Optoelectronic devices with organometal perovskites with mixed anions

0001The present invention relates to optoelectronic devices, including photovoltaic devices such as solar cells and light emitting devices.

0002The current increase in world population, coupled with the development of developing countries towards higher industrial economies, has led to an increase in demand for safe and sustainable energy supplies. Therefore, there is an urgent need to create new optoelectronic devices that meet the global demand for low carbon emissions.

0003Solar energy is seen as a clean solution that provides high efficiency. However, the high cost of manufacturing devices that utilize solar energy, including high material costs, has historically hindered its use.

0004The production of low-cost optoelectronic devices such as photovoltaic elements made of abundant materials can be rapidly manufactured using the real-to-real manufacturing method, and therefore simple wet chemistry. Law is a fast-growing research area. In recent years, the power conversion efficiency of optoelectronic devices has been steadily increasing. However, with the use of traditional photovoltaic devices, it seems that even more significant increases in power conversion efficiency cannot be taken advantage of. Therefore, there is a real need for new solar cell technologies that focus on low cost.

0005Dye-sensitized solar cells are dye-sensitized mesoporous TiO impregnated with a redox active electrolyte.₂Consists of [O'Regan et al., Nature, 353, 737-740, 1991]. This battery is a real competitor capable of generating electricity on the largest scale. However, despite the most efficient devices verified at 11.4% and even more recently at up to 12.3% [Yella et al., Science, 334 (6056), 629-634, 2011], widespread commercialization It has not been realized yet. One of the decisive reasons for the lack of commercial uptake is the nature of the redox pair liquid used in electrolyte cells, which is highly volatile and corrosive, resulting in a particularly high temperature. There are considerable constraints on both processing and long-term stability. A good competitor that can also generate such efficiencies and is more compatible with large scale machining and long-term stability is a solid dye sensitized solar cell in which the redox active electrolyte is replaced by a solid hole conductor. [Snaith et al., Advanced Materials, 19, 3187-3200, 2007]. However, at present, the most efficient solid DSC is only slightly over 7% [Burschka et al., J. Am. Chem. Soc., 133 (45), 18042-18405, 2011]. The main reason for this lower performance is the combination of faster charge recombination and limited ability to penetrate thick mesoporous photoanodes, limiting the maximum thickness of solid DSCs to around 2 μm. That is [Snaith et al., Advanced Materials, 19, 3187-3200, 2007]. At a thickness of 2 μm, the sensitizer does not absorb light with a wide spectrum enough to generate enough photocurrent, and the short-circuit photocurrent is 20 mAcm in the best electrolyte cell.^-2In contrast, generally 10mAcm^-2Limited to a degree.

0006Recently, there has been a renewed interest in "ultra-thin absorber" (ETA) solar cells, which are equivalent to solid DSCs, but the dye is mesoporous TiO.₂It has been replaced with an ultra-thin layer of inorganic semiconductor coated at the interface between the hole conductor and the hole conductor. Antimony sulfide Sb as an absorber₂S₃Although an efficiency close to 6% has been reported by using (Chang et al., Nano Lett., 12 (4), 1863-1867, 2012), it is possible to generate a high photocurrent with this material. However, the open circuit voltage is low and overall performance is limited.

0007As an alternative absorber material, organometallic halide perovskite is considered a good candidate and has an extremely high extinction coefficient in thin films. Organic metal halide perovskite can be easily processed from precursor solutions, transistors [Kagan et al., Science, 286, 945, 1999] and light emitting diodes (Era et al., Appl. Phys. Lett., 65, 676, It has been proven to be excellent in other application examples, such as being an excellent candidate as 1994). Recently, they have also been reported as sensitizers for liquid electrolyte-based photoelectrochemical batteries, delivering solar power conversion efficiencies between 3.5 and 6.5% (Kojima et al., J. Am. Chem). .Soc., 131, 6050, 2009; Im et al., Nanoscale, 3, 4088, 2011). However, in this previously reported electrolyte system, the perovskite absorber rapidly collapsed and the solar cells deteriorated after only 10 minutes.

0008The present invention has found that optoelectronic devices containing mixed anion perovskite are surprisingly stable and exhibit unexpectedly high power conversion efficiencies and photocurrents. Optoelectronic devices are also relatively inexpensive to manufacture and may be relatively easy to produce on a large scale.

0009An important requirement for any optoelectronic device is that it be stable for the intended life of the device. We have found that devices according to the invention are far less susceptible to vapor-induced chromism than devices containing a single halide perovskite.

0010The additional advantages of the device of the present invention are the relatively high power conversion efficiency and the photocurrent delivered by the device. 1sun (AM 1.5G 100mWcm^-2), The light conversion efficiency of 11.5% was observed. These efficiencies exceed the efficiencies exhibited by devices containing a single halide perovskite. Moreover, the performance of the device of the present invention is unprecedented in solid-state sensitized solar cells and directly competes with the very best performing electrolyte cells. In the optoelectronic device of the present invention, the photocurrent is 21 mAcm.^-2Was observed. This value exceeds the photocurrent observed with the most efficient solid-state DSC currently available.

0011In addition, the mixed anion perovskite provides a highly flexible framework that can be manipulated by adjusting the individual components of the material, thus allowing exceptional control at the molecular level. Therefore, the properties of the mixed anion perovskite can be easily adjusted to enhance the performance of the optoelectronic devices in which it is utilized.

0012All of these advantages are less noticeable when large-scale production is excluded due to the costly or complex manufacturing methods required to produce optoelectronic devices. However, this does not apply to the optoelectronic device of the present invention. The materials used in the device are relatively abundant and inexpensive. In addition, devices can be generated by methods that enable large-scale production methods.

0013Thus, in the first aspect, the invention is a photoelectron device comprising a mixed anion perovskite, wherein the mixed anion perovskite contains two or more different anions selected from a halide anion and a chalcogenide anion. Provide a device.

0014In the second aspect, the present invention relates to formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₁R₂R₃R₄N)⁺At least one of the organic cations of (i) R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is the two or more different halide anions mentioned above] To provide a mixed halide perovskite.

0015Typically, in the second aspect of the invention (i) A is (CH₃SMALL₃)⁺Is an organic cation and B is Sn²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of (a) chloride and bromide ions or (b) bromide and iodide ions. (ii) A is (CH₃SMALL₃)⁺Is an organic cation and B is Pb²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of chloride and bromide ions.

0016In a third aspect, the present invention relates to formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₅R₆N=CH-NR₇R₈)⁺At least one of the organic cations of (i) R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is two or more different halide anions] To provide a mixed halide perovskite.

0017In another aspect, the invention is the use of mixed anion perovskite as a sensitizer in optoelectronic devices, wherein the mixed anion perovskite comprises two or more different anions selected from halide anions and cargogenide anions. Includes, provides use.

0018The present invention is also a photosensitizer for optoelectronic devices, including mixed anion perovskite, wherein the mixed anion perovskite contains two or more different anions selected from halide anions and chalcogenide anions. Provide a sensitizing material.

0019<figref num="1">FIG. 6 is a schematic representation of a photovoltaic device containing a mixed anion perovskite.</figref><figref num="2(a)">TiO₂Perovskite CH prepared above₃SMALL₃PbBr₃UV-Vis (ultraviolet-visible) absorbance spectrum of. In the graph, the wavelength with nm as the unit is plotted on the x-axis, and the absorbance of any unit is plotted on the y-axis.</figref><figref num="2(b)">TiO₂Perovskite CH prepared above₃SMALL₃PbI₃UV-Vis absorbance spectrum of. In the graph, the wavelength with nm as the unit is plotted on the x-axis, and the absorbance of any unit is plotted on the y-axis.</figref><figref num="3">Isometric cross-sectional view of a typical nanostructured solar cell: (1) metal cathode, (2) hole-conducting material, nanostructured mesoporous metal oxide with absorber, and hole-conducting material (clarify) Therefore, (see Fig. 4), (3) transparent conductive metal oxide (anode), (4) transparent substrate, (5) metal anode, and (6) dense metal oxide.</figref><figref num="4">Schematic representation of a cross section of the "active layer" of a typical nanostructured solar cell: (2 (i)) photosensitive absorber, (2 (ii)) metal oxide, metal cathode, (6) dense Metal oxide, (7) hole conduction material.</figref><figref num="5">TiO at 20% by volume₂Organometallic mixed halide layered perovskite prepared above: K330 (CH)₃SMALL₃PbCl₂I) and K331 (CH)₃SMALL₃PbCl₂It is a UV-Vis absorbance spectrum of Br). In the graph, wavelengths in nm are plotted on the x-axis and absorbance in any unit is plotted on the y-axis. The dark line is K330 and the light line is K331.</figref><figref num="6">2-layer structure: F:SnO₂/ Dense TiO₂100mWcm of device assembled in / K330 / Spiro OMeTAD / Ag^-2It is a figure which shows the current-voltage characteristic under the simulated AM1.5G illumination (top curve) and dark place (bottom curve). In the graph, the voltage in volts is plotted on the x-axis, mAcm^-2The current density in units of is plotted on the y-axis.</figref><figref num="7">Absorber sensitized structure with hole conductor: F: SnO₂/ Dense TiO₂/ Mesoporous TiO₂It is a figure which shows the current-voltage characteristic under the simulated AM1.5G illumination of the device assembled in / K330 / Spiro OMeTAD / Ag. In the graph, the voltage in volts is plotted on the x-axis, mAcm^-2The current density in units of is plotted on the y-axis.</figref><figref num="8">Absorber sensitized structure with hole conductor: F: SnO₂/ Dense TiO₂/ Mesoporous TiO₂It is a figure which shows the current-voltage characteristic under the simulated AM1.5G illumination of the device assembled in / K330 / P3HT / Ag. In the graph, the voltage in volts is plotted on the x-axis, mAcm^-2The current density in units of is plotted on the y-axis.</figref><figref num="9">Mesoporous absorber structure with hole conductors: F: SnO₂/ Dense TiO₂/ Mesoporous TiO₂It is a figure which shows the conversion efficiency (IPCE) action spectrum from an incident photon to an electron of the device assembled in / K330 / spiro OMeTAD / Ag. In the graph, wavelengths in nm are plotted on the x-axis and IPCE is plotted on the y-axis.</figref><figref num="10">Absorber sensitized structure with hole conductor: F: SnO₂/ Dense TiO₂/ Mesoporous TiO₂It is a figure which shows the conversion efficiency (IPCE) action spectrum from an incident photon to an electron of the device assembled in / K330 / P3HT (dark line) or PCPDTBT (light line) / Ag. In the graph, wavelengths in nm are plotted on the x-axis and IPCE is plotted on the y-axis.</figref><figref num="11">Absorber sensitized structure with hole conductor, sealed with sirline and epoxy by light soaking under simulated AM1.5G illumination over time: F: SnO₂/ Dense TiO₂It is a figure which shows the UV-Vis absorbance spectrum about the device assembled in / mesoporous oxide / K330 / spiro OMeTAD. In the graph, wavelengths in nm are plotted on the x-axis and absorbance in any unit is plotted on the y-axis.</figref><figref num="12">Absorber sensitized structure with hole conductors sealed using sirline and epoxy: F: SnO₂/ Dense TiO₂/ Mesoporous TiO₂It is a figure which shows the UV-Vis absorbance spectrum obtained by the light soaking of 500 nm under the simulated AM1.5G illumination with respect to the device assembled in the / K330 / Spiro OMeTAD. In the graph, time (unit: hour) is plotted on the x-axis and absorbance in any unit is plotted on the y-axis.</figref><figref num="13">It is a figure which shows the X-ray diffraction (XRD) spectrum of K330 of 35% by volume on the glass. Frequencies in units of 2θ are plotted on the x-axis, and counts in any unit are plotted on the y-axis.</figref><figref num="14">Mesoporous TiO₂It is a figure which shows the cross section of the scanning electron microscope (SEM) image of.</figref><figref num="15">Mesoporous TiO₂It is a figure which shows the scanning electron microscope (SEM) image cross section of / K330.</figref><figref num="16">Mesoporous TiO₂It is a figure which shows the scanning electron microscope (SEM) image cross section of / K330 / Spiro OMeTAD.</figref><figref num="17(a)">A series of FOPbI_3yBr_{3 (1-y)}It is a figure which shows the UV-vis absorption spectrum of perovskite.</figref><figref num="17(b)">It is a figure which shows the photoluminescence spectrum of the same sample in a steady state.</figref><figref num="18(a)">General perovskite ABX₃It is a schematic diagram of a unit cell.</figref><figref num="18(b)">It is a schematic diagram of a cubic perovskite lattice structure (a unit cell is shown as an overlapping square).</figref><figref num="18(c)">BX₆Of the tetragonal perovskite lattice structure resulting from octahedral distortion (the unit cell is shown as a larger overlapping square, and the pseudo-cubic unit cell that can describe it is shown as a smaller overlapping square). It is a schematic diagram.</figref><figref num="18(d)">FOPbI at various values where y ranges from 0 to 1_3yBr_{3 (1-y)}It is a figure which shows the X-ray diffraction data about a perovskite.</figref><figref num="18(e)">It is an enlarged view of the transition between (100) cubic peak and (110) tetragonal peak corresponding to (100) pseudo-cubic peak when the system moves from bromide to iodide.</figref><figref num="18(f)">It is the figure which plotted the bandgap with respect to the calculated pseudo-cubic lattice constant.</figref><figref num="19(a)">FOPbI with spiro-OMeTAD as hole transporter, measured in simulated AM1.5 sunlight_3yBr_{3 (1-y)}It is a figure which shows the average current-voltage characteristic about the batch of the solar cell containing the perovskite sensitized mesoporous titania.</figref><figref num="19(b)">It is a figure which shows the normalized external quantum efficiency about a typical cell.</figref><figref num="19(c)">FOPbI_3yBr_{3 (1-y)}In perovskite, as a function of iodine fraction y, it is a diagram plotting device parameters that are beneficial to batch.</figref>

0020The present invention provides a photoelectron device comprising a mixed anion perovskite, wherein the mixed anion perovskite contains two or more different anions selected from a halide anion and a chalcogenide anion.

0021An optoelectronic device is a device capable of converting light energy into electrical energy or converting electrical energy into light energy.

0022The term "perovskite" as used herein is CaTiO.₃A material having a three-dimensional crystal structure related to the structure of, or CaTiO₃Refers to a material containing a material layer having a structure related to the structure of. CaTiO₃The structure of is the formula ABX₃In the formula, A and B are cations of different sizes and X is an anion. In the unit cell, the A cation is at (0,0,0), the B cation is at (1 / 2,1 / 2,1 / 2), and the X anion is at (1 / 2,1 / 2,0). It is in. The A cation is usually larger than the B cation. For those skilled in the art, when A, B, and X change, the structure of the perovskite material changes due to the difference in ion size.₃It will be understood that the structure is distorted into a less symmetric strain structure away from the structure adopted by. Symmetry is that the material is CaTiO₃It is also low when it contains a layer having a structure related to the structure of. Materials containing layers of perovskite material are well known. For example, K₂NiF₄The structure of the material that employs the mold structure includes a layer of perovskite material. For those skilled in the art, the perovskite material is the formula [A] [B] [X]₃It will also be understood that in the formula A is at least one cation, B is at least one cation, and X is at least one anion. If the perovskite contains multiple A cations, the various A cations may be distributed on the A site in an ordered or chaotic manner. If the perovskite contains multiple B cations, the various B cations may be distributed on the B site in an ordered or chaotic manner. If the perovskite contains multiple X anions, the various X anions may be distributed on the X site in an ordered or chaotic manner. The symmetry of a perovskite containing multiple A cations, multiple B cations, or multiple X cations is CaTiO.₃Is lower than the symmetry of.

0023As used herein, the term "mixed anion" refers to a compound containing at least two different anions.

0024The term "halide" refers to Group 7 elements, i.e. halogen anions. Typically, the halide refers to a fluoride anion, a chloride anion, a bromide anion, an iodide anion, or an asttide anion.

0025As used herein, the term "chalcogenide anion" refers to a Group 6 element, the chalcogen anion. Cargogenide typically refers to an oxide anion, a sulfide anion, a serene anion, or a telluride anion.

0026In the optoelectronic device of the present invention, the mixed anion perovskite may contain a first cation, a second cation, and two or more different anions.

0027Those skilled in the art will appreciate that mixed anion perovskite may contain other cations or other anions. For example, the mixed anion perovskite may contain 2, 3, or 4 different cations, or 2, 3, or 4 different anions.

0028In one embodiment, the perovskite comprises two different anions selected from a halide anion and a chalcogenide anion. The two different anions may be halide and chalcogenide anions, two different halide anions, or two different chalcogenide anions.

0029Typically, in the optoelectronic device of the present invention, the second cation in the mixed anion perovskite is a metal cation. More typically, the second cation is a divalent metal cation. For example, the second cation is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺May be selected from. Usually the second cation is Sn²⁺And Pb²⁺Is selected from.

0030In the optoelectronic device of the present invention, the first cation in the mixed anion perovskite is usually an organic cation.

0031The term "organic cation" refers to a carbon-containing cation. The cation may contain other elements, for example the cation may contain hydrogen, nitrogen, or oxygen.

0032Changes to organic cations (or multiple organic cations) within the perovskite will usually affect the structural and / or physical properties of the perovskite. By controlling the organic cations used, the electronic and optical properties of the material may be controlled. This flexible control of the properties exhibited by perovskite is particularly useful for adjusting the properties of optoelectronic devices containing said perovskite. For example, the conductivity of the material may be increased or decreased by changing the organic cation. In addition, changing the organic cations can change the band structure of the material, thus allowing control of the bandgap of semiconductor materials, for example.

0033Generally, in the optoelectronic device of the present invention, the organic cation is of the formula (R).₁R₂R₃R₄N)⁺Has, in the formula, R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0034The alkyl groups used herein can be substituted or unsubstituted linear or branched chain saturated radicals, which are often substituted or unsubstituted linear saturated radicals and more often unsubstituted. It is a linear saturated radical. C₁~C₂₀Alkyl groups are unsubstituted or substituted linear or branched saturated hydrocarbon radicals having 1 to 20 carbon atoms. Typically C₁~C₁₀Alkyl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl, or C₁~C₆Alkyl, such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, or C₁~C₄Alkyl, such as methyl, ethyl, i-propyl, n-propyl, t-butyl, s-butyl, or n-butyl.

0035If the alkyl group is substituted, typically substituted or unsubstituted C₁~C₂₀Alkyl, substituted or unsubstituted aryl (as defined herein), cyano, amino, C₁~C₁₀Alkylamino, di (C₁~C₁₀) Alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamide, hydroxy, oxo, halo, carboxy, ester, acyl, acyloxy, C₁~C₂₀Alkoxy, aryloxy, haloalkyl, sulfonic acid, sulfhydryl (ie, thiol, -SH), C₁~C₁₀It has one or more substituents selected from alkylthio, arylthio, sulfonyl, phosphoric acid, phosphoric acid esters, phosphonic acids, and phosphonic acid esters. Examples of substituted alkyl groups include haloalkyl, hydroxyalkyl, aminoalkyl, alkoxyalkyl, and alkalil groups. As used herein, the term alkaline is C in which at least one hydrogen atom has been replaced with an aryl group.₁~C₂₀Regarding alkyl groups. Examples of such groups include benzyl (phenylmethyl, PhCH).₂-), Benz Hydrill (Ph)₂CH-), trityl (triphenylmethyl, Ph₃C-), phenethyl (phenylethyl, Ph-CH₂CH₂-), Styril (Ph-CH = CH-), Shinnamil (Ph-CH = CH-CH)₂-) Is included, but not limited to these.

0036Typically, the substituted alkyl group retains 1, 2, or 3 substituents, such as 1 or 2 substituents.

0037Aryl groups are substituted or unsubstituted monocyclic or bicyclic aromatic groups typically containing 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms in the ring moiety. Examples include phenyl, naphthyl, indenyl, and indanyl groups. Aryl groups are either unsubstituted or substituted. If the aryl group defined above is substituted, it is typically an unsubstituted C (to form an aralkyl group).₁~C₆Alkyl, unsubstituted aryl, cyano, amino, C₁~C₁₀Alkylamino, di (C₁~C₁₀) Alkylamino, arylamino, diarylamino, arylalkylamino, amide, acylamide, hydroxy, halo, carboxy, ester, acyl, acyloxy, C₁~C₂₀Alkoxy, aryloxy, haloalkyl, sulfhydryl (ie, thiol, -SH), C_1~10It has one or more substituents selected from alkylthio, arylthio, sulfonic acid, phosphoric acid, phosphoric acid ester, phosphonic acid, and phosphonic acid ester, and sulfonyl. Typically, this group carries 0, 1, 2, or 3 substituents. The substituted aryl group is a single C₁~C₆Alkyl group or formula -X- (C₁~C₆) Alkylene or -X- (C₁~C₆) Alkylene-X-, where X is selected from O, S, and NR and R is H, aryl, or C₁~C₆Two positions may be substituted with a bidentate represented by the formula being alkyl. Therefore, the substituted aryl group may be an aryl group condensed with a cycloalkyl group or a heterocyclyl group. The ring atom of the aryl group may contain one or more heteroatoms (as in the heteroaryl group). Such aryl groups (heteroaryl groups) typically contain 6 to 10 atoms in a ring moiety containing one or more heteroatoms, either substituted or unsubstituted monocyclic or bicyclic. Formula is a heteroaromatic group. This is generally a 5- or 6-membered ring containing at least one heteroatom selected from O, S, N, P, Se, and Si, eg, containing 1, 2, or 3 heteroatoms. You may be doing it. Examples of heteroaryl groups include thiophenyl, pyridyl, pyrazinyl, pyrimidinyl, pyridadinyl, furanyl, thienyl, pyrazolydinyl, pyrrolyl, oxazolyl, oxadiazolyl, isooxazolyl, thiadiazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, quinolyl, and isoquinolyl. Heteroaryl groups may or may not be substituted, eg, those specified above with respect to aryl. Typically, this group carries 0, 1, 2, or 3 substituents.

0038Primarily, in the optoelectronic device of the present invention, the organic cation R₁Is hydrogen, methyl, or ethyl, R₂Is hydrogen, methyl, or ethyl, R₃Is hydrogen, methyl, or ethyl, R₄Is hydrogen, methyl, or ethyl. For example R₁Can be hydrogen or methyl, R₂Can be hydrogen or methyl, R₃Can be hydrogen or methyl, R₄May be hydrogen or methyl.

0039Alternatively, the organic cation is of the formula (R).₅SMALL₃)⁺[In the formula, R₅Is hydrogen, or unsubstituted or substituted C₁~C₂₀It is alkyl]. For example, R₅May be methyl or ethyl. Typically R₅Is methyl.

0040In some embodiments, the organic cation is of formula (R).₅R₆N=CH-NR₇R₈)⁺In the formula, R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0041Typically, R in organic cations₅Is hydrogen, methyl, or ethyl, R₆Is hydrogen, methyl, or ethyl, R₇Is hydrogen, methyl, or ethyl, R₈Is hydrogen, methyl, or ethyl. For example R₅Can be hydrogen or methyl, R₆Can be hydrogen or methyl, R₇Can be hydrogen or methyl, R₈May be hydrogen or methyl.

0042The organic cation is, for example, the formula (H).₂N=CH-SMALL₂)⁺May have.

0043In the optoelectronic device of the present invention, the perovskite is usually a mixed halide perovskite, and the two or more different anions are two or more different halide anions. Typically, these are two or three halide anions, and more typically two different halide anions. Usually, the halide anion is selected from fluoride, chloride, bromide, and iodide, such as chloride, bromide, and iodide.

0044Typically, in the optoelectronic device of the present invention, the perovskite is of formula (I). [A][B][X]₃ (I) [In the formula, [A] is at least one organic cation [B] is at least one metal cation, [X] is the two or more different anions mentioned above] Perovskite compound.

0045For example, the perovskite of formula (I) may contain 1, 2, 3, or 4 different metal cations, typically 1 or 2 different metal cations. The perovskite of formula (I) may contain, for example, 1, 2, 3, or 4 different organic cations, typically 1 or 2 different organic cations. The perovskite of formula (I) may contain, for example, 2, 3, or 4 different anions, typically 2 or 3 different anions.

0046Often, in the optoelectronic devices of the present invention, [X] is a halide anion and a chalcogenide anion, two different halide anions or two different chalcogenide anions.

0047Typically, in the optoelectronic device of the present invention, [B] in the mixed anion perovskite is at least one metal cation. More typically, [B] is at least one divalent metal cation. For example, [B] is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺At least one divalent metal cation that may be selected from. Normally, [B] is Sn²⁺And Pb²⁺At least one divalent metal cation selected from.

0048Usually, in the optoelectronic device of the present invention, [A] is the formula (R).₁R₂R₃R₄N)⁺Is at least one organic cation with Where, R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0049However, [A] is the formula (R₅R₆N=CH-NR₇R₈)⁺May be at least one organic cation with, in the formula, R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0050In one embodiment, the perovskite is formulated (IA). AB [X]₃ (HE) [In the formula. A is an organic cation B is a metal cation, [X] is the two or more different anions mentioned above] Perovskite compound.

0051Usually, [X] is two or more different halide anions. Preferably, [X] is two or three different halide anions. More preferably, [X] is two different halide anions. In another embodiment, [X] is three different halide anions.

0052Often, in the optoelectronic device of the present invention, [X] is a halide anion and a chalcogenide anion, two different halide anions or two different chalcogenide anions.

0053Typically, in the optoelectronic device of the present invention, B is a divalent metal cation. For example, B is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺It is a divalent metal cation that may be selected from. Usually B is Sn²⁺And Pb²⁺It is a divalent metal cation selected from.

0054Usually, in the optoelectronic device of the present invention, A is the formula (R).₁R₂R₃R₄N)⁺Is an organic cation with Where, R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0055But A is the formula (R₅R₆N=CH-NR₇R₈)⁺It may be at least one organic cation having, and in the formula, R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0056Typically, in the optoelectronic device of the invention, the perovskite is equation (II). ABX_3-yX_Y (II) [In the formula, A is an organic cation B is a metal cation, X is the first halide anion, X'is a second halide anion that is different from the first halide anion, y is 0.05 to 2.95] Perovskite compound.

0057Usually y is 0.5 to 2.5, for example 0.75 to 2.25. Typically, y is 1 to 2.

0058Often, in the optoelectronic devices of the invention, X is a halide anion and X'is a chalcogenide anion, or X and X'are two different halide anions or two different chalcogenide anions.

0059Typically, in the optoelectronic device of the present invention, B may be a divalent metal cation. For example, B is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺It is a divalent metal cation that may be selected from. Usually B is Sn²⁺And Pb²⁺It is a divalent metal cation selected from.

0060Usually, in the optoelectronic device of the present invention, A is the formula (R).₁R₂R₃R₄N)⁺Is an organic cation with Where, R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0061In some embodiments of the optoelectronic device of the present invention, [B] is Pb.²⁺In the case of a single metal cation, one of the two or more different halide anions is iodide or fluoride; [B], but Sn.²⁺In the case of a single metal cation, one of the two or more different halide anions is a fluoride. Generally, in some embodiments of the optoelectronic device of the present invention, one of the two or more different halide anions is iodide or fluoride. Typically, in some embodiments of the optoelectronic device of the invention, one of the two or more different halide anions is iodide and the other of the two or more different halide anions. It is a fluoride or chloride. Often, in some embodiments of the optoelectronic device of the present invention, one of the two or more different halide anions is fluoride. Typically, in some embodiments of the optoelectronic device of the invention, (a) one of the two or more different anions is fluoride and the other of the two or more different anions is chloride. A substance, bromide, or iodide, or (b) one of the two or more different anions is iodide, and the other of the two or more different anions is fluoride or chloride.

0062Usually, in the optoelectronic device of the present invention, [X] is two different halide anions X and X'.

0063Often, in the optoelectronic device of the present invention, the divalent metal cation is Sn.²⁺Is. Alternatively, in some embodiments of the optoelectronic device of the present invention, the divalent metal cation is Pb.²⁺It may be.

0064In some embodiments, in the optoelectronic device of the present invention, the perovskite is of formula (IIa). ABX_3zX_{3 (1-d)} (IIa) [In the formula, A is the formula (R₅R₆N=CH-NR₇R₈)⁺Is an organic cation, where R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, B is a metal cation, X is the first halide anion, X'is a second halide anion that is different from the first halide anion, z is greater than 0 and less than 1] Perovskite compound.

0065Usually z is 0.05 to 0.95.

0066Preferably, z is 0.1 to 0.9, z may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or z is any one of these values. May range from to any other value of these values (eg, 0.2 to 0.7 or 0.1 to 0.8).

0067Typically, X is a halide anion and X'is a chalcogenide anion, or X and X'are two different halide anions or two different chalcogenide anions. Usually, X and X'are two different halide anions. For example, one of the two or more different halide anions may be iodide, and the other of the two or more different halide anions may be bromide.

0068Usually, B is a divalent metal cation. For example, B is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺It may be a divalent metal cation selected from. Usually B is Sn²⁺And Pb²⁺It is a divalent metal cation selected from. For example, B is Pb²⁺It may be.

0069Organic cations are, for example, (R₅R₆N=CH-NR₇R₈)⁺[In the formula, R₅,R₆,R₇, And R₈Independently, hydrogen, and unsubstituted or substituted C₁~C₆Selected from alkyl]. For example, the organic cation is (H₂N=CH-SMALL₂)⁺It may be.

0070In the optoelectronic device of the present invention, the perovskite is typically CH.₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnBrI₂, CH₃SMALL₃SnBrCl₂, CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnIBr₂, CH₃SMALL₃SnICl₂, CH₃SMALL₃SnF₂I,CH₃SMALL₃SnClBr₂, CH₃SMALL₃SnI₂Cl and CH₃SMALL₃SnF₂Selected from Cl. Typically, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnICl₂, CH₃SMALL₃SnF₂I,CH₃SMALL₃SnI₂Cl and CH₃SMALL₃SnF₂Selected from Cl. More typically, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnF₂I and CH₃SMALL₃SnF₂Selected from Cl. Normally, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃SnF₂Br and CH₃SMALL₃SnF₂Selected from I.

0071In some embodiments, the perovskite is an equation (H).₂N=CH-SMALL₂)PbI_3zBr_{3 (1-d)}Perovskite, where z is greater than 0 and less than 1 in the equation. z may be as further defined above.

0072The optoelectronic device of the present invention may include the perovskite and a single anion perovskite, the single anion perovskite being selected from a first cation, a second cation, a halide anion and a chalcogenide anion. The first and second cations, including anions, are as defined herein with respect to the mixed anion perovskite. For example, optoelectronic devices: CH₃SMALL₃PbICl₂And CH₃SMALL₃PbI₃; CH₃SMALL₃PbICl₂And CH₃SMALL₃PbBr₃; CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbI₃; Or CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbBr₃May include.

0073The optoelectronic device is the formula (H₂N=CH-SMALL₂)PbI_3zBr_{3 (1-d)}Perovskite may be included, in which z is as defined herein and (H).₂N=CH-SMALL₂)PbI₃Or (H₂N=CH-SMALL₂) PbBr₃Is a single anion perovskite such as.

0074Alternatively, the optoelectronic device of the present invention may include a plurality of perovskites, each perovskite being a mixed anion perovskite, said mixed anion perovskite as defined herein. For example, the optoelectronic device may include two or three types of the perovskite. The optoelectronic device of the present invention may include, for example, two types of perovskite, both of which are mixed anionic perovskites. For example, optoelectronic devices are: CH₃SMALL₃PbICl₂And CH₃SMALL₃PbIBr₂; CH₃SMALL₃PbICl₂And CH₃SMALL₃PbBrI₂; CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbIBr₂; Or CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbIBr₂May include.

0075The optoelectronic device may contain two different perovskites, each perovskite of formula (H).₂N=CH-SMALL₂)PbI_3zBr_{3 (1-d)}Perovskite, in which z is as defined herein.

0076The optoelectronic devices of the present invention typically include: photovoltaic devices; photodiodies; optical transistors; photomultiplier tubes; photodetectors; photodetectors; photosensitive detectors; solid triodes; battery electrodes; light emitting devices; A photomultiplier device selected from light emitting diodes; transistors; solar cells; lasers; and diode injection lasers.

0077Generally, the optoelectronic device of the present invention is a photovoltaic device. More usually, the device is a solar cell.

0078Alternatively, the optoelectronic device of the present invention may be a light emitting device, for example, a light emitting diode.

0079In one embodiment, the optoelectronic device of the present invention is With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) With the perovskite It is an optoelectronic device including.

0080The first and second electrodes are the anode and cathode, one or both of which are transparent to allow light to enter. What is selected for the first and second electrodes of the optoelectronic device of the present invention may depend on the structural type. Typically, an n-type layer is deposited on tin oxide, and more typically on a fluorine-doped tin oxide (FTO) anode, which is usually a transparent or translucent material. Is. Therefore, the first electrode is usually transparent or translucent and typically contains an FTO. Usually, the thickness of the first electrode is 200 nm to 600 nm, and more usually 300 to 500 nm. For example, the thickness may be 400 nm. Typically, the FTO is coated on a glass plate. Usually, the second electrode contains a metal with a high work function, such as gold, silver, nickel, palladium, or platinum, typically silver. Usually, the thickness of the second electrode is 50 nm to 250 nm, and more usually 100 nm to 200 nm. For example, the thickness of the second electrode may be 150 nm.

0081As used herein, the term "thickness" refers to the average thickness of the components of an optoelectronic device.

0082Typically, the optoelectronic device of the present invention With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) With the thin film containing the perovskite It is an optoelectronic device including.

0083In one embodiment, the optoelectronic device of the present invention is With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) Semiconductor layer and (b) With the perovskite It is an optoelectronic device including.

0084As used herein, the term "semiconductor" refers to a material having electrical conductivity that is intermediate in size between a conductor and an insulator. The semiconductor may be an intrinsic semiconductor, an n-type semiconductor, or a p-type semiconductor. Examples of semiconductors are perovskite; oxides of titanium, niobium, tin, zinc, cadmium, copper, or lead; antimony, copper, zinc, iron, or bismuth chalcogenides (eg, copper sulfide and iron sulfide); copper zinc. Zinc calcogenide, eg Cu₂ZnSnS₄Copper, zinc, tin sulfides such as (CZTS), and Cu₂ZnSn (S_1-xI know_x)₄Copper zinc tin sulfur selenium such as (CZTSSe); copper indium chalcogenide such as copper indium selenium (CIS); copper indium gallium selenium (CuIn)_1-xGa_xI know₂) (CIGS) and other copper indium gallium chalcogenides; and copper indium gallium disselenate. Further examples are group IV compound semiconductors (eg, silicon carbide); group III-V semiconductors (eg, gallium arsenide); group II-VI semiconductors (eg, cadmium selenium); group I-VII semiconductors (eg, chloride). First copper); IV-VI group semiconductors (eg, lead selenium); V-VI group semiconductors (eg, bismuth telluride); and II-V group semiconductors (eg, cadmium arsenide); ternary or quaternary Semiconductors (eg, copper indium serene, copper indium gallium dicelenide, copper zinc tin sulfide, or copper zinc tin sulfide selenium (CZTSSe).

0085Generally, the optoelectronic device of the present invention includes a first electrode, a second electrode, and (a) an n-type layer and (b) the perovskite arranged between the first and second electrodes. It is an optoelectronic device.

0086As used herein, the term "n-type layer" refers to a layer containing an n-type or electron transport material.

0087Alternatively, the optoelectronic device of the present invention comprises a first electrode, a second electrode, and (a) a p-type layer and (b) the perovskite disposed between the first and second electrodes. It is an optoelectronic device.

0088As used herein, the term "p-type layer" refers to a layer containing a p-type or hole-transporting material.

0089In one embodiment, the optoelectronic device of the present invention is With the first electrode, With the second electrode Arranged between the first and second electrodes, (a) n-type layer (b) The perovskite and (c) With p-type layer It is an optoelectronic device including.

0090The optoelectronic device of this embodiment may be any of those listed above, such as a photovoltaic device. Perovskite is typically a sensitizer material.

0091As used herein, the term "sensitizer" refers to a material capable of photoinduced charge generation, photoelectron emission, or electron emission.

0092Often, the sensitizer is also capable of transporting charges (holes or electrons). For example, if the sensitizer is the perovskite, the sensitizer can also transport charges.

0093Usually, the n-type layer contains a metal oxide semiconductor, and the p-type layer contains a hole transport material. Metal oxide semiconductors and hole transport materials are as defined herein.

0094Alternatively, the p-type layer contains a metal oxide semiconductor and the n-type layer contains an electron transport material. For example, the metal oxide semiconductor may contain an oxide of nickel, molybdenum, copper, or vanadium, or a mixture thereof. Often the electron transport material is fullerene or perylene or a derivative thereof, poly {[N, N0-bis (2-octyldodecyl) -naphthalene-1,4,5,8-bis (dicarboxyimide) -2,6- Diyl] -alt-5,50-(2,20-bithiophene)} (P (NDI2OD-T2)), or contains electrolytes.

0095In one embodiment, the optoelectronic device may be a thin film device. Usually, the n-type layer will contain a metal oxide, a metal sulfide, a metal selenium, or a metal telluride. Often, metal oxides are oxides of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or mixtures thereof. For example, the n-type layer is TiO₂,SnO₂,ZnO,Nb₂O₅, Ta₂O₅,WHERE₃,IN₂O₅,In₂O₃, Ga₂O₃,Nd₂O₃, PbO, or CdO may be included. Often metal oxides are TiO₂Is. Typically, the sulfide will be a sulfide of cadmium, tin, copper, zinc, or a mixture thereof. For example, sulfide is FeS₂, CdS, or Cu₂ZnSnS₄It may be. Usually, the selenium is a selenium of cadmium, zinc, indium, or gallium, or a mixture thereof. For example, selenium is Cu (In, Ga) Se.₂It may be. Typically, the tellenide is a cadmium, zinc, cadmium, or tin terenide. For example, the telenide may be CdTe.

0096The optoelectronic device may include a tunnel junction. For example, the optoelectronic device may be a multi-junction solar cell or a tandem cell.

0097In one embodiment, the optoelectronic device of the present invention is With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) Porous layer of semiconductor and (b) With the sensitizer material containing the perovskite It is an optoelectronic device including.

0098Typically, the optoelectronic device of the present invention is located between a first electrode, a second electrode, and first and second electrodes, (a) a porous layer of semiconductor, (b) said. An optoelectronic device comprising a sensitizer material containing a perovskite and (c) a charge transport material.

0099The optoelectronic device of the present invention is, for example, With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) Porous layer of semiconductor, which is a porous layer of p-type semiconductor, (b) A sensitizer material containing the perovskite, and (c) With charge transport material, which is an electron transport material It may be an optoelectronic device including.

0100Generally, when the porous layer of a semiconductor is a porous layer of a p-type semiconductor, the porous layer contains an oxide of nickel, vanadium, copper, or molybdenum. For example, the porous layer is NiO, V₂O₅,MoO₃, Or CuO may be contained.

0101Typically, the porous layer of the p-type semiconductor contacts the dense layer of the p-type semiconductor. For example, the dense layer of a p-type semiconductor may contain oxides of nickel, vanadium, copper, or molybdenum. Normally, the dense layer of p-type semiconductors is NiO, V.₂O₅,MoO₃, Or contains CuO.

0102Often, when the charge transport material is an electron transport material, the charge transport material comprises fullerenes or perylenes or derivatives thereof, ie P (NDI2OD-T2). For example, the charge transport material may be P (NDI2OD-T2).

0103Alternatively, the optoelectronic device of the present invention is With the first electrode, With the second electrode Arranged between the first and second electrodes, (a) Porous layer of semiconductor, which is a porous layer of n-type semiconductor, (b) A sensitizer material containing the perovskite, and (c) With a charge transport material, which is a hole transport material It may be a photovoltaic device including.

0104Typically, when the porous layer of a semiconductor is a porous layer of an n-type semiconductor, the porous layer of the n-type semiconductor is titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium. , Palladium, or cadmium oxides, or mixtures thereof. For example, the porous layer of a semiconductor is TiO.₂,SnO₂,ZnO,Nb₂O₅, Ta₂O₅,WHERE₃,IN₂O₅,In₂O₃, Ga₂O₃,Nd₂O₃, PbO, or CdO may be included. Often, the porous layer of an n-type semiconductor contains mesoporous oxides of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or mixtures thereof.

0105As used herein, the term "mesoporous" means that the pores of the porous layer are microscopic and have a size, usually measured in nanometers (nm). The average pore size of the pores in the "mesoporous" structure may be, for example, in the range of 1 nm to 100 nm, or for example, in the range of 2 nm to 50 nm. The individual pores may be of different sizes or of any shape. The term "pore size" as used herein defines the size of the pores. For spherical pores, the pore size is equal to the diameter of the sphere. For non-spherical pores, the pore size is equal to the diameter of the sphere and the volume of the sphere is equal to the volume of the non-spherical pore. This definition of pore size applies to the pores in the mesoporous single crystal and the pores in the porous template.

0106Normally, when the porous layer of the semiconductor is the porous layer of the n-type semiconductor, the porous layer of the semiconductor is TiO.₂including. More usually, the porous layer is mesoporous TiO₂including.

0107Often, the porous layer of an n-type semiconductor contacts the dense layer of an n-type semiconductor. Usually, the dense layer of an n-type semiconductor contains an oxide of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or a mixture thereof. Typically, the dense layer of an n-type semiconductor is TiO.₂including. Generally, the dense layer of an n-type semiconductor has a thickness of 50 nm to 200 nm, typically about 100 nm.

0108When the charge transport material is a hole transport material, the hole transport material of the optoelectronic device of the present invention may be any suitable p-type or hole transport semiconductor material. Typically, the hole transport material is a small molecule or polymer based hole conductor.

0109Typically, when the charge transport material is a hole transport material, the charge transport material is a solid hole transport material or a liquid electrolyte.

0110Often, when the charge transport material is a hole transport material, the charge transport material is a polymer or molecular hole transporter. Typically, the hole transport material is spiro-OMeTAD (2,2', 7,7'-tetrax- (N, N-di-p-methoxyphenylamine) 9,9'-spirobifluorene)). , P3HT (poly (3-hexylthiophene)), PCPDTBT (poly [2,1,3-benzothiasiazol-4,7-diyl [4,4-bis (2-ethylhexyl))-4H-cyclopentane [2,1- b: 3,4-b'] Dithiophene-2,6-diyl]]), PVK (poly (N-vinylcarbazole)), HTM-TFSI (1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl)) ) Imid), Li-TFSI (lithium bis (trifluoromethanesulfonyl) imide), or tBP (tert-butyl pyridine). Usually, the hole transport material is selected from spiro-OMeTAD, P3HT, PCPDTBT, and PVK. Preferably, the hole transport material is spiro-OMeTAD.

0111When the charge transport material is a hole transport material, the charge transport material is, for example, a molecular hole transporter or a polymer or copolymer. Often, the charge-transporting material is a molecular hole-transporting material, and the polymer or copolymer has the following parts: thiophenyl, phenalenyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrolyl, ethoxydithiophenyl, amino, triphenylamino. , Carbozolyl, ethylenedioxythiophenyl, dioxythiophenyl, or fluorenyl.

0112Alternatively, when the charge transport material is a hole transport material, the charge transport material is an inorganic hole transporter such as CuI, CuBr, CuSCN, Cu.₂It may be O, CuO, or CIS.

0113In one embodiment, in the optoelectronic device of the present invention, the porous layer of the semiconductor may have a thickness of 50 nm to 3 μm, for example 100 nm to 2 μm. Often the porous layer of an n-type semiconductor has a thickness of 0.6 μm.

0114Typically, the optoelectronic device of the present invention has a distance between the second electrode and the porous layer of the n-type semiconductor of 50 nm to 400 nm, more typically 150 nm to 250 nm. Often, the distance between the second electrode and the porous layer of the n-type semiconductor is on the order of 200 nm.

0115Often, the optoelectronic device of the present invention is a device AM1.5G 100mWcm^-2It is a photovoltaic device with a power conversion efficiency of 7.3% or more. Typically, the device AM1.5G 100mWcm^-2The power conversion efficiency is 11.5% or more.

0116Typically, the optoelectronic device of the present invention has a photocurrent of 15 mA cm.^-2The above photovoltaic device. More typically, the optoelectronic device of the present invention has a photocurrent of 20 mA cm.^-2The above photovoltaic device.

0117Generally, in the optoelectronic device of the present invention, perovskite does not decompose when exposed to oxygen or moisture for a time of 10 minutes or longer. Typically, perovskite does not decompose when exposed to oxygen or moisture for more than 24 hours.

0118The present invention further describes the formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₁R₂R₃R₄N)⁺At least one of the organic cations, where (i) R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is the two or more different halide anions mentioned above] To provide a mixed halide perovskite.

0119The following proviso usually applies: (i) A is (CH₃SMALL₃)⁺Is an organic cation and B is Sn²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of (a) chloride and bromide ions, or (b) bromide and iodide ions. (ii) A is (CH₃SMALL₃)⁺Is an organic cation and B is Pb²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of chloride and bromide ions.

0120Often, mixed halide perovskite is expressed in formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₁R₂R₃R₄N)⁺At least one of the organic cations of (i) R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is the two or more different halide anions mentioned above] It is a mixed halide perovskite.

0121The following proviso usually applies: (i) A is (CH₃SMALL₃)⁺Is an organic cation and B is Sn²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of (a) chloride and bromide ions, (b) bromide and iodide ions or (c) chloride and iodide ions. , (ii) A is (CH₃SMALL₃)⁺Is an organic cation, and B is Pb.²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of chloride and bromide ions.

0122Often, mixed halide perovskite is expressed in formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₁R₂R₃R₄N)⁺At least one of the organic cations, where (i) R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is the two or more different halide anions mentioned above. However, (i) [A] is (CH₃SMALL₃)⁺Is a single organic cation, and [B] is Sn²⁺In the case of a single metal cation, the mixed halide perovskite is (a) free of chloride and bromide ions, or (b) bromide and iodide, and (ii) [A] is (ii) [A]. CH₃SMALL₃)⁺Is a single organic cation and [B] is Pb²⁺If it is a single metal cation, it is assumed that the mixed halide perovskite is free of chloride and bromide ions] It is a mixed halide perovskite.

0123The perovskite of formula (I) may contain 1, 2, 3, or 4 different divalent metal cations, typically 1 or 2 different divalent metal cations. The perovskite of equation (I) is, for example, equation (R).₁R₂R₃R₄N)⁺1, 2, 3, or 4 different organic cations, typically the formula (R)₁R₂R₃R₄N)⁺It may contain one or two different organic cations of. The perovskite of formula (I) may contain, for example, 2, 3, or 4 different halide anions, typically 2 or 3 different halide anions.

0124Often, in the mixed halide perovskite of the present invention, [B] is Pb.²⁺In the case of a single metal cation, one of the two or more different halide anions is iodide or fluoride; [B], but Sn.²⁺In the case of a single metal cation, one of the two or more different halide anions is a fluoride.

0125Typically, in the mixed halide perovskite of the present invention, one of the two or more different halide anions is iodide or fluoride.

0126Usually, in the mixed halide perovskite of the present invention, one of the two or more different halide anions is fluoride.

0127Typically, in the mixed halide perovskite of the present invention, [X] is two different halide anions X and X'. Typically, these are two or three halide anions, and more typically two different halogenated anions. Usually, the halide anion is selected from fluoride, chloride, bromide, and iodide, such as chloride, bromide, and iodide. Alternatively, [X] may be three different halide ions.

0128Usually, in the mixed halide perovskite of the present invention, [B] is Ca.²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺At least one divalent metal cation selected from. More usually, [B] is Sn²⁺And Pb²⁺At least one divalent metal cation selected from.

0129Typically, [B] is a single divalent metal cation. A single divalent metal cation is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺May be selected from. More usually, [B] is Sn²⁺Or Pb²⁺Is a single divalent metal cation.

0130Primarily, in the mixed halide perovskite of the present invention, R in organic cations₁Is hydrogen, methyl, or ethyl, R₂Is hydrogen, methyl, or ethyl, R₃Is hydrogen, methyl, or ethyl, R₄Is hydrogen, methyl, or ethyl. For example, R₁Can be hydrogen or methyl, R₂Can be hydrogen or methyl, R₃Can be hydrogen or methyl, R₄May be hydrogen or methyl.

0131Typically, in the mixed halide perovskite of the present invention, the organic cation is of formula (R).₅SMALL₃)⁺Has, in the formula, R₅Is hydrogen, or unsubstituted or substituted C₁~C₂₀It is alkyl. R₅May be, for example, methyl or ethyl. Typically R₅Is methyl.

0132In one embodiment, the mixed halide perovskite of the present invention is of formula (II). ABX_3-yX_Y (II) [In the formula, A is an organic cation B is a divalent metal cation, X is the first halide anion, X'is a second halide anion that is different from the first halide anion, y is 0.05 to 2.95, However, (i) A is (CH₃SMALL₃)⁺Is an organic cation and B is Sn²⁺In the case of a divalent metal cation, the mixed halide perovskite is free of (a) chloride and bromide ions, or (b) bromide and iodide ions. (ii) A is (CH₃SMALL₃)⁺Is an organic cation and B is Pb²⁺If it is a divalent metal cation, it is assumed that the mixed halide perovskite is free of chloride and bromide ions] Perovskite compound.

0133Usually y is 0.5 to 2.5, for example 0.75 to 2.25. Typically, y is 1 to 2.

0134Typically, X is iodide and X'is fluoride or chloride, or X is fluoride and X'is chloride, bromide, or iodide.

0135Often, X or X'is an iodide.

0136Typically, B is Sn²⁺Other than.

0137Usually, in the mixed halide perovskite of the present invention, X is iodide and X'is fluoride or chloride.

0138More usually, X or X'is a fluoride.

0139Typically, in the mixed halide perovskite of the present invention, B is Sn.²⁺Is.

0140Alternatively, in the mixed halide perovskite of the present invention, B is Pb.²⁺Is.

0141The mixed halide perovskite of the present invention is often CH.₃SMALL₃PbBrI₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnICl₂, CH₃SMALL₃SnF₂I,CH₃SMALL₃SnI₂Cl and CH₃SMALL₃SnF₂Selected from Cl. More often, the mixed halide perovskites of the present invention are often CH.₃SMALL₃PbBrI₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnF₂I and CH₃SMALL₃SnF₂Selected from Cl. Normally, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃SnF₂Br and CH₃SMALL₃SnF₂Selected from I.

0142Generally, the mixed halide perovskite of the present invention does not decompose when exposed to oxygen or moisture for more than 10 minutes. Typically, perovskite does not decompose when exposed to oxygen or moisture for more than 24 hours.

0143The present invention further describes the formula (I). [A][B][X]₃ (I) [In the formula, [A] is the formula (R₅R₆N=CH-NR₇R₈)⁺At least one of the organic cations, where (i) R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, [B] is at least one divalent metal cation, [X] is two or more different halide anions] To provide a mixed halide perovskite.

0144The perovskite of formula (I) may contain 1, 2, 3, or 4 different divalent metal cations, typically 1 or 2 different divalent metal cations. The perovskite of equation (I) is, for example, equation (R).₅R₆N=CH-NR₇R₈)⁺1, 2, 3, or 4 different organic cations, typically the formula (R)₅R₆N=CH-NR₇R₈)⁺It may contain one or two different organic cations of. The perovskite of formula (I) may contain, for example, 2, 3, or 4 different halide anions, typically 2 or 3 different halide anions.

0145Typically, [X] is two different halide anions X and X'. Typically, these are two or three halide anions, more typically two different halide anions. Usually, the halide anion is selected from fluoride, chloride, bromide, and iodide, such as chloride, bromide, and iodide. The halide anion may be, for example, iodine or bromine. Alternatively, [X] may be three different halide ions.

0146Usually [B] is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺At least one divalent metal cation selected from. More usually, [B] is Sn²⁺And Pb²⁺At least one divalent metal cation selected from, eg Pb²⁺Is.

0147Typically, [B] is a single divalent metal cation. A single divalent metal cation is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺May be selected from. More usually, [B] is Sn²⁺Or Pb²⁺Is a single divalent metal cation, eg Pb²⁺Is.

0148Primarily, in the mixed halide perovskite of the present invention, R in organic cations₅Is hydrogen, methyl, or ethyl, R₆Is hydrogen, methyl, or ethyl, R₇Is hydrogen, methyl, or ethyl, R₈Is hydrogen, methyl, or ethyl. For example, R₅Can be hydrogen or methyl, R₆Can be hydrogen or methyl, R₇Can be hydrogen or methyl, R₈May be hydrogen or methyl.

0149Typically, in the mixed halide perovskite of the present invention, the organic cation is of formula (H).₂N=CH-SMALL₂)⁺Have.

0150In one embodiment, the mixed halide perovskite is of formula (IIa). ABX_3zX_{3 (1-d)} (IIa) [In the formula, A is the formula (R₅R₆N=CH-NR₇R₈)⁺Is an organic cation, where (i) R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii)R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, B is Sn²⁺And Pb²⁺Is a metal cation selected from X is the first halide anion, X'is a second halide anion that is different from the first halide anion, z is greater than 0 and less than 1] Perovskite compound.

0151Usually z is 0.05 to 0.95, for example 0.1 to 0.9. z may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or z may be from any one of these values to any other of these values. It may be in the range of values (eg, 0.2 to 0.7, or 0.1 to 0.8).

0152Typically, X is iodide and X'is fluoride, bromide, or chloride, for example X is iodide and X'is bromide.

0153Typically, B is Pb²⁺Is.

0154Organic cations are usually (R)₅R₆N=CH-NR₇R₈)⁺[In the formula, R₅,R₆,R₇, And R₈Independently, hydrogen, and unsubstituted or substituted C₁~C₆Selected from alkyl]. For example, the organic cation is (H₂N=CH-SMALL₂)⁺It may be.

0155The mixed halide perovskite is described, for example, by the formula (H).₂N=SMALL₂)PbI_3zBr_{3 (1-d)}In the equation, z is greater than 0 and less than 1. Usually z is 0.05 to 0.95, for example 0.1 to 0.9. z is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or z is from any one of these values to any other of these values. It may be in the range (eg, z may be 0.2 to 0.7, or 0.1 to 0.8).

0156Generally, the mixed halide perovskite of the present invention does not decompose when exposed to oxygen or moisture for more than 10 minutes. Typically, perovskite does not decompose when exposed to oxygen or moisture for more than 24 hours.

0157The present invention further provides the use of mixed anion perovskite as a sensitizer in optoelectronic devices, the mixed anion perovskite comprising two or more different anions selected from halide anions and chalcogenide anions. A perovskite is a perovskite as defined herein.

0158Often, in the use of the present invention, the optoelectronic device is a photovoltaic device.

0159Alternatively, in the use of the present invention, the optoelectronic device is a light emitting device, such as a light emitting diode.

0160Generally, the optoelectronic device of the present invention is a photovoltaic device, AM1.5G 100mWcm of the device.^-2The power conversion efficiency is 7.3% or more. Typically, the device AM1.5G 100mWcm^-2The power conversion efficiency is 11.5% or more.

0161Typically, the optoelectronic device of the present invention has a photocurrent of 15 mA cm.^-2The above photovoltaic device. More typically, the optoelectronic device of the present invention has a photocurrent of 20 mA cm.^-2The above photovoltaic device.

0162The present invention also provides photosensitizers for optoelectronic devices, including mixed anion perovskite, which comprises two or more different anions selected from halide anions and chalcogenide anions. A perovskite is a perovskite as defined herein.

0163The optoelectronic device of the present invention may further include encapsulated metal nanoparticles. For example, the optoelectronic device of the present invention may further include encapsulated metal nanoparticles disposed between the first and second electrodes.

0164The mixed anion perovskite used in the devices of the present invention, i.e., a perovskite containing two or more different anions selected from halide anions and chalcogenide anions. With (a) a first compound containing (i) a first cation and (ii) a first anion, With (i) a second cation and (ii) a second compound containing a second anion Is the step of mixing The first and second cations are as defined herein and Steps where the first and second anions are different anions selected from halide anions and chalcogenide anions It can be generated by a method including. Typically, the first and second anions are different anions selected from the halide anions.

0165Alternatively, this method involves (1) (i) a first cation and (ii) a first compound containing (ii) a first anion, (i) a second cation and (ii) a first anion. (B) A step of treating with a second compound to produce a first product, wherein the first and second cations are as defined herein and the first. The anion is a step selected from a halide anion and a chalcogenide anion, and (i) a first compound containing (2) (i) a first cation and (ii) a second anion, and (i) a second. A step of treating with a cation and (ii) a second compound containing a second anion to produce a second product, wherein the first and second cations are defined herein. As done, the second anion may include a step in which the halide anion and the chalcogenide anion are selected. Usually, the first and second anions are different anions selected from halide anions and chalcogenide anions. Typically, the first and second anions are different anions selected from the halide anions. This method is usually the step of treating the first product of the first quantity with the second product of the second quantity, whether the first and second quantities are the same or different. Includes more good steps.

0166The mixed anion perovskite produced by this method may contain other cations or other anions. For example, the mixed anion perovskite may contain 2, 3, or 4 different cations, or 2, 3, or 4 different anions. Therefore, the method for producing a mixed anion perovskite may include the step of mixing other cations or other compounds containing other anions. In addition or as an alternative, methods for producing mixed anion perovskite comprises (a) and (b) and (i) a first cation and (ii) a second anion (c) a third compound. , Or may include the step of mixing (i) a second cation and (ii) a fourth compound containing a first anion.

0167Typically, in the method for producing a mixed anion perovskite, the second cation in the mixed anion perovskite is a metal cation. More typically, the second cation is a divalent metal cation. For example, the first cation is Ca²⁺, Sr²⁺,Cd²⁺,With²⁺, Ni²⁺,Mn²⁺,Fe²⁺,What²⁺, Pd²⁺,Give²⁺,Sn²⁺,Pb²⁺,Sn²⁺,Yb²⁺, And Eu²⁺May be selected from. Usually the second cation is Sn²⁺And Pb²⁺Is selected from.

0168Often, in methods for producing mixed anion perovskite, the first cation in the mixed anion perovskite is an organic cation.

0169Usually, the organic cation is of the formula (R).₁R₂R₃R₄N)⁺Have, Where, R₁Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₂Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₃Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₄Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl.

0170Mainly in organic cations, R₁Is hydrogen, methyl, or ethyl, R₂Is hydrogen, methyl, or ethyl, R₃Is hydrogen, methyl, or ethyl, R₄Is hydrogen, methyl, or ethyl. For example R₁Can be hydrogen or methyl, R₂Can be hydrogen or methyl, R₃Can be hydrogen or methyl, R₄May be hydrogen or methyl.

0171Alternatively, the organic cation is of the formula (R)₅SMALL₃)⁺[In the formula, R₅Is hydrogen, or unsubstituted or substituted C₁~C₂₀It is alkyl]. For example R₅May be methyl or ethyl. Typically R₅Is methyl.

0172In another embodiment, the organic cation is of formula (R).₅R₆N=CH-NR₇R₈)⁺Has, in the formula, R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl. Organic cations are, for example, (R₅R₆N=CH-NR₇R₈)⁺And in the formula, R₅,R₆,R₇, And R₈Independently, hydrogen, unsubstituted or substituted C₁~C₂₀It may be selected from alkyl or unsubstituted or substituted aryl. For example, organic cations are (H₂N=CH-SMALL₂)⁺It may be.

0173In a method for producing a mixed anion perovskite, the perovskite is usually a mixed anion perovskite, wherein the two or more different anions are two or more different halide anions.

0174Typically, in the method for producing mixed anion perovskite, the perovskite is of formula (I). [A][B][X]₃ (I) [In the formula, [A] is at least one organic cation [B] is at least one metal cation, [X] is the two or more different anions mentioned above] Perovskite compound, This method With (a) a first compound containing (i) a metal cation and (ii) a first anion, With (i) organic cations and (ii) second compounds containing (ii) second anions Including the step of mixing The first and second anions are different anions selected from halide anions or chalcogenide anions.

0175The perovskite of formula (I) may contain, for example, 1, 2, 3, or 4 different metal cations, typically 1 or 2 different metal cations. The perovskite of formula (I) may contain, for example, 1, 2, 3, or 4 different organic cations, typically 1 or 2 different organic cations. The perovskite of formula (I) may contain, for example, 2, 3, or 4 different anions, typically 2 or 3 different anions. Therefore, the method may include mixing other compounds, including cations and anions.

0176Typically, [X] is two or more different halide anions. Therefore, the first and second anions are typically halide anions. Alternatively, [X] may be three different halide ions. Therefore, the method may include mixing the third compound with the first and second compounds, the third compound being (i) anion and (ii) a third halogen. A compound anion is included, and the third anion is a halide anion different from the first and second halide anions.

0177Often, in the method for producing mixed anion perovskite, the perovskite is of formula (IA). AB [X]₃ (HE) [In the formula, A is an organic cation B is a metal cation, [X] is the two or more different anions mentioned above] Perovskite compound, This method With (a) a first compound containing (i) a metal cation and (ii) a first halide anion, With (i) a second compound containing (i) an organic cation and (ii) a second halide anion Including the step of mixing The first and second halide anions are different halide anions.

0178Usually, [X] is two or more different halide anions. Preferably, [X] is two or three different halide anions. More preferably, [X] is two different halide anions. In another embodiment, [X] is three different halide anions.

0179Typically, in the method for producing mixed anion perovskite, the perovskite is expressed in equation (II). ABX_3-yX_Y (II) [In the formula, A is an organic cation B is a metal cation, X is the first halide anion, X'is a second halide anion that is different from the first halide anion, y is 0.05 to 2.95] Perovskite compound, This method With (a) the first compound containing (i) metal cations and (ii) X, With (i) organic cations and (ii) a second compound containing (ii) X' Including the step of mixing X'is different from X The ratio of X to X'in the mixture is equal to (3-y): y.

0180(3-y): In order to achieve the above ratio of X to X'equal to y, this method may include mixing the other compounds with the first and second compounds. .. For example, the method may include mixing the third compound with the first and second compounds, where the third compound is (i) a metal cation and (ii) X'. Is included. Alternatively, the method comprises mixing a third compound with the first and second compounds, the third compound comprising (i) an organic cation and (ii) X. You may.

0181Usually y is 0.5 to 2.5, for example 0.75 to 2.25. Typically, y is 1 to 2.

0182Typically, in the method for producing mixed anion perovskite, the first compound is BX.₂And the second compound is AX'.

0183Often, the second compound is of formula (R)₅SMALL₂), And R in the formula₅Is hydrogen, or unsubstituted or substituted C₁~C₂₀It is produced by reacting a compound that is alkyl with a compound of formula HX'. Typically R₅Can be methyl or ethyl, often R₅Is methyl.

0184Normal, formula (R₅SMALL₂) And the compound of formula HX'react in a molar ratio of 1: 1. Often the reaction occurs in a nitrogen atmosphere and usually in absolute ethanol. Typically, absolute ethanol is about 200 proof. More typically, the equation (R)₅SMALL₂) Compounds 15 to 30 ml and HX'about 15 to 15 ml are reacted in a nitrogen atmosphere, usually in 50 to 150 ml of absolute ethanol. The method may include the step of recovering the mixed anion perovskite. Rotary evaporators are often used to extract crystalline AX'.

0185Usually, the step of mixing the first and second compounds is the step of dissolving the first and second compounds in a solvent. The first and second compounds may be dissolved in a ratio of 1:20 to 20: 1, typically in a ratio of 1: 1. Typically, the solvent is dimethylformamide (DMF) or water. Metal cation is Pb²⁺If, the solvent is usually dimethylformamide. The metal cation is Sn²⁺If, the solvent is usually water. The use of DMF or water as a solvent is advantageous as these solvents are not very volatile.

0186Often, in the method for producing mixed anion perovskite, [B] is Pb.²⁺Is a single metal cation of, and one of the two or more different halide anions is iodide or fluoride; [B], but Sn²⁺In the case of a single metal cation, one of the two or more different halogenated anions is fluoride.

0187Typically, in the method for producing mixed anion perovskite, X or X'is iodide. Alternatively, X or X'is a fluoride.

0188Often, in the method for producing mixed anion perovskite, perovskite is CH.₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnBrI₂, CH₃SMALL₃SnBrCl₂, CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnIBr₂, CH₃SMALL₃SnICl₂, CH₃SMALL₃SnF₂I,CH₃SMALL₃SnClBr₂, CH₃SMALL₃SnI₂Cl and CH₃SMALL₃SnF₂A perovskite selected from Cl. Typically, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnICl₂, CH₃SMALL₃SnF₂I,CH₃SMALL₃SnI₂Cl and CH₃SMALL₃SnF₂Selected from Cl. More typically, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃PbClBr₂, CH₃SMALL₃PbI₂Cl,CH₃SMALL₃SnF₂Br,CH₃SMALL₃SnF₂I and CH₃SMALL₃SnF₂Selected from Cl. Normally, perovskite is CH₃SMALL₃PbBrI₂, CH₃SMALL₃PbBrCl₂, CH₃SMALL₃PbIBr₂, CH₃SMALL₃PbICl₂, CH₃SMALL₃SnF₂Br and CH₃SMALL₃SnF₂Selected from I.

0189In some embodiments, in a method for producing a mixed anion perovskite, the perovskite is of formula (IIa). ABX_3zX_{3 (1-d)} (IIa) [In the formula, A is the formula (R₅R₆N=CH-NR₇R₈)⁺Is an organic cation, where (i) R₅Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (ii) R₆Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iii) R₇Is hydrogen, unsubstituted or substituted C₁~C₂₀Alkyl, or unsubstituted or substituted aryl, (iv) R₈Is hydrogen, unsubstituted or substituted C₁~C₂₀A cation that is alkyl, or unsubstituted or substituted aryl, B is Sn²⁺And Pb²⁺Is a metal cation selected from X is the first halide anion, X'is a second halide anion that is different from the first halide anion, z is greater than 0 and less than 1] It is a perovskite compound and This method The first compound, which contains (1) (i) metal cations and (ii) X, is treated with (i) the first compound, which contains (i) organic cations and (ii) X, and (b) the second compound. And the steps to generate the product of The (i) first compound containing (i) metal cations and (ii) X'was treated with (i) the second compound containing (i) organic cations and (ii) X'. The steps to generate the second product, (3) It is a step of treating the first product of the first quantity with the second product of the second quantity, and the first and second quantities may be the same or different. With steps including.

0190Generally, z is 0.05 to 0.95, and z may be as further defined above.

0191In a method for producing a mixed anion perovskite, the perovskite is described, for example, in the formula (H).₂N=CH-SMALL₂)PbI_3zBr_{3 (1-d)}In the equation, z is as defined above.

0192The methods for producing photoelectronic devices are usually: photovoltaic devices; photodiodies; optical transistors; photomultiplier tubes; photomultiplier tubes; photodetectors; photodetectors; solid triodes; battery electrodes; light emitting devices; A method for producing devices selected from light emitting diodes; transistors; solar cells; lasers; and diode injection lasers. Typically, the optoelectronic device is a photovoltaic device.

0193Usually, the method for producing an optoelectronic device is a method for producing a photovoltaic device. More usually, the device is a solar cell.

0194Alternatively, the method for producing the optoelectronic device may be a method for producing a light emitting device, for example, a light emitting diode.

0195A method for producing optoelectronic devices, in which optoelectronic devices are With the first electrode, With the second electrode, Arranged between the first and second electrodes, (a) With the perovskite Methods that include are usually (i) The step of providing the first electrode and (ii) The step of depositing the perovskite and (iii) With the step of providing the second electrode It is a method including.

0196As will be appreciated by those skilled in the art, the methods for producing optoelectronic devices will vary depending on the optoelectronic device being manufactured, especially depending on the various components of the device. .. The methods discussed and embodied below are (a) n-type layers and (b) the perovskite located between the first electrode, the second electrode, and the first and second electrodes. And (c) a method for producing an optoelectronic device, including a p-type layer. However, as will be appreciated by those skilled in the art, the same method may be used to produce other devices of the invention with different components and different laser structures. These include, for example, the optoelectronic device of the present invention, including, for example, a first electrode, a second electrode, and (a) a thin film containing the perovskite disposed between the first and second electrodes. Is done. Further, the method described in the present specification includes (a) a semiconductor layer and (b) the perovskite arranged between the first electrode, the second electrode, and the first and second electrodes. An optoelectronic device comprising, or a photoelectron comprising (a) an n-type layer and (b) said perovskite disposed between a first electrode, a second electrode, and the first and second electrodes. The optoelectronic device, which can be used to generate the device, is located between the first electrode, the second electrode, and the first and second electrodes, (a) p-type layer and (b) The perovskite may be included.

0197A method for producing optoelectronic devices, in which optoelectronic devices are With the first electrode, With the second electrode Arranged between the first and second electrodes, (a) n-type layer, (b) The perovskite and (c) With p-type layer Methods that include are usually (i) The step of providing the first electrode and (ii) Steps to deposit layers of n-type material, (iii) The step of depositing the perovskite and (iv) Steps to deposit layers of p-type material, (v) With the step of providing the second electrode It is a method including.

0198The first and second electrodes are the anode and cathode, one or both of which are transparent to allow light to enter. What is selected for the first and second electrodes of the optoelectronic device of the present invention may depend on the structural type. Typically, the n-type layer is deposited on tin oxide, more typically on a fluorine-doped tin oxide (FTO) anode, which is usually a transparent or translucent material. .. Therefore, the first electrode is usually transparent or translucent and typically contains an FTO. Generally, the thickness of the first electrode is 200 nm to 600 nm, and more usually 300 to 500 nm. For example, the thickness may be 400 nm. Typically, the FTO is coated on the glass plate. Often, TFO-coated glass plates are etched with zinc powder and acid to produce the required electrode pattern. Usually, the acid is HCl. Often, the concentration of HCl is about 2 mol. Typically, these glass plates are cleaned and then usually treated under oxygen plasma to remove any organic residues. Treatment under oxygen plasma typically lasts less than an hour, typically about 5 minutes.

0199Usually, the second electrode contains a metal with a high work function, such as gold, silver, nickel, palladium, or platinum, typically silver. Usually, the thickness of the second electrode is 50 nm to 250 nm, and more usually 100 nm to 200 nm. For example, the thickness of the second electrode may be 150 nm.

0200Usually, the n-type layer contains a metal oxide semiconductor, and the p-type layer contains a hole transport material. Metal oxide semiconductors and hole transport materials are as defined herein.

0201Alternatively, the p-type layer contains a metal oxide semiconductor and the n-type layer contains an electron transport material. For example, the metal oxide semiconductor may contain an oxide of nickel, molybdenum, copper, or vanadium, or a mixture thereof. Often, electron transport materials include fullerenes or perylenes, or derivatives thereof, ie P (NDI2OD-T2). For example, the electron transport material may be P (NDI2OD-T2).

0202In one embodiment, the optoelectronic device may be a thin film device. Usually, the n-type layer will contain metal oxides, sulfides, serenes, or tellurides. Often, metal oxides are oxides of titanium, tin, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or mixtures thereof. For example, the n-type layer is TiO₂,SnO₂,ZnO,Nb₂O₅, Ta₂O₅,WHERE₃,IN₂O₅,In₂O₃, Ga₂O₃,Nd₂O₃, PbO, or CdO may be included. Often the metal oxide is TiO₂Is. Typically, the sulfide will be a sulfide of cadmium, tin, copper, or a mixture thereof. For example, sulfide is FeS₂, CdS, or Cu₂ZnSnS₄It may be. Usually, the selenium is a selenium of cadmium, zinc, indium, or gallium, or a mixture thereof. For example, selenium is Cu (In, Ga) Se₂It may be. Typically, the telenide is a cadmium, zinc, cadmium, or tin telenide. For example, the telenide may be CdTe.

0203The optoelectronic device may include a tunnel junction. For example, the optoelectronic device may be a multi-junction solar cell or a tandem cell.

0204In one embodiment of the method for generating a photovoltaic device, the device is: With the first electrode, With the second electrode Arranged between the first and second electrodes, (a) Porous layer of semiconductor, (b) A sensitizer material containing the perovskite, and (c) With charge transport material Including, this method (i) The step of providing the first electrode and (ii) Steps to deposit the porous layer of the semiconductor, (iii) The step of depositing the sensitizer containing the perovskite, and (iv) Steps to deposit charge transport material and (v) With the step of providing the second electrode including.

0205Usually, the porous layer of a semiconductor contains an oxide of titanium, aluminum, tin, zinc, or magnesium. The porous layer may contain a mixture of oxides of titanium, aluminum, tin, zinc, or magnesium. Typically, the porous layer comprises an oxide of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or a mixture thereof. For example, the layer is TiO₂,SnO₂,ZnO,Nb₂O₅, Ta₂O₅,WHERE₃,IN₂O₅,In₂O₃, Ga₂O₃,Nd₂O₃, PbO, or CdO may be included. Typically, the porous layer of the semiconductor is TiO₂including. More typically, the porous layer of the semiconductor is a mesoporous TiO.₂including.

0206Metal oxide pastes are typically used to form a porous layer of metal oxide. More typically, TiO₂Nanoparticle paste is used. The volume of the porous layer of the semiconductor usually includes the steps of doctor blade coating, screen printing, or spin coating of the paste. The porous layer of the semiconductor usually has a thickness of 50 nm to 3 μm, for example, the thickness may be 200 nm to 2 μm. Often, the layer thickness may be 0.6 μm. Usually, in the step of depositing the porous layer of an n-type semiconductor, the layer is heated to a first temperature of 400 to 600 ° C, typically to a temperature of about 500 ° C. The temperature of the porous layer of the semiconductor is slowly raised to the first temperature, typically over 15 to 45 minutes, typically about 30 minutes.

0207Typically, the step of depositing the porous layer of the semiconductor further comprises the step of surface treating the layer of the semiconductor. The surface treatment step may be used to improve the packing of the sensitizer in the semiconductor layer. In addition or as an alternative, the surface treatment step may be to provide a blocking layer between the sensitizers in the semiconductor layer. C₆₀The self-assembled single layer of the above may be used as the blocking layer. Often, the composition used in the surface treatment step is C₆₀, Metal chlorides, metal oxides, dyes, and CDCA. Metal oxides include, for example, MgO, SiO₂, NiO, and Al₂O₃May be selected from. Often, metal chlorides are expressed in formula MY₄In the formula, M is a metal cation, typically Ti.⁴⁺And X is a halide anion, typically a chloride. Usually, the semiconductor layer is placed in a solution of metal chloride. Often the solution is TiCl₄A solution of 0.005 to 0.03 M of the aqueous solution of. More often, the solution is TiCl₄It is a solution of about 0.015M of the aqueous solution of. Layers of n-type semiconductors are typically placed in solution for 30 minutes to 2 hours, typically about 1 hour. The solution is usually at a first temperature of 50 to 100 ° C, usually about 70 ° C. Often the semiconductor layer is of formula MY₄After being placed in the solution of, the layers are typically washed with deionized water. The semiconductor layer may then be dried in air and / or heated to a second temperature of at least 500 ° C, typically 500 to 600 ° C. For example, the semiconductor layer may be heated to a second temperature of about 500 ° C. The layer of the n-type semiconductor may remain retained at the second temperature for at least 30 minutes. Typically, the residence time is 30 minutes to 2 hours, usually about 45 minutes. Often, the semiconductor layer is at a second temperature and the layer is exposed to airflow. The semiconductor layer is then typically cooled to a third temperature of 50 to 150 ° C, typically a third temperature of about 70 ° C. The semiconductor layer is then usually left in the dye solution for 5 to 24 hours, typically about 12 hours.

0208The semiconductor layer is typically deposited on a dense layer of semiconductor. Usually, the dense layer of a semiconductor contains oxides of titanium, tin, zinc, niobium, tantalum, tungsten, indium, gallium, neodymium, palladium, or cadmium, or mixtures thereof. For example, the layer is TiO₂,SnO₂,ZnO,Nb₂O₅, Ta₂O₅,WHERE₃,IN₂O₅,In₂O₃, Ga₂O₃,Nd₂O₃, PbO, or CdO may be included. Typically, the dense layer of the semiconductor is TiO₂including. Often a dense layer is deposited on the first electrode. Therefore, methods for producing photovoltaic devices typically include the step of depositing a dense layer of semiconductor.

0209The step of depositing the dense layer of the semiconductor may include, for example, the step of depositing the dense layer of the semiconductor by aerosol spray pyrolysis deposition. Typically, aerosol spray pyrolysis deposits of a solution containing titanium diisopropoxide bis (acetylacetonate), usually at a temperature of 200-300 ° C, often at a temperature of about 250 ° C. Including sedimentation. Usually, the solution contains titanium diisopropoxide bis (acetylacetonate) and ethanol, typically in a ratio of 1: 5 to 1:20, more typically in a ratio of about 1:10.

0210Often, the step of depositing a dense layer of semiconductor is the step of depositing a dense layer of semiconductor with a thickness of 50 nm to 200 nm, typically about 100 nm.

0211In the step of depositing a sensitizer containing the perovskite, the perovskite is the perovskite described herein. The step of depositing the sensitizer containing the perovskite usually includes the step of depositing the sensitizer on the porous layer of the semiconductor. Often, the step of depositing a sensitizer containing the perovskite comprises a step of spin-coating the perovskite. Spin coating is usually performed in air at a speed of typically 1000 to 2000 rpm, more typically at a speed of about 1500 rpm, and / or often for 15 to 60 seconds, usually for about 30 seconds. .. The sensitizer is usually placed in a solvent prior to spin coating. Usually, the solvent is DMF, typically the volume of solution used is 1 to 200 μl, more typically 20 to 100 μl. The concentration of the solution is often 1 to 50% by volume of perovskite, usually 5 to 40% by volume. The solution is, for example, metered onto a layer of the porous layer of semiconductor prior to spin coating and left to stand for about 5 to 50 seconds, typically about 20 seconds. After spin coating the sensitizer, the layer of sensitizer containing the perovskite is typically arranged at a temperature of 75 to 125 ° C, more typically at a temperature of about 100 ° C. The layer of sensitizer containing the perovskite is then left at this temperature for at least 30 minutes, more usually for 30-60 minutes. Often, the layer of sensitizer containing the perovskite is left at this temperature for about 45 minutes. Typically, the layer of sensitizer containing the perovskite will change color from, for example, light yellow to dark brown. The discoloration may be used to indicate the formation of the desired sensitizer layer.

0212Normally, the perovskite in the sensitizer does not decompose when exposed to oxygen or moisture for more than 10 minutes. Typically, perovskite does not decompose when exposed to oxygen or moisture for more than 24 hours.

0213Often, the step of depositing the sensitizer containing the perovskite may include the step of depositing the perovskite and the single anion perovskite, wherein the single anion perovskite has a first cation and a second cation. And anions selected from halide anions and chalcogenide anions, the first and second cations are as defined herein with respect to the mixed anion perovskite. For example, the sensitizer is CH₃SMALL₃PbICl₂And CH₃SMALL₃PbI₃; CH₃SMALL₃PbICl₂And CH₃SMALL₃PbBr₃; CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbI_3;Or CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbBr₃May include.

0214Alternatively, the step of depositing the sensitizer containing the perovskite may include the step of depositing a plurality of perovskites, each perovskite being a mixed anion perovskite, the mixed anion perovskite defined herein. It's a street. For example, the sensitizer may contain two or three of the perovskites. The sensitizer may contain two types of perovskite, both of which are mixed anionic perovskites. For example, the sensitizer is CH₃SMALL₃PbICl₂And CH₃SMALL₃PbIBr₂; CH₃SMALL₃PbICl₂And CH₃SMALL₃PbBrI₂; CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbIBr₂; Or CH₃SMALL₃PbBrCl₂And CH₃SMALL₃PbIBr₂May include.

0215As another alternative, the step of depositing the sensitizer containing the perovskite comprises at least one perovskite, eg, formula (H).₂N=CH-SMALL₂)PbI_3zBr_{3 (1-d)}It may contain at least one perovskite having.

0216The step of depositing the charge transport material usually includes the step of depositing the charge transport material, which is a solid hole transport material or a liquid electrolyte. The hole-transporting material of the optoelectronic device of the present invention may be any suitable n-type or electron-transporting semiconductor material, or any p-type or hole-transporting semiconductor material.

0217When the charge transport material is an electron transport material, the charge transport material is fullerene or perylene or a derivative thereof, poly {[N, N0-bis (2-octyldodecyl) -naphthalene-1,4,5,8-bis. It may contain (dicarboxyimide) -2,6-diyl] -alt-5,50- (2,20-bithiophene)} (P (NDI2OD-T2)), or an electrolyte.

0218When the charge transport material is a hole transport material, the hole transport material of the optoelectronic device of the present invention may be a small molecule or polymer based hole conductor.

0219Typically, when the charge transport material is a hole transport material, the charge transport material is a solid hole transport material or a liquid electrolyte.

0220Often, when the charge transport material is a hole transport material, the charge transport material is a polymeric or molecular hole transporter. Typically, the hole transport material is spiro-OMeTAD (2,2', 7,7'-tetrax- (N, N-di-p-methoxyphenylamine) 9,9'-spirobifluorene)). , P3HT (poly (3-hexylthiophene)), PCPDTBT (poly [2,1,3-benzothiasiazol-4,7-diyl [4,4-bis (2-ethylhexyl))-4H-cyclopentane [2,1- b: 3,4-b'] Dithiophene-2,6-diyl]]), PVK (poly (N-vinylcarbazole)), HTM-TFSI (1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl)) ) Imid), Li-TFSI (lithium bis (trifluoromethanesulfonyl) imide), or tBP (tert-butyl pyridine). Usually, the hole transport material is selected from spiro-OMeTAD, P3HT, PCPDTBT, and PVK. Preferably, the hole transport material is spiro-OMeTAD.

0221When the charge transport material is a hole transport material, the charge transport material may be, for example, a molecular hole transporter or a polymer or copolymer. Often, the charge transport material is a molecular hole transport material, and the polymer or copolymer has the following parts: thiophenyl, phenelenyl, dithiazolyl, benzothiazolyl, diketopyrrolopyrrolyl, ethoxydithiophenyl, amino, triphenylamino, carbozolyl, Includes one or more of ethylenedioxythiophenyl, dioxythiophenyl, or fluorenyl.

0222Alternatively, when the charge transport material is a hole transport material, the charge transport material is an inorganic hole transporter such as CuI, CuBr, CuSCN, Cu.₂It may be O, CuO, or CIS.

0223Prior to the step for depositing the charge transport material, the charge transport material is often dissolved in a solvent, typically chlorobenzene. Usually, the concentration of chlorobenzene is 150 to 225 mg / ml, and more usually the concentration is about 180 mg / ml. Typically, the charge transport material is dissolved in the solvent at a temperature of 75 to 125 ° C, more typically at a temperature of about 100 ° C. The charge transport material is typically dissolved for 25 to 60 minutes, more usually about 30 minutes. Additives may be added to the charge transport material. The additive may be, for example, tBP, Li-TFSi, an ionic liquid, or an ionic liquid having a mixed halide.

0224Usually, the charge transport material is spiro-OMeTAD. Often, tBP is also added to the charge transport material prior to the step of depositing the charge transport material. For example, tBP may be added such that the volume-to-mass ratio of tBP: Spiro-OMeTAD is 1:20 to 1:30 (μl / mg). Typically, tBP may be added such that the volume to mass ratio of tBP: Spiro-OMeTAD is 1:26 (μl / mg). In addition or as an alternative, Li-TFSi may be added to the hole transport material prior to the step of depositing the charge transport material. For example, Li-TFSi may be added so that the ratio of Li-TFSi: spiro-OMeTAD is 1: 5 to 1:20 (μl / mg). Generally, Li-TFSi may be added so that the ratio of Li-TFSi: spiro-OMeTAD is 1:12 (μl / mg).

0225The step of depositing the charge transport material often involves spin coating a solution containing the charge transport material onto the sensitizer material containing the perovskite. Usually, prior to spin coating, a small amount of solution containing the charge transport material is deposited on the sensitizer containing the perovskite. A small amount is usually 5 to 100 μl, more usually 20 to 70 μl. The solution containing the charge transport material is left in place prior to spin coating, typically for at least 5 seconds, more typically for 5 to 60 seconds. For example, a solution containing a charge transport material is left in place for about 20 seconds prior to spin coating. Spin coating of charge transport material is typically performed at 500 to 3000 rpm, typically about 1500 rpm. Spin coating is often performed in air for 10-40 seconds, more often for about 25 seconds.

0226The step of producing the second electrode usually involves depositing the second electrode on the charge transport material. Typically, the second electrode is a silver-containing electrode. Often, the step of producing a second electrode involves placing a coating containing a charge transport material in a thermal evaporator. Usually, the step of producing the second electrode involves depositing the second electrode through a shadow mask under high vacuum. Typically, the vacuum is about 10^-6mBar. The second electrode may be, for example, an electrode having a thickness of 100 to 300 nm. Typically, the second electrode is an electrode with a thickness from 200 nm.

0227Typically, the distance between the second electrode and the porous layer of the semiconductor is 50 nm to 400 nm, and more typically 150 nm to 250 nm. Often, the distance between the second electrode and the porous layer of the semiconductor is on the order of 200 nm.

0228Often, the method for producing the optoelectronic device of the present invention is AM1.5G 100mWcm for photovoltaic devices.^-2This is a method for producing a photovoltaic device having a power conversion efficiency of 7.3% or more. Typically AM1.5G 100mWcm^-2The power conversion efficiency is 11.5% or more.

0229Typically, the method for producing the optoelectronic device of the present invention has a photovoltaic device with a photocurrent of 15 mA cm.^-2This is a method for generating the above-mentioned photovoltaic device. More typically, the photocurrent is 20 mAcm^-2That is all.

0230The present invention will be further described in the following examples.

<p num="0231"><u style="single">Description of the experiment</u>: 1. Synthesis of organometallic halide perovskite: 1.1. Preparation of methylammonium iodide precursor Methylamine (CH)₃SMALL₂) In anhydrous ethanol (Sigma-Aldrich) and 57 wt% solution of hydrogen iodide in water (Sigma-Aldrich) in 200 proof of absolute ethanol (Sigma-Aldrich). The reaction was carried out in a nitrogen atmosphere at a molar ratio of 1: 1. Typical amounts were 24 ml of methylamine, 10 ml of hydrogen iodide, and 100 ml of ethanol. Methylammonium iodide (CHNH)₃Crystallization of I) was achieved using a rotary evaporator and a white precipitate was formed, indicating that the crystallization was successful.</p><p num="0232"> Methylamine can be used in place of other amines such as ethylamine, n-butylamine, tert-butylamine, octylamine to alter the properties of the subsequent perovskite. In addition, instead of hydroiodic acid, other acids such as hydrochloric acid can be used to form different perovskites.</p><p num="0233"><u style="single">1.2. Methylammonium iodide lead (II) chloride (CH)</u>_{<u style="single">3</u>}<u style="single">SMALL</u>_{<u style="single">3</u>}<u style="single">PbCl</u>_{<u style="single">2</u>}<u style="single">I) Preparation of perovskite solution</u> Methylammonium iodide (CHNH)₃I) Precipitate and lead (II) chloride (Sigma-Aldrich) with dimethylformamide (C)₃H₇It was dissolved in NO) (Sigma-Aldrich) in a molar ratio of 1: 1 at 20% by volume.</p><p num="0234"> To make different perovskites, different precursors, such as different lead (II) halides, or completely different metal halides such as Sn iodide, are all together.</p><p num="0235"><u style="single">1.3. Generalization of organometallic halide perovskite structures</u> Perovskite structure is ABX₃[In the formula, A = cation (0,0,0) -ammonium ion, B = cation (1 / 2,1 / 2,1 / 2) -valent metal ion, and X = anion (1/2, 1 / 2,0) -Halogen ion] is defined. The table below shows the possible mixed anion perovskite. Fixed: [A] = Methylammonium, [B] = Pb, Various [X] = Any Halogen<tables num="1"><img id="000002" he="125" wi="168" file="JP2017193576A_D0001.tif" img-format="tif" img-content="drawing" /></tables>Fixed: [A] = Methylammonium, [B] = Sn, Various [X] = Any Halogen<tables num="2"><img id="000003" he="158" wi="168" file="JP2017193576A_D0001.tif" img-format="tif" img-content="drawing" /></tables>Fixed: [A] = Methylammonium, [B] = Sn, Various [X] = Any Halogen</p><p num="0236"> [A] may be varied using different organic elements, for example, US Pat. No. 5,882,548 (1999) by Liang et al. And US Pat. No. 6,429,318 (2002) by Mitzi et al.</p><p num="0237"><u style="single">1.4 Blended perovskite</u><tables num="3"><img id="000004" he="125" wi="168" file="JP2017193576A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0238"><u style="single">1.5 Stability of mixed halide perovskite to single halide perovskite</u> We have found that a photovoltaic device containing a mixed halide perovskite absorbs light and operates as a solar cell. When the coating is made from a single halide perovskite, it is under ambient conditions. Perovskite is formed but fades rapidly. This fading appears to be due to the adsorption of water on the surface of the perovskite, which has been shown to fade the material. When a complete solar cell is constructed in ambient conditions using these single halide perovskites, the battery works in very poor condition with a complete photovoltaic conversion efficiency of less than 1%. In contrast, mixed halide perovskite can be processed in air and exhibits a negligible fading state during the device fabrication process. A complete solar cell incorporating a mixed halide perovskite works unexpectedly well in ambient conditions, with a complete solar power conversion efficiency of over 10%.</p><p num="0239"><u style="single">1.6 Preparation of perovskite containing formaminidium cations</u> Form amidinium iodide (FOI) and form amidinium bromide (FOBr) in a 0.5 Mmolar solution of formamidinium acetate in ethanol and a 3-fold molar excess of hydroiodic acid (for FOI) or bromide It was synthesized by reacting with hydrogen acid (for FOBr). The acid was added dropwise at room temperature with stirring and then left to stir for an additional 10 minutes. Drying at 100 ° C formed a yellow-white powder, which was then dried overnight in a vacuum furnace before use. FOPbI₃And FOPbBr₃FOI and PbI to form precursor solution₂Or FOBr and PbBr₂Was dissolved in anhydrous N, N-dimethylformamide at a molar ratio of 1: 1 at 0.88 mmol per ml, respectively, to give a 0.88 M perovskite solution. FOPbI_3zBr_{3 (1-d)}FOPbI the mixture in the required ratio to form the perovskite precursor₃And FOPbBr₃Made from 0.88 M solution of [in the formula, z ranges from 0 to 1].</p><p num="0240"> The characterization or device fabrication coating was spin coated in a nitrogen-filled glove box and annealed in a nitrogen atmosphere at 170 ° C. for 25 minutes.</p><p num="0241"><u style="single">2. Electrode cleaning and etching:</u> The perovskite solar cells used and presented in these examples were made as follows: Fluorine-doped tin oxide (F: SnO).₂A glass plate coated with / FTO (TEC 15, 15Ω / square, Pilkington USA) was etched with zinc powder and HCl (2M) to obtain the required electrode pattern. These glass plates were subsequently cleaned with soap (2% aqueous solution of Hellemanex), distilled water, acetone, ethanol and finally treated under oxygen plasma for 5 minutes to remove any organic residues.</p><p num="0242"><u style="single">3. Dense TiO</u>_{<u style="single">2</u>}<u style="single">Layer deposition:</u> The patterned FTO sheet was then subjected to a titanium diisopropoxide bis (acetylacetone) ethanol solution at 250 ° C using air as the carrier gas (volume ratio of titanium diisopropoxide bis (acetylacetone) to ethanol 1:10. ) Aerosol spray pyrolysis deposition (Kavan, L. and Gratzel, M.), a highly efficient semiconductor TiO prepared by aerosol pyrolysis.₂Photoelectrode (Highly efficient semiconducting TiO₂ photoelectrodes prepared by aerosol pyrolysis), Electrochim.Acta 40, 643 (1995); Snaith, HJ and Gratzel, M. a "Schottky Barrier" at an Electron-Collection Electrode in Solid-State Dye-Sensitized Solar Cells), Adv.Mater.18, 1910 (2006)), TiO₂It was coated with a (100 nm) dense layer.</p><p num="0243"><u style="single">4. Mesoporous TiO</u>_{<u style="single">2</u>}<u style="single">Capsule deposition:</u> Standard TiO such as the commercially available diesol 18NR-T₂Nanoparticle paste, dense TiO₂The top was coated with a doctor blade, screen printed or spin coated to obtain a dry film thickness between 200 nm and 2 μm, which is dominated by the height of the doctor blade. These sheets were then slowly heated to 500 ° C. (raised over 30 minutes) and baked at this temperature for 30 minutes under an oxygen stream. After cooling, the sheet was cut into slides of the required size and stored in the dark until further use.</p><p num="0244"> TiCl nanoporous coating before making each set of devices₄Soaked in a 0.015M aqueous solution at 70 ° C for 1 hour. Mesoporous TiO this procedure₂Above TiO₂Used to grow a thin shell. TiCl₄After treatment, the coating was rinsed with deionized water, dried in air and baked again at 500 ° C. for 45 minutes under air flow. After cooling to 70 ° C, they were placed in the dye solution overnight.</p><p num="0245"><u style="single">5. Accumulation of perovskite precursor solution and formation of mesoporous perovskite semiconductor electrodes:</u> A solution of a perovskite precursor solution in DMF with a volume concentration of 5 to 40% by volume (methylammonium iodide lead (II) chloride (CH) (CH).₃SMALL₃PbCl₂A small volume of I)) between 20 and 100 μl was metered and distributed on the prepared mesoporous electrode coatings, left to stand for 20 seconds, and then spin coated in air at 1500 rpm for 30 minutes. The coated coating was then placed on a hot plate set at 100 degrees Celsius and allowed to cool in air at this temperature for 45 minutes. During the drying procedure at 100 degrees, the coated electrodes turned from light yellow to dark brown, indicating that the desired perovskite coating with semiconducting properties was formed.</p><p num="0246"><u style="single">6. Hole transporter deposition and device assembly:</u> The hole transport material used was Spiro-OMeTAD (Lumtec, Taiwan) dissolved in chlorobenzene at a typical concentration of 180 mg / ml. After complete dissolution of Spiro-OMeTAD at 100 ° C for 30 minutes, the solution is cooled and tert-butylpyridine (tBP) is dissolved in a 1:26 (μl / mg) tBP: Spiro-MeOTAD volume-to-mass ratio. Was added directly to. Lithium bis (trifluoromethylsulfonyl) amine salt (Li-TFSI) ion dopant was pre-dissolved in acetonitrile at 170 mg / ml, then in hole transporter solution, Li-TFSI solution: Spiro-MeOTAD 1:12 It was added so as to be (μl / mg). A small amount (20-70 μl) of spiro-OMeTAD solution was weighed and dispensed into each of the perovskite-coated mesoporous coatings, left for 20 seconds, and then spin-coated in air at 1500 rpm for 30 seconds. The coating is then placed in a thermal evaporator, where a 200 nm thick silver electrode is placed in a high vacuum (10).^-6Deposited through a shadow mask under mBar).</p><p num="0247"><u style="single">7.FOPbI</u>_{<u style="single">3z</u>}<u style="single">Br</u>_{<u style="single">3 (1-d)</u>}<u style="single">Manufacture of devices including</u> The device was made on a glass substrate coated with fluorine-doped tin oxide. These were sequentially cleaned with hallmanex, acetone, propan-2-ol, and oxygen plasma. TiO₂The dense layer of Titanium Isopropoxide was deposited by spin coating with a slowly acidic solution of titanium isopropoxide in ethanol. This was dried at 150 ° C. for 10 minutes. TiO₂The mesoporous layer was formed by diluting Dyesol 18NR-T paste in ethanol at a weight ratio of 1: 7 and spin-coating it at 2000 rpm to form a layer of about 150 nm. The layers were then sintered in air at 500 ° C. for 30 minutes. After cooling, the perovskite precursor was spin-coated in a nitrogen-filled glove box at 2000 rpm and then annealed in a nitrogen atmosphere at 170 ° C. for 25 minutes. The hole transport layer was added with tert-butylpyridine (tBP) and lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI) to add 2,2', 7,7'-tetrax- (N, N-di). An 8 wt% solution of -p methoxyphenylamine) 9,9'-spirobifluorene (spiro-OMeTAD) in chlorobenzene was deposited by spin coating. The device was completed by vapor deposition of 60 nm Au contacts.</p><p num="0248"><u style="single">Experimental result</u> FIG. 1 shows a schematic cross-sectional view of a solid perovskite sensitized solar cell. Light enters from the bottom. The device includes a flat coating of fluorene-doped tin oxide (FTO) coated on a glass substrate. The FTO is the anode in the presented configuration. At the top of the FTO, the dense TiO₂The thin (about 50 nm thick) layer acts as a hole blocking and electron collection intermediate layer to ensure selective collection of electrons at this anode. Dense TiO₂Above, TiO₂It is coated with a mesoporous film and acts as a high surface area n-type anode. This mesoporous TiO₂Is coated with a perovskite material that acts as a sensitizer. The role of the sensitizer is to absorb sunlight and TiO photoexcited electrons.₂And the holes are transferred to the hole transporter. Perovskite sensitized mesoporous TiO₂The pores of the coating are mainly filled with hole transporters. The role of the hole transporter is to accept photogenerated holes from the valence band of the perovskite sensitizer and transport these holes from the device to an external circuit. Cap the device with metal electrodes to complete the solar cell. Further examples of the structure of the solar cell and the composition of the components are shown in FIGS. 3 and 4.</p><p num="0249"> Figure 2 shows the UV-Vis absorption spectrum for a single halide perovskite. In Figure 2a, lead bromide perovskite (CH), which appears yellow to the eye₃SMALL₃PbBr₃) Is shown. In Figure 2b, UV-Vis-NIR (ultraviolet-visible-near infrared) lead iodide perovskite (CH) appears dark brown to the eye.₃SMALL₃PbI₃) Is shown. Lead iodide perovskite has a very good absorption spectrum for potential use in solar cells. However, due to the instability of the material, it does not work well when used as a sensitizer for solid perovskite sensitized solar cells.</p><p num="0250"> FIG. 5 shows the UV-Vis-NIR absorption spectrum of the mixed halide perovskite. Lead Iodiate Chloride Perovskite (CH)₃SMALL₃PbCl₂I) appears dark brown to the eye, which is indicated by a dark line, lead bromide chloride perovskite (CH).₃SMALL₃PbCl₂Br) appears red to the eye, which is indicated by a thin line. The inventors of the present invention are CH₃SMALL₃PbCl₂I Perovskite K330, CH₃SMALL₃PbCl₂Name Br as K331. Lead iodide chloride perovskite is particularly promising as it absorbs very strongly from the entire visible light to the near infrared region of the solar spectrum.</p><p num="0251"> A flat layer solar cell was constructed to first test the photovoltaic power of the perovskite absorber. Figure 6 shows the current-voltage curve for a flat layer K330 solar cell. 3.5mAcm^-2The photocurrent is quite high for a flat layer sensitized solar cell.</p><p num="0252"> Spiro-OMeTAD is used as the hole-transporter and CH is used as the perovskite absorber.₃SMALL₃PbCl₂Simulated sunlight of AM1.5 100 mWcm for a completed solar cell, described and illustrated in Figure 1, using I.^-2The current-voltage curve measured under irradiance is shown in FIG. Photocurrent is 20mAcm^-2The overall power conversion efficiency is 11.5%. This level of performance is unexpectedly high for a solid-state sensitized solar cell, demonstrating an absolute breakthrough in performance in this technology. By comparison, the highest efficiency reported for solid dye-sensitized solar cells was only over 7%, and the highest efficiency verified for liquid electrolyte dye-sensitized solar cells was 11.4%.</p><p num="0253"> In Fig. 8, P3HT is used as the hole transporter and CH is used as the perovskite absorber.₃SMALL₃PbCl₂Simulated sunlight of AM1.5 100 mWcm for a completed solar cell, described and illustrated in Figure 1, using I.^-2A current-voltage curve measured under irradiance is shown. This device works as well, but not as much as a device using spiro-OMeTAD as a hole transporter.</p><p num="0254"> FIG. 9 shows the external quantum efficiency (EQE) action spectrum for a K330 sensitized solar cell using spiro-OMeTAD as the hole transporter. The unexpectedly high EQE of 80% at the peak and its widespread function over the entire absorption range prove the high photocurrent measured under simulated sunlight.</p><p num="0255"> FIG. 10 shows an external quantum efficiency action spectrum for a K330 sensitized solar cell using semiconductor polymers, P3HT and PCPDTBT as hole transporters. The EQE spectrum has a recess in which the polymer absorbs light, with a maximum P3HT absorption between 500 and 600 nm and a maximum PCPDTBT absorption at 700 nm. These recesses in the EQE spectrum indicate that the polymer is actually absorbing light that would otherwise have been absorbed by the perovskite sensitizer. When light is absorbed by the polymer, it does not appear to generate charges very efficiently. This "optical filtering effect" proves that the photocurrent is lower in perovskite-sensitized solar cells with the polymer hole conductor P3HT than in the hole conductor Spiro-OMeTAD, which has a wide bandgap of small molecules. To do.</p><p num="0256"> FIG. 11 shows the UV-Vis-NIR absorption spectrum of a fully photoactive solar cell containing K330 and spiro-OMeTAD. The coating is sealed in nitrogen. 100mWcm^-2At constant illumination over 1000 hours from AM1.5 sunlight at irradiance, there is a negligible change in the absorption spectrum. This indicates that perovskite is stable in the photoactive layer of the solar cell.</p><p num="0257"> FIG. 12 shows the optical density at 500 nm as a function of time under Am1.5 illumination, extracted from the data in FIG.</p><p num="0258"> The X-ray diffraction pattern shown in FIG. 13 is a CH coated on a glass slide by using an X'pert Pro X-ray diffractometer.₃SMALL₃PbCl₂Extracted from I thin film at room temperature.</p><p num="0259"> Figure 13 shows methylammonium dichloromonoiodine (II); CH on a glass substrate.₃SMALL₃PbCl₂The typical X-ray diffraction pattern of the I coating is shown. X-ray diffraction pattern is ABX₃Confirm the type cubic (a = b = c = 90) perovskite structure (Pm3m). CH₃SMALL₃PbCl₂I has 14.20 diffracted peaks assigned as planes (100), (200), and (300) of the cubic perovskite structure with lattice constants a) 8.835 Å, b) 8.835, and c) 11.24 Å, respectively. , 28.58, and 43.27 °. The sharp diffraction peak A at (h00: but h = 1 ~ 3) suggests that the coating formed on the glass substrate is mainly monophasic and highly oriented by the a-axis self-assembly. ["Organometal Halide perovskites as Visible-Light Sensitizers for Photovoltaic Cells", Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka, J. et al. Am.Chem.Soc.2009, 131, 6050].</p><p num="0260"> CH₃SMALL₃⁺Cations cannot be assigned on X-rays given their dynamic orientation, CH₃SMALL₃⁺Does not conform to molecular symmetry and therefore the cations remain chaotic within this phase at room temperature. Therefore, the effective involvement of C and N atoms in total diffraction intensity is much smaller than the involvement from Pb and X (Cl and I) ["Alkylammonium lead halide Part 2 CH".₃SMALL₃PbX₃(X = Cl, Br, I) Perovskite: Cuboctahedron halide cage with isotropic cation reorientation (Alkylammonium lead halides.Part 2.CH₃SMALL₃PbX₃(X=C1,Br,I)perovskites:cuboctahedral halide cages with isotropic cation reorientation)",Osvaldkn OPas well asRodericke Wasylishenm,Can.J.Chem.1990,68,412.].</p><p num="0261"> Synthesized mixed CH at (h, 0, 0)₃SMALL₃PbCl₂The peak position of I shifts towards the lower 2θ and is pure methylammonium trihalogen leadate, ie CH₃SMALL₃PbI₃And CH₃SMALL₃PbCl₃Positioned between and ["Dynamic disorder in methylammonium trihalogenoplumbates (II) observed by millimeter-wave spectroscopy", A. Poglitsch and D.Weber, J.Chem.Phys.1987, 87, 6373.] Also, pure "Cl" based perovskite, ie CH, with the addition of "I".₃SMALL₃PbCl₃CH compared to (a = 5.67Å)₃SMALL₃PbCl₂The high lattice constant of the I-coat (a = 8.835 Å) provides proof that a mixed halide perovskite was formed [CH.₃SMALL₃PbX₃Optical properties of CH (X = halogen) and their mixed halide crystals₃SMALL₃PbX₃(X=halogen) and their mixed-halide crystals)",N.Kitazawa,Y.Watanabe,as well asY Nakamura,J.Mat Sci.2002,37,3585.].</p><p num="0262"> In the diffraction patterns of the products contained in several unidentified peaks, they are some impurities (eg Pb (OH) Cl, CH₃SMALL₃It may be involved in a variety of factors, including the presence of X; X = Cl and / or I, or related compounds that can be produced during synthesis even when a slight excess of reactants is used. It may also be involved in the hygroscopicity of compounds that may result in the formation of unwanted impurities [Alkylammonium Lead Halide Part 2 CH.₃SMALL₃PbX₃(X = Cl, Br, I) Perovskite: Cuboctahedron halide cage with isotropic cation reorientation (Alkylammonium lead halides.Part 2.CH₃SMALL₃PbX₃(X = C1, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation) , Osvaldkn OP and Rodericke Wasylishenm et al., Can.J.Chem.1990, 68, 412.]. In addition, a pure "I" based perovskite (CH)₃SMALL₃PbI₃Given the fact that) forms a square structure, the "I" ions present in the lattice may split some of the peaks at room temperature ["Alkylammonium lead halides. Part 1) Isolated ~ b 1 6 i ~ on-s in (CH₃SMALL₃)₄Pb₁₆-2H₂O , Beverlyr Vincent K, Robertsont, Stanlecya merona, N Dosvaldk, Can.J.Chem.1987, 65, 1042 .; Organometal Halide perovskites as a visible light sensitizer for photovoltaic cells as Visible-Light Sensitizers for Photovoltaic Cells), Akihiro Kojima, Kenjiro Teshima, Yasuo Shirai, and Tsutomu Miyasaka, J.Am.Chem.Soc.2009, 131, 6050].</p><p num="0263"> Figure 14 shows mesoporous TiO coated on the FTO electrode.₂A scanning electron microscopy (SEM) cross-sectional image of the coating is shown. Perovskite precursor solution is porous TiO via spin coating₂Coated inside. To elaborate on this coating method, there is an extensive previous study investigating how solution-cast materials infiltrate into mesoporous oxides (HJ Snaith et al., Nanotechnology 19, 424003-4210 15 (2008)). ; T.Leijtens et al., ACS Nano 6, 1455 ~ 1462 (2012); J.Melas-Kyriazi et al., Adv.Energy.Mater.1, 407 ~ 414 (2011); IK.Ding et al., Adv.Funct.Mater. 19, 2431 ~ 2436 (2009); A. Abrusci et al., Energy Environ.Sci.4, 3051 ~ 3058 (2011)). If the concentration of the solution is low enough and the solubility of the cast material is high enough, the material will fully penetrate into the pores as the solvent evaporates. The usual result is that the material forms a "wet" layer on the inner surface of the mesoporous coating, uniformly but incompletely filling the pores over the entire thickness of the electrode. The degree of "pore filling" is controlled by varying the solution concentration. If the concentration of the cast solution is high, in addition to the high degree of pore filling, a "capping layer" will be formed on the top of the mesoporous oxide. Figure 15 shows mesoporous TiO coated with a perovskite absorber.₂A cross-sectional SEM image of the coating is shown. The capping layer is not visible, suggesting that the perovskite is predominantly within the mesoporous coating. To complete the photoactive layer, a hole transporter, Spiro-OMeTAD, is spin coated onto the top of the perovskite-coated electrode. FIG. 16 shows a cross-sectional SEM image of the complete photoactive coating, where it is clear that the spiro-OMeTAD formed a capping layer.</p><p num="0264"> 17 to 19 show perovskite containing formamidinium cations and FOPbI._3yBr_{3 (1-y)}Regarding devices including. In general, perovskite is considered advantageous for preserving the 3D crystal structure, as opposed to producing layered perovskite, which will inevitably have a higher exciton binding energy (Journal of Luminescence 60 &amp; 61 (1994) 269 274. ). It is also advantageous to be able to adjust the bandgap of the perovskite. The bandgap can be changed by changing either the metal cation or the halide, which directly affects both the electron orbit and the crystal structure. Alternatively, the crystal structure can be changed by changing the organic cation (for example, changing from a methylammonium cation to a formamidinium cation). However, in order to fit the perovskite crystal, the following geometric conditions: (R_A+R_x=t2(R_B+R_X)[In the formula, R_{A, B, and X}Is the ionic radius of the ABX ion]. We have unexpectedly found that the formamidinium cation (FO) is indeed FOPbBr.₃Or FOPbI₃It has been found that a cubic structure forms a perovskite structure in perovskite and a mixed halide perovskite thereof.</p>