Method for forming a layer of a perovskite material

Abstract

13. A method comprising the steps of depositing a lead halide precursor ink on a substrate, drying the lead halide precursor ink to form a first thin film, annealing the first thin film, and forming a perovskite material layer, wherein forming the perovskite material layer comprises depositing a benzyl ammonium halide precursor ink on the first thin film, drying the benzyl ammonium halide precursor ink, depositing a formamidinium halide precursor ink on the benzyl ammonium halide precursor ink, drying the formamidinium halide precursor ink to form a second thin film, and annealing the second thin film.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 283,525, filed November 28, 2021, entitled "Method of Forming a Perovskite Material Layer," the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] The use of photovoltaics (PV) to generate electricity from solar energy or solar radiation may offer many advantages, including, for example, power source, low or zero emissions, power generation independent of the power grid, durable physical structure (no moving parts), stable and reliable systems, modular construction, relatively quick installation, safe manufacture and use, and good public opinion and acceptance of use. Perovskite photovoltaics, as an emerging highly efficient and low-cost photovoltaic technology, face obstacles such as lead leakage. Summary of the Invention [Problem to be solved by the invention]

[0003] PV incorporates a layer of perovskite material as the photoactive layer that produces electricity when exposed to light. Some perovskite photovoltaic devices contain lead and other metal ions, which can be prone to leakage. Therefore, improved lead and metal ion isolation techniques and materials are desirable. [Means for solving the problem]

[0004] In some embodiments, the method includes forming a lead halide precursor thin film, the forming the lead halide precursor thin film includes depositing a lead halide precursor ink on a substrate, drying the lead halide precursor ink to form a first thin film, and annealing the first thin film. In some embodiments, the method further includes forming a perovskite material layer, the forming the perovskite material layer includes depositing a benzyl ammonium halide precursor ink on the first thin film, drying the benzyl ammonium halide precursor ink, depositing a formamidinium halide precursor ink on the benzyl ammonium halide precursor ink, drying the formamidinium halide precursor ink to form a second thin film, and annealing the second thin film. [Brief description of the drawings]

[0005] [Figure 1] FIG. 1 is a schematic diagram illustrating components of a photovoltaic device according to certain embodiments of the present disclosure. [Diagram 2] FIG. 1 illustrates components of an exemplary PV device according to certain embodiments of the present disclosure. [Diagram 3] FIG. 1 illustrates components of an exemplary PV device according to certain embodiments of the present disclosure. [Figure 4] FIG. 1 illustrates components of an exemplary PV device according to certain embodiments of the present disclosure. [Diagram 5] FIG. 2 shows an X-ray diffraction pattern of a perovskite material according to an embodiment of the present disclosure. [Figure 6] FIG. 1 is a schematic diagram of a blade coating setup for producing a perovskite material layer. [Figure 7] FIG. 1 is a schematic diagram of a blade coating setup for forming a perovskite material layer. [Figure 8] FIG. 1 is a schematic diagram of a slot die coating setup for producing a perovskite material layer. [Figure 9] FIG. 1 is a schematic diagram illustrating components of a photovoltaic device according to certain embodiments of the present disclosure. [Figure 10] FIG. 1 is a schematic diagram of a slot die coating setup for producing a perovskite material layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] The features and advantages of the present disclosure will be readily apparent to those skilled in the art, and many modifications may be made by those skilled in the art that fall within the scope of the present invention.

[0007] The present disclosure generally relates to compositions, apparatus and methods of use of materials in photovoltaic cells in generating electrical energy from solar radiation, and some or all of the materials according to certain embodiments of the present disclosure may be advantageously used in any organic or other electronic device, some examples of which include, but are not limited to, batteries, field effect transistors (FETs), light emitting diodes (LEDs), nonlinear optical devices, transistors, ionizing radiation detectors, memristors, capacitors, rectifiers, and / or rectifying antennas.

[0008] In certain embodiments, the present disclosure may provide PV and other similar devices (e.g., batteries, hybrid PV cells, multi-junction PVs, FETs, LEDs, X-ray detectors, gamma ray detectors, photodiodes, CCDs, etc.). In some embodiments, such devices may have improved active materials, interfacial layers (IFLs), and / or one or more perovskite materials. The perovskite materials may be incorporated into one or more various aspects of the PV or other devices. Perovskite materials according to various embodiments are described in more detail below.

[0009] (Photovoltaic cells and other electronic devices) Some PV embodiments are described by reference to an exemplary depiction of a perovskite material device as shown in FIG. 1. An exemplary PV architecture according to an embodiment may be substantially in the form of substrate-anode-IFL-active layer-IFL-cathode. The active layer of some embodiments may be photoactive and / or include photoactive materials. Other layers and materials may be utilized in the cell as known in the art. Additionally, it should be noted that the use of the term "active layer" is not meant to explicitly or implicitly limit or define the properties of any other layers. For example, in an embodiment, either or both of the IFLs may be active, so long as they may be semiconducting. In particular, referring to FIG. 1, a generic PV cell 1000 is shown, illustrating the highly interfacial nature of some layers within the PV. The PV 1000 represents a generic architecture applicable to some PV devices, such as perovskite material PV embodiments. The PV cell 1000 includes transparent substrate layers 1010 and 1070, which may be glass (or a similar material transparent to solar radiation) allowing solar radiation to pass through the layers. The transparent layers of some embodiments are also referred to as superstrates or substrates, which may include any one or more of a variety of rigid or flexible materials, such as glass, polyethylene, polypropylene, polycarbonate, polyimide, PMMA, PET, PEN, Kapton, or quartz. In general, the term substrate is used to describe the material on which the device is deposited during fabrication. The photoactive (PAM) layer 1040 may be comprised of electron donors or p-type materials, and / or electron acceptors or n-type materials, and / or ambipolar semiconductor materials that exhibit both p-type and n-type material properties, and / or intrinsic semiconductors that exhibit neither n-type nor p-type material properties. In some embodiments, the photoactive layer 1040 may be a perovskite material as described herein. The active layer, i.e., PAM layer 1040 as shown in Figure 1, is sandwiched between two conductive electrode layers 1020 and 1060. In Figure 1, electrode layer 1020 may be a transparent conductor, such as tin-doped indium oxide (ITO material), or other materials described herein.In some embodiments, the second electrode 1060 may be transparent. The second electrode layer 1060 may be an aluminum material or other metal, or other conductive material such as carbon. Other materials known in the art may be used. The cell 1100 also includes an interfacial layer (IFL) 1030, as shown in the example of FIG. 1. The IFL may aid in charge separation. In other embodiments, the IFL 1030 may include a multi-layer IFL. For example, the perovskite material device may include zero, one, two, three, four, five, or more interfacial layers (such as the example device of FIG. 2, which includes five interfacial layers 3903, 3905, 3907, 3909, and 3911). There may also be an IFL 1050 adjacent to the second electrode 1060. In some embodiments, the IFL 1050 adjacent to the second electrode 1060 may additionally or instead have a multi-layer IFL. The IFL according to an embodiment may be semiconducting in nature and may be either intrinsic, ambipolar, p-type, or p-type. Alternatively, it may be dielectric in nature. In an embodiment, the IFL on the cathode side of the device (e.g., IFL 1050 shown in FIG. 1) may be p-type and the IFL on the anode side of the device (e.g., IFL 1030 shown in FIG. 1) may be n-type. However, in other embodiments, the cathode side IFL may be n-type and the anode side IFL may be p-type. The cell 1100 may be attached to electrical leads by the electrodes 1060 and 1020 and a discharge unit such as a battery, a motor, a capacitor, an electrical grid, or any other electrical load.

[0010] Various embodiments of the present disclosure provide improved materials and / or designs in various aspects of solar cells and other devices, including, among others, active materials (including hole transport layers and / or electron transport layers), interfacial layers, and overall device design.

[0011] In various embodiments, the device has an interface layer between any two other layers and / or materials, if necessary. However, the device does not necessarily have to include an interface layer. For example, a perovskite material device may include zero, one, two, three, four, five, or more interface layers (such as the exemplary device of FIG. 2, which includes five interface layers 3903, 3905, 3907, 3909, and 3911). The interface layer may include any suitable material that enhances charge transport and / or charge collection between two layers or materials. This may help to inhibit or reduce the possibility of charge recombination after charge is transported from one of the materials adjacent to the interface layer. The interface layer may further homogenize the substrate physically and electrically, resulting in changes in the substrate's roughness, dielectric constant, adhesion, and creation or annihilation of defects (e.g., charge traps, surface states). Suitable interface materials include Ag, Al, Au, B, Bi, Ca, Cd, Ce, Co, Cu, Fe, Ga, Ge, H, In, Mg, Mn, Mo, Nb, Ni, Pt, Sb, Sc, Si, Sn, Ta, Ti, V, W, Y, Zn, Zr; carbides of any of the aforementioned metals (e.g., SiC, Fe 3 C, WC, VC, MoC, NbC); silicides of any of the aforementioned metals (e.g., Mg 2 Si, SrSi 2 , Sn 2 Si; any oxide of the aforementioned metals (e.g., alumina, silica, titania, SnO), including transparent conductive oxides ("TCOs") such as indium tin oxide, aluminum doped zinc oxide (AZO), cadmium oxide (CdO), and fluorine doped tin oxide (FTO). 2 , ZnO, NiO, ZrO 2 , HfO 2 ); sulfides of any of the aforementioned metals (e.g., CdS, MoS 2 , SnS 2 ); any nitride of the aforementioned metals (e.g., GaN, Mg 3 N 2 , TiN, BN, Si 3 N 4 ); any selenide of the above metals (e.g., CdSe, FeS 2 , ZnSe); tellurides of any of the above metals (e.g., CdTe, TiTe 2, ZnTe); any phosphide of the above metals (e.g., InP, GaP, GaInP); any arsenide of the above metals (e.g., CoAs 3 , GaAs, InGaAs, NiAs; any antimonide of the above metals (e.g., AlSb, GaSb, InSb); any halide of the above metals (e.g., CuCl, CuI, BiI 3 ); any pseudohalide of said metals (e.g., CuSCN, AuCN, Fe(SCN) 2 ); any carbonate of said metals (e.g., CaCO 3 , Ce 2 (CO 3 ) 3 ); functionalized or non-functionalized alkylsilyl groups; graphite; graphene; fullerenes; carbon nanotubes; any mesoporous and / or interfacial materials discussed elsewhere herein; and combinations thereof (including, in some embodiments, bilayers, triple layers, or multilayers of combined materials). In some embodiments, the interfacial layer may comprise a perovskite material. Additionally, the interfacial layer may comprise doped embodiments of any of the interfacial materials described herein (e.g., Y-doped ZnO, N-doped single-walled carbon nanotubes). The interfacial layer may also comprise a compound comprising three of the above materials (e.g., CuTiO 3 , Zn 2 SnO 4 ), or a compound containing four of the above materials (e.g., CoNiZnO). The foregoing materials may exist in planar, mesoporous, or other nanostructured morphologies (e.g., rods, spheres, flowers, pyramids), or aerogel structures. Additional types of interfacial layers and suitable materials for the IFLs of the present disclosure are described in U.S. Pat. No. 11,171,290, which is incorporated herein by reference.

[0012] Also, some perovskite material PV cells may have so-called "tandem" PV devices that include two or more perovskite photoactive layers. FIG. 2 shows an example of a tandem PV device that includes two photoactive materials 2040 and 2060. In some embodiments, both photoactive materials 2040 and 2060 in FIG. 2 may be perovskite materials. FIG. 2 shows a two-terminal tandem PV device 2000. That is, two photoactive materials are integrated into a single monolithic PV cell. In such a tandem PV cell, the interface layer between the two photoactive layers, such as IFLs 2050 and 2055 in FIG. 2, may include a multi-layer or composite IFL. In some embodiments, the layer sandwiched between the two photoactive layers of the tandem PV device may include an electrode layer. In some embodiments, the tandem PV device may be a four-terminal device, such as the device shown in FIG. 9. A four-terminal tandem PV device has two subcells that are electrically independent from each other but may be optically coupled.

[0013] A two-terminal tandem PV device may have the following layers, in order, from top to bottom or bottom to top: a first substrate, a first electrode, a first interfacial layer, a first perovskite material, a second interfacial layer, a second electrode, a third interfacial layer, a second perovskite material, a fourth interfacial layer, and a third electrode. In an embodiment, the first and third interfacial layers may be hole transporting interfacial layers and the second and fourth interfacial layers may be electron transporting interfacial layers. In other embodiments, the first and third interfacial layers may be electron transporting interfacial layers and the second and fourth interfacial layers may be hole transporting interfacial layers. In yet another embodiment, the first and fourth interfacial layers may be hole transporting interfacial layers and the second and third interfacial layers may be electron transporting interfacial layers. In other embodiments, the first and fourth interfacial layers may be electron transporting interfacial layers and the second and third interfacial layers may be hole transporting interfacial layers. In a tandem PV device, the first and second perovskite materials may have different bandgaps. In some embodiments, the first perovskite material is formamidinium lead bromide (FAPbBr 3), and the second perovskite material is formamidinium lead iodide (FAPbI 3 In another embodiment, the first perovskite material is methylammonium lead bromide (MAPbBr 3 ), and the second perovskite material may be formamidinium lead iodide (FaPbI 3 In another embodiment, the first perovskite material may be methylammonium lead bromide (MAPbBr 3 ), and the second perovskite material may be methylammonium lead iodide (MAPbI 3 ) may also be used.

[0014] (Perovskite materials) The perovskite material may be incorporated into one or more aspects of a PV or other device. The perovskite material according to some embodiments has the general formula w M y X z wherein C comprises one or more cations (e.g., amines, ammonium, phosphonium, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds); M comprises one or more metals (e.g., including Be, Mg, Ca, Sr, Ba, Fe, Cd, Co, Ni, Cu, Ag, Au, Hg, Sn, Ge, Ga, Pb, In, Tl, Sb, Bi, Ti, Zn, Cd, Hg, and Zr); X comprises one or more anions; and w, y, and z represent real numbers between 1 and 20. In some embodiments, C may comprise one or more organic cations. In certain embodiments, each organic cation C may be larger than each metal M, and each anion X may be capable of binding to both the cation C and the metal M.

[0015] In certain embodiments, C is ammonium, a group having the general formula [NR 4 ] +where the R groups can be the same or different. Suitable R groups include, but are not limited to, hydrogen, methyl, ethyl, propyl, butyl, pentyl groups or isomers thereof; any alkane, alkene, or alkyne C x H y , where x=1-20 and y=1-42; cyclic, branched, or linear; halogenated alkyl, C x H y X z , x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes containing at least one N in the ring (e.g., pyridine, pyrrole, pyrrolidine, piperidine, tetrahydroquinoline); any sulfur-containing group (e.g., sulfoxide, thiol, alkylsulfide); any nitrogen-containing group (nitroxide, amine); any phosphorus-containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (e.g., acetic acid, propanoic acid); and their ester or amide derivatives; any amino acid including α, β, γ, and larger derivatives (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histidine, 5-ammonium valerate); any silicon-containing group (e.g., siloxane); and any alkoxy or group -OC x H y , where x=0~20, y=1~42;

[0016] In certain embodiments, C is a formamidinium, having the general formula [R 2 NCRNR 2 ] + where the R groups can be the same or different. Suitable R groups include, but are not limited to, hydrogen, methyl, ethyl, propyl, butyl, pentyl groups or isomers thereof; any alkane, alkene, or alkyne C x H y , where x=1-20, y=1-42, cyclic, branched or linear; halogenated alkyl, Cx H y X z , x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes containing at least one N in the ring (e.g., imidazole, benzimidazole, pyrimidine, (azolidinylidenemethyl)pyrrolidine, triazole); any sulfur-containing group (e.g., sulfoxide, thiol, alkylsulfide); any nitrogen-containing group (nitroxide, amine); any phosphorus-containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and its ester or amide derivatives; any amino acid including α, β, γ and larger derivatives (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histidine, 5-ammonium valerate); any silicon-containing group (e.g., siloxane); and any alkoxy or group -OC. x H y , where x=0~20, y=1~42;

[0017] [ka] Formula 1 includes the general formula [R 2 NCRNR 2 ] + Formula 2 shows the structure of some example formamidinium cations that can function as the cation "C" in perovskite materials.

[0018] [ka] In certain embodiments, C is guanidinium, a compound having the general formula [(R 2 N)2C=NR 2 ] +where the R groups can be the same or different groups. Suitable R groups include, but are not limited to, hydrogen, methyl, ethyl, propyl, butyl, pentyl groups or isomers thereof; any alkane, alkene, or alkyne C x H y , where, x=1-20, y=1-42, cyclic, branched or linear); alkyl halide, C x H y X z , x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in which at least one nitrogen is contained within the ring (e.g., octahydropyrimido[1,2-a]pyrimidine, pyrimido[1,2-a]pyrimidine, hexahydroimidazo[1,2-a]imidazole, hexahydropyrimidin-2-imine); any sulfur-containing group (e.g., sulfoxide, thiol, sulfur, any nitrogen-containing group (nitroxide, amine); any phosphorus-containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and its ester or amide derivatives; any amino acid including alpha, beta, gamma and larger derivatives (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histidine, 5-ammonium valerate); any silicon-containing group (e.g., siloxane); and any alkoxy or group O-C. x H y , where x=0~20, y=1~42;

[0019] [ka] Formula 3 includes the general formula [(R 2 N) 2 C=NR 2 ] + Formula 4 shows the structure of some example guanidinium cations that can function as the cation "C" in perovskite materials.

[0020] [ka] In certain embodiments, C is an ethenetetramine cation, having the general formula [(R 2 N) 2 C=C(NR 2 ) 2 ] + where the R groups can be the same or different groups. Suitable R groups include, but are not limited to, hydrogen, methyl, ethyl, propyl, butyl, pentyl groups or isomers thereof; any alkane, alkene, or alkyne C x H y , where x=1-20 and y=1-42; cyclic, branched, or linear; halogenated alkyl, C x H y X z , x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in which at least one nitrogen is contained within the ring (e.g., 2-hexahydropyrimidin-2-ylidenehexahydropyrimidine, octahydropyrazino[2,3-b]pyrazine, pyrazino[2,3-b]pyrazine, quinoxalino[2,3-b]quinoxaline); any sulfur-containing group ( any nitrogen-containing group (nitroxide, amine); any phosphorus-containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and its ester or amide derivatives; any amino acid including alpha, beta, gamma and larger derivatives (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histidine, 5 ammonium valerate); any silicon-containing group (e.g., siloxane); and any alkoxy or group OC. x H y , where x = 0 to 20 and y = 1 to 42;

[0021] [ka] Equation 5 is a general formula as described above: [(R 2 N) 2 C=C(NR 2 ) 2 ] + Formula 6 shows the structure of some example ethenetetraamine ions that can function as the cation "C" in perovskite materials.

[0022] [ka] In certain embodiments, C is an imidazolium cation, having the general formula [CRNRCRNRCR] + where the R groups can be the same or different. Suitable R groups include, but are not limited to, hydrogen, methyl, ethyl, propyl, butyl, pentyl groups or isomers thereof; any alkane, alkene, or alkyne C x H y , where x=1-20 and y=1-42; cyclic, branched or linear; halogenated alkyl, C x H y X z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes containing at least one nitrogen in the ring (e.g., 2-hexahydropyrimidin-2-ylidenehexahydropyrimidine, octahydropyrazino[2,3-b]pyrazine, pyrazino[2,3-b]pyrazine, quinoxalino[2,3-b]quinoxaline); any sulfur-containing group (e.g., sulfoxide, thiol, , alkyl sulfides); any nitrogen-containing group (nitroxides, amines); any phosphorus-containing group (phosphates); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and its ester or amide derivatives; any amino acid including alpha, beta, gamma and larger derivatives (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histidine, 5-ammonium valerate); any silicon-containing group (e.g., siloxanes); and any alkoxy or group -OC. x H y , where x = 0 to 20 and y = 1 to 42;

[0023] [ka] In some embodiments, X may include one or more halides. In certain embodiments, X may additionally or alternatively include a Group 16 anion. In certain embodiments, the Group 16 anion may be an oxide, sulfide, selenide, or telluride. In certain embodiments, X may additionally or alternatively include one or more pseudohalides (e.g., cyanide, cyanate, isocyanate, fulminate, thiocyanate, isothiocyanate, azide, tetracarbonylcobaltate, carbamoyldicyanomethanide, dicyanonitrosomethanide, dicyanoamide, and tricyanomethanate). For illustration, and without any limitation implied, formula C may be used. w M y X z Exemplary embodiments of perovskite materials having the formula:

[0024] In one embodiment, the perovskite material has the empirical formula CMX 3 M may comprise one of the metals above and C may comprise one or more of the cations above, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds.

[0025] In another embodiment, the perovskite material has the empirical formula C'M 2 X 6 where C' comprises a cation having a 2+ charge, including one or more of the above cations, butanediammonium, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds.

[0026] In another embodiment, the perovskite material has the empirical formula C'MX 4 where C' comprises a cation having a 2+ charge and includes one or more of the above cations, diammonium butane, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds. In such embodiments, the perovskite material may have a 2D structure.

[0027] In one embodiment, the perovskite material has the following empirical formula C 3 M 2 X 9 where C includes one or more of said cations, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds.

[0028] In one embodiment, the perovskite material has the empirical formula CM 2 X 7 C may comprise one or more of the above cations, Group 1 metals, Group 2 metals, and / or other cations or cation-like compounds.

[0029] In one embodiment, the perovskite material has the following empirical formula C 2 MX 4where C includes one or more of the cations, group 1 metals, group 2 metals, and / or other cations or cation-like compounds. The perovskite material may also have a mixed ion composition, where C, M, or X includes two or more species. In some embodiments, the perovskite material may include two or more anions or three or more anions. In some embodiments, the perovskite material may include two or more cations or three or more cations. In certain embodiments, the perovskite material may include two or more metals or three or more metals.

[0030] In one example, the perovskite material in the active layer is CMX 3-y X' y (0≧y≧3), where C comprises one or more cations (e.g., amines, ammonium, Group 1 metals, Group 2 metals, formamidinium, guanidinium, ethenetetramine, phosphonium, imidazolium, and / or other cations or cation-like compounds); M comprises one or more metals (e.g., Be, Mg, Ca, Sr, Ba, Fe, Cd, Co, Ni, Cu, Ag, Au, Hg, Sn, Ge, Ga, Pb, In, Tl, Sb, Bi, Ti, Zn, Cd, Hg, and Zr); and X and X′ comprise one or more anions. In one embodiment, the perovskite material is CPbI 3-y Cl y In another example, the perovskite material in the active layer may comprise a compound represented by formula C 1-x C' x MX 3 (0≧x≧1), where C and C′ comprise one or more cations as described above. In another example, the perovskite material in the active layer may have the formula CM 1-z M' z X 3 (0≧z≧1), where M and M′ comprise one or more metals as described above. In one example, the perovskite material in the active layer may have the formula C 1-x C' x M 1-z M' z X 3-y X'y (0≧x≧1; 0≧y≧3; 0≧z≧1). C and C' comprise one or more cations as described above; M and M' comprise one or more metals as described above; and X and X' comprise one or more anions as described above.

[0031] For purposes of illustration, and without implying any limitation, an exemplary embodiment of a perovskite material is Cs 0.1 FA 0.9 Pb(I 0.9 Cl 0.1 ) 3 ;Rb 0.1 FA 0.9 Pb(I 0.9 Cl 0.1 ) 3 , Cs 0.1 FA 0.9 PbI 3 ;FAPb 0.5 Sn 0.5 I 3 ;FA 0.83 Cs 0.17 Pb(I 0.6 Br 0.4 ) 3 ;FA 0.83 Cs 0.12 Rb 0.05 Pb(I 0.6 Br 0.4 ) 3 and F.A. 0.85 MA 0.15 Pb(I 0.85 Br 0.15 ) 3 may be also possible.

[0032] (Composite Perovskite Material Device Design) In certain embodiments, the present disclosure may provide hybrid designs of PV and other similar devices (e.g., batteries, hybrid PV cells, FETs, LEDs, nonlinear optical elements (NLOs), waveguides, etc.) that include one or more perovskite materials. For example, one or more perovskite materials may function as either or both of the first and second active materials of certain embodiments (e.g., active materials 3906a and 3908a in FIG. 3). More generally, certain embodiments of the present disclosure provide PV or other devices having an active layer that includes one or more perovskite materials. In such embodiments, perovskite materials (i.e., materials that include any one or more perovskite materials) may be used in active layers of various configurations. Furthermore, a perovskite material may function as any one or more components of the active layer, as described in more detail below. In certain embodiments, the same perovskite material may perform multiple such functions, while in other embodiments, multiple perovskite materials may be included in a device, with each perovskite material performing one or more such functions. In certain embodiments, regardless of the role the perovskite material plays, it may be prepared and / or present in the device in various states. For example, in some embodiments, it may be substantially solid. A solution or suspension may be coated or deposited within the device (e.g., onto another component of the device, such as a mesoporous, interfacial, charge transport, photoactive, or other layer, and / or electrode). The perovskite material in some embodiments may be formed in-situ on a surface of another component of the device (e.g., by deposition of an underlying layer as a thin film solid). Any other suitable means of forming a layer comprising the perovskite material may be used.

[0033] In general, a perovskite material device may have a first electrode, a second electrode, and an active layer comprising a perovskite material, with the active layer being at least partially disposed between the first electrode and the second electrode. In some embodiments, the first electrode may be one of the anode and the cathode, and the second electrode may be the other of the anode and the cathode. The active layer according to certain embodiments may include any one or more active layer components, including one or more of a charge transport material, a liquid electrolyte, a mesoporous material, a photoactive material (e.g., dye, silicon, cadmium telluride, cadmium sulfide, cadmium selenide, copper indium gallium selenide, gallium arsenide, germanium indium phosphide, semiconducting polymers, other photoactive materials), and an interface material. Any one or more of these active layer components may include one or more perovskite materials. In some embodiments, some or all of the active layer components may be disposed in whole or in part in a sublayer. For example, an active layer may include any one or more of an interfacial layer including an interfacial material, a mesoporous layer including a mesoporous material, and a charge transport layer including a charge transport material. Additionally, in some embodiments, an interfacial layer may be included between any two or more other layers of the active layer and / or between an active layer member and an electrode. Reference to a layer may include the final arrangement (e.g., substantially separate portions of each material that are separately definable within a device) and / or reference to a layer may refer to the arrangement of a device during construction, regardless of the possibility of subsequent mixing of the materials in each layer.

[0034] In some embodiments, a layer may comprise a distinct, substantially continuous material (eg, a layer may be in the form as stylistically shown in FIG. 1).

[0035] In some embodiments, the perovskite material device may be a field effect transistor (FET). The FET perovskite material device may include a source electrode, a drain electrode, a gate electrode, a dielectric layer, and a semiconducting layer. In some embodiments, the semiconducting layer of the FET perovskite material device may be a perovskite material.

[0036] Perovskite material devices according to certain embodiments may include one or more substrates, if necessary. In certain embodiments, one or both of the first electrode and the second electrode may be coated or otherwise disposed on a substrate, with the electrodes disposed substantially between the substrate and the active layer. The materials of the components of the device (e.g., substrate, electrodes, active layer and / or active layer components) may be either rigid or flexible in whole or in part in various embodiments. In some embodiments, the electrodes may function as substrates, thereby eliminating the need for a separate substrate.

[0037] Furthermore, perovskite material devices according to certain embodiments may include an anti-reflective layer or coating (ARC) if required.

[0038] Some description of the various materials that may be included in a perovskite material device is provided in part with reference to FIG. 2. FIG. 2 is a schematic diagram of a tandem two-terminal perovskite material device 3900 according to an embodiment. While in FIG. 2 and other figures of the present disclosure illustrating perovskite devices (e.g., FIGS. 1, 3-4, and 9), various components of the device are shown as separate layers comprising continuous materials, it should be understood that such figures are schematic. Thus, embodiments according thereto may have such separate layers, and / or substantially intermixed non-continuous layers, consistent with the use of "layer" discussed above. The device 3900 includes a first substrate 3901 and a second substrate 3913. A first electrode 3902 is disposed on an inner surface of the first substrate 3901, and a second electrode 3912 is disposed on an inner surface of the second substrate 3913. An active layer 3950 is sandwiched between the two electrodes 3902 and 3912. The active layer 3950 includes a mesoporous layer 3904, first and second photoactive materials 3906 and 3908, a charge transport layer (CTL) 3910, and several interfacial layers. Figure 2 further illustrates an example of a device 3900 according to an embodiment, where the sub-layers of the active layer 3950 are separated by interfacial layers, which are further disposed on each of the electrodes 3902 and 3912. In particular, second, third, and fourth interfacial layers 3905, 3907, and 3909 are disposed between the mesoporous layer 3904, the first photoactive material 3906, the second photoactive material 3908, and the charge transport layer 3910, respectively. The first and fifth interfacial layers 3903 and 3911 are disposed between (i) the first electrode 3902 and the mesoporous layer 3904, and (ii) the charge transport layer 3910 and the second electrode 3912, respectively. Thus, the architecture of the exemplary device shown in FIG. 2 can be characterized as substrate-electrode-active layer-electrode-substrate. The structure of the active layer 3950 can be characterized as interfacial layer-mesoporous layer-interfacial layer-photoactive material-interfacial layer-photoactive material-interfacial layer-charge transport layer-interfacial layer. In some embodiments, no interfacial layers may be present. Alternatively, one or more interfacial layers may be included only between some but not all components of the active layer and / or components of the device.

[0039] Substrates, such as one or both of the first substrate 3901 and the second substrate 3913, may be flexible or rigid. If two substrates are included, at least one should be transparent or semi-transparent to electromagnetic (EM) radiation (e.g., UV, visible, or IR radiation, etc.). If one substrate is included, it may be transparent or semi-transparent as well, although this is not necessary as long as some portion of the device allows EM radiation to contact the active layer 3950. Suitable substrate materials include any one or more of glass, sapphire, magnesium oxide (MgO), mica, polymers (e.g., PEN, PET, PEG, polyolefins, polypropylene, polyethylene, polycarbonate, PMMA, polyamide, vinyl, Kapton), ceramic, carbon, composites (e.g., fiberglass, Kevlar, carbon fiber), fabrics (e.g., cotton, nylon, silk, wool), wood, drywall, tile (e.g., ceramic, composite, or clay), metal, steel, silver, gold, aluminum, magnesium, concrete, and combinations thereof.

[0040] As previously mentioned, an electrode (e.g., one of electrodes 3902 and 3912 in FIG. 2) may be either an anode or a cathode. In some embodiments, one electrode may function as a cathode and the other electrode as an anode. One or both of electrodes 3902 and 3912 may be coupled to leads, cables, wires, or other means that allow charge transport to and / or from device 3900 and / or device 118. The electrodes may be constructed of any conductive material, and at least one electrode should be transparent or semi-transparent to EM radiation and / or positioned such that EM radiation can contact at least a portion of active layer 3950. Suitable materials include any one or more of indium tin oxide or tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), cadmium oxide (CdO), zinc indium tin oxide (ZITO), aluminum zinc oxide (AZO), aluminum (Al), gold (Au), silver (Ag), calcium (Ca), chromium (Cr), copper (Cu), magnesium (Mg), titanium (Ti), steel, carbon (and its allotropes), doped carbon (e.g., nitrogen-doped), nanoparticles in a core-shell configuration (e.g., silicon-carbon core-shell structures), and combinations thereof.

[0041] The mesoporous material (e.g., the material included in mesoporous layer 3904 of FIG. 2) may include any pore-containing material. In certain embodiments, the pores may have a diameter ranging from about 1 to about 100 nm. In other embodiments, the diameter of the pores may range from about 2 to about 50 nm. Suitable mesoporous materials include any interfacial material and / or mesoporous material described elsewhere herein, aluminum (Al), bismuth (Bi), cerium (Ce), hafnium (Hf), indium (In), molybdenum (Mo), niobium (Nb), nickel (Ni), silicon (Si), titanium (Ti), vanadium (V), zinc (Zn), zirconium (Zr), oxides of any one or more of the foregoing metals (e.g., alumina, ceria, titania, zinc oxide, zirconia, etc.), sulfides of any one or more of the foregoing metals, nitrides of any one or more of the foregoing metals, and any combination thereof. In some embodiments, any of the materials disclosed herein as IFLs may be mesoporous materials. In other embodiments, the device shown in Figure 2 may not include a mesoporous material layer, but may include only a non-mesoporous thin film, or "compact" IFL.

[0042] The photoactive material (e.g., first or second photoactive material 3906 or 3908 in FIG. 2) can be silicon (e.g., polycrystalline silicon, single crystal silicon, or amorphous silicon), cadmium telluride, cadmium sulfide, cadmium selenide, copper indium gallium selenide, copper indium selenide, copper zinc tin sulfide, gallium arsenide, germanium, germanium indium phosphide, indium phosphide, one or more semiconductor polymers (e.g., polythiophenes (e.g., poly(3-hexylthiophene) and its derivatives, or P3HT); polyheptadecanylcarbazole dithienylbenzothiadiazole and its derivatives, or P3HT); poly(phenylene phosphate) dithienylbenzothiadiazole ... (e.g., PCDTBT); other copolymers such as polycyclopentadithiophene-benzothiadiazole and its derivatives (e.g., PCDTBT), polybenzodithiophenyl-thienothiophenediyl and its derivatives (e.g., PTB6, PTB7, PTB7-th, PCE-10); poly(triarylamine) compounds and their derivatives (e.g., PTAA); polyphenylenevinylene and its derivatives (e.g., MDMO-PPV, MEH-PPV), and any one or more of combinations thereof.

[0043] In certain embodiments, the photoactive material may additionally or alternatively include a dye (e.g., N719, N3, other ruthenium-based dyes). In some embodiments, the dye (regardless of composition) may be coated onto another layer (e.g., the mesoporous layer and / or the interfacial layer). In some embodiments, the photoactive material may include one or more perovskite materials. The perovskite-containing photoactive material may be in solid form, or in some embodiments, may take the form of a dye containing suspension or solution that includes the perovskite material. Such a solution or suspension may be coated onto other device components in a similar manner as other dyes. In some embodiments, the solid perovskite-containing material may be deposited by any suitable means (e.g., vapor deposition, solution deposition, direct placement of solid material). Devices according to various embodiments may include one, two, three, or more photoactive compounds (e.g., one, two, three, or more perovskite materials, dyes, or combinations thereof). In certain embodiments including multiple dyes or other photoactive materials, each of the two or more dyes or other photoactive materials may be separated by one or more interfacial layers or may be at least partially intermixed.

[0044] As used herein, "charge transport material" refers to any solid, liquid, or other material that can collect and / or transport charge carriers (electrons or holes). The charge transport material (e.g., the charge transport material of charge transport layer 3910 in FIG. 2) may include a solid charge transport material (i.e., colloquially labeled solid electrolyte) or may include a liquid electrolyte and / or an ionic liquid. In a PV device according to an embodiment, the charge transport material may be capable of transporting charge carriers to an electrode. The charge carriers may include holes (whose transport makes the charge transport material just aptly labeled "hole transport material") and electrons. Depending on the placement of the charge transport material relative to either the cathode or anode in a PV or other device, the holes may be transported toward the anode and the electrons may be transported toward the cathode. Suitable examples of charge transport materials according to certain embodiments include perovskite materials; I- / I3-; Co complexes; polythiophenes (e.g., poly(3-hexylthiophene) and its derivatives, or P3HT); carbazole-based copolymers, such as polyheptadecanylcarbazole dithienylbenzothiadiazole and its derivatives (e.g., PCDTBT); other copolymers, such as polycyclopentadithiophene benzothiadiazole and its derivatives (e.g., PCDTBT), polybenzodithiophenyl-thienothiophenediyl and its derivatives (e.g., PTB6, PTB7, PTB7-th, PCE-10); poly(triarylamine) compounds and their derivatives (e.g., PTAA); spiro-OMeTAD; polyphenylenevinylene and its derivatives (e.g., MDMO-PPV, MEH-PPV); fullerenes and / or fullerene derivatives (e.g., C 60, PCBM); carbon nanotubes; graphite; graphene; carbon black; amorphous carbon; glassy carbon; carbon fiber; and combinations thereof. The charge transport material of some embodiments may be an n-type or p-type active, ambipolar, and / or intrinsic semiconductor material. The charge transport material may be disposed in proximity to one of the electrodes of the device. In some embodiments, it may be disposed adjacent to the electrode, while in other embodiments, an interfacial layer may be disposed between the charge transport material and the electrode (e.g., as shown by the fifth interfacial layer 3911 in FIG. 2). In certain embodiments, the type of charge transport material may be selected based on the electrode it is adjacent to. For example, if the charge transport material collects and / or transports holes, it may be disposed in proximity to the anode and holes may be transported to the anode. However, the charge transport material may instead be disposed in proximity to the cathode and selected or constructed to transport electrons to the cathode.

[0045] As an example, Figure 3 illustrates an embodiment of a tandem two-terminal perovskite material device 3900a having a similar structure to the perovskite material device 3900 illustrated in Figure 2. Figure 3 is a schematic diagram of a perovskite material device 3900a according to an embodiment including active layers 3906a and 3908a. In some embodiments, one or both of the active layers 3906a and 3908a may comprise any of the perovskite photoactive materials described above with respect to Figure 2. In other embodiments, one or both of the active layers 3906a and 3908a may comprise any of the photoactive materials described herein, such as thin film semiconductors (e.g., CdTe, CZTS, CIGS), photoactive polymers, dye-sensitized photoactive materials, fullerenes, small molecule photoactive materials, and crystalline and polycrystalline semiconductor materials (e.g., silicon, GaAs, InP, Ge). In yet another embodiment, one or both of the active layers 3906a and 3908a may include a light emitting diode (LED), a field effect transistor (FET), a thin film battery layer, or a combination thereof. In an embodiment, one of the active layers 3906a and 3908a may include a photoactive material and the other may include an LED, a FET, a thin film battery layer, or a combination thereof. Other layers shown in FIG. 3, such as layers 3901a, 3902a, 3903a, 3904a, 3905a, 3907a (i.e., recombination layer), 3909a, 3910a, 3911a, 3912a, and 3913a, may be similar to the corresponding layers as described herein with respect to FIG. 2.

[0046] Further, in some embodiments, the perovskite material may have more than two active layers. As an example, Figure 4 is a schematic diagram illustrating an embodiment of a tandem two-terminal perovskite material device 3900b that includes three active layers and has a similar structure to the perovskite material device 3900 shown in Figure 2. Figure 4 has active layers 3904b, 3906b, and 3908b. In an embodiment, one or more of the active layers 3904b, 3906b, and 3908b may include any of the photoactive materials described above with respect to Figures 2 and 3. Other layers shown in FIG. 4, such as layers 3901b, 3902b, 3903b, 3904b, 3905b (i.e., recombination layer), 3907b (i.e., recombination layer), 3909b, 3910b, 3911b, 3912b, and 3913b, may be similar to the corresponding layers as described with respect to FIGS. 2 and 3.

[0047] In an embodiment, the tandem PV device may be a four-terminal device, as shown in FIG. 9. The four-terminal device 2300 may include two subcells 2400 and 2500 that are electrically independent of each other. In an embodiment, the four-terminal device has two subcells 2400 and 2500 that are mechanically stacked on top of each other and optically coupled, so that light transmitted through the front subcell 2400 reaches the rear subcell 2500. The four-terminal PV 2300 has a first substrate layer 2310, which may be glass (or a similar material transparent to solar radiation) through which solar radiation can be transmitted. The transparent layer in an embodiment may also be referred to as a superstrate or substrate, and may comprise any one or more of a variety of rigid or flexible materials as discussed above.

[0048] The first PAM layer 2350 of the front subcell 2400 may be composed of an electron donor or p-type material, and / or an electron acceptor or n-type material, and / or an ambipolar material that exhibits both p-type material properties and p-type properties, and / or an intrinsic semiconductor that exhibits neither n-type nor p-type properties. The photoactive layer 2350 may include any of the photoactive materials described with respect to Figures 2-3 in some embodiments. The active layer, or photoactive layer 2350 as shown in Figure 9, is sandwiched between two conductive electrode layers 2320 and 2370. As previously mentioned, the active layer in some embodiments is not necessarily photoactive, but in the device shown in Figure 63, it is. In Figure 9, the electrode layer 6320 may be a transparent conductor, such as fluorine doped tin oxide (FTO material) or other materials described herein. In other embodiments, the second substrate 2390 and the second electrode 2370 may be transparent. The electrode layer 2370 may be a transparent conductor, such as an indium zinc oxide (IZO material) material, or other electrode materials described herein or known in the art. The front subcell 2400 also includes interfacial layers (IFLs) 2330, 2340, 2350, 2355. The IFLs may include any suitable material as previously described. Although shown with two IFLs on either side of the photoactive layer 2350, the front subcell 2400 may include zero, one, two, three, four, five, or more interfacial layers on either side of the photoactive material layer 2350. The IFLs according to certain embodiments may be semiconducting in nature, intrinsic, ambipolar, p-type, or n-type, or may be dielectric in nature. In some embodiments, the IFL on the cathode side of the device (e.g., IFLs 2355 and 2360 shown in FIG. 9) may be n-type and the IFL on the anode side of the device (e.g., IFLs 2330 and 2340 shown in FIG. 9) may be p-type, although in other embodiments the cathode side IFL may be p-type and the anode side IFL may be n-type. The front subcell 2400 may be attached to electrical leads by electrodes 2320 and 2370 and a discharging unit such as a battery, motor, capacitor, electrical grid, or any other electrical load.

[0049] The rear subcell 2500 of the PV device 2300 may have a similar or different architecture to the front subcell 2400. The rear subcell 2500 may include a second photoactive material, and in some embodiments, may include any of the photoactive materials described with respect to FIGS. 2-4. In one example, the rear subcell 2500 may have electrodes, IFLs, and other layers of the same or different architecture as the front subcell 2400. In some embodiments, one or both of the photoactive layers of the front subcell 2400 and the rear subcell 2500 may include any of the photoactive materials described with respect to FIGS. 2-4, or one may include a photoactive material and the other may include an LED, FET, thin film battery layer, or a combination thereof. The layers, such as the substrate, electrodes, and IFLs, of the front subcell 2400 and the rear subcell may be similar to the corresponding layers as described with respect to FIGS. 2-4 and may include any of the materials or configurations described as suitable for these corresponding layers.

[0050] A non-conductive layer 2380 may be disposed between and adjacent to the front subcell 2400 and the rear subcell 2500. As used herein, "non-conductive layer" means a layer that is electrically non-conductive and is not intended to define the thermal properties of the non-conductive layer, which may be thermally conductive or thermally insulating. In some embodiments, the non-conductive layer 2380 may include, but is not limited to, adhesives, epoxies, glass, laminates, waxes, polymers, resins, elastomers, thermosets, or any combination thereof. In some embodiments, the non-conductive layer 6010 may include polyvinyl acetate, polyolefins, polystyrene, polyglycols, polyorganic acids, natural rubbers, synthetic rubbers, polyesters, nylons, polyamides, polyaryls, polynucleic acids, polysaccharides, polyurethanes, acrylonitrile butadiene styrene, acrylics, acrylic polymers, acrylic resins, cross-linked porous resins, and any combination or derivative thereof. Examples of polymers suitable for certain embodiments include, but are not limited to, poly(ethylene-vinyl acetate) (EVA), high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polyethylene glycol (PEG / PEO), poly(methyl methacrylate) (PMMA), polyoxymethylene (POM), poly(acrylonitrile butadiene styrene) (ABS), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polyvinyl chloride (PCC), polyvinyl chloride (PCF), polyvinyl chloride (PCT ... FE), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polylactic acid (PLA), polycarbonate (PC), polyether ether ketone (PEEK), polybutylene terephthalate (PBT), butylene rubber, polyisoprene, polyurethane (PU), polydimethylsiloxane (PDMS), urea formaldehyde resin, epoxy resin, phenol formaldehyde resin (PF), derivatives thereof, and any combination thereof. The configuration of the polymer backbone of the binding polymer may be isotactic, syndiotactic, or atactic. In one example, the non-conductive layer 2380 is transparent. In another example, the non-conductive layer 2380 is not transparent.

[0051] Additional more specific example embodiments of perovskite devices are further discussed with respect to another schematic drawing of an exemplary device. The schematic nature of these depictions of Figures 2-4 and 9 is likewise not intended to limit the types of devices that may be constructed according to any one or more of Figures 2-4 and 9 in an embodiment. That is, the architectures shown in Figures 2-4 and 9 may be adapted to provide BHJs, batteries, FETs, hybrid PV cells, series multi-cell PVs, parallel multi-cell PVs, and other similar devices of other embodiments of the present disclosure according to any suitable means, including both those explicitly discussed elsewhere in this application and other suitable means apparent to those of ordinary skill in the art having the benefit of this disclosure.

[0052] (Formation of perovskite material active layer) In certain embodiments, the perovskite material may be deposited onto a substrate layer as an active layer in a PV device, for example by blade coating, drop casting, spin casting, slot-die printing, screen printing, or inkjet printing, using the steps described below.

[0053] First, a lead halide precursor ink is formed. A quantity of lead halide may be collected in a clean, dry container in a controlled atmosphere environment (e.g., a controlled atmosphere box with a globe-containing porthole allows for material manipulation in an air-free environment). Suitable lead halides include, but are not limited to, lead (II) iodide, lead (II) bromide, lead (II) chloride, and lead (II) fluoride. The lead halide may include a single species of lead halide or may have a mixture of lead halides in precise ratios. In certain embodiments, the lead halide mixture may have any binary, ternary, or quaternary ratio of 0.001 to 100 mole % iodide, bromide, chloride, or fluoride. In one embodiment, the lead halide mixture may have lead (II) chloride and lead (II) iodide in a ratio of about 10:90 mol:mol. In other embodiments, the lead halide mixture may have lead(II) chloride and lead(II) iodide in a ratio of about 5:95, about 7.5:92.5, or about 15:85 mol:mol.

[0054] Alternatively, other lead salt precursors may be used in conjunction with or in place of the lead halide salt to form the precursor ink. Suitable precursor salts may have lead(II) or lead(IV) in any combination with the following anions: nitrate, nitrite, carboxylate, acetate, acetonylacetonate, formate, oxalate, sulfate, sulfite, thiosulfate, phosphate, tetrafluoroborate, hexafluorophosphate, tetra(perfluorophenyl)borate, hydride, oxide, peroxide, hydroxide, nitride, arsenate, arsenite, perchlorate, carbonate, bicarbonate, chromate, dichromate, iodate, bromate, chlorate, chlorite, hypochlorite, hypobromite, cyanide, cyanate, isocyanate, fulminate, thiocyanate, isothiocyanate, azide, tetracarbonylcobaltate, carbamoyldicyanomethanide, dicyanonitrosomethanide, dicyanamide, tricyanomethanate, amide, and permanganate.

[0055] The precursor ink may further comprise, as a salt of the aforementioned anions, a lead(II) salt or a lead(IV) salt with respect to the following metal ions Be, Mg, Ca, Sr, Ba, Fe, Cd, Co, Ni, Cu, Ag, Au, Hg, Sn, Ge, Ga, Pb, In, Tl, Sb, Bi, Ti, Zn, Cd, Hg, and Zr in a molar ratio of 0 to 100%.

[0056] A solvent may then be added to the container to dissolve the lead solids and form the lead halide precursor ink. Suitable solvents include, but are not limited to, dry N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide, dialkylformamide, dimethylsulfoxide (DMSO), methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, alkylnitriles, arylnitriles, acetonitrile, alkoxyalcohols, alkoxyethanols, 2-methoxyethanol, glycols, propylene glycol, ethylene glycol, and combinations thereof. In one embodiment, the lead solids are dissolved in dry dimethylformamide (DMF). In some embodiments, the solvent may further include 2-methoxyethanol and acetonitrile. In certain embodiments, the 2-methoxyethanol and acetonitrile may be added in a volume ratio of about 25:75 to about 75:25, or at least 25:75. In certain embodiments, the solvent may have a ratio of 2-methoxyethanol and acetonitrile to DMF of about 1:100 to about 1:1, or about 1:100 to about 1:5, by volume. In certain embodiments, the solvent may have a ratio of 2-methoxyethanol and acetonitrile to DMF of at least about 1:100, by volume.

[0057] In an embodiment, the lead solids may be dissolved at a temperature of about 20° C. to about 150° C. In one embodiment, the lead halide solids are dissolved at about 85° C. The lead solids are dissolved long enough to form a solution, which may be carried out for a period of up to about 72 hours. The resulting solution forms the base of the lead halide precursor ink. In an embodiment, the lead halide precursor ink may have a lead halide concentration of between about 0.001 M and about 10 M, or about 1 M.

[0058] Optionally, certain additives may be added to the lead halide precursor ink to affect the crystallinity and stability of the final perovskite. In an embodiment, the lead halide precursor ink may further comprise an amino acid (e.g., 5-aminovaleric acid, histidine, glycine, lysine), an amino acid hydrohalide salt (e.g., 5-aminovaleric acid hydrochloride), an IFL surface modification (SAM) agent (discussed earlier herein), or a combination thereof. Suitable amino acids for the lead halide precursor ink include, but are not limited to, α-amino acids, β-amino acids, γ-amino acids, δ-amino acids, and any combination thereof. In an embodiment, formamidinium chloride may be added to the lead halide precursor ink. In other embodiments, halides of any cation discussed earlier herein may be used. In an embodiment, a combination of additives may be added to the lead halide precursor ink, including, for example, a combination of formamidinium chloride and 5-aminovaleric acid hydrochloride.

[0059] In some embodiments, additives including formamidinium chloride and / or 5-aminovaleric acid hydrochloride may be added to the lead halide precursor ink at various concentrations depending on the desired properties of the resulting perovskite material. In some embodiments, the additives may be added at a concentration of about 1 nM to about 1 M, about 1 μM to about 1 M, or about 1 μM to about 1 mM.

[0060] Optionally, in certain embodiments, water may be added to the lead halide precursor ink. For purposes of illustration and not to limit the present disclosure to any particular theory or mechanism, the presence of water affects perovskite thin film crystal growth. Under normal circumstances, water is absorbed as vapor from the air. However, by adding water directly to the lead halide precursor ink at a specific concentration, it is possible to control the crystallinity of the perovskite PV. Suitable water includes distilled water, deionized water, or any other water source that is substantially free of contaminants (including minerals). Based on optical IV sweeps, it has been found that the light-to-electrical power conversion efficiency of perovskite PV can be nearly tripled by the addition of water compared to a completely dry device.

[0061] Water may be added to the lead halide precursor ink in various concentrations depending on the desired properties of the resulting perovskite material, hi some embodiments, water may be added at a concentration of about 1 nL / mL to about 1 mL / mL, about 1 μL / mL to about 0.1 mL / mL, or about 1 μL / mL to about 20 μL / mL.

[0062] The lead halide precursor ink may then be deposited on a desired substrate. Suitable substrate layers may include any substrate layer previously identified in this disclosure. As previously described, the lead halide precursor ink may be deposited by various means, including, but not limited to, drop casting, spin coating, slot die printing, inkjet printing, gravure printing, screen printing, sputtering, PE-CVD, atomic layer deposition, thermal evaporation, spray coating, and any combination thereof. In certain embodiments, the lead halide precursor ink may be spin coated on the substrate at a speed of about 500 rpm to about 10,000 rpm for a time period of about 5 seconds to about 600 seconds. In one embodiment, the lead halide precursor ink may be spin coated on the substrate at about 3000 rpm for about 30 seconds. The lead halide precursor ink may be deposited on the substrate in an ambient atmosphere within a humidity range of about 0% relative humidity to about 50% relative humidity. The lead halide precursor ink may then be dried in a substantially water-free atmosphere, ie, less than 30% relative humidity, to form a thin film.

[0063] The thin film may then be thermally annealed at a temperature of about 20° C. to about 300° C. for up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The perovskite material active layer may then be completed by a conversion process. In this process, the precursor film is immersed in or rinsed with a solution containing a solvent or mixture of solvents (e.g., DMF, isopropanol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethylsulfoxide, water) at a concentration between 0.001 M and 10 M and a salt (e.g., methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide, 5-aminovaleric acid hydroiodide). Also, in certain embodiments, the thin film may be thermally post-annealed in the same manner as in the first line of this paragraph.

[0064] In an embodiment, a lead salt precursor may be deposited on a substrate to form a lead salt thin film. The substrate may have a temperature approximately equal to ambient temperature or a controlled temperature between 0° C. and 500° C. The lead salt precursor may be deposited by any of the methods previously described for the lead halide precursor ink. In certain embodiments, deposition of the lead salt precursor may include a sheet-to-sheet or roll-to-roll manufacturing method. Deposition of the lead salt precursor may be carried out in various atmospheres at ambient pressure, or at atmospheric or subambient pressure (e.g., 1 mTorr to 500 mTorr). Deposition atmospheres may include ambient air, controlled humidity environments (e.g., 0 to 100 g H 2 O / m 3 Gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of the aforementioned gases. The controlled humidity environment may include an environment in which the absolute humidity or % relative humidity is maintained at a fixed value, or an environment in which the absolute humidity or % relative humidity varies according to a predetermined set point or function. In certain embodiments, deposition may be performed in a controlled humidity environment having a % relative humidity between 0% and 50%. In other embodiments, deposition may be performed in a controlled humidity environment having a % relative humidity between 0 gH 2 O / m 3 Gas or more, 20 gH 2 O / m 3 It may be carried out in a controlled humidity environment below 100° C. Unless otherwise stated, any annealing or deposition steps described herein may be carried out under the aforementioned conditions.

[0065] The lead salt precursor may be a liquid, gas, solid, or a combination of these states of matter, such as a solution, suspension, colloid, foam, gel, or aerosol. In some embodiments, the lead salt precursor may be a solution containing one or more solvents. For example, the lead salt precursor may contain one or more of N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide, dialkylformamide, dimethylsulfoxide (DMSO), acetonitrile, methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, and combinations thereof. The lead salt precursor may be a single lead salt (e.g., lead(II) iodide, lead(II) thiocyanate), or any combination disclosed herein (e.g., PbI 2 +PbCl 2 ;PbI 2 +Pb(SCN) 2 ). The lead salt precursor may also contain one or more additives, such as an amino acid (e.g., 5-aminovaleric hydroiodic acid), 1,8-diiodooctane, 1,8-dithiooctane, formamidinium halide, acetic acid, trifluoroacetic acid, methylammonium halide, or water. The lead salt precursor may be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film. The lead salt thin film may then be thermally annealed under the same conditions and for the same time as described above for the lead halide precursor ink thin film. The annealing environment may have the same pressure and atmosphere as the lead salt deposition environment and conditions described above. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the annealing may be performed at 0 gH 2 O / m 3 More than 20gH 2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0066] After the lead salt precursor is deposited, a second salt precursor (e.g., formamidinium iodide, formamidinium thiocyanate, guanidinium thiocyanate) may be deposited on the lead salt thin film. The lead salt thin film may have a temperature approximately equal to ambient temperature or may have a controlled temperature between 0°C and 500°C. In an embodiment, the second salt precursor may be deposited at ambient temperature or at an elevated temperature of about 25°C to 125°C. The second salt precursor may be deposited by any of the methods previously described for the lead halide precursor ink. The deposition of the second salt precursor may be carried out in the same environment and under the same conditions previously described for the first salt precursor.

[0067] In certain embodiments, the second salt precursor may be a solution containing one or more solvents (eg, one or more of the solvents described above for the first lead salt precursor).

[0068] After deposition of the lead salt precursor and the second salt precursor, the substrate may be annealed. Annealing the substrate converts the lead salt precursor and the second salt precursor into a perovskite material (e.g., FAPbI 3 , GAPb(SCN) 3 , FASnI 3 The annealing may be performed in the same environment as the lead salt deposition environment and under the same conditions as those described above. In certain embodiments, the annealing may be performed in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the annealing may be performed in a controlled humidity environment having a relative humidity % of 0 gH or more and 50% or less. 2 O / m 3 Gas over 20gH 2 O / m 3 It may be performed in a gas or less controlled humidity environment. In an embodiment, the annealing may be performed at a temperature between 50° C. and 300° C.

[0069] For example, in certain embodiments, FAPbI can be prepared by the following process: 3 A perovskite material may be formed by first dissolving PbI in anhydrous DMF. 2 and PbCl 2A lead(II) halide precursor having a molar ratio of about 90:10 may be deposited on the substrate by spin coating or slot die printing. The lead halide precursor ink may be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, for about 1 hour (±15 minutes) to form a thin film. The thin film may then be thermally annealed at a temperature of about 50° C. (±10° C.) for about 10 minutes. A formamidinium iodide precursor comprising formamidinium iodide at a concentration of 25 to 60 mg / mL dissolved in anhydrous isopropyl alcohol may then be deposited on the lead halide thin film by spin coating or slot die printing. After the lead halide precursor and formamidinium iodide precursor are deposited, the substrate may be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity (about 4 to 7 gH 2 O / m 3 air) and annealed between about 125 and 200°C to formamidinium lead iodide (FAPbI 3 ) Perovskite materials may be formed.

[0070] In another embodiment, the perovskite material is C'CPbX 3 where C' is one or more Group 1 metals (e.g., Li, Na, K, Rb, Cs). In certain embodiments, M' may be cesium (Cs). In yet other embodiments, the perovskite material may include C' v C w Pb y X z where C′ is one or more Group 1 metals and v, w, y, and z represent real numbers between 1 and 20. In certain embodiments, the perovskite material may be deposited as an active layer in a PV device onto a substrate layer by, for example, drop casting, spin casting, gravure coating, blade coating, reverse gravure coating, slot-die printing, screen printing, or inkjet printing.

[0071] First, a lead halide solution is formed. The lead halide solution may be prepared in any of the same manners and of similar composition as the lead halide precursor inks described above. Other lead salt precursors (such as those described above with respect to the lead halide precursor inks) may be used in conjunction with or in place of the lead halide salt to form the lead salt solution.

[0072] A Group 1 metal halide solution is then formed. A quantity of Group 1 metal halide may be mass collected in a clean, dry container under controlled atmosphere environment. Suitable Group 1 metal halides include, but are not limited to, cesium iodide, cesium bromide, cesium chloride, cesium fluoride, rubidium iodide, rubidium bromide, rubidium chloride, rubidium fluoride, lithium iodide, lithium bromide, lithium chloride, lithium fluoride, sodium iodide, sodium bromide, sodium chloride, sodium fluoride, potassium iodide, potassium bromide, potassium chloride, potassium fluoride. The Group 1 metal halide may comprise a single Group 1 metal halide or may have a mixture of Group 1 metal halides in precise ratios.

[0073] Alternatively, other Group 1 metal salt precursors may be used along with or in place of the Group 1 metal halide salt to form a Group 1 metal salt solution. Suitable precursor Group 1 metal salts may include any combination of Group 1 metals and the following anions: nitrate, nitrite, carboxylate, acetate, formate, oxalate, sulfate, sulfite, thiosulfate, phosphate, tetrafluoroborate, hexafluorophosphate, tetra(perfluorophenyl)borate, hydride, oxide, peroxide, hydroxide, nitride, arsenate, arsenite, perchlorate, carbonate, bicarbonate, chromate, dichromate, iodate, bromate, chlorate, chlorite, hypochlorite, hypobromite, cyanide, cyanate, isocyanate, fulminate, thiocyanate, isothiocyanate, azide, tetracarbonylcobaltate, carbamoyldicyanomethanide, dicyanonitrose, dicyanamide, tricyanomethanate, amide, and permanganate.

[0074] A solvent may then be added to the vessel to dissolve the Group 1 metal halide solids and form a Group 1 metal halide solution. Suitable solvents include, but are not limited to, dry N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide (DMF), dialkylformamide, dimethylsulfoxide (DMSO), acetonitrile, methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, and combinations thereof. In an embodiment, the lead solids are dissolved in dry dimethylsulfoxide (DMSO). The Group 1 metal halide solids may be dissolved at a temperature between about 20° C. and about 150° C. In one embodiment, the Group 1 metal halide solids are dissolved at room temperature (i.e., about 25° C.). The Group 1 metal halide solids may be dissolved for as long as necessary to form a solution, which may be carried out for up to about 72 hours. The resulting solution forms a Group 1 metal halide solution. In some embodiments, the Group 1 metal halide solution may have a Group 1 metal halide concentration of between about 0.001 M and about 10 M, or about 1 M. In some embodiments, the Group 1 metal halide solution may further comprise an amino acid (e.g., 5-aminovaleric acid, histidine, glycine, lysine), an amino acid hydrohalide (e.g., 5-aminovaleric acid hydrochloride), an IFL surface modification (SAM) agent (discussed earlier in the specification), or a combination thereof.

[0075] The lead halide solution and the Group 1 metal halide solution are then mixed to form a thin film precursor ink. The lead halide solution and the Group 1 metal halide solution may be mixed in a ratio such that the resulting thin film precursor ink has a molar concentration of the Group 1 metal halide that is between 0% and 25% of the molar concentration of the lead halide. In certain embodiments, the thin film precursor ink may have a molar concentration of the Group 1 metal halide that is 1%, 5%, 10%, 15%, 20%, or 25% of the molar concentration of the lead halide. In some embodiments, the lead halide solution and the Group 1 metal halide solution may be agitated during or after mixing.

[0076] The thin film precursor ink may then be deposited on a desired substrate via any deposition means previously described. Suitable substrate layers may include any substrate layers previously identified in this disclosure. In certain embodiments, the thin film precursor ink may be spin-coated on the substrate at a speed of about 500 rpm to about 10,000 rpm for a time of about 5 seconds to about 600 seconds. In one embodiment, the thin film precursor ink may be spin-coated on the substrate at about 3000 rpm for about 30 seconds. The thin film precursor ink may be deposited on the substrate in an ambient atmosphere at a humidity range of about 0% relative humidity to about 50% relative humidity. The thin film precursor ink may then be deposited on the substrate in a substantially water-free atmosphere, i.e., a relative humidity of less than 30% or 7 gH 2 O / m 3 The solution may be dried at less than 200° C. to form a thin film.

[0077] The thin film may then be thermally annealed at a temperature of about 20° C. to about 300° C. for a time period up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The perovskite material active layer is then completed by a conversion process in which the precursor film is immersed or rinsed in a solvent or mixture of solvents (e.g., DMF, isopropyl alcohol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethyl sulfoxide, water) and a salt solution containing a salt (e.g., methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide, 5-aminovaleric acid hydroiodide) at a concentration of 0.001 M to 10 M. Also, in certain embodiments, the perovskite material thin film may be thermally post-annealed in the same manner as in the first line of this paragraph.

[0078] In an embodiment, the salt solution may be prepared by collecting the salt in a clean, dry container in a controlled atmosphere environment. Suitable salts include, but are not limited to, methylammonium iodide, formamidinium iodide, guanidinium iodide, imidazolium iodide, ethenetetramine iodide, 1,2,2-triaminovinylammonium iodide, and 5-aminovaleric acid hydroiodide. Other suitable salts may include any organic cation previously described in the chapter entitled "Perovskite Materials". The salt may have a single species or may have a mixture of salts in the correct ratio. A solvent may then be added to the container to dissolve the salt solids and form a salt solution. Suitable solvents include those described in the previous paragraph and combinations thereof. In one embodiment, the formamidinium iodide salt solids are dissolved in isopropanol. The salt solids may be dissolved at a temperature between about 20° C. and about 150° C. In one embodiment, the salt solids are dissolved at room temperature (i.e., about 25° C.). The salt solids are dissolved for as long as necessary to form a solution, which may be for up to about 72 hours. The resulting solution forms a salt solution. In some embodiments, the salt solution may have a salt concentration of about 0.001 M to about 10 M. In some embodiments, the salt solution has a salt concentration of about 1 M.

[0079] For example, the process described above using lead(II) iodide solution, cesium iodide solution, and methylammonium iodide (MA) salt solution can be used to obtain cations of the general formula Cs i MA 1-i PbI 3 where i is equal to a number between 0 and 1. As another example, a lead(II) iodide solution, a rubidium iodide solution, and a formamidinium iodide (FA) salt solution may be used to obtain a perovskite material having Rb i FA 1-i PbI 3 A perovskite material may be obtained having a chemical formula of: where i is equal to a number between 0 and 1. As another example, a lead(II) iodide solution, a cesium iodide solution, and a formamidinium iodide (FA) salt solution may be used to produce Cs iFA 1-i PbI 3 A perovskite material having the general formula: where i is equal to a number between 0 and 1 may be obtained. As another example, a lead(II) iodide solution, a potassium iodide solution, and a formamidinium iodide (FA) salt solution may be used to obtain a perovskite material having the general formula: i FA 1-i PbI 3 , where i is equal to a number from 0 to 1. As another example, a perovskite material having a structure of Na iodide may be obtained by using a lead(II) iodide solution, a sodium iodide solution, and a formamidinium iodide (FA) salt solution. i FA 1-i PbI 3 A perovskite material having the general formula: where i is equal to a number between 0 and 1 may be obtained. As another example, by using a lead(II) iodide-lead chloride mixed solution, a cesium iodide solution, and a formamidinium iodide (FA) solution, Cs i FA 1-i PbI 3 A perovskite material is obtained having the general formula:

[0080] In a particular embodiment, the lead halide solution is 90:10 PbI on a molar basis. 2 vs. PbCl 2 The ratio of CsI to FAPbI may be obtained by adding a cesium iodide (CsI) solution to the lead halide solution using the method described above, to form a thin film precursor ink having 10 mol % CsI. 3 Perovskite materials may be produced. As previously described, cesium ions may be added via a CsI solution to allow the chloride anions and cesium atoms to form FAPbI. 3 The chloride ions may be incorporated into the crystal lattice. This can result in a greater degree of lattice contraction than without the addition of chloride ions and, as previously described, with the addition of cesium or rubidium ions. Table 1 below lists the compounds with 10 mol% rubidium and 20 mol% chloride (e.g., 10 mol% PbCl 2), 10 mol% cesium, and 10 mol% cesium with 20 mol% chloride, FAPbI 3 The lattice parameters of the perovskite materials are shown in Table 1, where the mol% concentration represents the concentration of the additive relative to the lead atoms in the lead halide solution. As can be seen from Table 1, the cesium and chloride doped FAPbI 3 The perovskite material has a smaller lattice constant than the other two perovskite material samples.

[0081] [Table 1] The data also include data for FAPbI spiked with rubidium, cesium and / or chloride. 3 The perovskite material has a Pm3-m cubic structure. FAPbI containing up to 10 mol% Rb and 10 mol% Cl, or 10 mol% Cs, or 10 mol% Cs and 10 mol% Cl. 3 The perovskites are observed to maintain the cubic Pm3-m cubic crystal structure. Figure 5 shows the X-ray diffraction patterns corresponding to each sample listed in Table 1. Tables 2-4 provide the X-ray diffraction peaks and intensities for the three perovskite materials listed in Table 1. Data were collected at ambient conditions on a Rigaku Miniflex 600 using a CuKα radiation source at a scan rate of 1.5 degrees 2θ / min.

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4] Table 5 shows the geometrically expected X-ray diffraction patterns of a cubic Pm3-m material with a lattice constant of 6.3375 Å under Cu-Kα irradiation. As can be seen from the data, perovskite materials made with 10 mol% Rb and 10 mol% Cl, 10 mol% Cs, and 10% Cs and 10% Cl each have diffraction patterns that match the pattern expected for a cubic Pm3-m perovskite material.

[0085] [Table 5] (Method of forming a perovskite material layer) Methods for producing perovskite materials are described below and may be applied to any suitable perovskite material, including those discussed in the sections "Perovskite Materials" and "Formation of Perovskite Material Active Layers".

[0086] In certain embodiments, the method includes forming a lead halide precursor thin film, where forming the lead halide precursor thin film includes depositing a lead halide precursor ink on a substrate, drying the lead halide precursor ink to form a first thin film, and annealing the first thin film. In some embodiments, the method further includes forming a perovskite material layer, where forming the perovskite material layer includes depositing a benzyl ammonium halide precursor ink on the first thin film, drying the benzyl ammonium halide precursor ink, depositing a formamidinium halide precursor ink on the benzyl ammonium halide precursor ink, drying the formamidinium halide precursor ink to form a second thin film, and annealing the second thin film.

[0087] First, a lead halide precursor ink is formed as described in paragraphs

[0061] to

[0069] . Next, a lead halide precursor ink (e.g., PbI 2The resulting solution may be deposited onto a desired substrate. Suitable substrate layers may include any of the substrate layers previously identified in this disclosure. In certain embodiments, a lead halide precursor ink (e.g., PbI 2 The solution) is deposited on the NiO thin film. The preparation method of the NiO thin film is shown below.

[0088] Although reference is made herein to NiO and / or nickel oxide, it should be noted that various ratios of nickel to oxygen can be used to form nickel oxide. Thus, while certain embodiments are described with respect to NiO, such description is not intended to define the necessary ratio of nickel in oxygen. Rather, embodiments may have any one or more nickel-oxygen compounds, each of which may include NiO, ... x O y where x may be any value, integer or non-integer, between about 1 and 100. In some embodiments, x may be about 1 to 3 (again, not necessarily an integer). Similarly, y may be any value, integer or non-integer, between 0.1 and 100. In some embodiments, y may be 2 to 4 (again, not necessarily an integer). Additionally, Ni x O y Various crystalline forms of may be present in various embodiments, for example, alpha, gamma, and / or amorphous forms.

[0089] The NiO precursor inks of the present disclosure may include nickel nitrate and / or nickel acetate and may have a metal nitrate or metal acetate dissolved in a solvent mixture that includes a diol, water, and an alcohol-amine. In some embodiments, the NiO precursor ink includes nickel nitrate and one or more metal acetates dissolved in a solvent mixture that includes a diol, water, and an alcohol. In other embodiments, the NiO precursor ink includes nickel acetate and one or more metal nitrates, but no nickel nitrate, dissolved in a solvent mixture that includes a diol, water, and an alcohol-amine.

[0090] In certain embodiments, the NiO precursor ink of the present disclosure may have other metals as described herein. These metals may function as dopants in the resulting nickel oxide thin film, resulting in a hole-transporting or electron-transporting nickel oxide thin film, depending on the metal dopant included in the NiO precursor ink. Examples of compounds for preparing NiO precursor inks include, but are not limited to, anhydrous nickel nitrate, nickel nitrate hexahydrate, nickel nitrate nonahydrate, nickel nitrate tetrahydrate, nickel nitrate dihydrate, and any derivative hydrate of nickel nitrate, as well as anhydrous nickel acetate, nickel acetate dihydrate, nickel acetate tetrahydrate, and anhydrous copper nitrate, copper nitrate monohydrate, copper nitrate sesquihydrate, copper nitrate hemipentahydrate, copper nitrate trihydrate, copper nitrate hexahydrate, and any derivative hydrate of copper nitrate, as well as anhydrous copper acetate, copper acetate monohydrate. In certain embodiments, the NiO precursor ink of the present disclosure may be prepared by dissolving nickel nitrate (Ni(NO) in a diol solvent with an alcohol-amine additive. 3 ) 2 ), a metal acetate, and water. In a particular embodiment, the metal acetate is nickel acetate (Ni(CH 3 CO 2 ) 2 ) or copper acetate (Cu(CH 3 CO 2 ) 2 ), and further amines, diamines, and acetylacetone (and their derivatives) may be included in the NiO precursor ink.

[0091] In some embodiments, the nickel oxide precursor ink may be formulated with a mixture of nickel nitrate, nickel acetate, water, and ethanolamine in an ethylene glycol solvent. In other embodiments, the nickel oxide precursor ink may be formulated with a mixture of nickel nitrate, nickel acetate, water, ethanolamine, and acetylacetone in an ethylene glycol solvent. In yet other embodiments, the nickel oxide precursor ink may be formulated with a mixture of nickel nitrate, copper acetate, water, and ethanolamine in an ethylene glycol solvent. In yet other embodiments, the nickel oxide precursor ink may be formulated with a mixture of nickel nitrate, copper acetate, water, ethanolamine, and acetylacetone in an ethylene glycol solvent. In other embodiments, the nickel oxide precursor ink may be formulated with nickel nitrate, copper acetate, water, ethanolamine, and acetylacetone in an ethylene glycol solvent. 3 CO 2 ) y where M is any metal (e.g., Cu, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Ce, Pr, Nd, Sm, Er, Gd, Tb, Dy, Ho, Er, Ym, Yb, Lu, Ac, Th, Pa, and U) and y is the metal M (e.g., y=2, where M is Cu2 + and y=6, where M is W 6+ In some embodiments, nickel nitrate hydrate (e.g., Ni(NO 3 ) 2 aH 2 O), nickel acetate hydrates (e.g., Ni(CH 3 CO 2 ) 2 bH 2 O), copper acetate hydrate (e.g., Cu(CH 3 CO 2 ) 2 ·cH 2O), or metal acetate hydrates (e.g., M(CH 3 CO 2 ) y dH 2 O) may be included in the nickel oxide precursor ink formulation, where a, b, c, and d in the above formula are H in the hydrate. 2 In some embodiments, the compound for preparing the NiO precursor ink is nickel nitrate hexahydrate (Ni(NO 3 ) 2 6H 2 O), nickel acetate tetrahydrate (Ni(CH 3 CO 2 ) 2 4H 2 O), copper nitrate trihydrate (Cu(NO 3 ) 2 3H 2 HO), and copper acetate monohydrate (Cu(CH 3 CO 2 )2·H 2 O).

[0092] Examples of solvents for preparing the NiO precursor ink may include, but are not limited to, one or more of glycerol, ethylene glycol, propylene glycol, methanol, ethanol, and any other compound containing at least one hydroxyl group, such as alcohols and diols, ammonia, acetone, acetylacetone, and any compound containing at least one carbonyl group, ethylamine, and any other aryl and alkyl amines, ethanolamine, and any amine containing at least one hydroxyl group, water, di- and polyamines, and any other solvent suitable for dissolving the compounds for preparing the NiO precursor ink. In certain embodiments, the solvent for preparing the NiO precursor ink may include ethylene glycol, ethanolamine, and water.

[0093] In certain embodiments, the solvent may comprise ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1. In certain embodiments, the NiO precursor ink comprises Ni(NO) dissolved in a solvent mixture consisting of a diol, an alcoholamine, and water. 3 ) 2 and Ni(CH 3 CO 2 ) 2 In another embodiment, the NiO precursor ink is composed of Ni(NO) dissolved in a solvent mixture consisting of diols, alcohol amines, and water. 3 ) 2 and metal acetates (M(CH 3 CO 2 ) y In another embodiment, the NiO precursor ink is composed of Ni(NO ) dissolved in a solvent mixture consisting of diols, alcohol amines, and water. 3 ) 2 , Ni(CH 3 CO 2 ) 2 , and metal acetates (M(CH 3 CO 2 ) y In another embodiment, the NiO precursor ink is composed of Ni(NO ) dissolved in a solvent mixture consisting of diols, alcohol amines, and water. 3 ) 2 , Ni(CH 3 CO 2 ) 2 , and metal nitrates (M(NO 3 ) y In another embodiment, the NiO precursor ink is composed of Ni(CH) dissolved in a solvent mixture consisting of diols, alcoholamines, and water. 3 CO 2 ) 2 and metal nitrates (M(NO 3 ) y )

[0094] An example NiO precursor ink formulation may include 0.7 to 0.8 M nickel nitrate hexahydrate and 50 to 110 mM nickel acetate tetrahydrate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 5 to 20:1 to 5:1 to 5, respectively. In a particular embodiment, the NiO precursor ink formulation may include 0.72 M nickel nitrate hexahydrate and 103 mM nickel acetate tetrahydrate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1. In an embodiment, the NiO precursor ink may additionally have 0 to 20 mol % copper, and 0 to 50 mol % acetate.

[0095] Another example formulation of the NiO precursor ink may include 0.7 to 0.8 M nickel nitrate and 50 to 110 mM metal acetate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 5 to 20:1 to 5:1 to 5, respectively. In a particular embodiment, the NiO precursor ink formulation may include 0.72 M nickel nitrate hexahydrate and 103 mM metal acetate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1. In an embodiment, the NiO precursor ink may additionally include 0 to 20 mol % copper and 0 to 50 mol % acetate.

[0096] Another example of a NiO precursor ink preparation may include 0.7 to 0.8 M nickel nitrate hexahydrate, 50 to 110 mM nickel acetate tetrahydrate, and 20 to 41.3 mM metal nitrate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 5 to 20:1 to 5:1 to 5, respectively. In a particular embodiment, the metal nitrate may be copper nitrate trihydrate. In a particular embodiment, the NiO precursor ink preparation may include 0.72 M nickel nitrate hexahydrate, 103 mM nickel acetate tetrahydrate, and 30 mM metal nitrate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1.

[0097] Another example of a NiO precursor ink preparation may include 0.7 to 0.8 M nickel nitrate hexahydrate, 50 to 110 mM nickel acetate tetrahydrate, and 20 to 41.3 mM metal acetate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 5 to 20:1 to 5:1 to 5, respectively. In some embodiments, the metal nitrate may be copper acetate. In a particular embodiment, the NiO precursor ink preparation may include 0.72 M nickel nitrate hexahydrate, 103 mM nickel acetate tetrahydrate, and 30 mM metal acetate in a solvent containing ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1.

[0098] Another example formulation of a NiO precursor ink may include 0.7 to 0.8 M metal nitrate and 50 to 110 mM nickel acetate tetrahydrate in a solvent comprising ethylene glycol, ethanolamine, and water in a volume ratio of 5 to 20:1 to 5:1 to 5, respectively. In a particular embodiment, the NiO precursor ink formulation may include 0.72 M metal nitrate and 103 mM nickel acetate tetrahydrate in a solvent comprising ethylene glycol, ethanolamine, and water in a volume ratio of 12:1.46:1.

[0099] An exemplary method for preparing a NiO precursor solution may include, but is not limited to, the following steps: First, a solvent is prepared that includes a diol and an amine that includes at least one hydroxyl group ("alcohol-amine"). For example, the solvent may be prepared by mixing ethanolamine in ethylene glycol. Next, Ni(NO 3 ) 2 aH 2 O is added to the solvent, where a can be 0, 4, 6, or 9. In certain embodiments, the nickel nitrate can be nickel nitrate hexahydrate (a=6). Ni(CH 3 CO 2 ) 2 bH 2O is added to the mixture, where b can be 0, 2, or 4. In certain embodiments, nickel acetate can be nickel acetate tetrahydrate. Water is then added to the mixture. The mixture is then heated. Finally, the mixture is cooled to form the NiO precursor ink. In certain embodiments, as each component is added to the mixture, the mixture may be mixed by shaking, stirring, homogenization, a combination of turbulence, vortex mixing, or any other known mixing method. In certain embodiments, the NiO layer is formed in an inert atmosphere, or in a high humidity (e.g., 4 grams H per liter of air) atmosphere. 2 The solution may be prepared in any atmosphere (above 100) at room temperature or above 250° C. In one embodiment, water is added prior to the cooling step to give a final concentration of nickel nitrate hexahydrate of 0.7 to 0.8 M and a final concentration of nickel acetate tetrahydrate of 50 to 110 mM.

[0100] In some embodiments, NiO thin films are deposited on electrode materials, such as FTO or ITO substrates. As an example, NiO thin films may be deposited on electrode substrates. In certain embodiments, the substrate may have a size of 50×50×1.1 mm or 50×50×2.2 mm. In some embodiments, the electrode substrate is cleaned with oxygen plasma before NiO deposition. NiO thin films may be deposited by various means, including but not limited to drop casting, spin casting, slot die coating, blade coating, screen printing, or inkjet printing. In some embodiments, NiO thin films are deposited on electrode substrates using slot die coating. Slot die coating of lead halide precursors may be performed in various atmospheres, at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or at atmospheric or subambient pressure (e.g., 1 mTorr to 500 mTorr). As an example, the NiO precursor solution is deposited on the electrode substrate using slot die coating at a shuttle speed of about 0.1 to about 50 mm / s, about 1 to about 25 mm / s, or about 1 to about 10 mm / s. In a particular embodiment, the NiO precursor solution is deposited on the electrode substrate using slot die coating at a shuttle speed of about 4 mm / s. In an example, the dispensing speed of the NiO precursor solution is about 0.1 to about 50 μl / s, about 1 to about 25 μl / s, or about 1 to about 10 μl / s. In a particular embodiment, the dispensing speed of the NiO precursor solution is about 5.5 μl / s.

[0101] In some embodiments, the NiO film may be moved onto a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt) for annealing. The NiO thin film may be thermally annealed at temperatures from about 20° C. to about 400° C. for up to about 24 hours. In a particular embodiment, the NiO thin film may be thermally annealed at 310° C. for 1.5 to 2 hours. The annealing process may be carried out in various atmospheres at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or atmospheric or subambient pressure (e.g., 1 mTorr to 500 mTorr). The annealing atmosphere may be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of these gases. Here, a "controlled humidity environment" includes an environment in which the absolute humidity or % relative humidity is held at a constant value, or an environment in which the absolute humidity or % relative humidity varies according to a pre-defined set point or function. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity between 0% and 50%. In other embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity between 0% and 50%. 2 O / m 3 More than 20gH 2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0102] In some embodiments, the electrode substrate with the NiO thin film may then be placed on a hotplate and allowed to cool (eg, for at least 5 minutes or at least 10 minutes) prior to deposition of the lead halide precursor ink.

[0103] Although described with respect to a substrate and NiO layer having dimensions of 50×50 mm, the NiO deposition techniques described herein are applicable to substrates of various sizes, including 50×150 mm, or 150×150 mm. Such techniques may also be scaled up to any suitable size, including sizes suitable for commercial production. For example, in certain embodiments, suitable dimensions of substrates and NiO layers formed using one or more methods described herein may have a first dimension of about 1 m to about 2.4 m and a second dimension of about 0.6 m to about 1.5 m. Those skilled in the art will appreciate that, having the benefit of this disclosure, the size of the substrate and NiO layer (as well as other types of layers) may be tailored using the techniques of this disclosure for a given material and application.

[0104] The lead halide precursor ink or thin film precursor ink may be deposited as described in paragraphs

[0070] and

[0084] .

[0105] In one or more embodiments, mechanical or laser scribing is performed on one or more layers of the PV device disclosed herein; At least a portion of one or more layers may be ablated. These layers include, but are not limited to, electrodes, substrates, IFLs, NiO layers, perovskite material layers, charge transport layers, mesoporous layers, non-conductive layers, and / or other layers such as insulating layers. In certain embodiments, the number of scribing steps performed during the formation of the PV device may range from 1 to 5, 1 to 4, 1 to 3, or 1 to 2. In certain embodiments, a first scribing step (e.g., P1) may include scribing a NiO layer during the formation of the PV device described herein. In certain embodiments, the first scribing step may, for example, separate a NiO film into two or more strips. In another embodiment, for example, the first scribing step may be performed after the perovskite layer is formed and the IFL and insulating layer (e.g., photoresist layer) are deposited. In some embodiments, a second scribing step (e.g., P2) may be performed after the deposition of one or more IFLs. In certain embodiments, the second scribe may open a path that forms an electrical connection between electrodes of one or more subcells of the PV device. In some embodiments, a third scribe (e.g., P3) may be performed on the electrode layer. For example, in certain embodiments, the third scribe may separate two subcells from each other. In certain embodiments, for example, a fourth scribe (e.g., P4) may be performed to separate a long cell of the PV device into smaller cells. For example, in some embodiments, the fourth scribe may be performed perpendicular to one or more of the other scribes. Those of skill in the art, with the benefit of this disclosure, will understand the number of scribes suitable for a given device and application, as well as when and how to apply such scribes.

[0106] In certain embodiments, the scribe may have a number of passes ranging from about 1 to about 100, from about 1 to about 50, or from about 5 to about 30. In certain embodiments, the one or more scribes may have a pitch of about 1 μm to about 1 mm, from about 0.001 mm to about 0.1 mm, or from about 0.001 mm to about 0.05 mm. In one or more embodiments involving laser scribing, the scribe may be performed at about 1 to about 100% power, from about 25 to about 100% power, or from about 40 to about 100% power. In one example, the first scribe may be performed at 100% power with 1 pass, the second scribe may be performed at 46.6% power with 28 passes and 0.008 mm pitch, the third scribe may be performed at 45.5% power with 10 passes and 0.008 mm pitch, and the fourth scribe may be performed at 100% power with 10 passes and 0.01 mm pitch. In an embodiment, the scribe of the fourth scribe may include a scribe-to-scribe distance of about 0.1 mm to about 100 mm, a scribe-to-scribe distance of about 1 mm to about 50 mm, and a scribe-to-scribe distance of about 5 mm to about 30 mm. The laser scribing may include a laser having a wavelength between about 500 nm and about 1100 nm. In a particular embodiment, the laser scribing may be performed using a laser having a wavelength of 532 nm or 1068 nm, or any combination thereof.

[0107] In an embodiment, the lead halide precursor ink may be deposited by blade coating. The substrate may have a temperature approximately equal to ambient temperature or may have a controlled temperature between 0° C. and 500° C. As an example, the lead halide precursor solution is deposited on the substrate using blade coating with a blade coater moving at a speed of about 0.1 mm / s to about 50 mm / s, about 1 mm / s to about 30 mm / s, or about 5 mm / s to about 20 mm / s. In a particular embodiment, the lead halide solution is deposited using blade coating with a blade coater moving at a speed of about 4 mm / s.

[0108] Blade coating of the lead halide precursor may be carried out at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in a variety of atmospheres at atmospheric or subambient pressures (e.g., 1 mTorr to 500 mTorr). Blade coating atmospheres can include ambient air, controlled humidity environments (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of the above gases. In certain embodiments, the blade coating may be performed in a controlled humidity environment with a relative humidity % between 0% and 50%. In other embodiments, the blade coating may be performed in a controlled humidity environment with a relative humidity % between 0% and 50%. 2 O / m 3 More than 20gH 2 O / m 3 This may be carried out in a controlled humidity environment containing the following gases: The lead halide precursor ink may then be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film. In one embodiment, the lead halide precursor ink (e.g., PbI 2 ) solution is filtered prior to blade coating. As an example, the lead iodide precursor ink may be filtered through a PTFE syringe filter.

[0109] The lead halide precursor may be a liquid, gas, solid, or a combination of these states of matter, such as a solution, suspension, colloid, foam, gel, or aerosol. In some embodiments, the lead halide precursor may be a solution including one or more solvents. For example, the lead halide precursor may have one or more of N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide, dialkylformamide, dimethylsulfoxide (DMSO), acetonitrile, methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, and combinations thereof. The lead halide precursor may be a single lead salt (e.g., lead(II) iodide, lead(II) thiocyanate), or any combination disclosed herein (e.g., PbI 2 +PbCl 2 ;PbI 2 +Pb(SCN) 2 ). The lead halide precursor may have one or more additives such as an amino acid (e.g., 5-aminovaleric hydroiodic acid), 1,8-diiodooctane, 1,8-dithiooctane, formamidinium halide, acetic acid, trifluoroacetic acid, methylammonium halide, or water. The lead halide precursor ink may be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film.

[0110] After blade coating, the thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The annealing process may be carried out at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in a variety of atmospheres at atmospheric or sub-ambient pressures (e.g., 1 mTorr to 500 mTorr). Annealing atmospheres may include ambient air, controlled humidity environments (e.g., 0 to 100 gH 2 O / m 3gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of these gases. A controlled humidity environment may include an environment in which the absolute humidity or % relative humidity is held at a fixed value, or an environment in which the absolute humidity or % relative humidity varies according to a predetermined set point or function. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0% and less than or equal to 50%. In other embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0 gH 2 O / m 3 More than 20gH 2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0111] The perovskite material may then be completed by a conversion process. In this process, the precursor film is immersed or rinsed in a solution containing a solvent or mixture of solvents (e.g., DMF, isopropyl alcohol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethylsulfoxide, water) at a concentration of 0.001M to 10M, and a salt (e.g., methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide, 5-aminovaleric acid hydroiodide). The conversion process may be carried out at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in various atmospheres at atmospheric or subambient pressures (e.g., 1 mTorr to 500 mTorr). The conversion atmosphere may be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2、 or any combination of these gases. In certain embodiments, the conversion process may be carried out in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the conversion process may be carried out in a controlled humidity environment having a relative humidity % of 0 gH 2 O / m 3 More than 20gH 2 O / m 3It may be carried out in a controlled humidity environment containing the following gases:

[0112] In certain embodiments, the thin film may be thermally post-annealed in various embodiments and environments as previously described for the other annealing steps.

[0113] Once the lead halide thin film is deposited, the substrate containing the lead halide thin film may be coated with one or more coatings of BzAI solution and then coated with one or more coatings of FAI solution. In other embodiments, the lead halide thin film may be coated with one, two or three coatings of BzAI solution and one, two or three coatings of FAI solution, and any combination thereof. In one example, the BzAI and / or FAI solutions are coated onto the lead halide thin film using slot die coating at a shuttle flow rate of about 0.1 to about 50 mm / sec, about 1 to about 25 mm / sec, or about 1 to about 10 mm / sec. In a particular embodiment, the BzAI and / or FAI solutions are deposited onto the electrode substrate using slot die coating at a shuttle flow rate of about 12 mm / sec. In one example, the slot die coating dispense rate of the BzAI solution and / or the FAI solution is about 0.1 to about 50 μl / sec, about 1 to about 25 μl / sec, or about 1 to about 10 μl / sec. In certain embodiments, the slot die coating dispense rate of the BzAI solution and / or the FAI solution is about 5.5 μl / sec. In certain embodiments, the BzAI and / or the FAI solution is deposited using blade coating with a blade coater moving at a speed of about 0.1 mm / sec to about 50 mm / sec, about 1 mm / sec to about 30 mm / sec, or about 5 mm / sec to about 20 mm / sec. In certain embodiments, the BzAI and / or the FAI solution is deposited using blade coating with a blade coater moving at a speed of about 4 mm / sec. The coating atmosphere of the BzAI and / or the FAI solution can be ambient air, a controlled humidity atmosphere (e.g., 0 to 100 gH 2 O / m 3gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of the above gases. In certain embodiments, the slot die or blade coating may be performed in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the slot die or blade coating may be performed in a controlled humidity environment having a relative humidity % of 0 gH 2 O / m 3 and 20gH 2 O / m 3 The drying may be carried out in a controlled humidity environment containing the following gases: The BzAI and / or FAI solution may then be dried in a substantially moisture free atmosphere, i.e., less than 30% relative humidity, to form a thin film. The BzAI and / or FAI solution may then be dried in a substantially moisture free atmosphere, i.e., less than 30% relative humidity, to form a thin film.

[0114] The substrate may then be moved to a heat source (e.g., hot plate, IR lamps, convection oven, conveyor belt) for annealing. After coating with the BzAI and / or FAI solution, the thin film may then be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The annealing may be carried out at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in a variety of atmospheres at atmospheric or sub-ambient pressures (e.g., 1 mTorr to 500 mTorr). The annealing atmosphere may be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2, or any combination of these gases. The controlled humidity environment may include an environment in which the absolute humidity or % relative humidity is maintained at a fixed value, or an environment in which the absolute humidity or % relative humidity varies according to a predetermined set point or function. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0% and less than or equal to 50%. In other embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0 gH 2 O / m 3 More than 20gH 2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0115] FIG. 6 is a schematic diagram of a blade coating setup according to certain embodiments. First, a lead halide precursor ink is deposited on one or more substrates including a NiO film, and then annealed to form a lead halide film. In the example shown in FIG. 6, a sample substrate with a NiO film is placed between an ITO dummy substrate and a blade. In certain embodiments, both the sample substrate and the dummy substrate may have dimensions of 50×50 mm. In other embodiments, the substrates may have different sizes, and one of ordinary skill in the art having the benefit of this disclosure will understand the appropriate size for a given deposition process. The two substrates are pressed together and a vacuum is applied to ensure tight contact between the substrates. Next, a lead halide precursor ink (e.g., PbI 2 A solution) is connected to the blade and the blade coater is set to advance at a constant speed (e.g., 14 mm / s). After the blade reaches a specific position on the ITO dummy substrate (e.g., 3 / 4 of the dummy substrate minimum), the blade coater is set to return to its original position and the vacuum is simultaneously turned off. The sample substrate may then be removed from the blade coater and annealed via a heat source (e.g., like a hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes.

[0116] Next, to form a perovskite material layer, the lead halide thin film on one or more substrates is placed back on the blade coater in the configuration shown in FIG. 6 and coated first with one coating of BzAI solution, followed by three coatings of FAI solution. After deposition of each coating of BzAI and FAI solutions, the coating is dried before deposition of the next coating. The BzAI and FAI solutions may be prepared in the manner described above by dissolving FAI and BzAI in IPA. In one example, the BzAI solution is coated on the lead iodide thin film at a constant speed (e.g., 12 mm / s). After the blade reaches a specific position on the ITO dummy substrate (e.g., 3 / 4 of the dummy substrate), the blade coater is set to return to its original position. The FAI solution is then connected to the blade coater and coated on the lead iodide film at a constant speed (e.g., 12 mm / s). After the blade reaches a specific position on the ITO dummy substrate (e.g., 3 / 4 minimum of the dummy substrate), the blade coater is set to return to its original position. The FAI coating process may be repeated once, twice, three times, or more times. In one example, three coats of FAI are deposited on the BzAI solution. The sample substrate may then be removed from the blade coater and annealed via a heat source (e.g., like a hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 157° C. for about 5 minutes.

[0117] FIG. 7 is a schematic diagram of another blade coating setup for forming a perovskite material layer. First, a lead halide precursor ink (e.g., PbI) is deposited on one or more substrates, including a NiO film. 2A lead halide precursor ink (e.g., PbI solution) is then deposited and then annealed to form a lead halide film. In the example shown in Figure 7, a dummy substrate measuring 150 x 50 mm is placed on a blade coater, and then the substrate with the NiO film is placed between the dummy substrate and the blade. The two substrates are pressed together and a vacuum is applied to ensure that the substrates are in contact with no gaps. A lead halide precursor ink (e.g., PbI 2 A solution) is connected to the blade and the blade coater is set to advance at a constant speed (e.g., 5 mm / s). After the blade reaches a specific position on the ITO dummy substrate (e.g., 3 / 4 of the dummy substrate minimum), the blade coater is set to return to its original position and the vacuum is simultaneously turned off. The sample substrate may then be removed from the blade coater and annealed via a heat source (e.g., like a hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes.

[0118] Next, to form a perovskite material layer, the lead halide thin film on one or more substrates is placed back on the blade coater in the configuration shown in FIG. 7 and coated first with one coating of BzAI solution and then with three coatings of FAI solution. After deposition of each coating of BzAI and FAI solutions, the coating is dried before deposition of the next coating. The BzAI and FAI solutions may be prepared as described above. In one example, the BzAI solution is coated on the lead iodide thin film at a constant speed (e.g., 7 mm / s). The blade coater is then connected to the FAI solution and the FAI solution is coated on the lead iodide film at a constant speed (e.g., 7 mm / s). The FAI coating process may be repeated once, twice, three times, or more times. In one example, three coatings of FAI are layered on the BzAI solution. The sample substrate may then be removed from the blade coater and annealed via a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 157° C. for about 5 minutes.

[0119] In an embodiment, the lead halide precursor ink may be deposited by slot die coating. Slot die coating of the lead halide precursor may be performed at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in various atmospheres at atmospheric or subambient pressures (e.g., 1 mTorr to 500 mTorr). As an example, the lead halide precursor solution is deposited on the substrate using slot die coating at a shuttle speed of about 0.1 to about 50 mm / s, about 1 to about 25 mm / s, or about 1 to about 10 mm / s. In a particular embodiment, the lead halide precursor solution is deposited on the electrode substrate using slot die coating at a shuttle speed of about 12 mm / s. In an example, the dispense rate of the lead halide precursor solution is about 0.1 to about 50 μl / s, about 1 to about 25 μl / s, or about 1 to about 10 μl / s. In a particular embodiment, the dispense rate of the lead halide precursor solution is about 5.5 μl / s.

[0120] The slot-die coating atmosphere can be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of the above gases. In certain embodiments, the slot die coating may be performed in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the slot die coating may be performed in a controlled humidity environment having a relative humidity % of 0 gH 2 O / m 3 More than 20gH 2 O / m 3 This may be carried out in a controlled humidity environment containing the following gases: The lead halide precursor ink may then be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film. In one embodiment, the lead halide precursor ink (e.g., PbI 2 The lead halide precursor ink (e.g., PbI solution) is filtered prior to slot-die coating. As an example, the lead iodide precursor ink may be filtered through a PTFE syringe filter. The lead halide precursor ink may then be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film. In one embodiment, the lead halide precursor ink (e.g., PbI 2 The solution) is filtered prior to slot die coating. As an example, the lead iodide precursor ink may be filtered through a PTFE syringe filter.

[0121] The lead halide precursor may be a liquid, gas, solid, or a combination of these states of matter, such as a solution, suspension, colloid, foam, gel, or aerosol. In some embodiments, the lead halide precursor may be a solution containing one or more solvents. For example, the lead halide precursor may include one or more of N-cyclohexyl-2-pyrrolidone, alkyl-2-pyrrolidone, dimethylformamide, dialkylformamide, dimethylsulfoxide (DMSO), acetonitrile, methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, tert-butylpyridine, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, and combinations thereof. The lead halide precursor may be a single lead salt (e.g., lead(II) iodide, lead(II) thiocyanate), or any combination disclosed herein (e.g., PbI 2 +PbCl 2 ;PbI 2 +Pb(SCN) 2 ). The lead halide precursor may also have one or more additives such as an amino acid (e.g., 5-aminovaleric hydroiodic acid), 1,8-diiodooctane, 1,8-dithiooctane, formamidinium halide, acetic acid, trifluoroacetic acid, methylammonium halide, or water. The lead halide precursor ink may be dried in a substantially water-free atmosphere, i.e., less than 30% relative humidity, to form a thin film.

[0122] After slot die coating, the thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The annealing process may be carried out at ambient pressure (e.g., about 1 atmosphere, depending on altitude and atmospheric conditions), or in a variety of atmospheres at atmospheric or sub-ambient pressures (e.g., 1 mTorr to 500 mTorr). Annealing atmospheres may include ambient air, controlled humidity environments (e.g., 0 to 100 gH 2 O / m 3gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of these gases. A controlled humidity environment may include an environment in which the absolute humidity or % relative humidity is maintained at a fixed value, or an environment in which the absolute humidity or % relative humidity varies according to a predetermined set point or function. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0% and less than or equal to 50%. In other embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0 gH 2 O / m 3 More than 20gH 2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0123] The perovskite material may then be completed by a conversion process, in which the precursor film is immersed or rinsed in a solution containing a solvent or mixture of solvents (e.g., DMF, isopropyl alcohol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethylsulfoxide, water) at a concentration of 0.001M to 10M, and a salt (e.g., methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide, 5-aminovaleric acid hydroiodide). The conversion process may be carried out at ambient pressure (e.g., about 1 atm, depending on altitude and atmospheric conditions), or in various atmospheres at atmospheric or subambient pressures (e.g., 1 mTorr to 500 mTorr). The conversion atmosphere may be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of these gases. In certain embodiments, the conversion process may be carried out in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the conversion process may be carried out in a controlled humidity environment having a relative humidity % of 0 gH 2 O / m 3 More than 20gH 2 O / m 3This may be performed in a controlled humidity environment containing the following gases: In certain embodiments, the thin film may be thermally post-annealed in the various embodiments and environments previously described for the other annealing steps.

[0124] Once the lead halide thin film is deposited, the substrate containing the lead halide thin film may be coated with one or more coatings of BzAI solution and then coated with one or more coatings of FAI solution. In other embodiments, the lead halide thin film may be coated with one, two or three coatings of BzAI solution and one, two or three coatings of FAI solution, and any combination thereof. In one example, the BzAI solution and / or FAI solution is coated onto the lead halide thin film using slot die coating at a shuttle flow rate of about 0.1 to about 50 mm / sec, about 1 to about 25 mm / sec, or about 1 to about 10 mm / sec. In a particular embodiment, the BzAI solution and / or FAI solution is deposited using slot die coating at a shuttle flow rate of about 12 mm / sec. In one example, the slot die coating dispense rate of the BzAI solution and / or FAI solution is about 0.1 to about 50 μl / sec, about 1 to about 25 μl / sec, or about 1 to about 10 μl / sec. In certain embodiments, the dispense rate of the slot die coating of the BzAI and / or FAI solutions is about 5.5 μl / sec. In certain embodiments, the BzAI and / or FAI solutions are deposited using blade coating with the blade coater set to move at a speed of about 0.1 mm / sec to about 50 mm / sec, about 1 mm / sec to about 30 mm / sec, or about 5 mm / sec to about 20 mm / sec. In certain embodiments, the BzAI and / or FAI solutions are deposited using blade coating with the blade coater set to move at a speed of about 4 mm / sec. The coating atmosphere of the BzAI and / or FAI solutions can be ambient air, a controlled humidity atmosphere (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2, or any combination of the above gases. In certain embodiments, the slot die or blade coating may be performed in a controlled humidity environment having a relative humidity % of 0% or more and 50% or less. In other embodiments, the slot die or blade coating may be performed in a controlled humidity environment having a relative humidity % of 0 gH 2 O / m 3 More than 20gH 2 O / m 3 The drying may be carried out in a controlled humidity environment containing the following gases: The BzAI and / or FAI solution may then be dried in a substantially moisture free atmosphere, i.e., less than 30% relative humidity, to form a thin film. The BzAI and / or FAI solution may then be dried in a substantially moisture free atmosphere, i.e., less than 30% relative humidity, to form a thin film.

[0125] The substrate may then be annealed via a heat source (such as, for example, a hot plate, IR lamp, convection oven, conveyor belt, etc.). After being coated with the BzAI and / or FAI solution, the thin film may then be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes. The annealing process may be carried out at ambient pressure (e.g., 1 atm, depending on altitude and atmospheric conditions), or in a variety of atmospheres at atmospheric or sub-ambient pressures (e.g., 1 mTorr to 500 mTorr). The annealing atmosphere may be ambient air, a controlled humidity environment (e.g., 0 to 100 gH 2 O / m 3 gas), pure argon, pure nitrogen, pure oxygen, pure hydrogen, pure helium, pure neon, pure krypton, pure CO 2 , or any combination of these gases. A controlled humidity environment may include an environment in which the absolute humidity or % relative humidity is maintained at a fixed value, or an environment in which the absolute humidity or % relative humidity varies according to a predetermined set point or function. In certain embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0% and less than or equal to 50%. In other embodiments, the annealing process may be performed in a controlled humidity environment having a % relative humidity greater than or equal to 0 gH 2 O / m 3 More than 20gH2 O / m 3 It may be carried out in a controlled humidity environment containing the following gases:

[0126] FIG. 8 is a schematic diagram of a slot die coating setup for producing a perovskite material layer. In the example shown in FIG. 8, the slot die coater has three horizontal sample substrates, each having a size of 50×150 mm, along with four dummy substrates of 150 mm, arranged as shown in FIG. 8. In other embodiments, the substrates may have different sizes, and one of ordinary skill in the art having the benefit of this disclosure will understand the appropriate size for a given slot die coating process. Next, a lead halide precursor ink (e.g., PbI 2 solution) is deposited on the substrate at a constant shuttle speed (e.g., 12 mm / s). The sample substrate may then be removed from the slot die coater and annealed via a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 50° C. for about 10 minutes.

[0127] Next, to form a perovskite material layer, the sample substrate including the lead halide thin film is placed back on the slot die coater with the dummy substrate in the configuration of FIG. 8 and then coated with one coating of BzAI solution followed by three coatings of FAI solution. In other embodiments, the lead halide thin film may be coated with one, two or three coatings of BzAI solution and one, two or three coatings of FAI solution, and any combination thereof. In one example, the BzAI solution is coated on the lead iodide thin film at a constant shuttle flow rate (e.g., 8 mm / s). Then, the FAI solution is connected to the slot die coater and the FAI solution is coated on the lead iodide thin film at a constant shuttle speed (e.g., 8 mm / s). In this example, the process is repeated until three coatings of FAI are deposited. The sample substrate may then be removed from the slot die coater and annealed via a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 157° C. for about 5 minutes.

[0128] FIG. 10 is a schematic diagram of a slot die coating setup for producing a perovskite material layer. In this embodiment, a first scribe is performed on the NiO layer on the substrate using a laser scribing device. In this example, the first scribe involves one pass at 100% power, although scribing parameters can be varied as previously described (including the use of a mechanical scribe). Additionally, the first scribe involves a C 60and may be reserved until after deposition of the bathocuproine layer. The scribed NiO sample substrate may then be annealed via a heat source (such as, for example, a hot plate, IR lamp, convection oven, conveyor belt, etc.). The NiO film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the NiO film may be thermally annealed at a temperature of about 310° C. for about 30 minutes. Next, a pre-prepared lead halide solution (prepared according to the above discussion) is filtered in a 15% humidity environment. The scribed NiO substrate having a size of 150×150 mm is then placed in a slot die coater along with four 50×150 mm dummy substrates as arranged in FIG. 10. In other embodiments, the substrate may have different sizes, and one of ordinary skill in the art having the benefit of this disclosure will understand the appropriate size for a given slot die coating process. The filtered lead halide precursor ink (e.g., PbI 2 solution) is deposited on the substrate at a constant shuttle speed (e.g., 12 mm / s) at 25% humidity. The sample substrate may then be removed from the slot die coater and annealed via a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the lead halide thin film may be thermally annealed at a temperature of about 50° C. for 10 minutes.

[0129] Next, to form a perovskite material layer, the sample substrate containing the lead halide thin film is placed back on the slot die coater with the dummy substrate in the configuration of FIG. 10 and then coated with one coat of BzAI solution followed by three coats of FAI solution. In other embodiments, the lead halide thin film may be coated with one, two or three coats of BzAI solution and one, two or three coats of FAI solution, and any combination thereof. In one example, the BzAI solution is coated on the lead iodide thin film at a constant shuttle flow rate (e.g., 8 mm / s). Then, the FAI solution is connected to the slot die coater and the FAI solution is coated on the lead iodide thin film at a constant shuttle speed (e.g., 8 mm / s). In this example, the process is repeated until three coats of FAI are deposited. The sample substrate is then removed from the slot die coater and may be annealed via a heat source (e.g., hot plate, IR lamp, convection oven, conveyor belt, etc.). The thin film may be thermally annealed at a temperature of about 20° C. to about 300° C. for a period of up to about 24 hours. In one embodiment, the thin film may be thermally annealed at a temperature of about 157° C. for about 5 minutes. The substrate is then heated to 300° C. for about 20 minutes. 60 layer, followed by a layer of bathocuproine (BCP). 60 The C layer and the bathocuproine (BCP) layer can be deposited by a variety of means, including, but not limited to, drop casting, spin casting, slot-die coating, blade coating, screen printing, or inkjet printing. 60 The layer may be about 0.1 to 1000 nm thick, and the bathocuproine (BCP) layer may be about 0.1 to about 1000 nm thick. 60 The layer may be 30 nm thick and the bathocuproine (BCP) layer may be about 15 nm thick. In certain embodiments, if the first scribe was not performed on the NiO layer, then an insulating layer (e.g., a photoresist layer) may be deposited and the first scribe may be performed on the insulating layer.

[0130] The edges of the substrate and thin film layer may then be manually scribed and a second scribe performed. In certain embodiments, the second scribe may include a number of passes ranging from about 1 to about 100, about 1 to about 50, or about 5 to about 30. In certain embodiments, the second scribe may include a pitch of about 1 μm to about 1 mm, about 0.001 mm to about 0.1 mm, or about 0.001 mm to about 0.05 mm. In one or more embodiments including laser scribing, the second scribe may be performed at about 1 to about 100% power, about 25 to about 100% power, or about 40 to about 100% power. In one example, the second scribe may be performed at 46.6% power with 28 passes and a pitch of 0.008 mm. The second scribe may be performed by laser or mechanical scribing.

[0131] A copper electrode layer and an alumina layer may then be deposited. The copper and alumina layers may be deposited by a variety of means, including but not limited to, drop casting, spin casting, slot die coating, blade coating, screen printing, or inkjet printing. In some embodiments, the copper and alumina layers may each be about 0.1 nm to 1,000 nm thick. For example, the copper layer may be 400 nm thick.

[0132] A third scribing may then be performed. In certain embodiments, the third scribing may include a number of passes ranging from about 1 to about 100, about 1 to about 50, or about 5 to about 30. In certain embodiments, the third scribing may include a pitch of about 1 μm to about 1 mm, about 0.001 mm to about 0.1 mm, or about 0.001 mm to about 0.05 mm. In one or more embodiments including laser scribing, the third scribing may be performed at about 1 to about 100% power, about 25 to about 100% power, or about 40 to about 100% power. In one example, the third scribing may be performed at 46.6% power with 28 passes and a 0.008 mm pitch. The third scribing may be performed by laser or mechanical scribing.

[0133] A fourth scribing may then be performed. In an embodiment, the fourth scribing may include a number of passes ranging from about 1 to about 100, about 1 to about 50, or about 5 to about 30. In an embodiment, the fourth scribing may include a pitch of about 1 μm to about 1 mm, about 0.001 mm to about 0.1 mm, or about 0.001 mm to about 0.05 mm. In one or more embodiments including laser scribing, the fourth scribing may be performed at about 1 to about 100% power, about 25 to about 100% power, or about 40 to about 100% power. In one example, the fourth scribing may be performed at 100% power with 10 passes and a pitch of 0.01 mm. The fourth scribing may be performed by laser or mechanical scribing.

[0134] Although described primarily with respect to substrates and perovskite material layers having dimensions of 50×50 mm, 50×150 mm, or 150×150 mm, the techniques described herein may be scaled up to any suitable size (e.g., suitable for commercial production). For example, in certain embodiments, suitable dimensions for substrates and perovskite material layers formed using one or more methods described herein may have a first dimension of about 1 m to about 2.4 m, and a second dimension of about 0.6 m to about 1.5 m. Those skilled in the art having the benefit of this disclosure will understand the sizes of substrates and perovskite material layers (and other types of layers) prepared using the techniques of this disclosure for a given material and application.

[0135] Numerous modifications, variations, and variations can be made to the described embodiments without departing from the scope of the invention as defined in the claims. The invention is not limited to the described embodiments, but is intended to have the full scope defined by the language of the claims and their equivalents.

Claims

1. 1. A method comprising forming a lead halide precursor thin film, comprising: The step of forming the lead halide precursor thin film comprises: depositing a lead halide precursor ink onto a substrate; drying the lead halide precursor ink to form a first thin film; annealing the first film; and Forming a perovskite material layer having The step of forming the perovskite material layer includes: depositing a benzyl ammonium halide precursor ink onto the first film; drying the benzyl ammonium halide precursor ink; depositing a formamidinium halide precursor ink onto the benzylammonium halide precursor ink; drying the formamidinium halide precursor ink to form a second thin film; annealing the second film; The method comprising:

2. 2. The method of claim 1, wherein the lead halide comprises lead(II) iodide.

3. The method of claim 1 , wherein the lead halide precursor ink is deposited on the substrate by blade coating or slot die coating.

4. The method of claim 1 , wherein the first thin film is annealed at 50° C. for 10 minutes.

5. 2. The method of claim 1, wherein the benzyl ammonium halide comprises benzyl ammonium iodide.

6. 2. The method of claim 1, wherein the formamidinium halide comprises formamidinium iodide.

7. The method of claim 1 , wherein the benzyl ammonium halide precursor ink and the formamidinium halide precursor ink are deposited on the substrate by blade coating or slot die coating.

8. The method of claim 1 , wherein the second thin film is annealed at 157° C. for 5 minutes.

9. The method of claim 1 , wherein the lead halide precursor ink is deposited on a nickel oxide substrate.

10. The nickel oxide substrate is depositing a nickel oxide precursor ink onto the electrode material to form a third thin film; annealing the third film; The method of claim 9 , wherein the compound is formed by a process comprising:

11. A perovskite material comprising:

1. A method for preparing a lead halide precursor thin film comprising the steps of: The step of forming the lead halide precursor thin film comprises: depositing a lead halide precursor ink onto a substrate; drying the lead halide precursor ink to form a first thin film; annealing the first film; and forming a layer of a perovskite material; having The step of forming the perovskite material layer includes: depositing a benzyl ammonium halide precursor ink onto the first film; drying the benzyl ammonium halide precursor ink; depositing a formamidinium halide precursor ink onto the benzylammonium halide precursor ink; drying the formamidinium halide precursor ink to form a second thin film; annealing the second film; The perovskite material has the following structure:

12. 12. The perovskite material of claim 11 , wherein the lead halide comprises lead(II) iodide.

13. 12. The perovskite material of claim 11, wherein the lead halide precursor ink is deposited on the substrate by blade coating or slot die coating.

14. 12. The perovskite material of claim 11, wherein the first thin film is annealed at 50°C for 10 minutes.

15. 12. The perovskite material of claim 11 , wherein the benzylammonium halide comprises benzylammonium iodide.

16. 12. The perovskite material of claim 11 , wherein the formamidinium halide comprises formamidinium iodide.

17. 12. The perovskite material of claim 11, wherein the benzylammonium halide precursor ink and the formamidinium halide precursor ink are deposited on the substrate by blade coating or slot die coating.

18. 12. The perovskite material of claim 11, wherein the second thin film is annealed at 157°C for 5 minutes.

19. 12. The perovskite material of claim 11 , wherein the lead halide precursor ink is deposited on a nickel oxide substrate.

20. The nickel oxide substrate is depositing a nickel oxide precursor ink onto the electrode material to form a third film; annealing the third film; 20. The perovskite material of claim 19 formed by a process comprising:

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