WO2018026326A1 - Halide perovskite film, solar cell including, and method of forming the same - Google Patents
Halide perovskite film, solar cell including, and method of forming the same Download PDFInfo
- Publication number
- WO2018026326A1 WO2018026326A1 PCT/SG2017/050391 SG2017050391W WO2018026326A1 WO 2018026326 A1 WO2018026326 A1 WO 2018026326A1 SG 2017050391 W SG2017050391 W SG 2017050391W WO 2018026326 A1 WO2018026326 A1 WO 2018026326A1
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- WIPO (PCT)
- Prior art keywords
- cation
- halide perovskite
- halide
- perovskite
- perovskite film
- Prior art date
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- 150000004820 halides Chemical class 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims abstract description 67
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- 150000001768 cations Chemical class 0.000 claims abstract description 93
- -1 halide anion Chemical class 0.000 claims abstract description 81
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- 229910001411 inorganic cation Inorganic materials 0.000 claims abstract description 16
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Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
- H10K71/15—Deposition of organic active material using liquid deposition, e.g. spin coating characterised by the solvent used
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- 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
Definitions
- Various aspects of this disclosure relate to a halide perovskite film.
- Various aspects of this disclosure relate to a solar cell including a halide perovskite film.
- Various aspects of this disclosure relate to a method of forming a halide perovskite film.
- renewable energy sources are perpetual and environmentally friendly. Many renewable energy sources are widely available, and are also well-suited for applications in off-grid remote locations. Among all the renewable energy sources, solar energy has the most potential to meet the challenges of increasing energy demands. In addition, photovoltaic technology may have other advantages such as being noiseless, and may be aesthetically pleasing when incorporated into building designs. Further, it may be used in small-scale plant deployment.
- a perovskite solution including a metal halide and organic halide components in a common solvent such as dimethylformamide (DMF), ⁇ -butyrolactone (GBL), dimethyl sulphoxide (DMSO) is used to form the perovskite film.
- a common solvent such as dimethylformamide (DMF), ⁇ -butyrolactone (GBL), dimethyl sulphoxide (DMSO)
- Various embodiments may provide a method of forming a halide perovskite film.
- the method may include mixing deuterium oxide with a halide perovskite solution to form a halide perovskite film.
- the halide perovskite solution may include a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
- Various embodiments may provide a halide perovskite film formed by a method described herein.
- Various embodiments may provide a crystal structure including a metal cation, an organic group cation, and a halide anion.
- the organic cation may include one or more carbon-deuterium bonds, and one or more carbon-protium bonds.
- FIG. 1 is a schematic showing a method of forming a halide perovskite film according to various embodiments.
- FIG. 2 shows a general illustration of a halide perovskite film according to various embodiments.
- FIG. 3 shows a general illustration of a solar cell according to various embodiments.
- FIG. 4 shows a schematic of an inverted inorganic/organic hybrid solar cell according to various embodiments.
- FIG. 5 shows (a) a cross-sectional scanning electron microscopy (SEM) image of a standard halide perovskite layer on a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ITO) glass substrate, and (b) a cross-sectional scanning electron microscopy (SEM) image of a halide perovskite film treated with 1% deuterium oxide (D 2 0) according to various embodiments on a poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide ( ⁇ ) glass substrate.
- SEM cross-sectional scanning electron microscopy
- FIG. 6 shows scanning electron microscopy images of top views of (a) a standard halide perovskite layer, (b) a halide perovskite layer treated with 1% deuterium oxide (D 2 0) according to various embodiments, (c) a magnified view of the image shown in (a), and (d) a magnified image of the image shown in (b).
- FIG. 7 shows X-ray diffraction patterns of (a) standard halide perovskite film (lower panel) and 1% deuterium oxide (D 2 0) treated halide perovskite film (upper panel) according to various embodiments, and (b) standard halide perovskite film (lower panel) and 1% water (H 2 0) treated halide perovskite film (upper panel).
- FIG. 7 shows X-ray diffraction patterns of (a) standard halide perovskite film (lower panel) and 1% deuterium oxide (D 2 0) treated halide perovskite film (upper panel) according to various embodiments, and (b) standard halide perovskite film (lower panel) and 1% water (H 2 0) treated halide perovskite film (upper panel).
- UV-VIS ultraviolet-visible
- FIG. 9 shows (a) a plot of current density (in milliamperes per square centimeter or mAcm "2 ) as a function of voltage (in volts or V) illustrating illuminated current density-voltage (J-V) characteristic curves of inverted solar cells with standard halide perovskite layer and halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PC 6 iBM), and (b) a plot of current density (in milliamperes per square centimeter or mAcm " 2 ) as a function of voltage (in volts or V) illustrating forward and reverse scans of the current density-voltage (J-V) characteristic curves of the inverted inorganic/organic hybrid solar cell with halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PCeiBM).
- PC 6 iBM pheny
- FIG. 10 is a table showing photovoltaic parameters of the standard halide perovskite layer, and halide perovskite films formed using 1% and 2% deuterium oxide (D 2 0) according to various embodiments.
- FIG. 11 shows (a) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of electron only perovskite devices (glass/indium tin oxide (ITO)/perovskite/[6,6]-phenyl-C61 -butyric acid methyl ester (PC6iBM)/silver (Ag)), wherein one device has a perovskite film treated with deuterium oxide (D 2 0) according to various embodiments and another device has a standard perovskite layer, and (b) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of hole only perovskite devices (glass/indium tin oxide ( ⁇ )/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS
- FIG. 12 is a plot of carrier density (x 10 17 per cubic centimeter or cm “3 ) as a function of photoluminescence (PL) intensity (in arbitrary units or a.u.) showing the photoexcited carrier density of a standard perovskite layer and a deuterium oxide (D 2 0) (1% vol) treated or added perovskite film according to various embodiments excited within low pump fluence regime ( ⁇ 30 ⁇ cm "2 ) at various measured photoluminescence (PL) intensities.
- PL photoluminescence
- FIG. 13 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard perovskite layer, a standard perovskite layer on a hole extraction layer including poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and a standard perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC 6 iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 1% deuterium oxide (D 2 0) treated or added perovskite film according to various embodiments, a 1% deuterium oxide (D 2
- FIG. 14 is a table showing the carrier lifetimes of deuterium treated methylammonium lead iodide (CH3NH3PM3) films, deuterium treated methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and deuterium treated methylammonium lead iodide (CH3NH3PM3) films on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and standard methylammonium lead iodideiCEbNEbPbL) films, standard methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and standard methylammonium lead iodide (CH3NH3PM3) films on poly(3,4-ethylenedioxythi
- FIG. 15 shows plots of intensity (in arbitrary units or a.u.) as a function of depth (in nanometers or nm) showing (a) the elemental depth profile of a sample with a standard perovskite layer (0% deuterium oxide or D 2 0) and (b) the elemental depth profile of a sample with a perovskite film treated with 1% deuterium oxide (D 2 0) according to various embodiments.
- FIG. 15 shows plots of intensity (in arbitrary units or a.u.) as a function of depth (in nanometers or nm) showing (a) the elemental depth profile of a sample with a standard perovskite layer (0% deuterium oxide or D 2 0) and (b) the elemental depth profile of a sample with a perovskite film treated with 1% deuterium oxide (D 2 0) according to various embodiments.
- D 2 0 deuterium oxide
- 16 is a table showing photovoltaic parameters of the standard halide perovskite layer, a halide perovskite film formed using 1% deuterium oxide (D 2 0) according to various embodiments, and a halide perovskite film formed using 1% water (H 2 0).
- FIG. 17 shows a schematic of another solar cell according to various embodiments.
- FIG. 18 is a plot of current density (in milliamperes per square centimeter) as a function of voltage (in volts or V) showing the current density - voltage characteristic curves of a device including a standard halide perovskite layer formed using a four cation (methylammonium, formamidinium, cesium, and rubidium) perovskite solution on a N 2 ,N 2 ,N 2 ,N 2 ,N 7 ,N 7 ,N 7 ,N 7 - octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) layer and a halide perovskite film formed using the four cation perovskite solution with deuterium oxide added on a Spiro-MeOTAD layer according to various embodiments.
- Spiro-MeOTAD a hal
- FIG. 19 is a table showing photovoltaic parameters of the device including a four-cation based standard halide perovskite layer untreated with deuterium oxide (D 2 0), a device including a four-cation based halide perovskite film formed using 1% deuterium oxide (D 2 0) according to various embodiments, a device including a four-cation based halide perovskite film formed using 2% deuterium oxide (D 2 0) according to various embodiments, a device including a four-cation based halide perovskite film formed using 4% deuterium oxide (D 2 0) according to various embodiments, and a device including a four-cation based halide perovskite film formed using 6% deuterium oxide (D 2 0) according to various embodiments.
- D 2 0 deuterium oxide
- FIG. 20 is a plot of absorbance (in arbitrary units or a.u.) as a function of wavelength (in nanometers or nm) showing the ultraviolet- visible absorbance (UV-VIS) spectra of a 4-cation based standard halide perovskite layer, and a 4-cation based halide perovskite film treated or added with 4% deuterium oxide (D 2 0) according to various embodiments.
- UV-VIS ultraviolet- visible absorbance
- FIG. 21 is a plot of carrier density (x 10 17 per cubic centimeters or cm "3 ) as a function of photoluminescence (PL) intensity showing the variation of photoexcited density with photoluminescence (PL) intensity of a four-cation based standard halide perovskite structure and a four-cation based halide perovskite film formed with 4% deuterium oxide (D 2 0) according to various embodiments.
- FIG. 22 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard 4-cation based perovskite layer, a standard 4-cation based perovskite layer on a hole extraction layer N N N 2 N 2 N ⁇ N ⁇ N 7 N 7' -octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'- tetramine (Spiro-MeOTAD), and a standard 4-cation based perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC 6 iBM), and (b) the time-resolved photoluminescence (PL)
- Embodiments described in the context of one of the methods or one of the halide perovskite films/solar cells is analogously valid for the other methods or halide perovskite films/solar cells.
- embodiments described in the context of a method are analogously valid for a halide perovskite film and/or a solar cell, and vice versa.
- the word “over” used with regards to a deposited material formed “over” a side or surface may be used herein to mean that the deposited material may be formed “directly on”, e.g. in direct contact with, the implied side or surface.
- the word “over” used with regards to a deposited material formed “over” a side or surface may also be used herein to mean that the deposited material may be formed "indirectly on” the implied side or surface with one or more additional layers being arranged between the implied side or surface and the deposited material.
- a first layer "over" a second layer may refer to the first layer directly on the second layer, or that the first layer and the second layer are separated by one or more intervening layers.
- FIG. 1 is a schematic 100 showing a method of forming a halide perovskite film according to various embodiments.
- the method may include, in 102, mixing deuterium oxide (D 2 0) with a halide perovskite solution to form a halide perovskite film.
- the halide perovskite solution may include a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
- a halide perovskite film may be formed by mixing deuterium oxide with a solution containing a metal cation, a halide anion, and a cation, i.e. either an organic cation or an inorganic cation.
- the organic cation may be any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium ion, a hydrazinium ion, an azetidinium ion, an imidazolium ion, a dimethylammonium ion, an ethylammonium ion, a phenethylammonium ion, a guanidinium ion, a tetramethylammonium ion, a thiazolium ion, a 3-pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
- the inorganic cation may be a cesium (Cs) cation, a rubidium (Rb) cation, or a potassium (K) cation.
- the halide perovskite solution may further include a further cation.
- the cation and the further cation may be of different elements.
- the halide perovskite solution may include different cations.
- the halide perovskite may include organic cations formed from different molecules, inorganic cations of different elements, or a mixture of one or more cations, and one or more anions.
- the halide perovskite solution may include a plurality of different organic cations and inorganic cations.
- the halide perovskite film formed may include different organic cations, or different inorganic cations or a mixture of one or more cations, and one or more anions.
- the metal cation may be a cation of an element of Group 11, Group 14, or Group 15.
- the metal cation may be any one selected from a group consisting of a lead (Pb) cation, a (Sn) tin cation, a germanium (Ge) cation, and a bismuth (Bi) cation.
- the halide perovskite solution may include different metal cations, i.e. cations of different metal elements.
- the halide perovskite solution may further include a further metal cation.
- the metal cation and the further metal cation may be of different elements.
- the halide perovskite film formed may include different mixtures of metal cations, e.g. (MA/Cs)(Pb/Sn)I 3 , where MA represents the methylammonium cation.
- the halide anion may be any one of a group consisting of a chloride anion, a bromide anion, and an iodide anion.
- the halide perovskite solution may include different anions, i.e. anions of different halide elements.
- the halide perovskite solution may further include a further anion.
- the anion and the further anion may be of different elements.
- the halide perovskite solution may include mixed halides.
- the halide perovskite film formed may include different anions, e.g. MAPbChl.
- a concentration of deuterium oxide in the resultant solution may be any value selected a range from 0.1 % to 10 % by volume, or a range from 0.5 % to 5 % by volume.
- the halide perovskite solution may further include a suitable solvent.
- the suitable solvent may be any one selected from a group consisting of dimethyformamide, ⁇ - butylrolactone, and dimethyl sulphoxide.
- the method may also include annealing a resultant solution formed by mixing deuterium oxide with a halide perovskite solution to form the halide perovskite film.
- the resultant solution may be annealed at any one temperature selected from 50 degrees Celsius (°C) to 90 degrees Celsius (°C).
- the resultant solution may be annealed at a temperature below the boiling point of deuterium oxide, which may be below 101 degrees Celsius.
- the resultant solution may be annealed at about 1 atmospheric pressure.
- the method may further include filtering the resultant solution to remove undissolved precursors before annealing the resultant solution to form the halide perovskite film.
- the filtering of the resultant solution may be carried out using a polytetrafluoroethylene (PTFE) filter.
- PTFE polytetrafluoroethylene
- the halide perovskite film may be coated onto a suitable substrate.
- the suitable substrate may include an indium tin oxide carrier, and a carrier transport layer on the indium tin oxide carrier.
- the method may also include dripping an anti-solvent onto the suitable substrate during the coating of the halide perovskite film onto the suitable substrate.
- the halide perovskite film may be spin-coated onto the suitable substrate.
- the anti-solvent may be toluene, chlorobenzene, dichlorobenzene, diethyl ether, a deuterated solvent, or any other suitable anti-solvent.
- Various embodiments may relate to a halide perovskite film formed by a method as described herein.
- the halide perovskite film may have improved quality compared to a halide perovskite film formed without adding or treating with deuterium oxide.
- the deuterium oxide may improve the perovskite precursors' solubility in the host solvent, improve the growth of perovskite crystal during film formation, and/or may reduce the defect density.
- D 2 0 may improve the perovskite film quality. The effectiveness of the mechanism or method may be dependent on the precursors.
- the halide perovskite film may have a structure or crystal structure including a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
- the organic cation may be an organic group cation.
- the method may result in substitution of protium (H) by deuterium (D) present in deuterium oxide (D 2 0). Some of the carbon-protium (C-H) bonds in the organic cation may be replaced by carbon-deuterium (C-D) bonds.
- the halide perovskite film may include or may be a three dimensional (3D) halide perovskite.
- the structure or crystal structure (of the three dimensional (3D) halide perovskite) may be represented by the formula ABX 3 .
- A may represent the organic cation or the inorganic cation
- B may represent the metal cation
- X may represent the halide anion.
- the halide perovskite film may include CH 3 NH 3 PbI 3 or CsPbI .
- the halide perovskite film i.e. three dimensional (3D) halide perovskite
- the structure or crystal structure i.e. double perovskite structure
- a 2 BX 6 may be represented by the formula A 2 BX 6 .
- A may represent the organic cation or the inorganic cation
- B may represent the metal cation
- X may represent the halide anion.
- the structure or crystal structure i.e. double perovskite structure
- AB2X5 the formula AB2X5.
- A may represent the organic cation or the inorganic cation
- B may represent the metal cation
- X may represent the halide anion.
- the halide perovskite film may include or may be a two dimensional (2D) halide perovskite.
- the halide perovskite film i.e. two dimensional (2D) halide perovskite
- the layer perovskite film may be represented by the formula (CH 3 (CH 2 ) 3 NH 3 )2A2y-iBxX 3y+ i , where "y” may be any positive integer, "A” may represent the organic cation or the inorganic cation, "B” may represent the metal cation, and "X" may represent the halide anion.
- the halide perovskite film may include or may be a mixed dimensional halide perovskite.
- the mixed dimensional halide perovskite may include a 2D halide perovskite and a 3D halide perovskite, and may be represented by the formula (3D perovskite) x (2D perovskite) l-x, where "x" may be any value between 0 and 1.
- FIG. 2 shows a general illustration of a halide perovskite film 200 according to various embodiments.
- the halide perovskite film 200 may have a crystal structure or structure 202 including a metal cation 204, an organic cation 206, and a halide anion 208.
- the organic cation may include one or more carbon-deuterium (C-D) bonds, and one or more carbon-protium (C-H) bonds.
- the halide perovskite film 200 may include an organic cation which is partially bonded to deuterium (D) and partially bonded to protium (H).
- Protium (H) is one isotope of hydrogen, and has a nucleus containing one proton. The nucleus of protium does not contain any neutron.
- Deuterium (D) is another isotope of hydrogen, and has a nucleus containing one neutron and one proton.
- the halide perovskite film 200 may include or may be a three dimensional (3D) halide perovskite.
- the structure or crystal structure 202 (of the three dimensional (3D) halide perovskite) may be represented by the formula ABX 3 .
- A may represent the organic cation 206
- B may represent the metal cation 204
- X may represent the halide anion 208.
- the halide perovskite film 200 i.e. three dimensional (3D) halide perovskite, may have a double perovskite structure.
- the structure or crystal structure 202 i.e. double perovskite structure
- A2BX6 the formula A2BX6.
- A may represent the organic cation 206
- B may represent the metal cation 204
- X may represent the halide anion 208.
- the structure or crystal structure 202 i.e. double perovskite structure
- the structure or crystal structure 202 may be represented by the formula AB2X5.
- A may represent the organic cation 206
- B may represent the metal cation 204
- X may represent the halide anion 208.
- the halide perovskite film 200 may include or may be a two dimensional (2D) halide perovskite.
- the halide perovskite film 200 i.e. the two dimensional (2D) halide perovskite, may include or may be a layer perovskite structure.
- the layer perovskite film 200 may be represented by the formula (CH3(CH2)3NH3)2A2y-iB x X3 y+ i , where "y” may be any positive integer, “A” may represent the organic cation 206, “B” may represent the metal cation 204, and “X” may represent the halide anion 208.
- the halide perovskite film 200 may include or may be a mixed dimensional halide perovskite.
- the mixed dimensional halide perovskite may include a 2D halide perovskite and a 3D halide perovskite, and may be represented by the formula (3D perovskite) x (2D perovskite) l-x, where "x" may be any value between 0 and 1.
- the organic cation may be any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium cation, a hydrazinium cation, an azetidinium cation, an imidazolium cation, a dimethylammonium cation, an ethylammonium cation, a phenethylammonium cation, a guanidinium cation, a tetramethylammonium ion, a thiazolium ion, a 3-pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
- a percentage of the one or more carbon-deuterium (C-D) bonds relative to a total of the one or more carbon- protium (C-H) bonds and the one or more carbon-deuterium bonds may be any one value selected from a range of 0.01% to 5.0%.
- the fraction or percentage of the carbon-deuterium bond relative to the total of the one or more carbon- protium bonds and the one or more carbon-deuterium bonds may be dependent on the solution concentrations of the various precursors, and/or the processing methods.
- the fraction or percentage of the carbon-deuterium bonds may also be dependent on the evaporation of D2O, and the solvent of the halide perovskite solution, e.g. DMF, which may vary.
- DMF host solvent
- FIG. 3 shows a general illustration of a solar cell 300 according to various embodiments.
- the solar cell 300 may include a halide perovskite film 302 as described herein.
- the solar cell 300 may further include an electron transport layer 304 on a first side of the halide perovskite film 302.
- the solar cell 300 may also include a hole transport layer 306 on a second side of the halide perovskite film 302 opposite the first side.
- the solar cell 300 may additionally include a first electrode 308 in electrical connection with the electron transport layer 304.
- the solar cell 300 may also include a second electrode 310 in electrical connection with the hole transport layer 306.
- the solar cell 300 may include a halide perovskite film 302 as described herein.
- the film 302 may be sandwiched by an electron transport layer 304 and a hole transport layer 306.
- the solar cell 300 may also include a first electrode 308 in contact with the electron transport layer 304, and a second electrode 310 in contact with the hole transport layer 306.
- a power conversion efficiency of the solar cell may be greater than 12%, e.g. greater than 13.5%.
- a fill factor of the solar cell may be greater than 0.75 (75%).
- a short circuit current density of the solar cell may be greater than 18.9 mA cm "2 .
- Various embodiments may relate to a device including a halide perovskite film as described herein.
- the device may be an optoelectronic device such as a light emitting diode, a light emitting field effect transistor, a light emitting transistor, a photodetector etc.
- the device may be an electronic device such as a memory device, a switch, a synaptic device etc., where solution processes or printable technologies are used.
- Various embodiments may relate to a straightforward method of developing efficient devices for solar cell applications.
- Various embodiments may relate to a method of preparing a high-quality perovskite film by using deuterium oxide or deuterated water (D 2 0) (also commonly known as heavy water) as a solvent additive in a single-step solution process, instead of more complex fabrication techniques such as sequential and physical vapour deposition methods.
- D 2 0 deuterium oxide or deuterated water
- D 2 0 may be widely used in the following applications: (i) preparation of deuterium to be used as a moderator in a nuclear reactor, (ii) as a solvent for nuclear magnetic resonance spectra, and (iii) as a tracer in studies of reactions occurring in living organisms and/or other chemical reactions.
- D2O may have never been used in any solar cell applications to enhance their photovoltaic efficiencies.
- Various embodiments may provide a halide perovskite film formed by using D 2 0 and/or a solar cell including the halide perovskite film formed by using D 2 0.
- Various embodiments may relate to a D20-added CH3NH 3 Pbl3 (MAPbI 3 ) based inverted solar cell 400 as shown in FIG. 4, which may demonstrate higher power conversion efficiencies (PCE) than the control or standard halide perovskite cells (without addition of D2O).
- FIG. 4 shows a schematic of an inverted inorganic/organic hybrid solar cell 400 according to various embodiments.
- the solar cell 400 may include a halide perovskite layer or film 402.
- the solar cell 400 may further include an electron transport layer 404, such as a [6,6] -phenyl-C61 -butyric acid methyl ester (PC 6 iBM) layer, in contact with a first side of the halide perovskite layer or film 402.
- the solar cell 400 may also include a hole transport layer 406, such as a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) layer, in contact with a second side of the halide perovskite layer or film 402 opposite the first side.
- PEDOT:PSS poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
- the solar cell 400 may also include a first electrode 408, such as a silver electrode, in contact with the electron transport layer 404.
- the solar cell 400 may additionally include a second electrode 410, such as an indium tin oxide (ITO) layer, in contact with the hole transport layer 406.
- ITO indium tin oxide
- the stacked arrangement including the halide perovskite layer or film 402, the electron transport layer 404, the hole transport layer 406, the first electrode 408, and the second electrode 410, may be on a substrate 412 such as glass.
- Various embodiments may relate to a high quality photo-absorption layer with better charge carrier transport.
- Various embodiments may relate to in-depth investigations on the influence of D2O on (i) device performance of the inverted-perovskite solar cell (ii) perovskite morphology (iii) transient photoluminescence and/or (iv) elemental depth profile.
- Various embodiments may relate to an easy and well-controlled single-step spin coating method which may be developed to make high quality halide perovskite films or layers such as CH3NH 3 Pbl3.
- FIG. 5 shows (a) a cross- sectional scanning electron microscopy (SEM) image of a standard halide perovskite layer on a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ITO) glass substrate, and (b) a cross-sectional scanning electron microscopy (SEM) image of a halide perovskite film treated with 1% deuterium oxide (D 2 0) according to various embodiments on a poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide ( ⁇ ) glass substrate.
- a standard halide perovskite layer may refer to a control halide perovskite layer without D 2 0 added or treated with D 2 0.
- the standard halide perovskite layer may be devoid of any significant amounts of D 2 0.
- FIG. 5(a) shows the pristine or standard perovskite layer which is prepared without D 2 0 additive on the hole transporting PEDOT:PSS layer (hole transport layer or HTL).
- FIG. 5(b) shows the cross-section morphology of a perovskite film formed from D 2 0 (1 % volume or vol) in stoichiometric 40 wt% CH 3 NH 3 PbI 3 halide perovskite solution.
- the presence of deuterated water may affect crystal formation, which may in turn influence the crystallization of the perovskite crystals, in particular promoting crystal formation along the entire periphery of the crystal. It should also be noted that all the perovskite crystal grains formed on the HTL are observed to be single crystals and unidirectional. Since the crystal grains are as thick as the film, the crystal grains may provide an excellent charge carrier transport pathway along the device in the absence of grain boundaries and voids.
- the addition of D 2 0 may form a very compact and continuous film covering most of the PEDOT:PSS surface.
- the halide perovskite film treated with D 2 0, i.e. with D 2 0 added, may be superior to the film without addition of D 2 0.
- FIG. 6 shows scanning electron microscopy images of top views of (a) a standard halide perovskite layer, (b) a halide perovskite layer treated with 1% deuterium oxide (D 2 0) according to various embodiments, (c) a magnified view of the image shown in (a), and (d) a magnified image of the image shown in (b).
- FIG. 6(c) and (d) show that the inclusion of D 2 0 in perovskite precursor solution cause a drastic drop in the fraction of the grain boundaries and increased crystal size.
- the grain boundaries and voids in the photo-absorbing (halide perovskite) layer may adversely affect solar cell performance because they act as charge carrier recombination sites and shunting paths, thus affecting the current density and open circuit voltage generated from the solar cell device. Accordingly, various embodiments may improve solar cell performance by reducing the number of grain boundaries and voids.
- halide perovskite crystals during spin coating and thermal annealing may depend on the solvent evaporation rate from the halide perovskite layer.
- D 2 0 the solvent evaporation may initialize earlier than in the case for samples with DMF only.
- perovskite crystallization may begin earlier in the former case (i.e., solutions with D 2 0).
- the addition of some D 2 0 to the deuterated solvents may also cause the solvent evaporation to initialize earlier.
- FIG. 7 shows X-ray diffraction patterns of (a) standard halide perovskite film (lower panel) and 1% deuterium oxide (D 2 0) treated halide perovskite film (upper panel) according to various embodiments, and (b) standard halide perovskite film (lower panel) and 1% water (H 2 0) treated halide perovskite film (upper panel).
- FIG. 7(a) The X-ray diffraction pattern of D 2 0 (1 % volume or vol) treated or added perovskite layer and the X-ray diffraction pattern of a standard halide perovskite film (without D20 added) are presented in FIG. 7(a).
- the stronger peak intensity confirms the higher crystallinity in D 2 0 treated or added perovskite layer due to the more uniform and slower grain growth.
- FIG. 8 is a plot of absorption (in arbitrary units or a.u.) as a function of wavelength (in nanometers or nm) showing the ultraviolet- visible (UV-VIS) absorption spectra of a standard halide perovskite layer, a 1% water added or treated halide perovskite layer, and a 1% deuterium oxide (D 2 0) treated or added halide perovskite layer according to various embodiments.
- UV-VIS ultraviolet- visible
- D 2 0 deuterium oxide
- solar photon absorption may increase for wavelengths shorter than 510 nm, but may almost be invariant for wavelengths longer than 510 nm.
- the absorbance of the D 2 0 added perovskite film has increased to ⁇ optical density (OD) 4.0 at 400 nm compared to ⁇ OD 2.25 in the standard perovskite film. This may translate to a 1.8 times increment in the absorption at 400 nm.
- the solubility of the perovskite precursors in the additive, and the bonding strength with additive may also be important.
- the ratio of C-H bonds to C-D bonds may be an important factor affecting the efficiency of halide perovskite devices.
- the D 2 0 (by volume) treated or added halide perovskite film may show superior properties compared to the reference films, which may be due to a presence of C-D bonds.
- a small presence of C-D bonds formed by the addition of 1% (by volume) D 2 0 may cause an improvement.
- further increase of the fraction of C-D bonds with the addition of e.g. more than 1% (by volume) D 2 0 may yield adverse effects in some embodiments.
- FIG. 9 shows (a) a plot of current density (in milliamperes per square centimeter or mAcm -2 ) as a function of voltage (in volts or V) illustrating illuminated current density-voltage (J-V) characteristic curves of inverted solar cells with standard halide perovskite layer and halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PC 6 iBM), and (b) a plot of current density (in milliamperes per square centimeter or mAcm "2 ) as a function of voltage (in volts or V) illustrating forward and reverse scans of the current density-voltage (J-V) characteristic curves of the inverted inorganic/organic hybrid solar cell with halide perov
- the halide perovskite film may be formed using methylammonium lead iodide (CH3NH3PM3), dimethylformamide (DMF), and 1% deuterium oxide (D 2 0), while the standard halide perovskite layer may be formed using methylammonium lead iodide (CH3NH3PM3) and dimethylformamide (DMF).
- FIG. 10 is a table 1000 showing photovoltaic parameters of the standard halide perovskite layer, and halide perovskite films formed using 1% and 2% deuterium oxide (D 2 0) according to various embodiments.
- the thickness of each perovskite layer or film may be in the range of 250 nm to 300 nm.
- PCE refers to power conversion efficiency
- Jsc refers to short circuit current density
- Voc refers to open circuit voltage
- FF refers to fill factor
- the table 1000 shows the parameters extracted from the measurements performed under 100 mW-cm "2 AM 1.5G.
- the devices prepared with 1.0 % vol D 2 0 additive achieved a promising efficiency of 13.76%, a -32% improvement as compared to 10.47% efficiency for a standard device fabricated under the same conditions.
- the efficiency enhancement by adding D2O may come from the increase of all the efficiency determining parameters i.e. Jsc, Voc and FF.
- the enhancement in device performance upon the inclusion of D2O may be attributed to the improved perovskite film quality, thus increasing energy harvesting and reducing charge carrier loss mechanisms occurring due to the voids and grain boundaries.
- the efficiency may be very sensitive to the amount of the additive included in the perovskite precursor solution.
- the efficiency may drop to 10.84% on further increase of the additive fraction of D2O to 2.0% vol as shown in FIG. 10.
- Various embodiments may relate to controlling the growth of the perovskite crystals and subsequently the PCE of the solar cell devices by varying the volume ratios of D2O additive.
- the D2O additive may be adjusted to be a value between 0.1 to 10 vol %, or between 0.5 to 1.5 vol %.
- FIG. 9(b) shows the forward and backward (reverse) scan J-V characteristics of D2O treated or added perovskite solar cell.
- the better perovskite film quality formed using D2O with significantly lower number of grain boundaries and number of voids may yield a nearly hysteresis-free solar cell. This may also be attributed to the efficient dissociation and transport of charge carriers into PEDOT:PSS/CH 3 NH 3 Pbl3/PC6iBM interface and bulk.
- a well-known Langmuir Child equation may be used to further determine the electron mobilities and hole mobilities in the perovskite films. Electron only devices may be fabricated by the deposition of a standard perovskite layer or a D 2 0 (1 % vol) treated / added perovskite film directly onto a ITO patterned glass substrate, followed by a thin layer of electron acceptor layer and a silver layer as counter electrode.
- Hole only devices may be formed using a similar way.
- a standard perovskite layer or D 2 0 (1 % vol) treated / added perovskite films may be deposited onto a PEDOT:PSS coated ITO glass substrate, followed by gold deposition.
- FIG. 11 shows (a) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of electron only perovskite devices (glass/indium tin oxide (ITO)/perovskite/[6,6]-phenyl-C61 -butyric acid methyl ester (PC6iBM)/silver (Ag)), wherein one device has a perovskite film treated with deuterium oxide (D 2 0) according to various embodiments and another device has a standard perovskite layer, and (b) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of hole only perovskite devices (glass/indium tin oxide ( ⁇ )/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT)
- FIG. 11 (a) and (b) show the current-voltage characteristics using a log-log scale.
- FIG. 11(a) and (b) show that charge carrier mobilities in D 2 0 treated or added perovskite devices may be superior to their standard counterparts, evident from an increase in electron mobility from 8.5xl0 "4 to 1.3xl0 "3 V-cm "2 -s _1 , and hole mobility increases from 7.0xl0 "6 to l.lxlO "5 V-cm "2 -s _1 .
- the improvement in carrier mobility in D 2 0 treated or added perovskite films may be directly attributed to the absence of the voids and grain boundaries in deuterated perovskite films.
- the voids and grain boundaries may cause charge carrier trapping and scattering sites in standard perovskite layers.
- FIG. 12 is a plot of carrier density (x 10 17 per cubic centimeter or cm “3 ) as a function of photoluminescence (PL) intensity (in arbitrary units or a.u.) showing the photoexcited carrier density of a standard perovskite layer and a deuterium oxide (D 2 0) (1% vol) treated or added perovskite film according to various embodiments excited within low pump fluence regime ( ⁇ 30 ⁇ cm "2 ) at various measured photoluminescence (PL) intensities.
- PL photoluminescence
- the trap density of perovskite may be estimated to be around 3.5 x 10 17 cm “3 which reduces slightly to 3.4 x 10 17 cm “3 when D 2 0 (1 % vol) is added as an additive.
- FIG. 13 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard perovskite layer, a standard perovskite layer on a hole extraction layer including poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and a standard perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC 6 iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 1% deuterium oxide (D 2 0) treated or added perovskite film according to various embodiments, a 1% deuterium oxide
- the optical measurements as presented in FIGS. 12 and 13 show that the perovskite film with D2O (1 % vol) may be superior than standard perovskite layer in terms of both lower trap densities and longer charge carrier lifetimes.
- the longer charge carrier lifetime in the perovskite film with D2O added may be attributed to better film morphology and coverage of the deuterated film than that of a standard perovskite layer, which may in turn be due to larger crystal grain sizes and/or crystal size uniformity of the deuterated film compared to that of the standard perovskite layer.
- FIG. 14 is a table 1400 showing the carrier lifetimes of deuterium treated methylammonium lead iodide (CH3NH3PM3) films, deuterium treated methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and deuterium treated methylammonium lead iodide (CH3NH3PM3) films on poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and standard methylammonium lead iodideiCE NEbPbb) films, standard methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and standard methylammonium lead iodide (CH3NH 3 Pbl3) films on poly(
- ⁇ represents the measured carrier lifetime corresponding to a drop in photoluminescence intensity corresponding to a value Ai
- ⁇ 2 represents the measured carrier lifetime corresponding to a drop in photoluminescence intensity corresponding to a value A 2
- the lower trap density of perovskite film with D 2 0 suggests that the traps which exist predominantly at the crystal grain boundaries may be reduced with disappearance of the grain boundaries upon the inclusion of D 2 0.
- the superior optical properties of perovskite films treated or added with D 2 0 may be in agreement with the higher power conversion efficiency (PCE) seen in devices made using perovskite treated or added with D 2 0.
- PCE power conversion efficiency
- the improved crystallinity observed from XRD diffraction, as well as the uniformity and size of crystal grains observed from scanning electron microscopy may imply that the D 2 0 additive may be beneficial for film formation, and may decrease the trap densities as well as increase carrier lifetimes.
- the elemental depth profiles of a standard perovskite layer and a D 2 0 (1 % vol) treated or added perovskite film may be investigated by secondary ion mass spectrometry (SIMS) to further prove that the D 2 0 is actually incorporated into the perovskite layer in the D 2 0 treated or added perovskite film.
- SIMS secondary ion mass spectrometry
- perovskite films may be deposited onto PEDOT:PSS coated ⁇ /glass substrate.
- An additional organic protection layer of PC 6 iBM may be further deposited on top of perovskite films to avoid water/oxygen attack to the perovskite films.
- FIG. 15 shows plots of intensity (in arbitrary units or a.u.) as a function of depth (in nanometers or nm) showing (a) the elemental depth profile of a sample with a standard perovskite layer (0% deuterium oxide or D 2 0) and (b) the elemental depth profile of a sample with a perovskite film treated with 1% deuterium oxide (D 2 0) according to various embodiments.
- the C “ and H " peaks are present the organic protection layer, and begin to decrease at around 150 nm.
- the ⁇ and Pb " peaks, which indicate the perovskite layer, become prominent between 150 nm to 350 nm. After 350 nm, the InO " peak rises dramatically, indicating the ITO layer. The curves of these elements look quite similar between in the two samples.
- the D " peak becomes higher in 1% D 2 0 added film as compared to the standard film, indicating that deuterium may be incorporated into the treated perovskite film and may remain there even after the film is annealed at 100 °C (close to the boiling point of D 2 0) for 30 minutes. This suggests that the presence of deuterium within the treated perovskite film may indeed help in better film formation, which may then result in higher power conversion efficiency (PCE).
- PCE power conversion efficiency
- FIG. 16 is a table 1600 showing photovoltaic parameters of the standard halide perovskite layer, a halide perovskite film formed using 1% deuterium oxide (D 2 0) according to various embodiments, and a halide perovskite film formed using 1% water (H 2 0).
- FIG. 16 shows that a better performance may be achieved with the addition of deuterated water (D 2 0) compared to the addition of standard water (H 2 0) or no addition at all.
- D 2 0 deuterated water
- H 2 0 standard water
- H 2 0 standard water
- FIG. 16 shows that a better performance may be achieved with the addition of deuterated water (D 2 0) compared to the addition of standard water (H 2 0) or no addition at all.
- D 2 0 (1 % vol) in perovskite films shows better photo-absorption and crystallinity as compared to inclusion of H 2 0 (1 % vol ) in perovskite films as shown by FIGS. 7 and 8.
- D 2 0 may work much better that H 2 0 as an additive solvent to grow perovskite under the similar or same conditions.
- the moisture and oxygen sensitive steps of fabricating the perovskite layer and the electron accepting layer were performed in a nitrogen filled glove box with ⁇ 0.1 parts per million (ppm) H 2 0 and ⁇ 2.0 ppm oxygen level.
- All the devices were fabricated on pre-patterned ITO glass substrates with a sheet resistance of -10 ⁇ /square.
- the substrates were firstly cleaned by soap water followed by ultrasonication in deionized water for 15 minutes. These substrates were further ultrasonicated for 30 min in a mixture of acetone and isopropanol solution in equal proportion by volume and dried at about 70 °C for at least 60 minutes. These cleaned substrates were further treated with plasma for 7 minutes to render the ITO surface hydrophilic.
- a thin film of PEDOT:PSS layer of approximately 30 nm was deposited by spin-coating on these substrates (at 3000 rpm for 60 s), followed by annealing at 130 °C for 15 minutes. Later, these substrates were transferred to the nitrogen filled glove box.
- This solution was filtered through 0.45 ⁇ pore size PTFE filter and deposited on PEDOT:PSS layer coated onto a 2.5 cm x 2.5 cm substrate at 5000 revolutions per minute (rpm) for 12 seconds.
- An anti-solvent toluene was dripped onto the substrates just after 3 seconds of the start of spin coating. The annealing of these substrates was performed at about 100 °C for 30 minutes to evaporate the solvent and to promote the perovskite formation.
- An electron acceptor layer was subsequently deposited onto the different fabricated perovskite layers by spin-coating at a speed of 1200 rpm for 45 seconds.
- the electron acceptor layer solution was prepared by dissolving 20 mg of PC 6 iBM in 1 ml of chlorobenzene.
- a metal shadow mask was attached to the electron acceptor layer (PC 6 iBM) coated substrates and transferred to the thermal evaporation chamber.
- 20 nm thick silver was deposited at a deposition rate of 0.1 - 0.2 A / s, followed by 80 nm thick silver at a deposition rate of 1.0 A /s to form a 100 nm thick silver layer.
- the effective device area was 0.07 cm 2 .
- Perovskite solar cells electrical measurements were performed under 100 mW-cm "2 AM 1.5G.
- the devices prepared with 1.0 % vol of D 2 0 additive achieved a promising efficiency of 13.76%, approximately 32% improvement as compared to the 10.47% efficient standard device.
- FIG. 17 shows a schematic of another solar cell 1700 according to various embodiments.
- the solar cell 1700 may include a halide perovskite film 1702.
- the solar cell 1700 may further include a mesoporous titanium oxide (meso - Ti0 2 ) layer 1704a in contact with a first side of the halide perovskite layer or film 1702.
- the solar cell 1700 may additionally include a compact titanium oxide (comp - T1O2) layer 1704b in contact with the mesoporous titanium oxide layer 1704a such that the halide perovskite film 1702 and the compact titanium oxide layer 1704b are on opposite sides of the meso titanium oxide (T1O2) layer 1704a.
- the layers 1704a, 1704b may function as electron transport layers.
- the solar cell 1700 may also include a hole transport layer 1706, such as a N 2 ,N 2 ,N 2' ,N 2' ,N 7 ,N 7 ,N 7' ,N 7' - octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-OMeTAD) layer, in contact with a second side of the halide perovskite layer or film 1702 opposite the first side.
- a hole transport layer 1706 such as a N 2 ,N 2 ,N 2' ,N 2' ,N 7 ,N 7 ,N 7' ,N 7' - octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-te
- the solar cell 1700 may also include a first electrode 1708, such as a fluorine- doped tin oxide (FTO) electrode, in contact with the compact titanium oxide layer 1704b.
- the solar cell 1700 may additionally include a second electrode 1710, such as a gold (Au) layer, in contact with the hole transport layer 1706.
- the halide perovskite film 1702 may be formed or prepared by mixing of four cations including a methylammonium (MA) cation, i.e. CH 3 NH3 + , a formamidinium (FA) cation, i.e. HC(NH2)2 + , a cesium (Cs) cation, i.e. Cs + , and a rubidium (Rb) cation, i.e. Rb + .
- MA methylammonium
- F formamidinium
- Cs cesium
- Rb rubidium
- the transparent fluorine-doped tin oxide-coated glass substrates may be cleaned by a procedure that is similar to that mentioned above.
- the FTO glass substrates were plasma treated for 10 min to improve the wettability of the FTO surface.
- a thin layer of compact T1O2 (comp-Ti02, with a concentration of 54.6 mg/ml in butanol) was coated on the substrates through spin coating in two steps (1000 rpm for 10 s + 2500 rpm 30 s). Substrates were sintered at 450°C for 1 hour and left to cool down to room temperature (25 °C).
- the substrates were treated using 15 mM aqueous TiCl 4 (Sigma- Aldrich, > 98%) solution at 70°C for 30 min, cleaned with deionized water and ethanol, and sintered again at 450 °C for 1 hour.
- a mesoporous T1O2 (meso-Ti02) layer was deposited on the comp-Ti02 layer by spin-coating a colloidal T1O2 solution containing 100 mg of T1O2 paste (Dyesol 30 NR-D) in 1 ml of anhydrous ethanol, at 2500 rpm for 20 s.
- the coated structure was then annealed at 450 °C for 1 h, and subsequently treated with TiCl 4 .
- these substrates were sintered again at 450°C for 1 hour and treated by plasma to improve the wettability of meso-Ti02 film before they were transferred into a dry nitrogen-filled glove box for further processing.
- the halide perovskite solution and solar cell devices may be prepared as highlighted below.
- the primary "mixed" perovskite solution was prepared by mixing 1 M formamidinium iodide (FAI), 1.1 M lead iodide (Pbl 2 ), 0.2 M methylammonium bromide (MABr) and 0.2 M lead bromide (PbBr 2 ) in anhydrous dimethylformamide : dimethyl sulfoxide (DMF:DMSO).
- the DMF: DMSO has a ratio of 4: 1 ratio by volume.
- the nominal composition of this solution is (MAo.nFAo.83)Pb(Io.83Bro.i7)3 and may be referred to as a double cation solution (MA/FA).
- a predissolved cesium iodide (Csl) salt in DMSO may be added to MA/FA precursor solution in a ratio of 5:95 by volume to get a triple cation perovskite solution.
- Csl cesium iodide
- DMSO DMSO
- a 1.5 M rubidium cation (Rbl) solution with DMSO as a solvent was added into as the prepared MA/FA/Cs solution (95% by volume) to get the quadruple/four cation perovskite solution (MA/FA/Cs/Pvb) having 0.9035% MAFA, 0.0475% Csl and 0.05% Rbl.
- the final perovskite solution was filtered through 0.45 ⁇ PTFE filter and spin coated on the Ti0 2 -coated substrate in a two-steps spin program, first at 1000 rpm for 10 s and then at 6000 rpm for 30 s. During the second step of spin coating, 100 ⁇ ⁇ of chlorobenzene was dripped on the spinning substrate 15 s after the start of the second program. In order to evaporate the residual solvent and to promote perovskite crystallization, the substrates were annealed on hot plate at 100 °C for 1.0 hr.
- N 2 ,N 2 ,N 2' ,N 2' ,N 7 ,N 7 ,N 7' ,N 7' -octakis(4- methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine Spiro-MeOTAD was spin- coated to form a hole transport layer on the perovskite film at 4000 rpm for 30 s.
- the Spiro- MeOTAD solution was prepared by first preparing a lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) solution (520 mg Li-TSFI in 1 ml acetonitrile (Sigma-Aldrich, 99.8 %)). Further, 17.5 ⁇ of the Li-TFSI solution is mixed together with 72.3 mg Spiro-MeOTAD (Merck), 28.8 ⁇ 4-tert-butyl pyridine in 1 ml of cholorobenzene (Sigma-Aldrich).
- Li-TFSI lithium bis(trifluoromethanesulfonyl)imide
- FIG. 18 is a plot of current density (in milliamperes per square centimeter) as a function of voltage (in volts or V) showing the current density - voltage characteristic curves of a device including a standard halide perovskite layer formed using a four cation (methylammonium, formamidinium, cesium, and rubidium) perovskite solution on a N 2 ,N 2 ,N 2' ,N 2' ,N 7 ,N 7 ,N 7' ,N 7' -octakis(4-methoxyphenyl)-9,9'-spirobi[9H- fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) layer, and a halide perovskite film formed using the four cation perovskite solution with deuterium oxide added on a Spiro-MeOTAD layer according to various embodiments.
- Spiro-MeOTAD
- the control device with the perovskite layer containing four cations achieved a power conversion efficiency of 13.21%.
- the presence of a small fraction of D 2 0 (1.0 % volume) in the perovskite solution improved the device efficiency to 13.34%.
- Increasing the D2O concentration to 4.0% by volume in the perovskite solution further improved device efficiency to 15.59%.
- concentrations higher than 4.0% D2O by volume adversely decreased the power conversion efficiency of the devices to approximately 13.0 %.
- FIG. 19 is a table 1900 showing photovoltaic parameters of the device including a four-cation based standard halide perovskite layer untreated with deuterium oxide (D2O), a device including a four-cation based halide perovskite film formed using 1% deuterium oxide (D2O) according to various embodiments, a device including a four-cation based halide perovskite film formed using 2% deuterium oxide (D2O) according to various embodiments, a device including a four-cation based halide perovskite film formed using 4% deuterium oxide (D2O) according to various embodiments, and a device including a four-cation based halide perovskite film formed using 6% deuterium oxide (D2O) according to various embodiments.
- D2O deuterium oxide
- UV-VIS ultraviolet-visible absorbance
- the importance of the fraction of C-D bonds may also be shown in the four cation based perovskite system. There is a decrease in device performance on addition of higher amounts of D 2 0 greater than 4 % by volume. In the previous example of a single cation based film, the device performance decreases on addition of higher amounts of D 2 0 greater than 1 % by volume.
- the optimum fraction of D 2 0 may be dependent on the number of organic cations, and the molar concentration used for perovskite solution preparation. In other words, the required value of optimal amount of D 2 0 may varys according the total population of C- H bonds present in perovskite solution.
- the population of C-H bonds may be indeed higher (1.3 M) than a single cation system MAPbI 3 (1M). Therefore, a higher fraction of D 2 0 may be required to obtain the optimum ratio of C-D to C-H bonds in perovskite solution to optimize device performance. Further increase of the population of C- D bonds may have an adverse effect on performance, which highlights the importance of the ratio of C-D bonds to C-H bonds.
- FIG. 21 is a plot of carrier density (x 10 17 per cubic centimeters or cm “3 ) as a function of photoluminescence (PL) intensity showing the variation of photoexcited density with photoluminescence (PL) intensity of a four cation based standard halide perovskite structure and a four-cation based halide perovskite film formed with 4% deuterium oxide (D 2 0) according to various embodiments.
- the films were excited by 600 nm pump laser within the low fluence regime ( ⁇ 22 ⁇ cm "2 ).
- the trap density in standard perovskite film is estimated to be around 2.9 x 10 17 cm “3 which reduces to 2.0 x 10 17 cm “3 on inclusion of D 2 0 (4 % vol) as an additive.
- the charge carrier lifetimes in standard and D 2 0 (4 % volume) perovskite films using TRPL are measured to be 27.7 nm and 33.5 ns, respectively as shown in FIG. 21.
- FIG. 22 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard 4-cation based perovskite layer, a standard 4-cation based perovskite layer on a hole extraction layer N 2 ,N 2 ,N 2' ,N 2' ,N 7 ,N 7 ,N 7' ,N 7' -octakis(4-methoxyphenyl)-9,9'-spirobi[9H- fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD), and a standard 4-cation based perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC 6 i
- perovskite film with D 2 0 (4 % vol) added may be superior in terms of both lower trap density and longer charge carrier lifetime.
- the longer lifetimes of charge carriers in perovskite film with D 2 0 added may be consistent with single cation methylammonium (MAPbI 3 ) perovskite system described above.
- TRPL time-resolved photoluminescence
- the superior optical properties of four cation-based perovskite with D 2 0 may be in agreement and may be consistent with the higher power conversion efficiency seen in devices formed from halide perovskite solution with D 2 0.
- Various embodiments may relate to a simple method of fabricating a compact and uniform perovskite layer as photo-absorbing material for efficient inorganic/organic hybrid solar cell.
- Deuterated water may be used as the solvent additive to improve the precursor solubility and film quality.
- the halide perovskite film may include a three dimensional (3D) halide perovskite structure.
- the photo-absorbing layer perovskite structure may include one or more metal halide (inorganic part) and one or more organic halide (organic) as main active layer represented by ABX3, wherein A represents the organic component such as a methylammonium (CH3NH3) (MA) cation, a formamidinium [HC(NH 2 )2] (FA) cation, a cesium (Cs) cation, or a rubidium (Rb) cation, or mixed cations such as (MA) n (FA) 1-n , (MA/FA) n (Cs) 1-n , (MA/FA/Cs) n (Ru)i- n (wherein n is any value between 0 and 1), or any other composition of cations, wherein B represents a cation of metallic elements such as a methylammonium (CH3
- X is a halide anion such as iodide (I) anion, bromide (Br) anion, chloride (CI) anion, or a mixed halide anion, e.g. [(I/Br/Cl) i- n [I/Br/Cl)n] (where n is any value between 0 and 1).
- the photo-absorbing layer perovskite may include a double perovskite structure as the main active layer.
- the double perovskite structure may be represented by A2BX6, AB2X5, or any other suitable perovskite structure, wherein A represents a potassium (K) cation, a rubidium (Rb) cation, a cesium (Cs) cation, or any organic cation, or any other composition of these cations, wherein B represents a cation of an element selected from group 11 (e.g. Cu, Ag etc.), group 14 (e.g.
- X is a halide anion such as a iodide (I) anion, a bromide (Br) anion, a chloride (CI) anion or a mixed halide anion, e.g. [(I/Br/Cl)i- n [I/Br/Cl)n] (where n is any value between 0 and 1).
- the halide perovskite film may include a two dimensional (2D) halide perovskite structure.
- X is a halide such as iodide (I), bromide (Br), chloride (CI) or mixed halide [(I/Br/Cl)i-n[I/Br/Cl)n] (where n is any value between 0 and 1).
- the photo-absorbing layer perovskite may be a mixed dimensional perovskite with a composition formulation (3D perovskite) x (2D perovskite) i_ x , wherein x is any value between 0 and 1.
- deuterated solvents with varying volume ratios may be used as additives to control the perovskite growth.
- Toluene may be used as an anti-solvent.
- the anti-solvent may alternatively be chlorobenzene, dichlorobenzene, diethyl ether, a deuterated solvent, or any other suitable anti-solvent.
- the developed method may be applicable for flexible substrates and roll-to-roll applications where low temperature processing is required.
- Usage of the deuterated solvents may also be extended to the fabrication of other optoelectronic devices such as light emitting diodes, field effect transistors, light emitting transistors, photodetectors etc., and/or other electronic devices such as memories, switches, synaptic devices etc. where solution processes or printable technologies are used.
- other optoelectronic devices such as light emitting diodes, field effect transistors, light emitting transistors, photodetectors etc.
- other electronic devices such as memories, switches, synaptic devices etc. where solution processes or printable technologies are used.
- Various embodiments may show significantly improved photo-absorption, active layer morphology, charge carrier diffusion length, and/or power conversion efficiency in deuterated water (or heavy water) added organic-inorganic perovskite solar cells as compared to standard reference devices.
- Various embodiments may provide highly efficient perovskite devices, which may be attractive for printable and foldable applications where low temperature processing is required.
- the addition of the deuterated water may show tremendous potential for photovoltaic, light emitting and others solution processed based electronic devices.
- the further inclusion of the deuterated solvent in lead-free perovskite based devices may further improve the utilization due to the reduced toxicity.
Abstract
The invention relates to a method of forming a halide perovskite film, wherein deuterium oxide is mixed with a halide perovskite solution to form a halide perovskite film. The halide perovskite solution includes a metal cation, such as a lead, tin, germanium or bismuth cation, a halide anion, and at least one selected from an organic cation, such as methylammonium or formamidinium, and an inorganic cation, such as cesium, rubidium or potassium. A halide perovskite film comprising an organic cation with one or more carbon-deuterium bonds, and a solar cell comprising said halide perovskite film are also disclosed.
Description
HALIDE PEROVSKITE FILM, SOLAR CELL INCLUDING, AND METHOD OF
FORMING THE SAME
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of priority of Singapore application No. 10201606391W filed on August 3, 2016, the contents of it being hereby incorporated by reference in its entirety for all purposes.
TECHNICAL FIELD
[0002] Various aspects of this disclosure relate to a halide perovskite film. Various aspects of this disclosure relate to a solar cell including a halide perovskite film. Various aspects of this disclosure relate to a method of forming a halide perovskite film.
BACKGROUND
[0003] Modern civilization is dependent upon energy more than ever in the past. The energy demand of the modern world is increasing every year. To accomplish these requirements, the dependency of the world on fossil fuels like coal, petroleum, oil, and natural gas to meet energy requirements has also increased. Since all these energy sources are non-renewable, there is worry about their complete depletion in near the future.
[0004] On the other hand, renewable energy sources are perpetual and environmentally friendly. Many renewable energy sources are widely available, and are also well-suited for applications in off-grid remote locations. Among all the renewable energy sources, solar energy has the most potential to meet the challenges of increasing energy demands. In addition, photovoltaic technology may have other advantages such as being noiseless, and may be aesthetically pleasing when incorporated into building designs. Further, it may be used in small-scale plant deployment.
[0005] Solar cells based on organic-inorganic hybrid perovskites (e.g. methylammonium lead iodide (CH3NH3PbI3) not only show higher power conversion efficiency, but can also be prepared by facile solution processes using inexpensive materials. Such perovskites may have outstanding optoelectronic properties, and have shown power conversion efficiency
exceeding 22%. These perovskite solar cells have outperformed other solar cells based on dye-sensitized solar cells (DSCs), small molecules, and polymer solar cells.
[0006] Many perovskite film formation and crystallization methods have been developed since Miyasaka et al. fabricated the first perovskite solar cell using lead halide based perovskite as light absorber in 2009. These include solvent vapour annealing, physical vapor deposition (PVD), single step coating method and sequential deposition method. However, these methods add substantial complexity to the fabrication process. Amongst these processing methods, the single step fabrication process may be the simplest and easiest to accomplish. In this process, a perovskite solution including a metal halide and organic halide components in a common solvent such as dimethylformamide (DMF), γ-butyrolactone (GBL), dimethyl sulphoxide (DMSO) is used to form the perovskite film.
[0007] Presently, only mesoscopic perovskite solar cell structures are able to demonstrate very high efficiencies, but processing of the titanium oxide (T1O2) in such structures may require very high-temperature (above 450 °C), which may mean that such structures are unsuitable for roll-to-roll production and other low temperature fabrication processes. Furthermore, other existing methods of forming high efficiency perovskite solar cells are either very complex or require a lot of processing time. Simple solution processable perovskite solar cell technology are thus fast losing attractiveness to more power efficient solar cells formed by more complex methods. There is thus a need to develop a method which uses straight forward fabrication techniques, which is able to form a solar cell with an efficiency comparable with solar cells formed by existing techniques involving high temperature processing, complex processes and/or longer fabrication time.
SUMMARY
[0008] Various embodiments may provide a method of forming a halide perovskite film. The method may include mixing deuterium oxide with a halide perovskite solution to form a halide perovskite film. The halide perovskite solution may include a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
[0009] Various embodiments may provide a halide perovskite film formed by a method described herein.
[0010] Various embodiments may provide a crystal structure including a metal cation, an organic group cation, and a halide anion. The organic cation may include one or more carbon-deuterium bonds, and one or more carbon-protium bonds.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the accompanying drawings, in which:
FIG. 1 is a schematic showing a method of forming a halide perovskite film according to various embodiments.
FIG. 2 shows a general illustration of a halide perovskite film according to various embodiments.
FIG. 3 shows a general illustration of a solar cell according to various embodiments.
FIG. 4 shows a schematic of an inverted inorganic/organic hybrid solar cell according to various embodiments.
FIG. 5 shows (a) a cross-sectional scanning electron microscopy (SEM) image of a standard halide perovskite layer on a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ITO) glass substrate, and (b) a cross-sectional scanning electron microscopy (SEM) image of a halide perovskite film treated with 1% deuterium oxide (D20) according to various embodiments on a poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ΓΓΌ) glass substrate.
FIG. 6 shows scanning electron microscopy images of top views of (a) a standard halide perovskite layer, (b) a halide perovskite layer treated with 1% deuterium oxide (D20) according to various embodiments, (c) a magnified view of the image shown in (a), and (d) a magnified image of the image shown in (b).
FIG. 7 shows X-ray diffraction patterns of (a) standard halide perovskite film (lower panel) and 1% deuterium oxide (D20) treated halide perovskite film (upper panel) according to various embodiments, and (b) standard halide perovskite film (lower panel) and 1% water (H20) treated halide perovskite film (upper panel).
FIG. 8 is a plot of absorption (in arbitrary units or a.u.) as a function of wavelength (in nanometers or nm) showing the ultraviolet-visible (UV-VIS) absorption spectra of a standard halide perovskite layer, a 1% water added or treated halide perovskite layer, and a 1% deuterium oxide (D20) treated or added halide perovskite layer according to various embodiments.
FIG. 9 shows (a) a plot of current density (in milliamperes per square centimeter or mAcm"2) as a function of voltage (in volts or V) illustrating illuminated current density-voltage (J-V) characteristic curves of inverted solar cells with standard halide perovskite layer and halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) a plot of current density (in milliamperes per square centimeter or mAcm" 2) as a function of voltage (in volts or V) illustrating forward and reverse scans of the current density-voltage (J-V) characteristic curves of the inverted inorganic/organic hybrid solar cell with halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PCeiBM).
FIG. 10 is a table showing photovoltaic parameters of the standard halide perovskite layer, and halide perovskite films formed using 1% and 2% deuterium oxide (D20) according to various embodiments.
FIG. 11 shows (a) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of electron only perovskite devices (glass/indium tin oxide (ITO)/perovskite/[6,6]-phenyl-C61 -butyric acid methyl ester (PC6iBM)/silver (Ag)), wherein one device has a perovskite film treated with deuterium oxide (D20) according to various embodiments and another device has a standard perovskite layer, and (b) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of hole only perovskite devices (glass/indium tin oxide (ΓΓΌ)/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/perovskite/gold (Au)), wherein one device has a perovskite film treated with deuterium oxide (D20) according to various embodiments and another device has a standard perovskite layer.
FIG. 12 is a plot of carrier density (x 1017 per cubic centimeter or cm"3) as a function of photoluminescence (PL) intensity (in arbitrary units or a.u.) showing the photoexcited carrier density of a standard perovskite layer and a deuterium oxide (D20) (1% vol) treated or added
perovskite film according to various embodiments excited within low pump fluence regime (< 30 μΐ cm"2) at various measured photoluminescence (PL) intensities.
FIG. 13 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard perovskite layer, a standard perovskite layer on a hole extraction layer including poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and a standard perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 1% deuterium oxide (D20) treated or added perovskite film according to various embodiments, a 1% deuterium oxide (D20) treated or added perovskite film on a hole extraction layer including poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and a 1% deuterium oxide (D20) treated or added perovskite film on an electron extraction layer including [6,6]-phenyl-C61- butyric acid methyl ester (PC6iBM) according to various embodiments.
FIG. 14 is a table showing the carrier lifetimes of deuterium treated methylammonium lead iodide (CH3NH3PM3) films, deuterium treated methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and deuterium treated methylammonium lead iodide (CH3NH3PM3) films on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and standard methylammonium lead iodideiCEbNEbPbL) films, standard methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and standard methylammonium lead iodide (CH3NH3PM3) films on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS).
FIG. 15 shows plots of intensity (in arbitrary units or a.u.) as a function of depth (in nanometers or nm) showing (a) the elemental depth profile of a sample with a standard perovskite layer (0% deuterium oxide or D20) and (b) the elemental depth profile of a sample with a perovskite film treated with 1% deuterium oxide (D20) according to various embodiments.
FIG. 16 is a table showing photovoltaic parameters of the standard halide perovskite layer, a halide perovskite film formed using 1% deuterium oxide (D20) according to various embodiments, and a halide perovskite film formed using 1% water (H20).
FIG. 17 shows a schematic of another solar cell according to various embodiments.
FIG. 18 is a plot of current density (in milliamperes per square centimeter) as a function of voltage (in volts or V) showing the current density - voltage characteristic curves of a device including a standard halide perovskite layer formed using a four cation (methylammonium, formamidinium, cesium, and rubidium) perovskite solution on a N2,N2,N2 ,N2 ,N7,N7,N7 ,N7 - octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) layer and a halide perovskite film formed using the four cation perovskite solution with deuterium oxide added on a Spiro-MeOTAD layer according to various embodiments.
FIG. 19 is a table showing photovoltaic parameters of the device including a four-cation based standard halide perovskite layer untreated with deuterium oxide (D20), a device including a four-cation based halide perovskite film formed using 1% deuterium oxide (D20) according to various embodiments, a device including a four-cation based halide perovskite film formed using 2% deuterium oxide (D20) according to various embodiments, a device including a four-cation based halide perovskite film formed using 4% deuterium oxide (D20) according to various embodiments, and a device including a four-cation based halide perovskite film formed using 6% deuterium oxide (D20) according to various embodiments. FIG. 20 is a plot of absorbance (in arbitrary units or a.u.) as a function of wavelength (in nanometers or nm) showing the ultraviolet- visible absorbance (UV-VIS) spectra of a 4-cation based standard halide perovskite layer, and a 4-cation based halide perovskite film treated or added with 4% deuterium oxide (D20) according to various embodiments.
FIG. 21 is a plot of carrier density (x 1017 per cubic centimeters or cm"3) as a function of photoluminescence (PL) intensity showing the variation of photoexcited density with photoluminescence (PL) intensity of a four-cation based standard halide perovskite structure and a four-cation based halide perovskite film formed with 4% deuterium oxide (D20) according to various embodiments.
FIG. 22 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence
(PL) kinetics or lifetime of low pump fluence of a device with a standard 4-cation based perovskite layer, a standard 4-cation based perovskite layer on a hole extraction layer N N N2 N2 N^N^N7 N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'- tetramine (Spiro-MeOTAD), and a standard 4-cation based perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film according to various embodiments, a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film on a hole extraction layer including N2,N2,N2 ,N2 ,N7,N7,N7 ,N7 -octakis(4- methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) according to various embodiments, and a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM) according to various embodiments.
DETAILED DESCRIPTION
[0012] The following detailed description refers to the accompanying drawings that show, by way of illustration, specific details and embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and structural, and logical changes may be made without departing from the scope of the invention. The various embodiments are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.
[0013] Embodiments described in the context of one of the methods or one of the halide perovskite films/solar cells is analogously valid for the other methods or halide perovskite films/solar cells. Similarly, embodiments described in the context of a method are analogously valid for a halide perovskite film and/or a solar cell, and vice versa.
[0014] Features that are described in the context of an embodiment may correspondingly be applicable to the same or similar features in the other embodiments. Features that are described in the context of an embodiment may correspondingly be applicable to the other embodiments, even if not explicitly described in these other embodiments. Furthermore, additions and/or combinations and/or alternatives as described for a feature in the context of
an embodiment may correspondingly be applicable to the same or similar feature in the other embodiments.
[0015] The word "over" used with regards to a deposited material formed "over" a side or surface, may be used herein to mean that the deposited material may be formed "directly on", e.g. in direct contact with, the implied side or surface. The word "over" used with regards to a deposited material formed "over" a side or surface, may also be used herein to mean that the deposited material may be formed "indirectly on" the implied side or surface with one or more additional layers being arranged between the implied side or surface and the deposited material. In other words, a first layer "over" a second layer may refer to the first layer directly on the second layer, or that the first layer and the second layer are separated by one or more intervening layers.
[0016] In the context of various embodiments, the articles "a", "an" and "the" as used with regard to a feature or element include a reference to one or more of the features or elements.
[0017] In the context of various embodiments, the term "about" or "approximately" as applied to a numeric value encompasses the exact value and a reasonable variance.
[0018] As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
[0019] FIG. 1 is a schematic 100 showing a method of forming a halide perovskite film according to various embodiments. The method may include, in 102, mixing deuterium oxide (D20) with a halide perovskite solution to form a halide perovskite film. The halide perovskite solution may include a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
[0020] In other words, a halide perovskite film may be formed by mixing deuterium oxide with a solution containing a metal cation, a halide anion, and a cation, i.e. either an organic cation or an inorganic cation.
[0021] In various embodiments, the organic cation may be any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium ion, a hydrazinium ion, an azetidinium ion, an imidazolium ion, a dimethylammonium ion, an ethylammonium ion, a phenethylammonium ion, a guanidinium ion, a tetramethylammonium
ion, a thiazolium ion, a 3-pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
[0022] In various embodiments, the inorganic cation may be a cesium (Cs) cation, a rubidium (Rb) cation, or a potassium (K) cation.
[0023] The halide perovskite solution may further include a further cation. The cation and the further cation may be of different elements. The halide perovskite solution may include different cations. The halide perovskite may include organic cations formed from different molecules, inorganic cations of different elements, or a mixture of one or more cations, and one or more anions. The halide perovskite solution may include a plurality of different organic cations and inorganic cations. The halide perovskite film formed may include different organic cations, or different inorganic cations or a mixture of one or more cations, and one or more anions.
[0024] The metal cation may be a cation of an element of Group 11, Group 14, or Group 15. The metal cation may be any one selected from a group consisting of a lead (Pb) cation, a (Sn) tin cation, a germanium (Ge) cation, and a bismuth (Bi) cation.
[0025] The halide perovskite solution may include different metal cations, i.e. cations of different metal elements. The halide perovskite solution may further include a further metal cation. The metal cation and the further metal cation may be of different elements. The halide perovskite film formed may include different mixtures of metal cations, e.g. (MA/Cs)(Pb/Sn)I3, where MA represents the methylammonium cation.
[0026] The halide anion may be any one of a group consisting of a chloride anion, a bromide anion, and an iodide anion.
[0027] The halide perovskite solution may include different anions, i.e. anions of different halide elements. The halide perovskite solution may further include a further anion. The anion and the further anion may be of different elements. The halide perovskite solution may include mixed halides. The halide perovskite film formed may include different anions, e.g. MAPbChl.
[0028] A concentration of deuterium oxide in the resultant solution may be any value selected a range from 0.1 % to 10 % by volume, or a range from 0.5 % to 5 % by volume.
[0029] The halide perovskite solution may further include a suitable solvent. The suitable solvent may be any one selected from a group consisting of dimethyformamide, γ- butylrolactone, and dimethyl sulphoxide.
[0030] The method may also include annealing a resultant solution formed by mixing deuterium oxide with a halide perovskite solution to form the halide perovskite film.
[0031] The resultant solution may be annealed at any one temperature selected from 50 degrees Celsius (°C) to 90 degrees Celsius (°C). The resultant solution may be annealed at a temperature below the boiling point of deuterium oxide, which may be below 101 degrees Celsius. The resultant solution may be annealed at about 1 atmospheric pressure.
[0032] The method may further include filtering the resultant solution to remove undissolved precursors before annealing the resultant solution to form the halide perovskite film. The filtering of the resultant solution may be carried out using a polytetrafluoroethylene (PTFE) filter.
[0033] The halide perovskite film may be coated onto a suitable substrate. The suitable substrate may include an indium tin oxide carrier, and a carrier transport layer on the indium tin oxide carrier.
[0034] The method may also include dripping an anti-solvent onto the suitable substrate during the coating of the halide perovskite film onto the suitable substrate. The halide perovskite film may be spin-coated onto the suitable substrate. The anti-solvent may be toluene, chlorobenzene, dichlorobenzene, diethyl ether, a deuterated solvent, or any other suitable anti-solvent.
[0035] Various embodiments may relate to a halide perovskite film formed by a method as described herein. The halide perovskite film may have improved quality compared to a halide perovskite film formed without adding or treating with deuterium oxide.
[0036] In various embodiments, the deuterium oxide may improve the perovskite precursors' solubility in the host solvent, improve the growth of perovskite crystal during film formation, and/or may reduce the defect density. D20 may improve the perovskite film quality. The effectiveness of the mechanism or method may be dependent on the precursors.
[0037] The halide perovskite film may have a structure or crystal structure including a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation. The organic cation may be an organic group cation.
[0038] In various embodiments, such as in a halide perovskite film including an organic cation, the method may result in substitution of protium (H) by deuterium (D) present in deuterium oxide (D20). Some of the carbon-protium (C-H) bonds in the organic cation may be replaced by carbon-deuterium (C-D) bonds.
[0039] In various embodiments, the halide perovskite film may include or may be a three dimensional (3D) halide perovskite.
[0040] In various embodiments, the structure or crystal structure (of the three dimensional (3D) halide perovskite) may be represented by the formula ABX3. "A" may represent the organic cation or the inorganic cation, "B" may represent the metal cation, and "X" may represent the halide anion. For instance, the halide perovskite film may include CH3NH3PbI3 or CsPbI .
[0041] In various embodiments, the halide perovskite film, i.e. three dimensional (3D) halide perovskite, may have a double perovskite structure.
[0042] In various embodiments, the structure or crystal structure, i.e. double perovskite structure, may be represented by the formula A2BX6. "A" may represent the organic cation or the inorganic cation, "B" may represent the metal cation, and "X" may represent the halide anion.
[0043] In various embodiments, the structure or crystal structure, i.e. double perovskite structure, may be represented by the formula AB2X5. "A" may represent the organic cation or the inorganic cation, "B" may represent the metal cation, and "X" may represent the halide anion.
[0044] In various embodiments, the halide perovskite film may include or may be a two dimensional (2D) halide perovskite.
[0045] In various embodiments, the halide perovskite film, i.e. two dimensional (2D) halide perovskite, may include or may be a layer perovskite structure. The layer perovskite film may be represented by the formula (CH3(CH2)3NH3)2A2y-iBxX3y+i , where "y" may be any positive integer, "A" may represent the organic cation or the inorganic cation, "B" may represent the metal cation, and "X" may represent the halide anion.
[0046] In various embodiments, the halide perovskite film may include or may be a mixed dimensional halide perovskite.
[0047] The mixed dimensional halide perovskite may include a 2D halide perovskite and a 3D halide perovskite, and may be represented by the formula (3D perovskite)x (2D perovskite) l-x, where "x" may be any value between 0 and 1.
[0048] FIG. 2 shows a general illustration of a halide perovskite film 200 according to various embodiments. The halide perovskite film 200 may have a crystal structure or structure 202 including a metal cation 204, an organic cation 206, and a halide anion 208. The organic cation may include one or more carbon-deuterium (C-D) bonds, and one or more carbon-protium (C-H) bonds.
[0049] In other words, the halide perovskite film 200 may include an organic cation which is partially bonded to deuterium (D) and partially bonded to protium (H).
[0050] Protium (H) is one isotope of hydrogen, and has a nucleus containing one proton. The nucleus of protium does not contain any neutron. Deuterium (D) is another isotope of hydrogen, and has a nucleus containing one neutron and one proton.
[0051] In various embodiments, the halide perovskite film 200 may include or may be a three dimensional (3D) halide perovskite.
[0052] In various embodiments, the structure or crystal structure 202 (of the three dimensional (3D) halide perovskite) may be represented by the formula ABX3. "A" may represent the organic cation 206, "B" may represent the metal cation 204, and "X" may represent the halide anion 208.
[0053] In various embodiments, the halide perovskite film 200, i.e. three dimensional (3D) halide perovskite, may have a double perovskite structure.
[0054] In various embodiments, the structure or crystal structure 202, i.e. double perovskite structure, may be represented by the formula A2BX6. "A" may represent the organic cation 206, "B" may represent the metal cation 204, and "X" may represent the halide anion 208.
[0055] In various embodiments, the structure or crystal structure 202, i.e. double perovskite structure, may be represented by the formula AB2X5. "A" may represent the organic cation 206, "B" may represent the metal cation 204, and "X" may represent the halide anion 208.
[0056] In various embodiments, the halide perovskite film 200 may include or may be a two dimensional (2D) halide perovskite.
[0057] In various embodiments, the halide perovskite film 200, i.e. the two dimensional (2D) halide perovskite, may include or may be a layer perovskite structure. The layer perovskite film 200 may be represented by the formula (CH3(CH2)3NH3)2A2y-iBxX3y+i , where "y" may be any positive integer, "A" may represent the organic cation 206, "B" may represent the metal cation 204, and "X" may represent the halide anion 208.
[0058] In various embodiments, the halide perovskite film 200 may include or may be a mixed dimensional halide perovskite.
[0059] The mixed dimensional halide perovskite may include a 2D halide perovskite and a 3D halide perovskite, and may be represented by the formula (3D perovskite)x (2D perovskite) l-x, where "x" may be any value between 0 and 1.
[0060] The organic cation may be any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium cation, a hydrazinium cation, an azetidinium cation, an imidazolium cation, a dimethylammonium cation, an ethylammonium cation, a phenethylammonium cation, a guanidinium cation, a tetramethylammonium ion, a thiazolium ion, a 3-pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
[0061] In various embodiments, a percentage of the one or more carbon-deuterium (C-D) bonds relative to a total of the one or more carbon- protium (C-H) bonds and the one or more carbon-deuterium bonds may be any one value selected from a range of 0.01% to 5.0%.
[0062] The fraction or percentage of the carbon-deuterium bond relative to the total of the one or more carbon- protium bonds and the one or more carbon-deuterium bonds may be dependent on the solution concentrations of the various precursors, and/or the processing methods. The fraction or percentage of the carbon-deuterium bonds may also be dependent on the evaporation of D2O, and the solvent of the halide perovskite solution, e.g. DMF, which may vary. The estimation of the exact C-D bonds present in final film may be difficult because of the variation of evaporation rates of host solvent (DMF) and D2O and left behind different fraction of residue. Considering that all the deuterium atoms are able to replace the protium from C-H bonds, it may be estimated that approximately 0.0369 % of C-H bonds may convert into C-D bonds on inclusion of 1% D2O by volume. These bonds may also remain in the final product and may be confirmed by secondary ion mass spectroscopy
(SIMS) measurements as described below, though the fraction or percentage of the bonds may vary slightly as compared to the percentage or fraction in solution form.
[0063] FIG. 3 shows a general illustration of a solar cell 300 according to various embodiments. The solar cell 300 may include a halide perovskite film 302 as described herein. The solar cell 300 may further include an electron transport layer 304 on a first side of the halide perovskite film 302. The solar cell 300 may also include a hole transport layer 306 on a second side of the halide perovskite film 302 opposite the first side. The solar cell 300 may additionally include a first electrode 308 in electrical connection with the electron transport layer 304. The solar cell 300 may also include a second electrode 310 in electrical connection with the hole transport layer 306.
[0064] In other words, the solar cell 300 may include a halide perovskite film 302 as described herein. The film 302 may be sandwiched by an electron transport layer 304 and a hole transport layer 306. The solar cell 300 may also include a first electrode 308 in contact with the electron transport layer 304, and a second electrode 310 in contact with the hole transport layer 306.
[0065] In various embodiments, a power conversion efficiency of the solar cell may be greater than 12%, e.g. greater than 13.5%.
[0066] In various embodiments, a fill factor of the solar cell may be greater than 0.75 (75%).
[0067] In various embodiments, a short circuit current density of the solar cell may be greater than 18.9 mA cm"2.
[0068] Various embodiments may relate to a device including a halide perovskite film as described herein. The device may be an optoelectronic device such as a light emitting diode, a light emitting field effect transistor, a light emitting transistor, a photodetector etc. The device may be an electronic device such as a memory device, a switch, a synaptic device etc., where solution processes or printable technologies are used.
[0069] Various embodiments may relate to a straightforward method of developing efficient devices for solar cell applications. Various embodiments may relate to a method of preparing a high-quality perovskite film by using deuterium oxide or deuterated water (D20) (also commonly known as heavy water) as a solvent additive in a single-step solution
process, instead of more complex fabrication techniques such as sequential and physical vapour deposition methods.
[0070] D20 may be widely used in the following applications: (i) preparation of deuterium to be used as a moderator in a nuclear reactor, (ii) as a solvent for nuclear magnetic resonance spectra, and (iii) as a tracer in studies of reactions occurring in living organisms and/or other chemical reactions.
[0071] D2O may have never been used in any solar cell applications to enhance their photovoltaic efficiencies. Various embodiments may provide a halide perovskite film formed by using D20 and/or a solar cell including the halide perovskite film formed by using D20. Various embodiments may relate to a D20-added CH3NH3Pbl3 (MAPbI3) based inverted solar cell 400 as shown in FIG. 4, which may demonstrate higher power conversion efficiencies (PCE) than the control or standard halide perovskite cells (without addition of D2O). FIG. 4 shows a schematic of an inverted inorganic/organic hybrid solar cell 400 according to various embodiments. The solar cell 400 may include a halide perovskite layer or film 402. The solar cell 400 may further include an electron transport layer 404, such as a [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM) layer, in contact with a first side of the halide perovskite layer or film 402. The solar cell 400 may also include a hole transport layer 406, such as a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) layer, in contact with a second side of the halide perovskite layer or film 402 opposite the first side. The solar cell 400 may also include a first electrode 408, such as a silver electrode, in contact with the electron transport layer 404. The solar cell 400 may additionally include a second electrode 410, such as an indium tin oxide (ITO) layer, in contact with the hole transport layer 406.
[0072] The stacked arrangement including the halide perovskite layer or film 402, the electron transport layer 404, the hole transport layer 406, the first electrode 408, and the second electrode 410, may be on a substrate 412 such as glass.
[0073] Various embodiments may relate to a high quality photo-absorption layer with better charge carrier transport. Various embodiments may relate to in-depth investigations on the influence of D2O on (i) device performance of the inverted-perovskite solar cell (ii) perovskite morphology (iii) transient photoluminescence and/or (iv) elemental depth profile.
[0074] Various embodiments may relate to an easy and well-controlled single-step spin coating method which may be developed to make high quality halide perovskite films or layers such as CH3NH3Pbl3.
[0075] FIG. 5 shows (a) a cross- sectional scanning electron microscopy (SEM) image of a standard halide perovskite layer on a poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ITO) glass substrate, and (b) a cross-sectional scanning electron microscopy (SEM) image of a halide perovskite film treated with 1% deuterium oxide (D20) according to various embodiments on a poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) coated indium tin oxide (ΓΓΌ) glass substrate. A standard halide perovskite layer may refer to a control halide perovskite layer without D20 added or treated with D20. The standard halide perovskite layer may be devoid of any significant amounts of D20.
[0076] The SEM image in FIG. 5(a) shows the pristine or standard perovskite layer which is prepared without D20 additive on the hole transporting PEDOT:PSS layer (hole transport layer or HTL). FIG. 5(b) shows the cross-section morphology of a perovskite film formed from D20 (1 % volume or vol) in stoichiometric 40 wt% CH3NH3PbI3 halide perovskite solution.
[0077] The presence of deuterated water may affect crystal formation, which may in turn influence the crystallization of the perovskite crystals, in particular promoting crystal formation along the entire periphery of the crystal. It should also be noted that all the perovskite crystal grains formed on the HTL are observed to be single crystals and unidirectional. Since the crystal grains are as thick as the film, the crystal grains may provide an excellent charge carrier transport pathway along the device in the absence of grain boundaries and voids. The addition of D20 may form a very compact and continuous film covering most of the PEDOT:PSS surface. The halide perovskite film treated with D20, i.e. with D20 added, may be superior to the film without addition of D20.
[0078] FIG. 6 shows scanning electron microscopy images of top views of (a) a standard halide perovskite layer, (b) a halide perovskite layer treated with 1% deuterium oxide (D20) according to various embodiments, (c) a magnified view of the image shown in (a), and (d) a magnified image of the image shown in (b).
[0079] FIG. 6(c) and (d) show that the inclusion of D20 in perovskite precursor solution cause a drastic drop in the fraction of the grain boundaries and increased crystal size. The grain boundaries and voids in the photo-absorbing (halide perovskite) layer may adversely affect solar cell performance because they act as charge carrier recombination sites and shunting paths, thus affecting the current density and open circuit voltage generated from the solar cell device. Accordingly, various embodiments may improve solar cell performance by reducing the number of grain boundaries and voids.
[0080] The formation of halide perovskite crystals during spin coating and thermal annealing may depend on the solvent evaporation rate from the halide perovskite layer. A solvent such as dimethylformamide (DMF) may have a higher boiling point (Tb = 153 °C) than D20 (Tb = 101 °C). With the addition of some D20 to DMF, the solvent evaporation may initialize earlier than in the case for samples with DMF only. Hence, perovskite crystallization may begin earlier in the former case (i.e., solutions with D20). Similarly for deuterated solvents (e.g., deuterated DMF, Tb = 153 °C), the addition of some D20 to the deuterated solvents may also cause the solvent evaporation to initialize earlier.
[0081] FIG. 7 shows X-ray diffraction patterns of (a) standard halide perovskite film (lower panel) and 1% deuterium oxide (D20) treated halide perovskite film (upper panel) according to various embodiments, and (b) standard halide perovskite film (lower panel) and 1% water (H20) treated halide perovskite film (upper panel).
[0082] The X-ray diffraction pattern of D20 (1 % volume or vol) treated or added perovskite layer and the X-ray diffraction pattern of a standard halide perovskite film (without D20 added) are presented in FIG. 7(a). As shown in FIG. 7(a), the primary ((100), 2Θ = 14.10°) diffraction peak is stronger for the D20 treated or added (1 % vol) perovskite as compared to the standard perovskite film. The stronger peak intensity confirms the higher crystallinity in D20 treated or added perovskite layer due to the more uniform and slower grain growth.
[0083] FIG. 8 is a plot of absorption (in arbitrary units or a.u.) as a function of wavelength (in nanometers or nm) showing the ultraviolet- visible (UV-VIS) absorption spectra of a standard halide perovskite layer, a 1% water added or treated halide perovskite layer, and a 1% deuterium oxide (D20) treated or added halide perovskite layer according to various embodiments. With the addition of D20, solar photon absorption may increase for
wavelengths shorter than 510 nm, but may almost be invariant for wavelengths longer than 510 nm. The absorbance of the D20 added perovskite film has increased to ~ optical density (OD) 4.0 at 400 nm compared to ~OD 2.25 in the standard perovskite film. This may translate to a 1.8 times increment in the absorption at 400 nm.
[0084] Comparing the perovskite growth using D20 (Tb = 101 °C, VP = 2.734 kPa) and H20 (Tb = 100 °C, VP = 3.165 kPa), it may be seen that a lower boiling point (Tb) and a higher vapor pressure (VP) as compared to the host solvent (DMF, Tb = 153 °C, VP = 0.516 kPa) may not be the only standard criteria to improve the perovskite growth.
[0085] The solubility of the perovskite precursors in the additive, and the bonding strength with additive may also be important. The presence of deuterium from the D20 may allow the formation of deuterium bonds (i.e., C-D binding energy = 418 kJ/mol) that are stronger than the protium bonds (i.e., C-H binding energy = 413 kJ/mol). This may have a positive effect on the growth control of the perovskite film that improves the organization of the perovskite. This may be evident from the higher photo-absorption and crystallinity in D20 (1 % vol) treated or added perovskite film as compared to H20 (1 % vol ) treated or added film as shown in FIGS. 7 - 8.
[0086] The ratio of C-H bonds to C-D bonds may be an important factor affecting the efficiency of halide perovskite devices. The D20 (by volume) treated or added halide perovskite film may show superior properties compared to the reference films, which may be due to a presence of C-D bonds. A small presence of C-D bonds formed by the addition of 1% (by volume) D20 may cause an improvement. However, as shown later, further increase of the fraction of C-D bonds with the addition of e.g. more than 1% (by volume) D20 may yield adverse effects in some embodiments.
[0087] Inverted-heteroj unction perovskite solar cell devices including active halide perovskite films without and with D20 have been fabricated. FIG. 9 shows (a) a plot of current density (in milliamperes per square centimeter or mAcm-2) as a function of voltage (in volts or V) illustrating illuminated current density-voltage (J-V) characteristic curves of inverted solar cells with standard halide perovskite layer and halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) a plot of current density (in milliamperes per square centimeter or mAcm"2) as a function of voltage (in volts or V) illustrating forward and reverse scans of the current density-voltage (J-V)
characteristic curves of the inverted inorganic/organic hybrid solar cell with halide perovskite film according to various embodiments on phenyl-C61 -butyric acid methyl ester (PC6iBM). The halide perovskite film may be formed using methylammonium lead iodide (CH3NH3PM3), dimethylformamide (DMF), and 1% deuterium oxide (D20), while the standard halide perovskite layer may be formed using methylammonium lead iodide (CH3NH3PM3) and dimethylformamide (DMF).
[0088] The current density voltage (J-V) characteristics of the devices without and with D2O (1 vol%) additives are shown in FIG. 9(a). FIG. 10 is a table 1000 showing photovoltaic parameters of the standard halide perovskite layer, and halide perovskite films formed using 1% and 2% deuterium oxide (D20) according to various embodiments. The thickness of each perovskite layer or film may be in the range of 250 nm to 300 nm. PCE refers to power conversion efficiency, Jsc refers to short circuit current density, Voc refers to open circuit voltage, and FF refers to fill factor
[0089] The table 1000 shows the parameters extracted from the measurements performed under 100 mW-cm"2 AM 1.5G. The devices prepared with 1.0 % vol D20 additive achieved a promising efficiency of 13.76%, a -32% improvement as compared to 10.47% efficiency for a standard device fabricated under the same conditions. Note that the efficiency enhancement by adding D2O may come from the increase of all the efficiency determining parameters i.e. Jsc, Voc and FF.
[0090] The enhancement in device performance upon the inclusion of D2O may be attributed to the improved perovskite film quality, thus increasing energy harvesting and reducing charge carrier loss mechanisms occurring due to the voids and grain boundaries. However, the efficiency may be very sensitive to the amount of the additive included in the perovskite precursor solution. The efficiency may drop to 10.84% on further increase of the additive fraction of D2O to 2.0% vol as shown in FIG. 10. Various embodiments may relate to controlling the growth of the perovskite crystals and subsequently the PCE of the solar cell devices by varying the volume ratios of D2O additive. For example, the D2O additive may be adjusted to be a value between 0.1 to 10 vol %, or between 0.5 to 1.5 vol %.
[0091] FIG. 9(b) shows the forward and backward (reverse) scan J-V characteristics of D2O treated or added perovskite solar cell. The better perovskite film quality formed using D2O with significantly lower number of grain boundaries and number of voids may yield a
nearly hysteresis-free solar cell. This may also be attributed to the efficient dissociation and transport of charge carriers into PEDOT:PSS/CH3NH3Pbl3/PC6iBM interface and bulk.
[0092] A well-known Langmuir Child equation may be used to further determine the electron mobilities and hole mobilities in the perovskite films. Electron only devices may be fabricated by the deposition of a standard perovskite layer or a D20 (1 % vol) treated / added perovskite film directly onto a ITO patterned glass substrate, followed by a thin layer of electron acceptor layer and a silver layer as counter electrode.
[0093] Hole only devices may be formed using a similar way. A standard perovskite layer or D20 (1 % vol) treated / added perovskite films may be deposited onto a PEDOT:PSS coated ITO glass substrate, followed by gold deposition.
[0094] FIG. 11 shows (a) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of electron only perovskite devices (glass/indium tin oxide (ITO)/perovskite/[6,6]-phenyl-C61 -butyric acid methyl ester (PC6iBM)/silver (Ag)), wherein one device has a perovskite film treated with deuterium oxide (D20) according to various embodiments and another device has a standard perovskite layer, and (b) a plot of current (in amperes or A) as a function of voltage (in volts or V) showing the current-voltage characteristics in log-log scale of hole only perovskite devices (glass/indium tin oxide (ΓΓΌ)/ poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/perovskite/gold (Au)), wherein one device has a perovskite film treated with deuterium oxide (D20) according to various embodiments and another device has a standard perovskite layer.
[0095] FIG. 11 (a) and (b) show the current-voltage characteristics using a log-log scale. FIG. 11(a) and (b) show that charge carrier mobilities in D20 treated or added perovskite devices may be superior to their standard counterparts, evident from an increase in electron mobility from 8.5xl0"4 to 1.3xl0"3 V-cm"2-s_1, and hole mobility increases from 7.0xl0"6 to l.lxlO"5 V-cm"2-s_1. The improvement in carrier mobility in D20 treated or added perovskite films may be directly attributed to the absence of the voids and grain boundaries in deuterated perovskite films. The voids and grain boundaries may cause charge carrier trapping and scattering sites in standard perovskite layers.
[0096] FIG. 12 is a plot of carrier density (x 1017 per cubic centimeter or cm"3) as a function of photoluminescence (PL) intensity (in arbitrary units or a.u.) showing the
photoexcited carrier density of a standard perovskite layer and a deuterium oxide (D20) (1% vol) treated or added perovskite film according to various embodiments excited within low pump fluence regime (< 30 μΐ cm"2) at various measured photoluminescence (PL) intensities.
[0097] The trap density of perovskite may be estimated to be around 3.5 x 1017 cm"3 which reduces slightly to 3.4 x 1017 cm"3 when D20 (1 % vol) is added as an additive.
[0098] FIG. 13 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard perovskite layer, a standard perovskite layer on a hole extraction layer including poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), and a standard perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 1% deuterium oxide (D20) treated or added perovskite film according to various embodiments, a 1% deuterium oxide (D2O) treated or added perovskite film on a hole extraction layer including poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and a 1% deuterium oxide (D2O) treated or added perovskite film on an electron extraction layer including [6,6]-phenyl-C61- butyric acid methyl ester (PC6iBM) according to various embodiments.
[0099] The optical measurements as presented in FIGS. 12 and 13 show that the perovskite film with D2O (1 % vol) may be superior than standard perovskite layer in terms of both lower trap densities and longer charge carrier lifetimes. The longer charge carrier lifetime in the perovskite film with D2O added may be attributed to better film morphology and coverage of the deuterated film than that of a standard perovskite layer, which may in turn be due to larger crystal grain sizes and/or crystal size uniformity of the deuterated film compared to that of the standard perovskite layer.
[00100] FIG. 14 is a table 1400 showing the carrier lifetimes of deuterium treated methylammonium lead iodide (CH3NH3PM3) films, deuterium treated methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and deuterium treated methylammonium lead iodide (CH3NH3PM3) films on poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) according to various embodiments, and standard methylammonium lead iodideiCE NEbPbb) films, standard
methylammonium lead iodide (CH3NH3PM3) films on [6,6] -phenyl-C61 -butyric acid methyl ester (PCBM), and standard methylammonium lead iodide (CH3NH3Pbl3) films on poly(3,4- ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). τι represents the measured carrier lifetime corresponding to a drop in photoluminescence intensity corresponding to a value Ai, and τ2 represents the measured carrier lifetime corresponding to a drop in photoluminescence intensity corresponding to a value A2. xeff represents the calculated effective carrier lifetime based on τι and τ2 weighted against their values of Ai and A2, calculated using the expression xeff = (Αιη2+ Α2τ2 2)/(Αιτι+ Α2τ2).
[00101] In addition, the lower trap density of perovskite film with D20 suggests that the traps which exist predominantly at the crystal grain boundaries may be reduced with disappearance of the grain boundaries upon the inclusion of D20. The superior optical properties of perovskite films treated or added with D20 may be in agreement with the higher power conversion efficiency (PCE) seen in devices made using perovskite treated or added with D20. The improved crystallinity observed from XRD diffraction, as well as the uniformity and size of crystal grains observed from scanning electron microscopy may imply that the D20 additive may be beneficial for film formation, and may decrease the trap densities as well as increase carrier lifetimes.
[00102] The elemental depth profiles of a standard perovskite layer and a D20 (1 % vol) treated or added perovskite film may be investigated by secondary ion mass spectrometry (SIMS) to further prove that the D20 is actually incorporated into the perovskite layer in the D20 treated or added perovskite film. To perform this experiment, perovskite films may be deposited onto PEDOT:PSS coated Π /glass substrate. An additional organic protection layer of PC6iBM may be further deposited on top of perovskite films to avoid water/oxygen attack to the perovskite films.
[00103] FIG. 15 shows plots of intensity (in arbitrary units or a.u.) as a function of depth (in nanometers or nm) showing (a) the elemental depth profile of a sample with a standard perovskite layer (0% deuterium oxide or D20) and (b) the elemental depth profile of a sample with a perovskite film treated with 1% deuterium oxide (D20) according to various embodiments.
[00104] The C" and H" peaks are present the organic protection layer, and begin to decrease at around 150 nm. The Γ and Pb" peaks, which indicate the perovskite layer, become
prominent between 150 nm to 350 nm. After 350 nm, the InO" peak rises dramatically, indicating the ITO layer. The curves of these elements look quite similar between in the two samples. On the other hand, the D" peak becomes higher in 1% D20 added film as compared to the standard film, indicating that deuterium may be incorporated into the treated perovskite film and may remain there even after the film is annealed at 100 °C (close to the boiling point of D20) for 30 minutes. This suggests that the presence of deuterium within the treated perovskite film may indeed help in better film formation, which may then result in higher power conversion efficiency (PCE).
[00105] H20 has been also experimented as a solvent additive. FIG. 16 is a table 1600 showing photovoltaic parameters of the standard halide perovskite layer, a halide perovskite film formed using 1% deuterium oxide (D20) according to various embodiments, and a halide perovskite film formed using 1% water (H20).
[00106] FIG. 16 shows that a better performance may be achieved with the addition of deuterated water (D20) compared to the addition of standard water (H20) or no addition at all. By switching H20 with D20, both the vibrational/translational motions and donor- accepting ability of water molecules may be changed. The presence of deuterium from the D20 may allow the formation of deuterium bonds that are stronger than the protium bonds. This may have a positive effect on the growth control of the perovskite film, thus improving the perovskite organization. Consequently, the inclusion of D20 (1 % vol) in perovskite films shows better photo-absorption and crystallinity as compared to inclusion of H20 (1 % vol ) in perovskite films as shown by FIGS. 7 and 8. D20 may work much better that H20 as an additive solvent to grow perovskite under the similar or same conditions.
[00107] To fabricate the inverted solar cell as shown in FIG. 4, the moisture and oxygen sensitive steps of fabricating the perovskite layer and the electron accepting layer were performed in a nitrogen filled glove box with < 0.1 parts per million (ppm) H20 and < 2.0 ppm oxygen level.
[00108] All the devices were fabricated on pre-patterned ITO glass substrates with a sheet resistance of -10 Ω/square. The substrates were firstly cleaned by soap water followed by ultrasonication in deionized water for 15 minutes. These substrates were further ultrasonicated for 30 min in a mixture of acetone and isopropanol solution in equal proportion by volume and dried at about 70 °C for at least 60 minutes. These cleaned substrates were
further treated with plasma for 7 minutes to render the ITO surface hydrophilic. A thin film of PEDOT:PSS layer of approximately 30 nm was deposited by spin-coating on these substrates (at 3000 rpm for 60 s), followed by annealing at 130 °C for 15 minutes. Later, these substrates were transferred to the nitrogen filled glove box.
[00109] To prepare the standard perovskite solution, Pbl2 and CH3NH3I was dissolved in 2 ml of Ν,Ν-dimethylformamide (DMF) at a concentration of 469 mg/ml and 161 mg/ml respectively and stirred at about 80 °C until complete dissolution of the solutes in the solvent. To prepare 1.0 % vol D20 added solution, about 10 microliters of deuterated solvent was added into 1 ml of the prepared solution to further improve the solubility of the precursors in DMF. The addition of the abovementioned volumes ensure a solution of 1% deuterated water in DMF is formed. This solution was filtered through 0.45 μιη pore size PTFE filter and deposited on PEDOT:PSS layer coated onto a 2.5 cm x 2.5 cm substrate at 5000 revolutions per minute (rpm) for 12 seconds. An anti-solvent toluene was dripped onto the substrates just after 3 seconds of the start of spin coating. The annealing of these substrates was performed at about 100 °C for 30 minutes to evaporate the solvent and to promote the perovskite formation.
[00110] An electron acceptor layer was subsequently deposited onto the different fabricated perovskite layers by spin-coating at a speed of 1200 rpm for 45 seconds. The electron acceptor layer solution was prepared by dissolving 20 mg of PC6iBM in 1 ml of chlorobenzene. A metal shadow mask was attached to the electron acceptor layer (PC6iBM) coated substrates and transferred to the thermal evaporation chamber. 20 nm thick silver was deposited at a deposition rate of 0.1 - 0.2 A / s, followed by 80 nm thick silver at a deposition rate of 1.0 A /s to form a 100 nm thick silver layer. The effective device area was 0.07 cm2. Perovskite solar cells electrical measurements were performed under 100 mW-cm"2 AM 1.5G. The devices prepared with 1.0 % vol of D20 additive achieved a promising efficiency of 13.76%, approximately 32% improvement as compared to the 10.47% efficient standard device.
[00111] FIG. 17 shows a schematic of another solar cell 1700 according to various embodiments. The solar cell 1700 may include a halide perovskite film 1702. The solar cell 1700 may further include a mesoporous titanium oxide (meso - Ti02) layer 1704a in contact with a first side of the halide perovskite layer or film 1702. The solar cell 1700 may
additionally include a compact titanium oxide (comp - T1O2) layer 1704b in contact with the mesoporous titanium oxide layer 1704a such that the halide perovskite film 1702 and the compact titanium oxide layer 1704b are on opposite sides of the meso titanium oxide (T1O2) layer 1704a. The layers 1704a, 1704b may function as electron transport layers. The solar cell 1700 may also include a hole transport layer 1706, such as a N2,N2,N2',N2',N7,N7,N7',N7'- octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-OMeTAD) layer, in contact with a second side of the halide perovskite layer or film 1702 opposite the first side. The solar cell 1700 may also include a first electrode 1708, such as a fluorine- doped tin oxide (FTO) electrode, in contact with the compact titanium oxide layer 1704b. The solar cell 1700 may additionally include a second electrode 1710, such as a gold (Au) layer, in contact with the hole transport layer 1706.
[00112] The halide perovskite film 1702 may be formed or prepared by mixing of four cations including a methylammonium (MA) cation, i.e. CH3NH3+, a formamidinium (FA) cation, i.e. HC(NH2)2 +, a cesium (Cs) cation, i.e. Cs+, and a rubidium (Rb) cation, i.e. Rb+.
[00113] The transparent fluorine-doped tin oxide-coated glass substrates (FTO glass) may be cleaned by a procedure that is similar to that mentioned above. The FTO glass substrates were plasma treated for 10 min to improve the wettability of the FTO surface. A thin layer of compact T1O2 (comp-Ti02, with a concentration of 54.6 mg/ml in butanol) was coated on the substrates through spin coating in two steps (1000 rpm for 10 s + 2500 rpm 30 s). Substrates were sintered at 450°C for 1 hour and left to cool down to room temperature (25 °C). The substrates were treated using 15 mM aqueous TiCl4 (Sigma- Aldrich, > 98%) solution at 70°C for 30 min, cleaned with deionized water and ethanol, and sintered again at 450 °C for 1 hour.
[00114] A mesoporous T1O2 (meso-Ti02) layer was deposited on the comp-Ti02 layer by spin-coating a colloidal T1O2 solution containing 100 mg of T1O2 paste (Dyesol 30 NR-D) in 1 ml of anhydrous ethanol, at 2500 rpm for 20 s. The coated structure was then annealed at 450 °C for 1 h, and subsequently treated with TiCl4. Before preparing the perovskite film, these substrates were sintered again at 450°C for 1 hour and treated by plasma to improve the wettability of meso-Ti02 film before they were transferred into a dry nitrogen-filled glove box for further processing.
[00115] The halide perovskite solution and solar cell devices may be prepared as highlighted below.
[00116] The primary "mixed" perovskite solution was prepared by mixing 1 M formamidinium iodide (FAI), 1.1 M lead iodide (Pbl2), 0.2 M methylammonium bromide (MABr) and 0.2 M lead bromide (PbBr2) in anhydrous dimethylformamide : dimethyl sulfoxide (DMF:DMSO). The DMF: DMSO has a ratio of 4: 1 ratio by volume. The nominal composition of this solution is (MAo.nFAo.83)Pb(Io.83Bro.i7)3 and may be referred to as a double cation solution (MA/FA). A predissolved cesium iodide (Csl) salt in DMSO (1.5 M) may be added to MA/FA precursor solution in a ratio of 5:95 by volume to get a triple cation perovskite solution. To prepare a quadruple/four cation perovskite solution, a 1.5 M rubidium cation (Rbl) solution with DMSO as a solvent (5% by volume) was added into as the prepared MA/FA/Cs solution (95% by volume) to get the quadruple/four cation perovskite solution (MA/FA/Cs/Pvb) having 0.9035% MAFA, 0.0475% Csl and 0.05% Rbl.
[00117] The final perovskite solution was filtered through 0.45 μιη PTFE filter and spin coated on the Ti02-coated substrate in a two-steps spin program, first at 1000 rpm for 10 s and then at 6000 rpm for 30 s. During the second step of spin coating, 100 μΐ^ of chlorobenzene was dripped on the spinning substrate 15 s after the start of the second program. In order to evaporate the residual solvent and to promote perovskite crystallization, the substrates were annealed on hot plate at 100 °C for 1.0 hr.
[00118] Subsequently, a thin layer of N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4- methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) was spin- coated to form a hole transport layer on the perovskite film at 4000 rpm for 30 s. The Spiro- MeOTAD solution was prepared by first preparing a lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) solution (520 mg Li-TSFI in 1 ml acetonitrile (Sigma-Aldrich, 99.8 %)). Further, 17.5 μΐ of the Li-TFSI solution is mixed together with 72.3 mg Spiro-MeOTAD (Merck), 28.8 μΐ 4-tert-butyl pyridine in 1 ml of cholorobenzene (Sigma-Aldrich). Subsequently, the solution was further doped with cobalt (III) tris(bis(trifluoromethylsulfonyl)imide) salt (FK202, Dynamo) in acetonitrile to improve the hole conductivity in Spiro-MeOTAD. Finally, 70-80 nm gold was deposited by thermal evaporation to complete the solar cell devices.
[00119] The devices were electrically characterized under 100 mW-cm"2 AM 1.5G calibrated solar simulator. The control device was prepared using a perovskite layer untreated with D20 additive as an absorption layer. FIG. 18 is a plot of current density (in milliamperes per square centimeter) as a function of voltage (in volts or V) showing the current density - voltage characteristic curves of a device including a standard halide perovskite layer formed using a four cation (methylammonium, formamidinium, cesium, and rubidium) perovskite solution on a N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[9H- fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD) layer, and a halide perovskite film formed using the four cation perovskite solution with deuterium oxide added on a Spiro-MeOTAD layer according to various embodiments.
[00120] The control device with the perovskite layer containing four cations achieved a power conversion efficiency of 13.21%. The presence of a small fraction of D20 (1.0 % volume) in the perovskite solution improved the device efficiency to 13.34%. Increasing the D2O concentration to 4.0% by volume in the perovskite solution further improved device efficiency to 15.59%. However, concentrations higher than 4.0% D2O by volume adversely decreased the power conversion efficiency of the devices to approximately 13.0 %.
[00121] Photovoltaic parameters extracted from current density - voltage (J-V) characteristics of different devices are summarized in FIG. 19. FIG. 19 is a table 1900 showing photovoltaic parameters of the device including a four-cation based standard halide perovskite layer untreated with deuterium oxide (D2O), a device including a four-cation based halide perovskite film formed using 1% deuterium oxide (D2O) according to various embodiments, a device including a four-cation based halide perovskite film formed using 2% deuterium oxide (D2O) according to various embodiments, a device including a four-cation based halide perovskite film formed using 4% deuterium oxide (D2O) according to various embodiments, and a device including a four-cation based halide perovskite film formed using 6% deuterium oxide (D2O) according to various embodiments.
[00122] Note that the efficiency improvement by adding 4.0 % D2O by volume significantly improves FF from 72.19 % to 79.33% with an increment of 0.05 V in Voc, which is in line with the example described above. This performance enhancement in efficiency by including D2O may be attributed to the superior perovskite film quality and improved energy harvesting. FIG. 20 is a plot of absorbance (in arbitrary units or a.u.) as a
function of wavelength (in nanometers or nm) showing the ultraviolet-visible absorbance (UV-VIS) spectra of a 4-cation based standard halide perovskite layer, and a 4-cation based halide perovskite film treated or added with 4% deuterium oxide (D20) according to various embodiments.
[00123] The importance of the fraction of C-D bonds may also be shown in the four cation based perovskite system. There is a decrease in device performance on addition of higher amounts of D20 greater than 4 % by volume. In the previous example of a single cation based film, the device performance decreases on addition of higher amounts of D20 greater than 1 % by volume. The optimum fraction of D20 may be dependent on the number of organic cations, and the molar concentration used for perovskite solution preparation. In other words, the required value of optimal amount of D20 may varys according the total population of C- H bonds present in perovskite solution. In case of four cation system, the population of C-H bonds may be indeed higher (1.3 M) than a single cation system MAPbI3 (1M). Therefore, a higher fraction of D20 may be required to obtain the optimum ratio of C-D to C-H bonds in perovskite solution to optimize device performance. Further increase of the population of C- D bonds may have an adverse effect on performance, which highlights the importance of the ratio of C-D bonds to C-H bonds.
[00124] FIG. 21 is a plot of carrier density (x 1017 per cubic centimeters or cm"3) as a function of photoluminescence (PL) intensity showing the variation of photoexcited density with photoluminescence (PL) intensity of a four cation based standard halide perovskite structure and a four-cation based halide perovskite film formed with 4% deuterium oxide (D20) according to various embodiments. The films were excited by 600 nm pump laser within the low fluence regime (< 22 μΐ cm"2). The trap density in standard perovskite film is estimated to be around 2.9 x 1017 cm"3 which reduces to 2.0 x 1017 cm"3 on inclusion of D20 (4 % vol) as an additive. The charge carrier lifetimes in standard and D20 (4 % volume) perovskite films using TRPL are measured to be 27.7 nm and 33.5 ns, respectively as shown in FIG. 21.
[00125] FIG. 22 shows plots of photoluminescence (PL) intensity (in arbitrary units or a.u.) as a function of time (in nanoseconds or ns) showing (a) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a standard 4-cation based perovskite layer, a standard 4-cation based perovskite layer on a hole
extraction layer N2,N2,N2',N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[9H- fluorene]-2,2',7,7'-tetramine (Spiro-MeOTAD), and a standard 4-cation based perovskite layer on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM), and (b) the time-resolved photoluminescence (PL) kinetics or lifetime of low pump fluence of a device with a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film according to various embodiments, a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film on a hole extraction layer including N2,N2,N2 N2',N7,N7,N7',N7'-octakis(4-methoxyphenyl)-9,9'-spirobi[9H-fluorene]-2,2',7,7'- tetramine (Spiro-MeOTAD) according to various embodiments, and a 4% deuterium oxide (D20) treated or added 4-cation based perovskite film on an electron extraction layer including [6,6] -phenyl-C61 -butyric acid methyl ester (PC6iBM) according to various embodiments.
[00126] Optical measurements as presented in FIG. 21 and FIG. 22 show that perovskite film with D20 (4 % vol) added may be superior in terms of both lower trap density and longer charge carrier lifetime. The longer lifetimes of charge carriers in perovskite film with D20 added may be consistent with single cation methylammonium (MAPbI3) perovskite system described above. To estimate the charge carrier diffusion lengths using time-resolved photoluminescence (TRPL), a layer of Spiro and PC6iBM were deposited as hole extraction layer and as electron extraction layer, respectively. Electron diffusion lengths improved from 140 nm to 340 nm, while hole diffusion lengths improved from 120 nm to 210 nm on inclusion of D20 (4 % vol) in the four cation-based perovskite films. The superior optical properties of four cation-based perovskite with D20 may be in agreement and may be consistent with the higher power conversion efficiency seen in devices formed from halide perovskite solution with D20.
[00127] Based on experimental evidence, there may be a correlation between D20 volume added to the halide perovskite solution and the deuterium fraction present in the halide perovskite film formed. The fraction of deuterium present in the film may increase with an increase of D20 volume in the solution, though there may not be direct proportional relationship between these values. The fraction of deuterium present in the film may also be affected by other factors such as host solvents, interaction between different precursors, methodology applied for perovskite film preparation etc. Therefore, it may be difficult to
estimate the exact fraction of deuterium present in the film only based on the amount of D20 added into perovskite solution.
[00128] Various embodiments may relate to a simple method of fabricating a compact and uniform perovskite layer as photo-absorbing material for efficient inorganic/organic hybrid solar cell. Deuterated water may be used as the solvent additive to improve the precursor solubility and film quality.
[00129] In various embodiments, the halide perovskite film may include a three dimensional (3D) halide perovskite structure. In various embodiments, the photo-absorbing layer perovskite structure may include one or more metal halide (inorganic part) and one or more organic halide (organic) as main active layer represented by ABX3, wherein A represents the organic component such as a methylammonium (CH3NH3) (MA) cation, a formamidinium [HC(NH2)2] (FA) cation, a cesium (Cs) cation, or a rubidium (Rb) cation, or mixed cations such as (MA)n(FA)1-n, (MA/FA)n(Cs)1-n, (MA/FA/Cs)n(Ru)i-n (wherein n is any value between 0 and 1), or any other composition of cations, wherein B represents a cation of metallic elements such as lead (Pb), tin (Sn), germanium (Ge), bismuth (Bi) or any other suitable metal selected from groups 11, 14, 15 of the periodic table, or mixed metal components, e.g. [MA(Pb/Sn)I3], and wherein X is a halide anion such as iodide (I) anion, bromide (Br) anion, chloride (CI) anion, or a mixed halide anion, e.g. [(I/Br/Cl) i-n[I/Br/Cl)n] (where n is any value between 0 and 1).
[00130] In various embodiments, the photo-absorbing layer perovskite may include a double perovskite structure as the main active layer. The double perovskite structure may be represented by A2BX6, AB2X5, or any other suitable perovskite structure, wherein A represents a potassium (K) cation, a rubidium (Rb) cation, a cesium (Cs) cation, or any organic cation, or any other composition of these cations, wherein B represents a cation of an element selected from group 11 (e.g. Cu, Ag etc.), group 14 (e.g. Pb, Sn etc.) or group 15 (Bi, Sb etc.) elements, or any other metal or mixed metal component, and wherein X is a halide anion such as a iodide (I) anion, a bromide (Br) anion, a chloride (CI) anion or a mixed halide anion, e.g. [(I/Br/Cl)i-n[I/Br/Cl)n] (where n is any value between 0 and 1).
[00131] In various embodiments, the halide perovskite film may include a two dimensional (2D) halide perovskite structure. In various embodiments, the photo- absorbing layer perovskite may include a layered perovskite structure represented by (CH3(CH2)3NH3)2A2y-
iByX3y+i (y = 1, 2, 3, 4, ..∞ etc.) as the main active layer, wherein A represents the organic component such as a methylammonium (CH3NH3) (MA) cation, a formamidinium [HC(NH2)2] (FA) cation, a cesium (Cs) cation, or a rubidium (Rb) cation, or mixed cations as (MA)n(FA)i_n, (MA/FA)n(Cs)i_n or (MA/FA/Cs)n(Ru)i-n (where n is any value between 0 and 1), or any other composition of cations, wherein B represents any metallic element from selected group 11 (e.g. Cu, Ag etc.), group 14 (e.g. Pb, Sn etc.), or group 15 (Bi, Sb etc.), or any other metal or mixed metal component, and wherein X is a halide such as iodide (I), bromide (Br), chloride (CI) or mixed halide [(I/Br/Cl)i-n[I/Br/Cl)n] (where n is any value between 0 and 1).
[00132] In various embodiments, the photo-absorbing layer perovskite may be a mixed dimensional perovskite with a composition formulation (3D perovskite)x(2D perovskite) i_x, wherein x is any value between 0 and 1.
[00133] In various embodiments, different deuterated solvents with varying volume ratios may be used as additives to control the perovskite growth.
[00134] Toluene may be used as an anti-solvent. The anti-solvent may alternatively be chlorobenzene, dichlorobenzene, diethyl ether, a deuterated solvent, or any other suitable anti-solvent.
[00135] Significantly enhanced efficiency may be expected with the careful selection of cell design, selection of precursors, and/or by controlling other processing parameters.
[00136] Significantly enhanced performance may also be achieved by the inclusion of the deuterated water/solvent in other perovskite fabrication methods such as sequential deposition process.
[00137] Due to low temperature fabrication processes, the developed method may be applicable for flexible substrates and roll-to-roll applications where low temperature processing is required.
[00138] Usage of the deuterated solvents may also be extended to the fabrication of other optoelectronic devices such as light emitting diodes, field effect transistors, light emitting transistors, photodetectors etc., and/or other electronic devices such as memories, switches, synaptic devices etc. where solution processes or printable technologies are used.
[00139] Various embodiments may show significantly improved photo-absorption, active layer morphology, charge carrier diffusion length, and/or power conversion efficiency in
deuterated water (or heavy water) added organic-inorganic perovskite solar cells as compared to standard reference devices. Various embodiments may provide highly efficient perovskite devices, which may be attractive for printable and foldable applications where low temperature processing is required. The addition of the deuterated water may show tremendous potential for photovoltaic, light emitting and others solution processed based electronic devices. The further inclusion of the deuterated solvent in lead-free perovskite based devices may further improve the utilization due to the reduced toxicity.
[00140] While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced.
Claims
1. A method of forming a halide perovskite film, the method comprising:
mixing deuterium oxide with a halide perovskite solution to form a halide perovskite film;
wherein the halide perovskite solution comprises a metal cation, a halide anion, and at least one selected from an organic cation and an inorganic cation.
2. The method according to claim 1,
wherein the organic cation is any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium ion, a hydrazinium ion, an azetidinium ion, an imidazolium ion, a
dimethylammonium ion, an ethylammonium ion, a phenethylammonium ion, a guanidinium ion, a tetramethylammonium ion, a thiazolium ion, a 3- pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
The method according to claim 1 or claim 2,
wherein the inorganic cation is a cesium (Cs) cation, a rubidium (Rb) cation, or a potassium (K) cation.
The method according to any one of claims 1 to 3,
wherein the halide perovskite solution comprises a plurality of different organic cations and inorganic cations.
The method according to any one of claims 1 to 4,
wherein the metal cation is a cation of an element of Group 11, Group 14, or Group 15.
6. The method according to any one of claims 1 to 5,
wherein the metal cation is any one selected from a group consisting of a lead cation, a tin cation, a germanium cation, and a bismuth cation.
7. The method according to any one of claims 1 to 6,
wherein the halide perovskite solution further comprises a further metal cation; and
wherein the metal cation and the further metal cation are of different elements.
8. The method according to any one of claims 1 to 7,
wherein the halide anion is any one of a group consisting of a chloride anion, a bromide anion, and an iodide anion.
9. The method according to any one of claims 1 to 8,
wherein the halide perovskite solution further comprises a further anion; and wherein the anion and the further anion are of different elements.
10. The method according to any one of claims 1 to 9,
wherein a concentration of deuterium oxide in the resultant solution is any value selected a range from 0.1 % to 10 % by volume.
11. The method according to claim 10,
wherein the concentration of deuterium oxide in the resultant solution is any value selected a range from 0.5 % to 5 % by volume.
12. The method according to any one of claims 1 to 11,
wherein the halide perovskite solution further comprises a suitable solvent.
13. The method according to claim 12,
wherein the suitable solvent is any one selected from a group consisting of dimethyformamide , γ-butylrolactone, and dimethyl sulphoxide.
14. The method according to any one of claims 1 to 13, further comprising: annealing a resultant solution formed by mixing deuterium oxide with a halide perovskite solution to form the halide perovskite film.
15. The method according to claim 14,
wherein the resultant solution is annealed at any one temperature selected from 50 degrees Celsius to 90 degrees Celsius.
16. The method according to claim 14 or claim 15, further comprising:
filtering the resultant solution to remove undissolved precursors before annealing the resultant solution to form the halide perovskite film.
17. The method according to claim 16,
wherein the filtering of the resultant solution is carried out using a polytetrafluoroethylene (PTFE) filter.
18. The method according to any one of claims 1 to 17,
wherein the halide perovskite film is coated onto a suitable substrate.
19. The method according to claim 18,
wherein the suitable substrate comprises an indium tin oxide carrier, and a carrier transport layer on the indium tin oxide carrier.
20. The method according to claim 18 or claim 19, further comprising:
dripping an anti-solvent onto the suitable substrate during the coating of the halide perovskite film onto the suitable substrate.
21. The method according to any one of claims 18 to 20,
wherein the halide perovskite film is spin-coated onto the suitable substrate.
22. A halide perovskite film formed by a method according to any one of claims 1 to 21.
23. A halide perovskite film comprising:
a crystal structure comprising a metal cation, an organic cation, and a halide anion;
wherein the organic cation comprises one or more carbon-deuterium bonds, and one or more carbon-protium bonds.
24. The halide perovskite film according to claim 23,
wherein the crystal structure is represented by a formula ABX3; wherein A represents the organic cation;
wherein B represents the metal cation; and
wherein X represents the halide anion.
25. The halide perovskite film according to claim 23,
wherein the crystal structure is represented by a formula A2BX6; wherein A represents the organic cation;
wherein B represents the metal cation; and
wherein X represents the halide anion.
26. The halide perovskite film according to claim 23,
wherein the crystal structure is represented by a formula AB2X5; wherein A represents the organic cation;
wherein B represents the metal cation; and
wherein X represents the halide anion.
27. The halide perovskite film according to claim 23,
wherein the halide perovskite film comprises a layer perovskite structure.
28. The halide perovskite film according to claim 23,
wherein the crystal structure is represented by a formula (CH3(CH2)3NH3)2A2y- iByX3y+i ;
wherein A represents the organic cation;
wherein B represents the metal cation;
wherein X represents the halide anion; and
wherein y is any positive integer.
29. The halide perovskite film according to claim 23,
wherein the halide perovskite film is a mixed dimensional perovskite.
30. The halide perovskite film according to any one of claims 23 to 29,
wherein the organic cation is any one selected from a group consisting of a methylammonium cation, a formamidinium cation, a hydroxylammonium cation, a hydrazinium cation, an azetidinium cation, an imidazolium cation, a dimethylammonium cation, an ethylammonium cation, a
phenethylammonium cation, a guanidinium cation, a tetramethylammonium ion, a thiazolium ion, a 3-pyrrolinium ion, a tropylium ion, a piperazinium ion, and a dabconium ion.
31. The halide perovskite film according to any one of claims 23 to 30,
wherein a percentage of the one or more carbon-deuterium bonds relative to a total of the one or more carbon- protium bonds and the one or more carbon- deuterium bonds is any one value selected from a range of 0.01% to 5.0%.
32. A solar cell comprising:
a halide perovskite film according to any one of claims 22 to 31; an electron transport layer on a first side of the halide perovskite film;
a hole transport layer on a second side of the halide perovskite film opposite the first side;
a first electrode in electrical connection with the electron transport layer; and a second electrode in electrical connection with the hole transport layer.
33. The solar cell according to claim 32,
wherein a power conversion efficiency of the solar cell is greater than 13.5%.
34. The solar cell according to claim 32 or claim 33,
wherein a fill factor of the solar cell is greater than 0.75.
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| CN109478596B (en) | 2023-07-21 |
| CN109478596A (en) | 2019-03-15 |
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