US20160122634A1 - SYNTHESIS OF CsSnI3 BY A SOLUTION BASED METHOD - Google Patents

SYNTHESIS OF CsSnI3 BY A SOLUTION BASED METHOD Download PDF

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US20160122634A1
US20160122634A1 US14/530,207 US201414530207A US2016122634A1 US 20160122634 A1 US20160122634 A1 US 20160122634A1 US 201414530207 A US201414530207 A US 201414530207A US 2016122634 A1 US2016122634 A1 US 2016122634A1
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solution
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sni
csi
cssni
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Yuhang Ren
Jin Zhang
Chunhui YU
Kai SHU
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Sun Harmonics Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the invention generally relates to the formation of materials for photovoltaic devices and more specifically to the synthesis of CsSnI 3 by solution based method.
  • the current photovoltaic technologies can be classified by the different 10 materials used for the light absorption in a solar cell. These materials include amorphous and polycrystalline silicon, CdTe, CuIn x Ga 1-x Se 2 (CIGS), GaAs, and photosensitive organic dyes. A transformative technology may emerge when a new and better material is discovered for photovoltaic applications.
  • CsSnI 3 is a unique phase-change material that exhibits four polymorphs.
  • the black polymorph of CsSnI 3 could be obtained through a phase transition from the yellow polymorph CsSnI 3 by increasing its temperature above 425 K. It was further demonstrated by differential thermal analysis and X-ray diffraction that during the cooling of the black CsSnI 3 from 450 K, its ideal cubic Perovskite structure (B- ⁇ ) deformed to a tetragonal structure (B- ⁇ ) at 426 K, and became an orthorhombic structure (B- ⁇ ) below 351 K.
  • B- ⁇ cubic Perovskite structure
  • B- ⁇ tetragonal structure
  • B- ⁇ orthorhombic structure
  • CsSnI 3 can be divided into solid-phase sintering and solution based methods.
  • the solid-phase sintering method needs vacuum and high temperature which means high production costs.
  • K. Shum and Z. Chen offered a simple way to synthesize CsSnI 3 , but the final product is not pure (U.S. Published Patent Application No. 2012/0306053).
  • This invention is directed to synthesizing cesium tin tri-iodide (CsSnI 3 ) by a solution based method.
  • one embodiment in accordance with the invention is directed to a process of forming homogeneous CsSnI 3 in an organic Perovskite precursor solvent, comprising steps of:
  • the substantially inert environment may be created within a glove box and comprises a protective gas, such as N 2 , including water vapor and oxygen the content of each of which is under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • a protective gas such as N 2
  • the content of each of which is under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • the homogeneous CsSnI 3 is formed by adding a SnI 2 solution into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials have fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI 3 precursor solution.
  • the CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent
  • the SnI 2 solution is about 25 mmol/L to 2 mol/L SnI 2 solution by fully dissolving SnI 2 powder (99% purity) in a solvent.
  • the solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 is in the form of a SnI 2 solution.
  • the solvent for dissolving SnI 2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 is in the form of a powder.
  • a process of forming homogeneous CsSnI (3-n) X n in an organic Perovskite precursor solvent comprises the steps of:
  • CsSnI (3-n) X n wherein X is a halogen element selected from Group VIIA of the periodic table consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine (At) and 0 ⁇ n ⁇ 3; and
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • the substantially inert environment may be created within a glove box and comprises a protective gas, such as N 2 , including water vapor and oxygen content both under 1 ppm and the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • a protective gas such as N 2
  • the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • the homogeneous CsSnI (3-n) X n is formed by adding a mixed solution of SnI 2 and SnX 2 into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneou s CsSnI (3-n) X n precursor solution.
  • the CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent
  • the mixed solution of SnI 2 and SnX 2 is about 25 mmol/L to 2 mol/L by fully dissolving SnI 2 and SnX 2 powder (99% purity) in a solvent.
  • the solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 and SnX 2 are in the form of a SnI 2 and SnX 2 solution.
  • the solvent for dissolving the SnI 2 and SnX 2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the the SnI 2 and SnX 2 are in the form of a powder.
  • the steps are preferably performed in a glove box under the protection of N 2 gas and the molar ratio of the SnI 2 and CsI in the mixture is essentially 1:1.
  • the CsI solution is made by fully dissolving CsI powder (99.999% purity) in a solvent selected from the Perovskite precursor solutions, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • the concentration of CsI solution is about 25 mmol/L to 500 mmol/L.
  • the SnI 2 solution is made by fully dissolving SnI 2 powder (99% purity) in a solvent selected from the Perovskite precursor solutions, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • concentration of SnI 2 solution is about 25 mmol/L to 500 mmol/L.
  • FIG. 1 shows the schematic diagram for the synthesis of CsSnI 3 ;
  • FIG. 2 shows the (a) X-ray diffraction data (XRD) profile taken from CsSnI 3 (concentrations of CsI and SnI 2 were both 50 mmol/L) and (b) standard XRD pdf card (43-1162) of black- ⁇ phase of CsSnI 3 .
  • XRD X-ray diffraction data
  • the CsSnI 3 exhibits outstanding optical, electrical, and ferroelectric properties. These features make CsSnI 3 ideally suited for a wide range of applications such as light emitting and photovoltaic devices.
  • CsSnI 3 is a promising material in the application of solar cells since CsSnI 3 was found to possess a direct band gap of 1.32 eV at room temperature, right in the narrow region of optimal band gaps for the Shockley-Queisser maximum efficiency limit of a solar cell.
  • An effective method to synthesize large domain size high quality Perovskite semiconductor according to the present invention is disclosed. More specifically, a solution based method to synthesize CsSnI 3 is disclosed according to the present invention.
  • the CsSnI 3 can be fabricated in an organic Perovskite precursor solvent as shown in FIG. 1 . This synthesis method of the CsSnI 3 further enhances the likelihood of using CsSnI 3 as a new absorption material for solar cells.
  • a process of forming homogeneous CsSnI 3 in an organic Perovskite precursor solvent comprises the steps of:
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • the substantially inert environment may be created within a glove box and comprises a protective gas, such as N 2 , including water vapor and oxygen content both under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • a protective gas such as N 2
  • water vapor and oxygen content both under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • the homogeneous CsSnI 3 is formed by adding a SnI 2 solution into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials have fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI 3 precursor solution.
  • the CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent
  • the SnI 2 solution is about 25 mmol/L to 2 mol/L SnI 2 solution by fully dissolving SnI 2 powder (99% purity) in a solvent.
  • the solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 is in the form of a SnI 2 solution.
  • the solvent for dissolving SnI 2 powder (99% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 is in the form of a powder.
  • a process of forming homogeneous CsSnI (3-n) X n in an organic Perovskite precursor solvent comprises steps of:
  • CsSnI (3-n) X n wherein X is a halogen element selected from Group VIIA of the periodic table consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine (At) and 0 ⁇ n ⁇ 3; and
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • the substantially inert environment may be created within a glove box and comprises a protective gas, such as N 2 , including water vapor and oxygen content both under 1 ppm and the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • a protective gas such as N 2
  • water vapor and oxygen content both under 1 ppm and the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • the homogeneous CsSnI (3-n) X n is formed by adding a mixed solution of SnI 2 and SnX 2 into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI (3-n) X n precursor solution.
  • the CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent
  • the mixed solution of SnI 2 and SnX 2 is about 25 mmol/L to 2 mol/L by fully dissolving SnI 2 and SnX 2 powder (99% purity) in a solvent.
  • the solvent for dissolving CsI powder (99.999% purity) is selected to serve as Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 and SnX 2 are in the form of a SnI 2 and SnX 2 solution.
  • the solvent for dissolving the SnI 2 and SnX 2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), ⁇ -butyrolactone (GBL) and mixtures thereof.
  • DMF N,N-dimethylformamide
  • GBL ⁇ -butyrolactone
  • the SnI 2 and SnX 2 are in the form of a powder.
  • reaction raw materials were milled and dissolved in a glove box under protect of N 2 gas.
  • the conditions in the glove box were: room temperature or temperature of 298.15 K (or 25° C., 77 F); water vapor and oxygen content are both under 1 ppm; and an absolute pressure of 100 kPa (or 14.504 psi, 0.986 atm).
  • the concentration range of the CsI solution was from about 25 mmol/L to 500 mmol/L.
  • the concentration range of the SnI 2 solution was from about 25 mmol/L to 500 mmol/L.
  • CsI and SnI 2 were both in a range of 25 mmol/L to 500 mmol/L, and their molar ratio was 1:1.
  • the mixed solution was stirred for 12 to 24 hours, and a uniform and transparent yellow CsSnI 3 solution was formed.
  • the homogeneous CsSnI 3 solution was dried until the solvent was all evaporated.
  • the heating temperature ranged from about 100° C. to 200° C.
  • the pure black CsSnI 3 powder with metallic luster was obtained as shown in FIG. 1 .
  • the chemical reaction for the mixed solution could be described as the following:
  • reaction was verified by identifying the end products of CsSnI 3 using the X-ray diffraction (XRD) data.
  • FIG. 2 ( a ) shows the XRD data profile taken from CsSnI 3 (concentrations of CsI and SnI 2 were both 50 mmol/L).
  • FIG. 2 ( b ) showed the standard XRD pdf card (43-1162) of black- ⁇ phase of CsSnI 3 .
  • CsSnI 3 was synthesized using the CsI and SnI 2 by solution based method.
  • a solution based method was employed to fabricate CsSnI 3 , especially suitable for solar cell applications.
  • the polycrystalline quality was characterized by XRD data.

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Abstract

This invention discloses a solution based synthesis of cesium tin tri-iodide (CsSnI3). More specifically, the CsSnI3 is fabricated in an organic Perovskite precursor solvent. CsSnI3 are ideally suited for a wide range of applications such as light emitting and photovoltaic devices.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The invention generally relates to the formation of materials for photovoltaic devices and more specifically to the synthesis of CsSnI3 by solution based method.
  • 2. Description of the Prior Art
  • The current photovoltaic technologies can be classified by the different 10 materials used for the light absorption in a solar cell. These materials include amorphous and polycrystalline silicon, CdTe, CuInxGa1-xSe2 (CIGS), GaAs, and photosensitive organic dyes. A transformative technology may emerge when a new and better material is discovered for photovoltaic applications.
  • CsSnI3 is a unique phase-change material that exhibits four polymorphs. The black polymorph of CsSnI3 could be obtained through a phase transition from the yellow polymorph CsSnI3 by increasing its temperature above 425 K. It was further demonstrated by differential thermal analysis and X-ray diffraction that during the cooling of the black CsSnI3 from 450 K, its ideal cubic Perovskite structure (B-α) deformed to a tetragonal structure (B-β) at 426 K, and became an orthorhombic structure (B-γ) below 351 K. [1] The CsSnI3 is unique in combining two generally contra-indicated properties, strong photoluminescence (PL) and high electrical conductivity. [2, 3]
  • A need still exists in the industry for developing synthesis methods for CsSnI3, especially in large scale. The successful implementation of these materials for various applications requires a detailed understanding of both their processing and materials properties.
  • At present, the synthesis of CsSnI3 can be divided into solid-phase sintering and solution based methods. The solid-phase sintering method needs vacuum and high temperature which means high production costs. [1] For solution based method, K. Shum and Z. Chen offered a simple way to synthesize CsSnI3, but the final product is not pure (U.S. Published Patent Application No. 2012/0306053). Here, we provide a simple solution based method to synthesize substantially pure CsSnI3.
    • SUMMARY OF THE INVENTION
  • This invention is directed to synthesizing cesium tin tri-iodide (CsSnI3) by a solution based method.
  • According to one aspect of the invention one embodiment in accordance with the invention is directed to a process of forming homogeneous CsSnI3 in an organic Perovskite precursor solvent, comprising steps of:
  • (1) forming CsI solution from CsI powder;
  • (2) providing SnI2;
  • (3) adding the SnI2 into the CsI solution to form a mixture wherein the molar ratio of the SnI2 and CsI in the mixture is approximately 1:1;
  • (4) heating the mixed solution at a temperature within the range of 50° C. to 250° C. until all the solvent is evaporated to form CsSnI3 powder; and
  • (5) the process steps (1) to (4) are performed in a substantially inert environment.
  • The substantially inert environment may be created within a glove box and comprises a protective gas, such as N2, including water vapor and oxygen the content of each of which is under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • The homogeneous CsSnI3 is formed by adding a SnI2 solution into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials have fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI3 precursor solution.
  • The CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent, and the SnI2 solution is about 25 mmol/L to 2 mol/L SnI2 solution by fully dissolving SnI2 powder (99% purity) in a solvent.
  • The solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • In the aforementioned process the SnI2 is in the form of a SnI2 solution.
  • The solvent for dissolving SnI2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 is in the form of a powder.
  • Other halides may be used to practice the invention. For example, a process of forming homogeneous CsSnI(3-n)Xn in an organic Perovskite precursor solvent, comprises the steps of:
  • (1) forming CsI solution from CsI powder;
  • (2) providing SnI2 and SnX2;
  • (3) adding the SnI2 and SnX2 into the CsI solution to form a mixture wherein the molar ratio of the raw materials is SnX2:SnI2:CsI=y:(1-y):1, where 0≦y≦1;
  • (4) heating the final mixed solution at a temperature within the range of 50° C. to 250° C. until all the solvent is evaporated to form CsSnI(3-n)Xn, wherein X is a halogen element selected from Group VIIA of the periodic table consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine (At) and 0≦n≦3; and
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • In the aforementioned process the substantially inert environment may be created within a glove box and comprises a protective gas, such as N2, including water vapor and oxygen content both under 1 ppm and the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • The homogeneous CsSnI(3-n)Xn is formed by adding a mixed solution of SnI2 and SnX2 into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI(3-n)Xn precursor solution.
  • The CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent, and the mixed solution of SnI2 and SnX2 is about 25 mmol/L to 2 mol/L by fully dissolving SnI2 and SnX2 powder (99% purity) in a solvent.
  • The solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 and SnX2 are in the form of a SnI2 and SnX2 solution.
  • The solvent for dissolving the SnI2 and SnX2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The the SnI2 and SnX2 are in the form of a powder.
  • In the process, the steps are preferably performed in a glove box under the protection of N2 gas and the molar ratio of the SnI2 and CsI in the mixture is essentially 1:1.
  • The CsI solution is made by fully dissolving CsI powder (99.999% purity) in a solvent selected from the Perovskite precursor solutions, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof. The concentration of CsI solution is about 25 mmol/L to 500 mmol/L.
  • The SnI2 solution is made by fully dissolving SnI2 powder (99% purity) in a solvent selected from the Perovskite precursor solutions, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof. The concentration of SnI2 solution is about 25 mmol/L to 500 mmol/L.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The accompanying drawings, which are incorporated in and form a part of the specification, illustrate preferred embodiments of the present invention, and together with the description, serve to explain the principles of the invention, in which:
  • FIG. 1 shows the schematic diagram for the synthesis of CsSnI3; and
  • FIG. 2 shows the (a) X-ray diffraction data (XRD) profile taken from CsSnI3 (concentrations of CsI and SnI2 were both 50 mmol/L) and (b) standard XRD pdf card (43-1162) of black-γ phase of CsSnI3.
    •  DETAILED DESCRIPTION AND EXAMPLES
  • The CsSnI3 exhibits outstanding optical, electrical, and ferroelectric properties. These features make CsSnI3 ideally suited for a wide range of applications such as light emitting and photovoltaic devices.
  • More specifically, CsSnI3 is a promising material in the application of solar cells since CsSnI3 was found to possess a direct band gap of 1.32 eV at room temperature, right in the narrow region of optimal band gaps for the Shockley-Queisser maximum efficiency limit of a solar cell.
  • An effective method to synthesize large domain size high quality Perovskite semiconductor according to the present invention is disclosed. More specifically, a solution based method to synthesize CsSnI3 is disclosed according to the present invention. The CsSnI3 can be fabricated in an organic Perovskite precursor solvent as shown in FIG. 1. This synthesis method of the CsSnI3 further enhances the likelihood of using CsSnI3 as a new absorption material for solar cells.
  • Examples of procedures for synthesizing polycrystalline CsSnI3 using reaction raw materials are described below. Generally, a process of forming homogeneous CsSnI3 in an organic Perovskite precursor solvent, comprises the steps of:
  • (1) forming CsI solution from CsI powder;
  • (2) providing SnI2;
  • (3) adding the SnI2 into the CsI solution to form a mixture wherein the molar ratio of the SnI2 and CsI in the mixture is substantially 1:1;
  • (4) heating the mixed solution at a temperature within the range of 50° C. to 250° C. until all the solvent is evaporated to form CsSnI3 powder; and
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • The substantially inert environment may be created within a glove box and comprises a protective gas, such as N2, including water vapor and oxygen content both under 1 ppm and the temperature while heating the mixed solution ranges from about 50° C. to 250° C.
  • The homogeneous CsSnI3 is formed by adding a SnI2 solution into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials have fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI3 precursor solution.
  • The CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent, and the SnI2 solution is about 25 mmol/L to 2 mol/L SnI2 solution by fully dissolving SnI2 powder (99% purity) in a solvent.
  • The solvent for dissolving CsI powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 is in the form of a SnI2 solution.
  • The solvent for dissolving SnI2 powder (99% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 is in the form of a powder.
  • Other halides may be used to practice the invention. More generally, a process of forming homogeneous CsSnI(3-n)Xn in an organic Perovskite precursor solvent, comprises steps of:
  • (1) forming CsI solution from CsI powder;
  • (2) providing SnI2 and SnX2;
  • (3) adding the SnI2 and SnX2 into the CsI solution to form a mixture wherein the molar ratio of the raw materials is SnX2:SnI2:CsI=y:(1-y):1, where 0≦y≦1;
  • (4) heating the final mixed solution at a temperature within the range of 50° C. to 250° C. until all the solvent is evaporated to form CsSnI(3-n)Xn, wherein X is a halogen element selected from Group VIIA of the periodic table consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and astatine (At) and 0≦n≦3; and
  • the process steps (1) to (4) are performed in a substantially inert environment.
  • The substantially inert environment may be created within a glove box and comprises a protective gas, such as N2, including water vapor and oxygen content both under 1 ppm and the temperature while heating the final mixed solution ranges from about 50° C. to 250° C.
  • The homogeneous CsSnI(3-n)Xn is formed by adding a mixed solution of SnI2 and SnX2 into a CsI solution to form a mixture, and stirring the mixture for 1 to 3 hours to insure that the raw materials fully reacted, and then the solution is aged for 12 to 24 hours to form the homogeneous CsSnI(3-n)Xn precursor solution.
  • The CsI solution is about 25 mmol/L to 2 mol/L CsI solution by fully dissolving CsI powder (99.999% purity) in a solvent, and the mixed solution of SnI2 and SnX2 is about 25 mmol/L to 2 mol/L by fully dissolving SnI2 and SnX2 powder (99% purity) in a solvent.
  • The solvent for dissolving CsI powder (99.999% purity) is selected to serve as Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 and SnX2 are in the form of a SnI2 and SnX2 solution.
  • The solvent for dissolving the SnI2 and SnX2 powder (99.999% purity) is selected to serve as a Perovskite ligand to form coordination complexes, such as N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The SnI2 and SnX2 are in the form of a powder.
  • The procedures of synthesizing polycrystalline CsSnI3 using reaction raw materials have been described.
  • The reaction raw materials were milled and dissolved in a glove box under protect of N2 gas.
  • The conditions in the glove box were: room temperature or temperature of 298.15 K (or 25° C., 77 F); water vapor and oxygen content are both under 1 ppm; and an absolute pressure of 100 kPa (or 14.504 psi, 0.986 atm).
    • WORKING EXAMPLES Example 1 Preparation of CsI Solution
  • Initially, 0.13 gram of CsI (99.999% purity) powder was added to 10 mL GBL. The CsI powder was fully dissolved in GBL. The CsI solution was stirred for 30 minutes.
  • CsI solution was colorless and stable in glove box.
  • It would be apparent to one skilled in the art that CsI solutions could be made using any solvents in addition to those used in the examples. Examples of solvents that can be used include but are not limited to N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof.
  • The concentration range of the CsI solution was from about 25 mmol/L to 500 mmol/L.
    • Example 2 Preparation of SnI2 Solution
  • Initially, 0.186 gram of SnI2 (99% purity) powder was added to 10 mL GBL. The SnI2 powder was fully dissolved in GBL. The SnI2 solution was stirred for 30 minutes.
  • SnI2 solution was yellow and stable in glove box.
  • It would be apparent to one skilled in the art that SnI2 solutions could be made using any solvents in addition to those used in the examples. Examples of solvents that can be used include but are not limited to, DMF, GBL or mixtures thereof.
  • The concentration range of the SnI2 solution was from about 25 mmol/L to 500 mmol/L.
    • Example 3 Synthesis of CsSnI3
  • A given amount of the prepared CsI solution was transferred to a reaction vial first. SnI2 solution or powder was then slowly added into the vial. The concentrations range of CsI and SnI2 were both in a range of 25 mmol/L to 500 mmol/L, and their molar ratio was 1:1.
  • The mixed solution was stirred for 12 to 24 hours, and a uniform and transparent yellow CsSnI3 solution was formed.
  • The homogeneous CsSnI3 solution was dried until the solvent was all evaporated. The heating temperature ranged from about 100° C. to 200° C. Then the pure black CsSnI3 powder with metallic luster was obtained as shown in FIG. 1. The chemical reaction for the mixed solution could be described as the following:

  • CsI+SnI2→CsSnI3
  • The reaction was verified by identifying the end products of CsSnI3 using the X-ray diffraction (XRD) data.
  • FIG. 2 (a) shows the XRD data profile taken from CsSnI3 (concentrations of CsI and SnI2 were both 50 mmol/L).
  • FIG. 2 (b) showed the standard XRD pdf card (43-1162) of black-γ phase of CsSnI3.
  • All the measured peaks were well matched to the black-γ phase of CsSnI3.
  • In summary, CsSnI3 was synthesized using the CsI and SnI2 by solution based method.
  • A solution based method, was employed to fabricate CsSnI3, especially suitable for solar cell applications. The polycrystalline quality was characterized by XRD data.
  • While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
    • APPENDIX
    • 1. I. Chung, J-H Song, J. Im, J. Androulakis, C. D. Malliakas, H. Li, A. J. Freeman, J. T. Kenney, and M. G. Kanatzidis, J. Am. Chem. Soc., 2012, 134, 8579-8587.
    • 2. K. Yamada, T. Matsui, T. Tsuritani, T. Z. Okuda, Naturforsch. A: Phys. Sci., 1990, 45, 307-312.
    • 3. K. Shum, Z. Chen, J. Qureshi, C. Yu, J. J. Wang, W. Pfenninger, N. Vockic, J. Midgley, J. T. Kenney, Appl. Phys. Lett., 2010, 96, 221903.

Claims (25)

1. A process of forming CsSnI3 powder, comprising the steps of:
(a) forming a CsI solution by dissolving CsI powder of purity equal to 99.999% in an organic solvent consisting of at least one of N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof;
(b) forming a SnI2 solution by dissolving SnI2 powder of purity equal to 99% in an organic solvent consisting of at least one of N,N-dimethylformamide (DMF), γ-butyrolactone (GBL) and mixtures thereof;
(c) adding the SnI2 solution into the CsI solution to form a composite solution wherein the molar ratio of the SnI2 and CsI in said composite solution is approximately 1:1;
(d) stirring said composite solution for at least one hour to obtain a homogeneous CsSnI3 precursor solution;
(e) aging said precursor solution at least for a predetermined time period after said stirring step;
(f) heating said precursor solution following said aging step at a temperature within the range of 50° C. to 250° C. until all the solvent is evaporated to form CsSnI3 powder exhibiting an XRD diffraction peak pattern for CsSnI3 corresponding to the standard XRD-PDF card (43-1162) for the B-gamma-CsSnI3 phase without exhibiting an XRD diffraction peak pattern for Cs2SnI6; and
(g) the process steps (a) to (f) are performed in a substantially inert environment including a protective gas and water vapor and oxygen each at a level below 1 ppm.
2. The process of claim 1, wherein said substantially inert environment is created within a glove box.
3. The process of claim (1), wherein said precursor solution is aged for 12 to 24 hours to form a homogeneous CsSnI3 precursor solution.
4. The process of claim 3, wherein the CsI solution is about 25 mmol/L to 2 mol/L CsI solution and the SnI2 solution is about 25 mmol/L to 2 mol/L SnI2 solution.
5. The process of claim 1, wherein said CsI powder is dissolved in said organic solvent to form CsI coordination complexes.
6. (canceled)
7. The process of claim 1, wherein said SnI2 powder is dissolved in said organic solvent to form SnI2 coordination complexes.
8. (canceled)
9. (canceled)
10. (canceled)
11. (canceled)
12. (canceled)
13. (canceled)
14. (canceled)
15. (canceled)
16. (canceled)
17. (canceled)
18. (canceled)
19. The process of claim 2, wherein said protective gas is N2.
20. (canceled)
21. (canceled)
22. (canceled)
23. (canceled)
24. (canceled)
25. (canceled)
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