율)이 20 이하，실질적으로유전율이 1내지 20인비극성용매일수있다.구체적인일 예로，비용매는펜타인,핵센,사이크로핵센， 1，4-다이옥센，벤젠,를루엔， 트리에틸아민，클로로벤젠,에틸아민，에틸에테르，클로로폼ᅳ에틸아세테이트， 아세틱액시드， 1,2-다이클로로벤젠， tert-부틸알콜, 2-부탄올，이소프로파놀및 메틸에틸케톤에서하나또는둘이상선택될수있으나,이에한정되는것은 아니다.
[166] 페로브스카이트화합물용액의도포후,기재에도포된페로브스카이트화합물 용액용액의용매가모두휘발제거되기전,즉，건조되기기재에비용매를 도포함으로써，도포된광흡수체용액과비용매간의접촉이이루어질수있다. 이때，페로브스카이트화합물용액에함유된용매의휘발성을고려하여, 페로브스카이트화합물용액의도포와비용매의도포는서로독립되어 순차적으로수행되거나，페로브스카이트화합물용액의도포도중비용매의 도포가이루어질수있다.비용매의도포또한，균일한액의도포，대면적처리및 빠른공정시간측면에서스핀코팅이좋다.실질적인일예로,광흡수체용액의 도포및비용매의도포는모두스핀코팅으로수행될수있다.이러한경우，스핀 코팅을이용한페로브스카이트화합물용액의도포가완료된후스핀코팅의 회전중심에비용매를주입하여비용매를도포하거나，페로브스카이트화합물 용액을회전중심에주입한후，주입된광흡수체용액을고르게분산시키기위해 기재를회전시키는도증회전중심에비용매를주입하여수행될수있다. 제조하고자하는소자의크기및페로브스카이트화합물용액에함유된용매의 휘발성을고려하여스핀코팅의회전중심에표면층제조용액이투입완료된 시점과비용매가투입되는시점간의시간간격이적절히조절될수있으나， 구체적이며비한정적인일예로，페로브스카이트화합물용액의투입이완료된 직후 1내지 100초후비용매의투입이이루어질수있다.보다상세한 페로브스카이트화합물용액의도포및비용매의접촉이라는 2-스텝도포 공정은본출원인의공개특허제 2014-0035285호,공개특허제 2014-0035284호 또는공개특허제 2014-0035286호를참고할수있으며，본발명은본출원인의 공개특허제 2014-0035285호，공개특허제 2014-0035284호또는공개특허 제 2014-0035286호에기재된내용을포함한다.
[167] 어닐링은잔류하는페로브스카이트화합물용액의용매나비용매를휘발 제거함과동시에，첨가제를제거하기위해수행될수있다.어닐링은 100내지 150°C,좋게는 130내지 150°C의온도로수행될수있다.어닐링시간은 안정적으로첨가제가제거되는정도면무방하며,구체적인일예로, 1분내지 10분동안수행될수있으나，이에한정되는것은아니다.
[168] 본발명은상술한페로브스카이트계화합물막 (제 1양태또는제 2양태)올
포함하는전자소자，광소자，메모리소자,열전소자또는센서를포함한다.
[169] 전자소자는트랜지스터를포함하며，광소자는발광다이오드나레이저를 포함하는발광소자,광검출소자 (광센서)또는광발전소자 (태양전지)를 포함하며，메모리소자는휘발성또는비휘발성메모리소자를포함하며，센서는 유기화합물또는생화학물질을검출하는검출센서를포함한다.
[170] 일예로,본발명은발광다이오드의기본구조인게 1전극 - n형
반도체 (전자전달체) -발광층 -P형반도체 (정공전달체) -제 2전극의구조를 기반하되,상술한페로브스카이트계화합물막을함유하는발광층을갖는발광 다이오드를포함한다.
[171] 일예로,본발명은저항변화형메모리의기본구조인
제 1전극 -반도체-제 2전극의구조를기반하되，상술한페로브스카이트계화합물 막을함유하는반도체를갖는저항변화형메모리를포함한다ᅳ이때，잘알려진 바와같이,제 1전극은일방향으로서로이격배열된금속스트립들일수있고, 계 2전극은제 1전극의금속스트립들과직교하도록다른일방향으로서로이격 배열된금속스트립들일수있다.
[172] 일예로，본발명은트랜지스터의기본구조인서로이격대향하는소스와 드레인및소스와드레인사이에위치하는반도체채널및절연막 (게이트 절연막)을사이에두고반도체채널의상부또는하부에위치하는게이트의 구조를기반하되,상술한페로브스카이트계화합물막을함유하는반도체 채널을갖는트랜지스터를포함한다.
[173] 상술한바와같이，트랜지스터와같은전자소자,광을발생하는발광소자, 메모리소자,광발전용소자 (태양전지)등,관련분야의종사자라면，목적하는 소자의알려진구조를기반으로，상술한페로브스카이트계화합물막을 포함하는구성요소를해당소자에적합하게설계변경함으로써 ,해당소자를 구현할수있음은자명하다.
[174] 페로브스카이트화합물의다양한웅용중，상업적으로중요한태양전지에의 웅용을보다구체적으로상술한다.
[175] 본발명은상술한페로브스카이트계화합물막을광흡수층으로함유하는
태양전지를포함한다.
[176] 본발명의일실시예에따른태양전지는제 1전극，제 1전극상위치하는제 1 전하전달체,제 1전하전달체상위치하는페로브스카이트계화합물막을 포함하는광흡수체，광흡수체상위치하는제 2전하전달체,게 2전하전달체상 위치하는제 2전극을포함할수있다.
[177] 제 1전극은기판상위치할수있으며，기판은딱딱한 (rigid)기판또는
플렉시블 (flexible)기판일수있다.구체적인일예로，기판은유리기판을 포함하는딱딱한 (rigid)기판또는폴리에틸렌테레프탈레이트 (PET);
폴리에틸렌나프탈레이트 (PEN):폴리이미드 (PI);폴리카보네이트 (PC);
폴리프로필렌 (PP);트리아세틸셀를로오스 (TAC);폴리에테르술폰 (PES)등을 포함하는유연한 (flexible)기판일수있다.그러나，본발명이기판의종류에의해 한정될수없음은물론이다.
[178] 제 1전극은게 1전하전달체와오믹접합되는전도성전극이면무방하며，
태양전지에서전면전극또는후면전극의전극물질로통상적으로사용되는 물질이면사용가능하다.비한정적인일예로，제 1전극이후면전극의
전극물질인경우，계 1전극은금，은，백금，팔라듐，구리 ,알루미늄，탄소， 황화코발트,황화구리，산화니켈및이들의복합물에서하나이상선택된물질일 수있다.비한정적인일예로,제 1전극이투명전극일경우,계 1전극은불소함유 산화주석 (FTO; Fouorine doped Tin Oxide),인듐함유산화주석 (ITO; Indium doped Tin Oxide), ZnO, CNT (카본나노류브)，그래핀 (Graphene)등과같은무기계전도성 전극일수있으며, PEDOT:PSS와같은유기계전도성전극일수있다.투명 태양전지를제공하고자하는경우，전극 (제 1전극및제 2전극)과기판이모두 투명전극및투명기판인것이좋다.또한，전극 (제 1전극또는제 2전극)이유기계 전도성전극인경우,플렉시블태양전지나투명태양전지를제공하고자할때 보다좋다.
[179] 제 1전극상부에위치하는제 1전하전달체는게 1전극과광흡수체간의직접적인 접촉을방지하며광흡수체에서생성되는광전자나광정공의전하가이동하는 이동경로를제공하는역할을수행할수있다.이때，제 1전하전달체와저 12 전하전달체는서로상보적인전하를이동시킬수있다.일예로,제 1
전하전달체가전자전달체인경우게 2전하전달체는정공전달체일수있고,제 1 전하전달체가정공전달체인경우게 2전하전달체는전자전달체일수있다.
[180] 이하，제 1전하전달체가전자전달체인경우를기준으로본발명의일예에따른 태양전지를상술하나，제 1전하전달체가정공전달체인경우제 1전하전달체는 후술하는제 2전하전달체관련상술한내용과동일내지유사한구성을가질수 있음은물론이다.
[181] 전자전달체는전자전도성유기물층또는무기물층일수있다.전자전도성 유기물은통상의유기태양전지에서, n형반도체로사용되는유기물일수있다. 구체적이며비한정적인일예로，전자전도성유기물은풀러렌 (C60, C70, C74, C76, C78, C82, C95), PCBM([6,6]-phenyl-C61butyric acid methyl ester))및
C71-PCBM, C84-PCBM, PC70BM([6,6]-phenyl C70-butyric acid methyl ester)을 포함하는풀러렌-유도체 (Fulleren-derivative), PBI(polybenzimidazole),
PTCBI(3 ,4,9, 10-perylenetetracarboxylic bisbenzimidazole), F4-TCNQ(tetra uorotetracyanoquinodimethane)또는이들의흔합물을포함할수있다.
[182] 전자전도성무기물은통상의양자점기반태양전지또는염료감웅형
태양전지에서,전자전달을위해사용되는전자전도성금속산화물일수있다. 구체적인일예로，전자전도성금속산화물은 n-형금속산화물반도체일수있다. n-형금속산화물반도체의비한정적인일예로， Ti산화물 , Ζη산화물， In산화물， Sn산화물, W산화물, Nb산화물, Mo산화물， Mg산화물, Ba산화물， Zr산화물， Sr산화물， Yr산화물, La산화물， V산화물, A1산화물, Y산화물， Sc산화물，
Sm산화물， Ga산화물， In산화물및 SrTi산화물에서하나또는둘이상선택된 물질을들수있으며，이들의흔합물또는이들의복합체 (composite)를들수 있다.
[183] 그구조에있어，전자전달체는다공성층 (다공막)이거나치밀층 (치밀막)일수 있다.치밀한전자전달체는상술한전자전도성유기물의막또는전자전도성 무기물의치밀막 (film)을들수있다.
[184] 다공성전자전달체는상술한전자전도성무기물의입자들로이루어진
다공막을들수있다.전자전달체의두께는 50nm내지 ΙΟμιη,구체적으로는 50nm 내지 lOOOnm일수있다.전자전달체가다공성인경우그비표면적은 10내지 100 mVg일수있으며，전자전달체를이루는전자전도성무기물입자의평균 입경 (diameter)은 5내지 500 nm일수있다ᅳ다공성전자전달체의기공률 (겉보기 기공률)은 30%내지 65%,구체적으로 40%내지 60%일수있다.
[185] 전자전달체가다공성구조인경우，제 1전극과전자전달체사이에는
전자전달막이더구비될수있다.전자전달막은광흡수체와제 1전극이직접 접촉하는것을미연에방지하는역할을함과동시에전자를전달하는역할을 수행할수있다.전자전달막은에너지밴드다이어그램상,다공성
금속산화물에서전자전달막올통해게 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， ZnSn산화물,이들의흔합물및이들의복합물중에서하나 이상선택된물질일수있다.전자전달막의두께는실질적으로 lOnm이상，보다 실질적으로 lOnm내지 lOOnm,보다더실질적으로 50nm내지 lOOnm일수있다.
[186] 전자전달체가다공성층 (다공막)인경우，기재상제 1전극및전자전달체를 형성한후，전자전달체상부에상술한페로브스카이트화합물막의제조방법에 따라,페로브스카이트화합물막을제조함으로써，전자전달체의기공을채우며， 전자전달체의상부를덮는막형태로페로브스카이트화합물의광흡수체가 제조될수있다.
[187] 전자전달체가치밀한층인경우，기재상제 1전극및전자전달체를형성한후， 전자전달체상부에상술한페로브스카이트화합물막의제조방법에따라， 페로브스카이트화합물막을제조함으로써,박막형의광흡수체를제조할수 있다.
[188] 제 2전하전달체는정공전달체일수있으며，정공전달체는유기정공전달체, 무기정공전달체또는이들의적층체일수있다.
[189] 정공전달체가무기정공전달체를포함하는경우,무기정공전달체는정공
전도도를갖는,즉, p형반도체인，산화물반도체，황화물반도체，할로겐화물 반도체또는이들의흔합물일수있다.
[190] 산화물반도체의예로는 NiO, CuO, CuA102, CuGa02등을들수있으며，황화물 반도체의예로는 PbS,할로겐화물반도체의예로는 Pbl2등을들수있으나,본 발명이무기정공전달체물질에의해한정되는것은아니다.
[191] 정공전달체는치밀층 (치밀막)일수있다.치밀한정공전달체는상술한 p형
반도체의치밀막 (film)을들수있다.무기정공전달체의두께는 50nm내지 ΙΟμιη, 구체적으로는 lOnm내지 lOOOnm,보다구체적으로 50nm내지 lOOOnm일수 있다.
[192] 정공전달체가유기정공전달체를포함하는경우，유기정공전달체는유기
정공전달물질，구체적으로단분자내지고분자유기정공전달물질 (정공전도성 . 유기물)을포함할수있다ᅳ유기정공전달물질은무기반도체양자점을염료로 사용하는통상의무기반도체기반태양전지에서사용되는유기
정공전달물질이면사용가능하며，안정성측면에서고분자유기
정공전달물질이좋다.
[193] 단분자내지저분자유기정공전달물질의비한정적인일예로,
펜타센 (pentacene),쿠마린 6(coumarin 6, s/// O 2/-so/J02Ml ε£09/-ϊ/-ϊοζAV7
寸 6【1〕
Figure imgf000025_0001
ψ¾1≤8寸) M1)a寸(IJPqdllagd/{χοχχ9λ30dBo§3OZBz- --
【1 ρζΙ6/Η^ϊ)6^죵 dxLD1ΙΡ1ΡΙΡμρalcd(ζ1ΗώΟΖΒ3?§υοΒΒδΖοζι------ Poly(4-butylphenyl-diphenyl-amine)및이들의공중합체에서하나또는둘이상 선택된물질을들수있다.비한정적이며구체적인일예로,정공전달체는유기 정공전달물질의박막일수있으며,박막의두께는 10 nm내지 500 nm일수있다.
[195] 유기정공전달체는통상의무기반도체양자점을염료로사용하는무기받도체 기반태양전지에서유기물기반홀전도층의전도도향상과같은특성향상을 위해통상적으로사용되는첨가제를더포함할수있음은물론이다.비한정적인 일예로,정공전달체는 TBP(tertiary butyl pyridine), LiTFSI(Lithium Bis(Trifluoro methanesulfonyl)Imide)및 Tris(2-(lH-pyrazol-l-yl)pyndine)cobalt(III)에서하나 또는둘이상선택된첨가제를더함유할수있으며,유기정공전달물질 lg당 0.05mg내지 lOOmg첨가제를함유할수있다.그러나，본발명이정공전달체의 첨가제유 /무，첨가제의종류및첨가제의함유량에의해한정될수없음은 물론이다.
[196] 계 2전극은정공전달체와오믹접합되는전도성전극이면무방하며，
태양전지에서전면전극또는후면전늑의전극물질로통상적으로사용되는 물질이면사용가능하다.비한정적인일예로，제 2전극이후면전극의
전극물질인경우，제 2전극은제 2전극은금,은,백금,팔라듐，구리,알루미늄， 탄소，황화코발트,황화구리,산화니켈및이들의복합물에서하나이상선택된 물질일수있다.비한정적인일예로,제 2전극이투명전극일경우,제 2전극은 불소함유산화주석 (FTO; Fouorine doped Tin Oxide),인듐함유산화주석 (ΠΌ; Indium doped Tin Oxide), ZnO, CNT (카본나노튜브),그래핀 (Graphene)과같은 무기계전도성전극일수있으며, PEDOT:PSS와같은유기계전도성전극일수 있다ᅳ투명태양전지를제공하고자하는경우，제 2전극이투명전극인것이좋고， 제 2전극이유기계전도성전극인경우,플렉시블태양전지나투명태양전지를 제공하고자할때보다좋다.
[197]
[198] (제조예 1)
[199] 다공성전자전달층및투명전극이형성된기재의제조
[200] 불소함유산화주석이코팅된유리기판 (FTO; F-doped Sn02, 8 ohms/cm2,
Pilkington,이하 FTO기판 (제 1전극))을 25 x 25 mm크기로절단한후，끝부분을 에칭하여부분적으로 FTO를제거하였다.
[201] 절단및부분에칭된 FTO기판위에금속산화물박막으로서 50 nm두께의 Ti02 치밀막을분무열분해법으로제조하였다.분무열분해는 TAA (Titanium acetylacetonate):EtOH( 1 :9 v/v%)용액올이용하여수행되었으며， 450 °C로유지된 열판위에올려진 FTO기판위에 3초간분무하고 10초간정지하는방법을 되풀이하는방법으로두께를조절하였다.
[202] 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.
[203] 제조된 Ti02분말페이스트에에탄올을첨가 (l(Ti02분말페이스트) :5(에탄올) 중량비)하여스핀코팅용 Ti02슬러리를제조하였다. FTO기판의 Ti02박막 위에，스판코팅용 Ti02슬러리를이용하여스핀코팅방법으로
코팅 (3000rpm)하고 500 °C에서 60분동안열처리한후, 60 °C의 30 mM TiCl4 수용액에열처리된기판을담그고， 30분동안방치한후，탈이온수와에탄올로 세척및건조하고다시 500 oC에서 30분동안열처리하여다공성 Ti02 박막 (다공성전자전달체)을제조하였다.이때，다공성 Ti02박막 (다공성 전자전달체)의두께는 lOOnm이었고，제조된다공성전자전달체의비표면적은 33m2/g이며，기공률 (겉보기기공률)은 50%이었다.
[204]
[205] (실시예 1) :
[206] 페로브스카이트화합물용액제조
[207] ^ᅀ¾13)085(] ᅀ1 81"3)0.15의조성을만족하도록，다이메틸포름아마이드 (DMF; dimethylformamide)와다이메틸설폭사이드 (DMSO; dimethyl sulfoxide)흔합 용액 (4: 1 vol/vol)에메틸암모늄아요다이드 (methylammonium iodide, CH3NH3I, 메틸암모늄 =MA로표기함),포름아미디니움아요다이드 (formamidinium iodide, CH(NH2)2I,포름아미디니움=? 로표기함),메틸암모늄
브로마이드 (methylammonium brimide, CH3NH3Br, MABr),포름아미디니움 브로마이드 (formamidinium bromide, CH(NH2)2Br, FABr), Pbl2및 PbBr2를흔합 용해시키고,첨가제로 (FAPbI3)0.85(MAPbBr3)0.15(=(FAa85MA0.15)PK^
기준 0.1몰, 0.25몰， 0.5몰, 0.75몰또는 1몰의몰비가되도록
메틸암모늄클로라이드를투입하여,페로브스카이트화합물용액을제조하였다.
[208] 제조예에서제조된다공성전자전달체상에,제조된페로브스카이트화합물 용액을회전중심에일괄도포 (주입)하고， 1500 rpm으로 60초후，스핀속도를 5000 rpm으로하여스핀코팅을진행하였다.스핀코팅시간이 50초가된시점에 스핀중인다공성전자전달체의회전중심에다시비용매인를루엔 (toluene) lmL를일괄도포 (주입)한후， 60초간동안스핀코팅올더진행하였다.
스핀코팅이수행된후 150oC의온도및상압조건에서 10분동안어닐링을 수행하여페로브스카이트화합물막을제조하였다.이때,페로브스카이트 화합물이다공성전자전달체의기공을채우며다공성전자전달체를덮는 치밀막 (두께약 250nm)형태로제조됨을확인하였다.페로브스카이트화합물막 제조시，주변환경은 25 °C의온도및 25%의상대습도를유지하였다.
[209] GIWAXS분석은 λ = 1.0688A (11.6keV),빔크기 15 ffli(h)xl20 n(v)
(FWHM:반가폭)을갖는 X-선을이용하여입사각 =0.3°조건에서수행되었으며, 포항가속기연구소의휨자석 (Bending magnet)광원 6D UNIST-PAL빔라인을 사용하여측정하였다.산란이미지는 2차원영역검출기 (제조사: Rayonix, 모델명: MX225-HS)를이용하여수집하였으며，검출기는샘플로부터
246.4118mm에위치하였다.샘플의측정면적은 0.15mm x 1mm (범진행방향의 수직방향길이 X빔방향길이)이었다.
[210] 도 1은실시예 1에서제조된페로브스카이트화합물막의 첨가제함량에따른 GIWAXS스펙트럼올도시한도면이다.도면에서흰색에.가까울수록큰회절 강도가검출된것이며,검은색에가까울수록작은회절강도가검출된것이다. 도 1에서 1:0은첨가제가첨가되지않고，실시예 1과동일하게제조된
페로브스카이트화합물막의결과를의미하며, FT(yri02 ref는페로브스카이트 화합물막이형성되기전,다공성전자전달체가형성된기판의 GIWAXS 스펙트럼을도시한도면이다.도 1의도면에도시된 1:0.1, 1:0.25， 1:0.5, 1:0.75, 1:1은페로브스카이트화합물 1몰기준 0.1몰， 0.25몰， 0.5몰， 0.75몰또는 1몰의 첨가제가첨가된샘플의결과를의미한다.도 1의 GIWAXS스펙트럼에서 q=0.99는페로브스카이트화합물 (100)결정면의회절패턴에해당하며， q=1.97은 (200)결정면의회절패턴에해당한다.
[211] 도 1에서 1:0의샘플결과를통해알수있듯이，순수하게페로브스카이트
화합물만이용해된액을도포한경우，랜덤한배향에의해원호형상의회절 패턴이나타나나， qxy=0(방위각 =90°)에서의우선적배향성은나타나지않으며， 방위각 250, 50°, 125°및 155°등몇몇특정방향에서강한회절이발생함올알수 있다ᅳ
[212] 그러나，도 1의 1: 0.25내지 1:0.5샘플의경우， q=0.99에서매우균일한강도를 갖는원호형태로회절패턴이발생함을알수있으며,페로브스카이트화합물： 첨가제의비가 1:0.75이상인경우，스팟 (spot)형태의불연속적인회절패턴이 발생함을할수있다.
[213] 즉,첨가제가첨가되지않은경우랜덤한배향과우선적인배향이공존하는 페로브스카이트화합물막이제조되나，바람직한배향인 (100)면이막 (기판)과 평행하게위치하는배향은나타나지않으며 ,페로브스카이트화합물：첨가제의 비가 1:0.2인경우，첨가제가첨가되지않았올때나타나던우선적배향성이 완전히사라지며특정배향성을나타내지않는극히 랜덤한배향을갖는 페로브스카이트화합물막이제조됨을알수있다.또한，페로브스카이트화합물 ：첨가제의비가내지 0.5인경우,랜덤한배향성과함께새로운우선적배향성， 즉, (100)면이막 (기판)의표면과평행하게위치하는배향성이나타남올알수 있다.
[214] 또한，첨가제의함량이 1: 0.75이상으로증가함에따라，랜덤한배향에서
특정한방향들로만 (100)면이위치하는고도의배향성을나타내며，불연속적인 스팟형태의패턴이나타남을알수있다.
[215] 또한,실시예 1에서롤루엔주입후,어닐링시간에따른 GIWAXS스펙트럼의 변화를살핀결과,톨루엔주입시점에서도 1과같은배향성이나타남을 확인하였다.
[216] 도 2는 1:1샘플의 GIWAXS스펙트럼 (흰색사각형은 index point임)을도시한 도면으로，도 2에서알수있듯이 qxy=0에서매우강한회절스팟이나타남을알 수있다.이는페로브스카이트화합물막을이루는대부분의결정립들이 (100) 결정면이막 (또는막표면과유리기판이평행함에따라기판면)과평행하도록 배향되어 있음을알수있다.
[217] 도 3은도 1에서, 1： 0.25샘플의 (100)면회절강도를방위각에따라도시한 것이며，도 4는도 1에서, 1： 0샘플의 (100)면회절강도를방위각에따라도시한 것이다.
[218] 도 3에서알수있듯이， 1:0.25샘플의경우전방위적인회절이발생함과
동시에,모든방향에서거의동일한회절강도를가짐을알수있다.
방위각 =90ο에서의강도를 10내지 170°의방위각범위에서의평균강도로나눈 값인 ΡΟ(100)이 1.618로,매우약하게 (100)면이막의표면과평행한배향성을 가짐을알수있다.또한， 10내지 170°의방위각범위에서의평균강도는
1231.162이었으며,이때강도의표준편차는 295.673로，그균일도 (UF)가 0.240로， 전방위적으로거의균일한회절이발생한것을알수있다.
[219] 도 1에서알수있듯이 , 1:().5의샘플의경우에도랜덤한배향성에의해
전방위적인회절이발생하여원호형상의연속적인회절이발생함을알수있다.
1:0.5샘플의경우， 10내지 170°의방위각범위에서의평균강도는 1231.162이며, 방위각 =90°에서의강도는 1992.099로 ΡΟ(100)이 6.888로 (100)면이막의표면과 평행한우선적배향성이매우뚜렷하게증가함을알수있다.
[220] 반면, 1:0샘플의경우，도 4에서알수있듯이，전방위적인회절과함께방위각 25°, 50°, 125°및 155°등의특정방향으로보다강한회절이발생하여，우선적 배향을갖는결정립들이존재함을알수있다.그러나,바람직한배향성인 qxy =0(방위각 =90°)에서의우선적배향성을살피면， 10내지 170°의방위각
범위에서의평균강도는 539.028이며，방위각 =90°에서의강도는 374.8()1로 PO(IOO)이 0.695로,우선적배향성이전혀나타나지않음을알수있다.또한， 25°, 50°, 125°및 155°등의배향성에의해,그균일도 (UF)가 0.527에이르러， 1:0.25 샘풀대비균일도가현저하게떨어짐을확인할수있다.
[221] 도 5는도 1에서, 1： 1샘플의 (100)면 (q=0.99)의회절강도를방위각에따라 도시한것이다.도 5에서알수있듯이,불연속적인피크의형태를가짐을알수 있으며，방위각 =90°에서극히강한회절피크가존재함을알수있다.도 5에서 알수있듯이， 1： 1샘플의경우， 90°방위각에위치하는피크의강도를기준으로 10%이상의강도를갖는피크의수는단지 4개뿐이며，이를통해,
페로브스카이트화합물을이루는결정립들중많은결정들이 (100)결정면이 막과평행하게배향되어존재하되 ,미량의결정들이 (100)결정면이막과 평행하지않은세방향으로배향되어존재함을알수있다.
[222] 90°방위각에위치하는피크의강도 (If)를두번째로큰피크 (방위각 170내지 178°에위치하는피크)의강도 (¾로나눈강도비 (1 )는 2.67로，페로브스카이트 화합물을이루는대부분의결정립들이 (100)결정면이막과평행하도록 배향되어 있음을알수있다. 1 : 1샘플의경우 90°방위각에위치하는피크의 반치폭 (FWHM)이 4.1°로샤프한피크가나타나며, 1 :0.75샘플또한, 90° 방위각에위치하는피크의반치폭 (FWHM)이 5.2°로 1 : 1샘플대비 약간의피크 브로드닝이존재하나， 1 : 1샘플과유사한 GIWAXS스펙트럼을가짐을 확인하였다.
[223] 도 6은 1 :0.5샘플의페로브스카이트화합물막의표면을관찰한
주사전자현미경사진이며,도 7은 1: 1샘플의페로브스카이트화합물막의 표면올관찰한주사전자현미경사진이다.
[224] 도 6및도 7에서알수있듯이,첨가제함량에의해페로브스카이트화합물 막의배향성이제어됨과동시에，페로브스카이트화합물결정립의현저한 조대화가발생함을알수있다.특히 1: 1샘플의경우평균그레인크기가 3~5 μιη로,고도의배향성을가지면서도극히조대한결정립들로이루어진 페로브스카이트화합물막이제조됨올알수있다ᅳ
[225] 도 8은실시예에서제조된페로브스카이트화합물막의 X-선회절
패턴 (Cu-Kot선을이용)을도시한도면이다.도 8에도시된 1:0.25， 1:0.5， 1 :0.75， 1 : 1은페로브스카이트화합물 1몰기준 0.25몰, 0.5몰, 0.75몰또는 1몰의 첨가제가첨가된샘풀의 X-선회절결과를의미한다.
[226] 도 8에서 알수있듯이,첨가제의함량이증가함에따라，페로브스카이트
화합물의결정상올나타내는피크 (2Θ=14°및 280, GIWAXS q=0.99및 q=1.97에 해당)의강도가현저하게증가함과동시에，피크의반치폭 (FWHM)또한점점 좁아짐올알수있다.이를통해， 1 :0.75내지 1 : 1의샘플의경우매우강한 배향성을나타내는막이제조됨을알수있으며,또한,결정성이우수한 페로브스카이트화합물막이제조됨을알수있다.
[227] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐，본발명은상기의실시예에한정되는것은아니며,본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[228] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며, 후술하는특허청구범위뿐아니라이특허청구범위와균둥하거나둥가적변형ᄋ 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
[청구항 1] 다결정체이며 , 1.0688A의 X-선파장을이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)스펙트럼 상，불연속적인 (100)면의산란강도를갖는무 /유기하이브리드 페로브스카이트화합물막.
[청구항 2] 제 1항에 있어서，
상기 (100)면의산란백터 (q,入 -1)에서， 3내지 15개의피크 (peak)가 존재하는무 /유기하이브리드페로브스카이트화합물막.
[청구항 3] 제 2항에 있어서，
상기산란스펙트럼은산란백터성분 를 y축으로，산란백터성분 를 X축으로한강도분포이며， (100)면의피크 (peak)중 qxy=0에상대적으로 가장강도가큰피크가위치하는무 /유기하이브리드페로브스카이트 화합물막.
[청구항 4] 제 3항에 있어서,
상기산란스펙트럼은하기관계식 1을만족하는무 /유기하이브리드 페로브스카이트화합물막.
(관계식 1)
2.0≤IA
(관계식 1에서 , If는 (100)면의피크 (peak)중상대적으로가장큰피크의 강도이며， 15는 (100)면의피크중상대적으로두번째큰피크의강도이다) [청구항 5] 다결정체이며 , 1.0688A의 X-선파장을이용한스침각입사광각 X-선
산란 (GIWAXS; Grazing Incidence Wide Angle X-ray Scattering)
스펙트럼에서,방위각 (azimuth)에따른 (100)면의산란강도기준， 10내지 170°의방위각범위에서연속적인산란강도를가지며，하기관계식 2로 규정되는배향성이하기관계식 3을만족하는무 /유기하이브리드 페로브스카이트화합물막.
(관계식 2)
Figure imgf000031_0001
(PO(IOO)은 (100)면이막에평행하게배향된배향성을의미하며， 190은 방위각 (azimuth)에따른 (100)면의산란강도기준, 90°방위각에서의 강도이며， Iave는동일한방위각에따른 (100)면의산란강도기준, 10내지 170°의방위각범위의평균산란강도이다)
(관계식 3)
1.0 < PO(100) < 25
[청구항 6] 제 5항에 있어서,
하기관계식 4로규정되는균일도가하기관계식 5를만족하는무 /유기 하이브리드페로브스카이트화합물막. (관계식 4)
UF = a I
(UF는균일도로， Iave는방위각 (azimuth)에따른 (100)면의산란강도기준, 10내지 170ο의방위각범위의평균산란강도이며， σ는 10내지 170°의 방위각범위의산란강도표준편차이다)
(관계식 5)
0.1 < UF < 0.4
[청구항 7] 제 1항내지제 6항중선택되는어느한항에있어서，
상기무 /유기하이브리드페로브스카이트화합물막의무 /유기 하이브리드페로브스카이트화합물은하기화학식 1，화학식 2또는 화학식 3을만족하는제조방법 .
(화학식 1)
ΑΜΧ3 ᅳ
(화학식 1에서， Α는 1가의양이온으로, A는유기암모늄이온， 아미디니움계 (amidinium group)이온또는유기암모늄이온과
아미디니움계이온이며 , Μ은 2가의금속이온이며， X는할로겐 이온이다)
(화학식 2)
Figure imgf000032_0001
(화학식 2에서， A는 1가의양이온으로， A는유기암모늄이온， 아미디니움계 (amidinium group)이온또는유기암모늄이은과
아미디니움계이온이며， M은 2가의금속이온이고， N은 1가의금속이온 및 3가의금속이온중하나이상선택되는도핑금속이온이며， a는
0<a≤ai인실수이며， X는할로겐이온이다)
(화학식 3)
A(NVbN2 b)X3
(화학식 3에서， A는 1가의양이온으로 , A는유기암모늄이은， 아미디니움계 (amidinium group)이온또는유기암모늄이은과
아미디니움계이온이며 , Ν1은 1가의금속이온이고 , Ν2는 3가의금속 이온이며, b는 0.4≤b≤0.6인실수이며， X는할로겐이온이다) [청구항 8] 기재상무 /유기하이브리드페로브스카이트화합물및
유기할로겐화물인첨가제를함유하는페로브스카이트화합물용액을 도포하는단계,및
기재상도포된페로브스카이트화합물용액과페로브스카이트화합물의 비용매를접촉시킨후어닐링하는단계；를포함하며，
상기페로브스카이트화합물용액내의첨가제함량을조절하여무 /유기 하이브리드페로브스카이트화합물막의결정배향성을제어하는 무 /유기하이브리드페로브스카이트화합물막의제조방법. [청구항 9] 제 8항에 있어서，
상기첨가제는메틸암모늄할로겐화물인무 /유기하이브리드 페로브스카이트화합물막의제조방법.
[청구항 10] 제 9항에 있어서,
상기페로브스카이트화합물용액은무 /유기하이브리드페로브스카이트 화합물 1몰기준 0.2내지 0.7몰의 첨가제를함유하는무 /유기하이브리드 페로브스카이트화합물막의제조방법 .
[청구항 11] 제 9항에 있어서,
상기페로브스카이트화합물용액은무 /유기하이브리드페로브스카이트 화합물 1몰기준 0.75내지 1.5몰의첨가제를함유하는무 /유기 하이브리드페로브스카이트화합물막의제조방법.
[청구항 1 제 8항에 있어서，
상기페로브스카이트용액의도포및비용매와의접촉은스핀코팅을 이용한페로브스카이트용액및비용매의순차적도포에의해수행되는 무 /유기하이브리드페로브스카이트화합물막의제조방법 .
[청구항 13] 제 1항내지제 6항에서선택되는어느한항의무 /유기하이브리드
페로브스카이트화합물막을포함하는소자.
[청구항 14] 제 13항에 있어서,
상기소자는전자소자,발광소자，메모리소자,광발전소자,광센서 또는열전소자에서선택되는어는하나인소자.
PCT/KR2017/003743 2016-04-05 2017-04-05 무/유기 하이브리드 페로브스카이트 화합물 막 및 이의 제조방법 Ceased WO2017176053A1 (ko)

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KR101877302B1 (ko) 2018-07-11
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