Liquid electrolyte-free, solid-state solar cells with inorganic hole transport materials

Abstract

Photovoltaic cells incorporating the compounds A/M/X compounds as hole transport materials are provide. The A/M/X compounds comprise one or more A moieties, one or more M atoms and one or more X atoms. The A moieties are selected from organic cations and elements from Group 1 of the periodic table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and the X atoms are selected from elements from Group 17 of the periodic table.

Claims

1. A solid state photovoltaic cell comprising: (a) a first electrode comprising an electrically conductive material; (b) a second electrode comprising an electrically conductive material; (c) a porous photoactive material disposed between, and in electrical communication with the first and second electrodes; and (d) a hole transporting material comprising an A/M/X compound, wherein the hole transporting material is disposed between the first and second electrodes and is configured to facilitate the transport of holes generated in the photoactive material to one of the first and second electrodes and further wherein the hole transporting material takes the form of a continuous conformal coating that overlies the porous film and also homogeneously infiltrates the pores within the porous film; wherein an A/M/X compound is a compound comprising one or more A moieties, one or more M atoms and on or more X atoms, where the A moieties are selected from elements from Group 1 of the periodic table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and the X atoms are selected from elements from Group 17 of the periodic table; and further wherein the solid state photovoltaic cell does not comprise a liquid electrolyte and the solid state photovoltaic cell also does not comprise a conducting polymer hole transport material.

2. The photovoltaic cell of claim 1, wherein the photoactive material comprises a porous film of semiconductor oxide having a photosensitizing dye adsorbed thereon.

3. The photovoltaic cell of claim 1, wherein the hole transporting material comprises a p-type semiconducting A/M/X compound and the photoactive material comprises an n-type semiconductor; and further wherein the photoactive material is in contact with the hole transporting material at an interface between the two layers and a pn-junction is formed at said interface.

4. The photovoltaic cell of claim 1, wherein the photoactive material is a photoactive organic polymer.

5. The photovoltaic cell of claim 1, wherein the A/M/X compound has a formula AMX.sub.3, where A is a Group I element, M is a Group 14 element and X is a Group 17 element.

6. The photovoltaic cell of claim 1, wherein the A/M/X compound is CsSnI.sub.3 doped with a metal halide.

7. The photovoltaic cell of claim 1, wherein the A/M/X compound is CsSnBr.sub.3 doped with a metal halide.

8. The photovoltaic cell of claim 1, wherein the A/M/X compound has a formula selected from AMX.sub.3, A.sub.2MX.sub.4, AM.sub.2X.sub.5, A.sub.2MX.sub.6 or AMX.sub.5, where A is a Group 1 element, M is a Group 14 element and X is a Group 17 element.

9. The photovoltaic cell of claim 1, wherein the A/M/X compound has a formula AMX.sub.3, where A is an organic cation, M is a Group 14 element and X is a Group 17 element.

10. The photovoltaic cell of claim 1, wherein the A/M/X compound has a formula selected from AMX.sub.3, A.sub.2MX.sub.4, AM.sub.2X.sub.5, A.sub.2MX.sub.6 or AMX.sub.5, where A is an organic cation, M is a Group 14 element and X is a Group 17 element.

11. The photovoltaic cell of claim 10, wherein the A/M/X compound is doped with a dopant selected from main group elements, transition metal elements, lanthanide elements, actinide elements or compounds comprising one of more of said elements.

12. The photovoltaic cell of claim 1, wherein the A/M/X compound is a compound comprising one or more A moieties, one or more M atoms and one or more X atoms, where the A moieties are selected from elements from Group 1 of the periodic table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and the X atoms are selected from elements from Group 17 of the periodic table.

13. A photovoltaic cell comprising: (a) a first electrode comprising an electrically conductive material; (b) a second electrode comprising an electrically conductive material; (c) a photoactive material disposed between, and in electrical communication with, the first and second electrodes; and (d) a hole transporting material comprising an A/M/X compound, wherein the hole transporting material is disposed between the first and second electrodes and is configured to facilitate the transport of holes generated in the photoactive material to one of the first and second electrodes; wherein an A/M/X compound is a compound comprising an A moiety, an M atom, and one or more X atoms, where A is Cs, M is Sn and X comprises one or more halide elements.

14. The photovoltaic cell of claim 13, wherein the photoactive material is in the form of a porous film and the hole transporting material takes the form of a coating that infiltrates the pores of the porous film.

15. The photovoltaic cell of claim 13, wherein the photoactive material comprises a porous film of semiconductor oxide having a photosensitizing dye adsorbed thereon.

16. The photovoltaic cell of claim 13, wherein the hole transporting material comprises a p-type semiconducting A/M/X compound and the photoactive material comprises an n-type semiconductor, and further wherein the photoactive material is in contact with the hole transporting material at an interface between the two layers and a pn-junction is formed at said interface.

17. The photovoltaic cell of claim 13, wherein the photoactive material is a photoactive organic polymer.

18. A photovoltaic cell comprising: (a) a first electrode comprising an electrically conductive material; (b) a second electrode comprising an electrically conductive material; (c) a photoactive material disposed between, and in electrical communication with, the first and second electrodes; and (d) a hole transporting material comprising an A/M/X compound, wherein the hole transporting material is disposed between the first and second electrodes and is configured to facilitate the transport of holes generated in the photoactive material to one of the first and second electrodes; wherein an A/M/X compound is a compound comprising one or more A moieties, one or more M atoms and two or more X elements, where the A moieties are selected from organic cations and elements from Group I of the periodic table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and further wherein the A/M/X compound has the formula AMX.sub.(3-x)X′.sub.x, where X and X′ are different halogen atoms and 0.01<x<0.99.

19. The photovoltaic cell of claim 18, wherein the A/M/X compound is doped with a metal halide, such that the material comprises a first phase comprising AMX.sub.(3-x)X′.sub.x and a second phase comprising the metal halide dopant.

20. The photovoltaic cell of claim 18, wherein X is I and X′ is F.

21. The photovoltaic cell of claim 20, wherein the A/M/X compound is doped with a metal halide, such that the material comprises a first phase comprising AMX.sub.(3-x)X′.sub.x and a second phase comprising the metal halide dopant.

22. The photovoltaic cell of claim 21, comprising CsSnI.sub.(3-x)F.sub.x doped with SnF.sub.2.

23. The photovoltaic cell of claim 18, wherein X is I and X′ is Br.

24. The photovoltaic cell of claim 23, wherein the A/M/X compound is doped with a metal halide, such that material comprises a first phase comprising AMX.sub.(3-x)X′.sub.x and a second phase comprising the metal halide dopant.

25. The photovoltaic cell of claim 24, comprising CsSnI.sub.(3-x)Br.sub.x.

26. The photovoltaic cell of claim 25, comprising CsSnI.sub.(3-x)Br.sub.x doped with SnF.sub.2.

27. The photovoltaic cell of claim 20, comprising CsSnI.sub.(3-x)F.sub.x.

28. A solid state photovoltaic cell comprising: (a) a first electrode comprising an electrically conductive material; (b) a second electrode comprising an electrically conductive material; (c) a porous photoactive material disposed between, and in electrical communication with, the first and second electrodes, the photoactive material comprising a porous film and a continuous conformal coating comprising an A/M/X compound that overlies the porous film and also homogeneously infiltrates the pores within the porous film, wherein an A/M/X compound is a compound comprising one or more A moieties, one or more M atoms and one or more X atoms, where the A moieties are selected from elements from Group 1 of the period table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the period table, and the X atoms are selected from elements from Group 17 of the periodic table; wherein the solid state photovoltaic cell does not comprise a liquid electrolyte and the solid state photovoltaic cell does not comprise a conducting polymer hole transport material.

29. A solid state photovoltaic cell comprising: (a) a first electrode comprising an electrically conductive material; (b) a second electrode comprising an electrically conductive material; (c) a porous photoactive material disposed between, and in electrical communication with, the first and second electrodes, the photoactive material comprising a porous film and a continuous conformal coating comprising an A/M/X compound that overlies the porous film and also homogeneously infiltrates the pores within the porous film, wherein an A/M/X compound is a compound comprising one or more A moieties, one or more M atoms and one or more X atoms, where the A moieties are selected from elements from Group 1 of the periodic table, the M atoms are selected from elements from at least one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and the X atoms are selected from elements from Group 17 of the periodic table; wherein the solid state photovoltaic cell does not comprise a liquid electrolyte.

30. The photovoltaic cell of claim 29, where A is Cs, M is Sn and X comprises one or more halide elements.

31. The photovoltaic cell of claim 30, comprising CsSnI.sub.(3-x)F.sub.x, where 0.01<x<0.99.

32. The photovoltaic cell of claim 29, wherein the A/M/X compound has a formula AMX.sub.3, where M is a Group 14 element and X is a Group 17 element.

33. The photovoltaic cell of claim 29, wherein the A/M/X compound is CsSnI.sub.3 doped with a metal halide.

34. The photovoltaic cell of claim 29, wherein the A/M/X compound is CsSnBr.sub.3 doped with a metal halide.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1. is a schematic diagram of a cross-section of a DSC comprising CsSnI.sub.3 as a solid state HTM.

(2) FIG. 2. shows absorbance spectra of DSCs with a photoanode comprising dye-loaded TiO.sub.2 (dye/TiO.sub.2) and with a photoanode comprising dye-loaded TiO.sub.2 with a CsSnI.sub.2.95F.sub.0.05 HTM (CsSnI.sub.2.95F.sub.0.05/dye/TiO.sub.2).

(3) FIG. 3. shows the J-V characteristics of DSCs comprising HTMs of CsSnI.sub.3, CsSnI.sub.2.95F.sub.0.05, and CsSnI.sub.2.95F.sub.0.05 doped with SnF.sub.2 under irradiation of 100 mW cm.sup.−2 simulated AM 1.5 sunlight.

(4) FIG. 4. shows the J-V characteristics of DSCs comprising HTMs of CsSnI.sub.2.95F.sub.0.05 doped with 5% SnF.sub.2, the same DSC with a fluorine-etched TiO.sub.2, and with stacks of ZnO photonic crystals under irradiation of 100 mW cm.sup.−2 simulated AM 1.5 sunlight.

(5) FIG. 5. Electrochemical impedance spectroscopy (EIS) analysis. (A) Nyquist and (B) Bode phase plots. (C) Magnitude of the impedance.

(6) FIG. 6 shows PL spectra for the Type I A/M/X materials, where A is Cs, M is Sn, and X is I.

(7) FIG. 7 shows the PL spectra for Type I A/M/X materials, where A is Cs, M is Sn and X is I, including some that are alloyed with oxides.

(8) FIG. 8. (A) shows the PL spectra for Type I A/M/X materials, where A is Cs, M is Sn and X is I, including some that are alloyed with hexafluorides. (B) shows the CS.sub.4Sn.sub.2SiF.sub.6I.sub.6 phase that saturates the detector, measured at a lower integration time. (C) shows the CS.sub.6Sn.sub.2SiF.sub.6I.sub.8 phase that saturates the detector, measured at a lower integration time.

(9) FIG. 9 shows a portion of the crystal structure of Type IIA material CH.sub.3NH.sub.3GeI.sub.3 highlighting the perovskite building block. Color code. Ge: mid-size, light gray; I: large, dark; N: small, dark; C: small, gray.

(10) FIG. 10 shows a portion of the crystal structure of CH.sub.3NH.sub.3SnI.sub.3 highlighting the perovskite building block. Color code. Sn: large, gray; I: large, dark; N: small, dark; C: small, gray.

(11) FIG. 11 shows a portion of the crystal structure of CH.sub.3NH.sub.3PbI.sub.3 highlighting the perovskite building block. Color code. Pb: large, gray; I: large, dark; N: small, dark; C: small, gray.

(12) FIG. 12 shows the unit cell of EVSn.sub.2I.sub.6 viewing along the 1-dimensional Sn.sub.2I.sub.6.sup.2− chains. Color code. Sn: large, gray; I: large, dark; N: small, dark; C: small, gray.

(13) FIG. 13 shows the unit cell of AcrSnI.sub.3 viewing along the 1-dimensional SnI.sub.3.sup.− chains. Color code. Sn: large, gray; I: large, dark; N: small, dark; C: small, gray.

(14) FIG. 14 shows the PL emission vs. energy data for (A) EVSn.sub.2I.sub.6 and (B) AcrSnI.sub.3.

(15) FIG. 15 shows the PL emission vs. wavelength data for CH.sub.3NH.sub.3SnIX.sub.2 phases.

(16) FIG. 16 shows the PL emission vs. wavelength spectra for HC(NH.sub.2).sub.2SnIX.sub.2 phases at a first emission wavelength range.

(17) FIG. 17 shows the PL emission vs. wavelength spectra for HC(NH.sub.2).sub.2SnIX.sub.2 phases at a second emission wavelength range.

(18) FIG. 18 shows the PL emission vs. wavelength spectra for CH.sub.3NH.sub.3PbIX.sub.2 phases at a first emission wavelength range.

(19) FIG. 19 shows the PL emission vs. wavelength spectra for CH.sub.3NH.sub.3PbIX.sub.2 phases at a second wavelength range.

(20) FIG. 20 shows PL emission vs. wavelength spectra for germanium iodide phases.

(21) FIG. 21 shows PL emission vs. wavelength spectra for CsSnF.sub.2I+ borosilicate and CsSnF.sub.2I+ alumina.

(22) FIG. 22 shows PL emission vs. wavelength spectra for CH.sub.3NH.sub.3Sn.sub.1-xPb.sub.xI.sub.3 for different values of x.

(23) FIG. 23 shows PL emission vs. wavelength spectra for CH.sub.3NH.sub.3SnCl.sub.2I, CH.sub.3NH.sub.3SnCl.sub.2I+10% mol. CoCl.sub.2-6H.sub.2O, and indium phosphide (InP).

(24) FIG. 24 shows the energy levels of the components of a CsSnI.sub.3-based solid-state solar cell. The valence band maximum (lower rectangles) and the conduction band minimum (upper rectangles) of TiO.sub.2 and CsSnI.sub.3 are represented in eV, along with the energy difference between the edges. The ground (orange) and excited states (blue) of N719 dye is also shown. The energy scale is referenced to the vacuum level.

(25) FIG. 25 shows the photocurrent density-voltage (J-V) characteristics of the solar cell devices of Example 7 under irradiation of 100 mWcm.sup.−2 simulated AM 1.5 sunlight. These solar cells incorporated CsSnI.sub.3, CsSnBr.sub.3 and CsSnI.sub.2Br, as well CsSnBr.sub.3 doped with SnF.sub.2 and CsSnI.sub.2Br doped with SnF.sub.2 as an HTL.

(26) FIG. 26 is a schematic diagram of a cross-section of a pn-junction photovoltaic cell comprising CsSnI.sub.3 or CsSnI.sub.(3-x)F.sub.x as a solid state HTM. Panels (i)-(iv) in the figure illustrate the fabrication of the cell.

(27) FIG. 27 is a graph of the J-V characteristics of the pn-junction cells of Example 8.

DETAILED DESCRIPTION

(28) A/M/X compounds for use as HTMs in photovoltaic cells are provided. Also provided are photovoltaic cells comprising the HTMs. The designation A/M/X is used to refer to a family of compounds that comprise A moieties (atoms or cations), M atoms and X atoms in various ratios, where A represents an atom from Group 1 of the periodic table or an organic cation, M represents an atom from one of Groups 3, 4, 5, 13, 14 or 15 of the periodic table, and X represents an atom from Group 17 of the periodic table. Alternatively, the A/M/X compound can be a chalcogenide or a chalcohalide, wherein the above-referenced M and/or X atoms are substituted with an atom from Group 16 of the periodic table.

(29) The A/M/X compounds that can be used as HTMs include infrared light emitting materials. In some embodiments, the compounds are medium-bandgap semiconductors with E.sub.g values in the range from 1.1-1.8 eV.

(30) The p-type inorganic semiconductors can be widely used as a hole transport material to replace conventional electrolytes in DSCs. Because they are p-type semiconductors, the A/M/X compounds can also be used as hole transport materials in solid-state p-n junction type solar cells.

(31) FIG. 1 shows one embodiment of a structure of a thin-layer DSC. The DSC comprises a photoanode comprising a porous film of semiconductor oxide (e.g., TiO.sub.2) 102 coated on a transparent conducting oxide (e.g., FTO) 104. The porous film of semiconductor oxide has a photosensitizing dye adsorbed thereon. The DSC also comprising a counter electrode comprising an electrically conducting metal film (e.g., Pt) 106 disposed on a transparent conducting oxide 108. A hole transport material 110 comprising an A/M/X compound is disposed between, and in electrical communication with, the photoanode and the counter electrode. Hole transport material 110 overlies and impregnates the porous film 102. Example 1 describes a method of making a DSC of the type shown in FIG. 1.

(32) DSCs incorporating the A/M/X compounds as solid state electrolytes can be free of liquid electrolytes and can provide a light to electricity conversion efficiency of 9.7% under AM 1.5 irradiation (100 mW cm.sup.−2) or better.

(33) FIG. 26 shows an embodiment of a structure of a pn-junction solar cell. A more detailed description of the solar cell and a method for fabricating the cell is provided in Example 8.

(34) Examples of A/M/X compounds that can be used as HTMs include those having the general formula AMX.sub.3, where A is a Group 1 element, M is a Group 14 element and X is a Group 17 element. The p-type semiconductor CsSnI.sub.3 and the p-type semiconductor CsSnI.sub.2.95F.sub.0.05, which can be doped with SnF.sub.2, are examples of such compounds. However, other A/M/X compounds can also be used, including those with the formulas AMX.sub.3, A.sub.2MX.sub.4, AM.sub.2X.sub.5, A.sub.2MX.sub.6 or AMX.sub.5, where A, M, and X atoms can be mixed with other congeners (compounds that differ in the number and/or position of the atoms in the structure), for example, CsSnI.sub.2Cl and Cs.sub.2SnI.sub.2Cl.sub.2. Doping of the compounds with other main group, transition metal, lanthanide, or actinide elements or their compounds, such as Al.sub.2O.sub.3, SnO, SnF.sub.2 and CsSn.sub.0.5F.sub.3 is also possible. Still other HTM materials are described below.

(35) The A/M/X compounds may be classified as, or incorporated into, five types of materials. These types are designated herein as Types I-V.

(36) Type I Materials.

(37) These include A/M/X compounds, such as CsSnI.sub.3 or CsSnBr.sub.3, that are alloyed with other compounds—particularly with: (A) M(II) oxides or (B) M(IV) hexafluorides. The resulting alloys can exhibit a significant increase in their photoluminescence properties. In addition, alloying of these A/X/M compounds can be used to provide a controlled shift in the emission wavelength of the materials. In some embodiments, the Type I materials are doped and/or alloyed with one or more of M(I) or M(III) oxides, M(I) or M(III) halides, and M(III) or M(V) hexahalides, to provide p- or n-type semiconductors. These, and other, A/M/X compounds may be mixed halides—that is, the X may represent two or more halide elements. In such compounds having a Type I structure, the “X” may represent an X.sub.(3-x)X′.sub.x structure, wherein X and X′ are different halide atoms.

(38) Type II Materials.

(39) These include two sub-types of materials, Type IIA and Type IIB. In Type IIA materials, the A moiety in the A/M/X compound comprises a monovalent organic cation (A′), examples of which include methylammonium (CH.sub.3NH.sub.3.sup.+), formamidinium (HC(NH).sub.2).sub.2.sup.+), methylformamidinium (H.sub.3CC(NH).sub.2).sub.2.sup.+) and guanidinium (C(NH).sub.2).sub.3.sup.+). At least some embodiments of these hybrid organic/inorganic materials are photoluminescent having the general formula A′MI.sub.3.

(40) In Type IIB materials, the A moiety in the A/M/X compound comprises a bulky π-conjugated organic dication (A″), examples of which include N,N′-alkyl bipyridines (RV's, where R═H, Me, Et, etc. . . . ) and acridine. Such materials can form phases having the formulas AMI.sub.3, A″MI.sub.4 or A″M.sub.2I.sub.6 capable of producing photoluminescence emission on red light excitation (785 nm).

(41) Type III Materials.

(42) In these materials, the X moiety of the A/M/X compound comprises at least two halides, wherein at least one equivalent of iodide is present. The halide, X, comprise I substituted with any other halide to form AMIX.sub.2 phases. These materials include A/M/X compounds in which A=Cs, methylammonium (CH.sub.3NH.sub.3.sup.+) or formamidinium (HC(NH).sub.2).sub.2.sup.+); and M=Ge, Sn, or Pb.

(43) Type IV Materials: Germanium Iodides.

(44) In these materials, the M moiety of the A/M/X compound comprises germanium and the X moiety comprises iodine. These germanium(IV) iodide compounds can display photoluminescence on green light irradiation (532 nm). Examples of these materials include those having AGeI.sub.5 or A.sub.2GeI.sub.6 phases, where A=a Group 1 metal, methylammonium (CH.sub.3NH.sub.3.sup.+), formamidinium (HC(NH).sub.2).sub.2.sup.+), methylformamidinium (H.sub.3CC(NH).sub.2).sub.2.sup.+) or guanidinium (C(NH).sub.2).sub.3.sup.+). Ge(II) iodides also display photoluminescence including GeI.sub.1, but these are being described in Type II and Type III phases, having the formula AGeI.sub.3.

(45) Type V Material.

(46) These materials comprise complex compositions of the general formula (AMX.sub.3).sub.x(A′M′X′.sub.3).sub.y(A″M″X″.sub.3).sub.x, where x+y+z=1 and where A, A′, A″ and M, M′, M″ and X, X′, X″ stand for any possible combination of Type I, Type II, Type III and/or Type IV materials.

EXAMPLES

Example 1

(47) This Example illustrates methods of making a DSC comprising CsSnI.sub.3 and CsSnI.sub.3-xF.sub.x as HTMs. Although this example describes only the preparation and use of CsSnI.sub.3 and its related F-doped compounds as HTMs, the same procedures can be readily adapted to provide HTMs comprising other A/M/X compounds.

(48) Materials and Methods.

(49) Preparation of CsSnI.sub.3 and Other A/M/X Compounds.

(50) Pure CsSnI.sub.3 was prepared by reaching a stoichiometric mixture of CsI and SnI.sub.2 in an evacuated pyrex or fused silica tube at an elevated temperature for 1 h, followed by quenching or cooling for 1-3 h to room temperature (−23° C.) (RT). The reaction of the stoichiometric mixture of CsI and SnI.sub.2 was carried out at a temperature in the range of 400°-700° C. However, for AMX.sub.3 compounds in which A is substituted with an organic cation, a temperature in the range of 150°-200° C. can be used.

(51) Doped CsSnI.sub.3-xF.sub.x was prepared by reaching a stoichiometric mixture of CsI, SnF.sub.2 and SnI.sub.2 in an evacuated pyrex or fused silica tube at an elevated temperature for 1 h, followed by quenching or cooling for 1-3 h to room temperature (−23° C.) (RT). The reaction of the stoichiometric mixture of CsI, SnF.sub.2 and SnI.sub.2 was carried out at a temperature in the range of 400°-700° C. This process gives either CsSnI.sub.(3-x)F.sub.x or CsSnI.sub.(3-x)F.sub.x+x % SnF.sub.2.

(52) TiO.sub.2 Electrode Preparation.

(53) High-purity anatase TiO.sub.2 nanoparticles (NPs) were obtained by a 2-step autoclaving technique. A quantity of 30 wt. % commercially available TiO.sub.2 powders (P25, Degussa) that consisted of ca. 30% rutile and 70% anatase crystalline phases were hydrothermally treated with 10 N NaOH in an autoclave at 130° C. for 20 h, followed by repeated washing with 0.1N HNO.sub.3 to reach a pH value of ca. 1.5 following the procedure described in the literature (Tsai, C.-C.; Teng, H. Chemistry of Materials 2005, 18, 367-373.). Pure anatase colloidal TiO.sub.2 NPs were obtained by autoclaving the low-pH titanate suspension at 240° C. for 12 h. The composition and morphology of the resulting anatase TiO.sub.2 NPs were investigated by a field-emission scanning electron microscope (SEM, S4800, Hitachi) equipped with an energy dispersive spectrometer (EDS). The anatase phase was confirmed by X-ray powder diffraction study (D/Max-A, Rigaku). A paste of anatase TiO.sub.2 powder was prepared by stirring a mixture of anatase TiO.sub.2 NPs (0.5 g), Triton X-100 (100 mL), polyethylene glycol (0.2 g, PEG, Fluka, M.w.=20,000) into acetic acid (3 mL, 0.1 M). The TiO.sub.2 paste was spread on a SnO.sub.2:F coated glass substrate (Pilkington, TEC 8 glass, 8 Ω/sq, 2.3 mm thick) by the doctor-blade technique to give a flat and smooth surface using adhesive tape spacer. The film thickness was governed by the height of adhesive tape. The exact thickness of the TiO.sub.2 film was determined by a surface profiler (Tencor P-10). Finally, the TiO.sub.2 coated electrode was gradually calcined to remove the polymer under an air flow at 150° C. for 15 min, at 320° C. for 10 min, and at 500° C. for 30 min, giving a pure anatase TiO.sub.2 NP film.

(54) For fluorine etching, the nanoporous TiO.sub.2 films were first etched before soaking in the dye solution as described in the literature (Lee, B.; Buchholz, D. B.; Guo, P. J.; Hwang, D. K.; Chang, R. P. H. Journal of Physical Chemistry C 2011, 115, 9787-9796.). ZnO photonic crystals were prepared as described in the literature (Lee, B.; Hwang, D. K.; Guo, P. J.; Ho, S. T.; Buchholtz, D. B.; Wang, C. Y.; Chang, R. P. H. J. Phys. Chem. B 2010, 114, 14582-14591.).

(55) DSC Assembly.

(56) The next step in the DSC fabrication was to infiltrate the A/M/X HTM materials through the adsorbed dye layer and into the porous TiO.sub.2 NP film. First, for photosensitization, the calcined TiO.sub.2 NP electrode was immersed in an ethanol solution containing purified 3×10.sup.−4 M cis-di(thiocynato)-N,N′-bis(2,2′-bipyridyl-4-carboxylic acid-4′-tetrabutylammonium carboxylate) ruthenium (II) (N719, Solaronix) for 18 h at RT. The resulting dye-adsorbed TiO.sub.2 photoanode was rinsed with ethanol and dried under a nitrogen flow. The counter-electrode was produced by coating F:SnO.sub.2 glass with a thin layer of a 5 mM solution of H.sub.2PtCl.sub.6 in isopropanol and heating the coated glass at 400° C. for 20 min. The two electrodes were sealed together with thermal melt polymer film (24 μm thick, DuPont). The typical active area of the cell was about 0.3 cm.sup.2. The exact area of the photoanode was calibrated by an optical scanner under a resolution of 600 dot per inch (dpi). Next, the A/M/X materials dispersed/dissolved in organic solvents were injected to the cell, followed by drying under N.sub.2 and sealing. Alternatively, the dye-loaded TiO.sub.2 NP electrode can be immersed in the A/M/X solutions.

(57) JV Characteristics.

(58) The devices were evaluated under 100 mW/cm.sup.2 AM 1.5G sunlight simulation with a class A solar cell analyzer (Spectra Nova Tech.). A silicon solar cell fitted with a KG3 filter tested and certified by the National Renewable Energy Laboratory (NREL) was used for calibration. The KG3 filter accounts for the different light absorptions of the dye sensitized solar cell and silicon, and ensures that the spectral mismatch correction factor approaches unity.

(59) TABLE-US-00001 TABLE 1 EIS analysis and J-V characteristics of the DSCs comprising CsSnI.sub.3, and its doped compounds, as HTMs. Impedance analysis JV characteristics Area R.sub.1 C.sub.1 R.sub.2 C.sub.2 R.sub.total V.sub.OC J.sub.sc FF η (cm.sup.2) (Ω) (10.sup.−5 F) (Ω) (10.sup.−3 F) (Ω) (V) (mA/cm.sup.2) (%) (%) CsSnI.sub.3 0.290 17.9 1.54 101.9 1.6 122.0 0.638 8.82 66.1 3.72 CsSnI.sub.2.95F.sub.0.05 0.290 5.72 1.04 55.7 4.0 64.0 0.649 12.2 70.7 5.62 CsSnI.sub.2.95F.sub.0.05 + 0.02 SnF.sub.2 0.287 5.07 3.32 42.3 4.4 49.6 0.666 15.7 65.2 6.81 CsSnI.sub.2.95F.sub.0.05 + 0.05 SnF.sub.2 0.291 5.01 1.64 31.9 2.2 37.3 0.688 16.3 69.4 7.78 CsSnI.sub.2.95F.sub.0.05 + 0.10 SnF.sub.2 0.302 6.03 0.99 59.2 3.9 67.8 0.654 13.6 61.4 5.46

(60) TABLE-US-00002 TABLE 2 J-V characteristics of the DSCs comprising an HTM of CsSnI.sub.3 doped with 5% SnF.sub.2 and an HTM made with an F-etched TiO.sub.2 photoanode. The effects of fluorine etching and the presence of stacks of 3-D ZnO photonic crystals (PhCs) are shown. Those with a mask are also presented. JV characteristics TiO.sub.2 thickness FF η Area (cm.sup.2) (μm) V.sub.OC (V) J.sub.sc (mA/cm.sup.2) (%) (%) CsSnI.sub.2.95F.sub.0.05 + 0.05 SnF.sub.2 0.291 16.3 0.688 16.3 69.4 7.78 CF.sub.4 etching 0.263 15.2 ± 0.5 0.721 15.6 72.3 8.62 With mask 0.263 15.2 ± 0.5 0.716 13.7 75.5 7.38 CF4/ZnO PhCs 0.263 15.2 ± 0.5 0.725 18.1 74.4 9.74 With mask 0.263 15.2 ± 0.5 0.720 15.3 75.0 8.27

(61) Results:

(62) The p-type semiconductor CsSnI.sub.3-xF.sub.x HTM was prepared by reacting a stoichiometric mixture of CsI, SnI.sub.2 and SnF.sub.2 at 400° C. for 1 h, followed by quenching to air. The resulting powders were dispersed in acetonitrile and injected into an n-type electrode comprising a nanoporous TiO.sub.2 film loaded with a N719 dye. The solutions were rapidly evaporated to form the liquid-free DSCs. A cross-sectional scanning electron microscopy (SEM) image of the CsSnI.sub.3 DSC showed that CsSnI.sub.3 solution homogeneously permeated deep into the TiO.sub.2 films. In addition, a cross-sectional back scattering image showed that the TiO.sub.2 and CsSnI.sub.3 were well distributed through the cell. This DSC structure is superior to DSC structures that employ conducting polymer HTMs because the penetration depth of the latter is about 4-5 μm, causing poor interfacial properties of the electrode and HTM. Furthermore, the use of polymerization processes in the fabrication of DSCs is complex and unfavorable for large-scale commercialization.

(63) The absorbance spectrum of a the DSC comprising CsSnI.sub.2.95F.sub.0.05/dye/TiO.sub.2 photoanode compared to that of a DSC comprising a dye/TiO.sub.2 photoanode revealed that the former can effectively absorb red and near infrared light with a well-defined absorption edge at 789 nm (FIG. 2). In fact, one of the drawbacks of the Ru dye is its poor performance in such a spectral range.

(64) FIG. 3 shows the photocurrent density-voltage (J-V) characteristics of the DSCs with the CsSnI.sub.3 and CsSnI.sub.2.95F.sub.0.05 HTMs with various amounts of SnF.sub.2 doping under 100 m W cm.sup.−2 AM 1.5 illumination. The detailed photovoltaic parameters of the open circuit voltage (V.sub.oc), fill factor (FF), short-circuit current density (J.sub.sc) and photovoltaic conversion efficiency (η) are given in Table 1. Introducing F atoms into the CsSnI.sub.3 significantly improved the photocurrent density. The J.sub.sc of the DSC increased from 8.82 mA cm.sup.−2 to 12.2 mA cm.sup.−2 when the 5% F-doped material (CsSnI.sub.2.95F.sub.0.05) was used. The SnF.sub.2 dopant was introduced to provide a continuous improvement of the J.sub.sc, which reached the maximum at 16.3 mA cm.sup.−2 at a doping level of 5% SnF.sub.2. As the J.sub.sc, the efficiency increased. The DSC comprising the HTM CsSnI.sub.2.95F.sub.0.05 doped with 5% SnF.sub.2 exhibited the highest efficiency of η=7.78%.

(65) To further improve the cell performance, the nanoporous TiO.sub.2 films were etched with a fluorine plasma, as described above. This provided an increase in the sizes of the nanopores and nanochannels in the TiO.sub.2 films and passivated the surfaces of the nanoporous TiO.sub.2. The DSC with CsSnI.sub.2.95F.sub.0.05 HTMs doped with 5% SnF.sub.2 using the etched TiO.sub.2 film showed an improved efficiency of 8.62% due to a higher V.sub.oc, of 0.721V and a fill factor of 72.3%, compared to that of a conventional TiO.sub.2 film (FIG. 4). The improvement in V.sub.oc possibly resulted from the passivation by fluorine etching to remove defect states of TiO.sub.2 nanoparticles.

(66) To fully employ the photon flux absorbed, a stack of two 3-D inverse photonic crystals of ZnO were attached to the same DSC, one with hole diameter of 375 nm and another with a hole diameter of 410 nm. The resulting DSC showed a significantly improved J.sub.sc of 18.1 mA cm.sup.−2 to give an efficiency of η=9.74%. The observed value may be the highest among DSCs with no I.sup.−/I.sub.3.sup.− electrolyte. The J-V characteristics showing the effects of fluorine etching and application of ZnO photonic crystal stacks are shown in Table 2.

(67) Electrochemical impedance spectroscopy (EIS) was used to characterize the internal resistance and charge transfer kinetics. FIGS. 5 (A), (B), and (C) show the Nyquist plots, Bode phase plots and magnitude of impedance, respectively. The details of EIS analysis are shown in Table 1 with J-V characteristics. F and SnF.sub.2 doping reduced the R.sub.total, giving higher efficiency. The trend in R.sub.total is inversely related to the trend in conversion efficiency.

(68) A schematic diagram of the relative energy levels of CsSnI.sub.3, TiO.sub.2 and the N719 dye is shown in FIG. 24. The positions of the conduction band minimum (CBM) and the valence band maximum (VBM) of CsSnI.sub.3 were aligned by the work function (4.92 eV) according to ultraviolet photoemission spectroscopy study and the energy gap (1.3 eV), relative to those of TiO.sub.2 and the N719 dye based on the literature. The diagram validates the fit of CsSnI.sub.3 in the present type of solid-state solar cell, giving excellent charge separation and replacing liquid electrolytes. The conduction band minimum lies nearly in the same energy level as the lowest unoccupied molecular orbital (LUMO) of the N719 dye and above the CBM of TiO.sub.2. The valence band maximum is positioned above the highest occupied molecular orbital (HOMO) of the dye. Consequently, electrons generated by the dye are transported to the n-type semiconductor TiO.sub.2 and the oxidized dye is readily regenerated by the p-type semiconductor CsSnI.sub.3 because it a fast hole transporter.

Example 2

(69) This Example provides some illustrative examples of Type I materials and processes for their synthesis. The Type I materials of this example include those comprising two phases, designated categories (A) and (B) in the description that follows.

(70) Type I materials of category (A) have the formula (Cs.sub.1+ySnI.sub.3+y).sub.x(MO.sub.y).sub.1-x: where M=a Group 14 element with y=1 or y=2; or M=a Group 13 or a Group 15 element. The Cs and I content (as CsI) can be varied in these materials to get the optimal photoluminescence intensity. Specific examples include: (α) (Cs.sub.1+ySnI.sub.3+y).sub.x(MO).sub.1-x, where M=Si, Ge, Sn, or Pb; and (β) (Cs.sub.1+ySnI.sub.3+y).sub.x(MO.sub.1.5).sub.1-x, where M=B, Al, Ga, In, Sc, or Y; (γ) (Cs.sub.1+ySnI.sub.3+y).sub.x(MO.sub.2).sub.1-x, where M=Si, Ge, Sn, or Pb.

(71) Type I materials of category (B) have the formula (Cs.sub.1+ySnI.sub.3+y).sub.x(Cs.sub.xMF.sub.6).sub.1-x: where M=a Group 15 or a Group 5 element and z=1; or M=a Group 14 or a Group 4 element and z=2; or M=a Group 13 or Group 3 element and z=3. The Cs and I content (as CsI) can be varied to get the optimal photoluminescence intensity. Specific examples include: (δ) (Cs.sub.1+ySnI.sub.3+y).sub.1-x(CsM.sub.0.5F.sub.3).sub.x, where M=Si, Ge, Sn, Ti, Zr, or Hf; (ε) (Cs.sub.1+ySnI.sub.3+y).sub.1-x(Cs.sub.1.5M.sub.0.5F.sub.3).sub.x, where M=Al, Ga, In, Sc, or Y; (στ) (Cs.sub.1+ySnI.sub.3+y).sub.1-x(Cs.sub.0.5M.sub.0.5F.sub.3).sub.x, where M=P, As, Sb, V, Nb, or Ta.

(72) Sample Synthetic Process 1:

(73) A pyrex ampule was loaded with CsI (1 equivalent) and an amount of SnI.sub.2 and SnO as solids. The SnI.sub.2/SnO ratio was fixed in such a way that the total Sn content was 1 equivalent. The ampule was sealed under a 10.sup.−4 mbar vacuum and heated up to 450° C. and cooled. The resulting solids were tested for photoluminescence.

(74) Sample Synthetic Process 2:

(75) A pyrex ampule was loaded with SnI.sub.2 (1 equivalent) and MO.sub.X (0.5 equiv) and a variable quantity of CsI. The ampule was and heated to 450° C. and cooled. The resulting solids were tested for photoluminescence.

(76) Sample Synthetic Process 3:

(77) A pyrex ampule was loaded with CsI (1 equivalent) and SnI.sub.2 and a variable amount of CsMF.sub.6. The ampule was heated up to 450° C. and cooled. The resulting solids were tested for photoluminescence.

(78) The PL spectra for the Type I materials are shown in FIGS. 6, 7 and 8(A)-(C).

Example 3

(79) This Example provides some illustrative examples of Type IIA materials and processes for their synthesis. The Type IIA materials of this example include those comprising the phase designated (C) in the description that follows.

(80) The phase of type (C) has the formula AMI.sub.3: where A=methylammonium (CH.sub.3NH.sub.3.sup.+), formamidinium (HC(NH).sub.2).sub.2.sup.+), methylformamidinium (H.sub.3CC(NH).sub.2).sub.2.sup.+) or guanidinium (C(NH).sub.2).sub.3.sup.+). The structural formulae of these organic cations is shown in Chart 1.

(81) ##STR00001##

(82) Specific examples include: (ζ) CH.sub.3NH.sub.3MI.sub.3, where M=Ge, Sn, or Pb; (η)HC(NH.sub.2).sub.2MI.sub.3, where M=Ge, Sn, or Pb; (θ)H.sub.3CC(NH.sub.2).sub.2MI.sub.3, where M=Ge, Sn, or Pb; and (.Math.) C(NH.sub.2).sub.3MI.sub.3, where or M=Ge, Sn, Pb.

(83) FIG. 9 shows a portion of the crystal structure of Type IIA material CH.sub.3NH.sub.3GeI.sub.3 highlighting the perovskite building block.

(84) Table 3 provides atomic coordinates (×10.sup.4) and equivalent isotropic displacement parameters (E.sup.2×10.sup.3) for the CH.sub.3NH.sub.3GeI.sub.3. U(eq) is defined as one third of the trace of the orthogonalized U.sup.ji tensor.

(85) TABLE-US-00003 TABLE 3 x y z U(eq) Ge 6667 3333  315(5)  29(1) I 5050(1) 4950(1) 1568(6)  57(1) C 6667 3333 5580(90) 130(30) N 6667 3333 4400(200) 370(110)

(86) FIG. 10 shows a portion of the crystal structure of CH.sub.3NH.sub.3SnI.sub.3 highlighting the perovskite building block.

(87) Table 4 provides crystal data structure refinement for the CH.sub.3NH.sub.3SnI.sub.3.

(88) TABLE-US-00004 TABLE 4 Empirical formula CH6I3NSn Formula weight  531.46 Temperature 293(2) K Wavelength 0.71073 E Crystal system Tetragonal Space group P4mm Unit cell dimensions a = 6.2302(9) E α = 90°. b = 6.2302(9) E β = 90°. c = 6.2316(12) E γ = 90°. Volume 241.88(7) E.sup.3 Z   1 Density (calculated) 3.649 Mg/m.sup.3 Absorption coefficient 12.128 mm.sup.−1 F(000)  228 Theta range for data collection 3.27 to 24.78°. Index ranges −7 <= h <= 7, −7 <= k <= 7, −7 <= l <= 7 Reflections collected 1520 Independent reflections 294 [R(int) = 0.0331] Completeness to theta = 24.78° 98.2% Refinement method Full-matrix least-squares on F.sup.2 Data/restraints/parameters 294/1/18 Goodness-of-fit on F.sup.2   0.794 Final R indices [I > 2sigma(I)] R1 = 0.0239, wR2 = 0.0839 R indices (all data) R1 = 0.0323, wR2 = 0.0984 Absolute structure parameter 0.6(5) Largest diff. peak and hole 0.574 and −0.538 e .Math. E.sup.−3

(89) Table 5 provides atomic coordinates (×10.sup.4) and equivalent isotropic displacement parameters (E.sup.2×10.sup.3) for the CH.sub.3NH.sub.3SnI.sub.3. U(eq) is defined as one third of the trace of the orthogonalized U.sup.ji tensor.

(90) TABLE-US-00005 TABLE 5 x y z U(eq) Sn 0 0 9484 28(1) I(1) −5000 0 9582(15) 84(1) I(2) 0 0 14608(10)  85(2) N 5000 5000  4800(200) 150(40) C 5000 5000 2840(90) 160(50)

(91) FIG. 11 shows a portion of the crystal structure of CH.sub.3NH.sub.3PbI.sub.3 highlighting the perovskite building block.

(92) Table 6 provides crystal data structure refinement for the CH.sub.3NH.sub.3PbI.sub.3.

(93) TABLE-US-00006 TABLE 6 Empirical formula CH6I3NPb Formula weight  619.96 Temperature 293(2) K Wavelength 0.71073 E Crystal system Tetragonal Space group P4mm Unit cell dimensions a = 6.2641(9) E α = 90°. b = 6.2641(9) E β = 90°. c = 6.3242(13) E γ = 90°. Volume 248.15(7) E.sup.3 Z   1 Density (calculated) 4.148 Mg/m.sup.3 Absorption coefficient 26.244 mm.sup.−1 F(000)  260 Theta range for data collection 3.25 to 24.96°. Index ranges −7 <= h <= 7, −7 <= k <= 7, −7 <= l <= 6 Reflections collected 1543 Independent reflections 275 [R(int) = 0.0316] Completeness to theta = 24.96° 95.1% Refinement method Full-matrix least-squares on F.sup.2 Data/restraints/parameters 275/1/15 Goodness-of-fit on F.sup.2   1.717 Final R indices [I > 2sigma(I)] R1 = 0.0631, wR2 = 0.1859 R indices (all data) R1 = 0.0650, wR2 = 0.1871 Absolute structure parameter 0.6(6) Largest diff. peak and hole 5.168 and −5.446 e .Math. E.sup.−3

(94) Table 7 provides atomic coordinates (×10.sup.4) and equivalent isotropic displacement parameters (E.sup.2×10.sup.3) for the CH.sub.3NH.sub.3PbI.sub.3. U(eq) is defined as one third of the trace of the orthogonalized U.sup.ji tensor.

(95) TABLE-US-00007 TABLE 7 x y z U(eq) Pb(1) 5000 5000 2547  26(1) I(3) 0 5000 2550(40) 177(5) I(2) 5000 5000 7550(30)  82(2) C(2) 0 0 8000(3000) 600(800) N(10) 0 0 7200(1900) 100(600)

(96) Sample Synthetic Process 4:

(97) A solution mixture of concentrated HI/H.sub.3PO.sub.2 (4/1 v/v) was prepared. Addition of SnI.sub.2 (1 equivalent) provided a clear solution which was maintained at 120° C. Subsequent addition of the corresponding organic iodide (1 equivalent), precipitated the desired material.

Example 4

(98) This Example provides some illustrative examples of Type IIB materials and processes for their synthesis. The Type IIB materials of this example include those comprising the phase designated (D) in the description that follows.

(99) The phase of type (D) has the formula ASn.sub.xI.sub.y: where A=alkyl viologen (RV, R=H, Me, Et, etc.) or a polyaromatic pyridine. The structural formulae of these organic cations is shown in Chart 2.

(100) ##STR00002##

(101) Specific examples include: (K) HVSnI.sub.4 and RVSn.sub.2I.sub.6, where R=methyl, ethyl, heptyl, etc. . . . ) and polymeric viologens; and (2) AcrSnI.sub.3 and ASnI.sub.3 materials, where A is a polyaromatic pyridine.

(102) FIG. 12 shows the unit cell of EVSn.sub.2I.sub.6 viewing along the 1-dimensional Sn.sub.2I.sub.6.sup.2− chains.

(103) Table 8 provides crystal data structure refinement for the of EVSn.sub.2I.sub.6.

(104) TABLE-US-00008 TABLE 8 Empirical formula C14I6N2Sn2 Formula weight  1194.94 Temperature 293(2) K Wavelength 0.71073 E Crystal system Monoclinic Space group P2.sub.1/c Unit cell dimensions a = 12.116(2) E α = 90°. b = 13.941(3) E β = 90.51(3)°. c = 24.677(5) E γ = 90°. Volume 4167.8(14) E.sup.3 Z   6 Density (calculated) 2.857 Mg/m.sup.3 Absorption coefficient 8.465 mm.sup.−1 F(000)  3096 Theta range for data collection 1.65 to 25.00°. Index ranges −14 <= h <= 14, −16 <= k <= 16, −29 <= l <= 29 Reflections collected 26382 Independent reflections 7347 [R(int) = 0.1134] Completeness to theta = 25.00° 100.0% Refinement method Full-matrix least-squares on F.sup.2 Data/restraints/parameters 7347/0/325 Goodness-of-fit on F.sup.2   0.928 Final R indices [I > 2sigma(I)] R1 = 0.0626, wR2 = 0.0733 R indices (all data) R1 = 0.1489, wR2 = 0.0896 Largest diff. peak and hole 0.845 and −1.153 e .Math. E.sup.−3

(105) Table 9 provides atomic coordinates (×10.sup.4) and equivalent isotropic displacement parameters (E.sup.2×10.sup.3) for the EVSn.sub.2I.sub.6. U(eq) is defined as one third of the trace of the orthogonalized U.sup.ji tensor.

(106) TABLE-US-00009 TABLE 9 x y z U(eq) I(72) 8381(1) 3448(1) 1032(1) 57(1) Sn(2) 6690(1) 4993(1) 543(1) 44(1) I(3) 15001(1) 13469(1) −48(1) 52(1) I(4) 8300(1) 80(1) 4496(1) 53(1) Sn(5) 9950(1) 6716(1) −16(1) 50(1) Sn(6) 3403(1) 3423(1) 1174(1) 58(1) I(8) 8102(1) 6733(1) 946(1) 59(1) I(9) 8543(1) 8026(1) −735(1) 64(1) I(10) 4536(1) 1677(1) 1536(1) 91(1) I(11) 11097(1) 8305(1) 539(1) 81(1) I(12) 2292(1) 3768(1) 2202(1) 88(1) C(2) 7783(11) 1974(10) 2886(6) 44(4) C(3) 4537(12) 2867(14) 3261(10) 101(8) N(4) 10994(10) 918(13) 2549(7) 72(4) C(9) 4559(17) 3953(17) 3417(12) 120(9) C(13) 12153(13) 623(19) 2424(9) 108(8) C(15) 14412(10) 9952(13) −123(6) 53(4) C(19) 12081(16) −199(16) 2004(11) 108(8) C(20) 8916(11) 1589(12) 2763(6) 50(4) N(22) 12369(10) 9799(11) −572(6) 65(4) C(26) 7119(14) 2404(14) 2482(7) 78(6) C(27) 14059(13) 9072(11) −331(8) 71(6) C(30) 6335(15) 2134(13) 3515(7) 72(5) N(31) 5692(10) 2555(10) 3128(7) 64(4) C(34) 7391(12) 1840(14) 3403(6) 64(5) C(36) 10461(13) 533(14) 2954(6) 63(5) I(40) 5331(1) 4855(1) 1609(1) 64(1) C(47) 12989(13) 9044(14) −555(9) 81(6) C(49) 12674(15) 10652(13) −376(8) 72(5) C(61) 11205(11) 9720(15) −812(8) 79(6) C(66) 6073(14) 2688(16) 2628(9) 83(7) C(70) 11262(14) 10040(20) −1384(10) 117(9) C(74) 9403(12) 852(13) 3067(6) 62(5) C(8) 9515(15) 2016(16) 2329(7) 91(7) C(18) 10576(16) 1623(16) 2235(8) 85(6) C(12) 13746(14) 10770(13) −136(9) 85(6)

(107) FIG. 13 shows the unit cell of AcrSnI.sub.3 viewing along the 1-dimensional SnI.sub.3.sup.− chains.

(108) Table 10 provides crystal data structure refinement for the of AcrSnI.sub.3.

(109) TABLE-US-00010 TABLE 10 Empirical formula C13H10I3NSn Formula weight  679.61 Temperature 293(2) K Wavelength 0.71073 E Crystal system Monoclinic Space group P2.sub.1/n Unit cell dimensions a = 4.6467(9) E α = 90°. b = 24.710(5) E β = 90.18(3)°. c = 14.817(3) E γ = 90°. Volume 1701.2(6) E.sup.3 Z   4 Density (calculated) 2.653 Mg/m.sup.3 Absorption coefficient 6.930 mm.sup.−1 F(000)  1216 Theta range for data collection 1.60 to 24.99°. Index ranges −5 <= h <= 5, −29 <= k <= 29, −17 <= 1 <= 17 Reflections collected 12633 Independent reflections 2956 [R(int) = 0.0548] Completeness to theta = 24.99° 98.1% Refinement method Full-matrix least-squares on F.sup.2 Data/restraints/parameters 2956/0/164 Goodness-of-fit on F.sup.2   1.088 Final R indices [I > 2sigma(I)] R1 = 0.0483, wR2 = 0.0896 R indices (all data) R1 = 0.0636, wR2 = 0.0989 Largest diff. peak and hole 1.311 and −1.427 e .Math. E.sup.−3

(110) Table 11 provides atomic coordinates (×10.sup.4) and equivalent isotropic displacement parameters (E.sup.2×10.sup.3) for the AcrSnI.sub.3. U(eq) is defined as one third of the trace of the orthogonalized U.sup.ji tensor.

(111) TABLE-US-00011 TABLE 11 x y z U(eq) I(1) 2328(3) 1337(1) 1439(1) 56(1) Sn(2) 7159(3) 413(1) 1325(1) 49(1) I(2) 2383(3) −493(1) 1123(1) 59(1) I(3) 6881(3) 315(1) 3333(1) 58(1) C(1) −2270(40) −2498(5) 4865(8) 52(4) C(2) −4220(40) −2514(5) 5577(10) 54(4) C(3) −1990(40) −1508(5) 4997(8) 50(4) N(1) −3840(30) −1535(4) 5707(8) 52(3) C(4) 1890(40) −1456(7) 3552(10) 76(5) C(5) −880(40) −1003(6) 4713(11) 56(4) C(6) 990(40) −1954(8) 3827(11) 77(6) C(7) −1150(40) −1995(6) 4567(9) 55(4) C(8) 1050(40) −967(7) 3993(12) 71(5) C(9) −470(40) −1994(6) 894(10) 52(4) C(10) 8260(50) 2511(7) 2998(10) 70(5) C(11) 7160(40) 2024(5) 3270(8) 56(4) C(12) 5100(30) 2016(5) 3991(9) 45(3) C(13) −2480(50) −1992(5) 1582(10) 72(5)

(112) Sample Synthetic Process 5:

(113) A solution mixture of concentrated HI/H.sub.3PO.sub.2 (4/1 v/v) was prepared. Addition of SnI.sub.2 (1 equivalent) provided a clear solution which was maintained at 120° C. Subsequent addition of the corresponding organic iodide (1 equivalent), precipitated the desired material.

(114) FIG. 14 shows the PL emission vs. energy data for Type IIB materials on 785 nm (1.58 eV) excitation as measured using a Raman scattering setup. (Note, the above-described Type IIA and Type IIB materials are parent phases for the Type III materials described below. Therefore, PL data for the Type IIA materials are included in the description of Type III materials as well.)

Example 5

(115) This Example provides some illustrative examples of Type III materials and processes for their synthesis. The Type III materials of this example include those comprising the phase designated (E) in the description that follows.

(116) The phase of type (E) has the formula AMIX.sub.2: where, in some embodiments, A=Cs, methylammonium (CH.sub.3NH.sub.3.sup.+), formamidinium (HC(NH).sub.2).sub.2.sup.+), methylformamidinium (H.sub.3CC(NH).sub.2).sub.2.sup.+) or guanidinium (C(NH).sub.2).sub.3.sup.+), M=a Group 14 element and X=a Group 17 element. Specific examples include: (μ) CsMIX.sub.2, where M=Ge, Sn, or Pb and X can be any combination of halides; (ν) CH.sub.3NH.sub.3MIX.sub.2, where M=Ge, Sn, or Pb and X can be any combination of halides; (ξ) HC(NH.sub.2).sub.2MIX.sub.2, where M=Ge, Sn, or Pb and X can be any combination of halides; (o) H.sub.3CC(NH).sub.2).sub.2MIX.sub.2, where M=Ge, Sn, or Pb and X can be any combination of halides; and (π) C(NH).sub.2).sub.3MIX.sub.2, where M=Ge, Sn, or Pb and X can be any combination of halides.

(117) FIG. 15 shows the PL emission vs. wavelength data for CH.sub.3NH.sub.3SnIX.sub.2 phases.

(118) Sample Synthetic Process 6:

(119) A pyrex ampule was loaded with CH.sub.3NH.sub.3X or HC(NH.sub.2).sub.2X (1 equivalent), SnX.sub.2 or PbX.sub.2 or mixtures of them (1 equivalent), where X is a Group 17 element, to achieve the corresponding X/I ratio. The ampule was heated up to 350° C. and cooled. The resulting solids were tested for photoluminescence.

(120) FIG. 16 shows PL emission vs. wavelength for HC(NH.sub.2).sub.2SnIX.sub.2 phases for the first emission wavelength.

(121) FIG. 17 shows PL emission vs. wavelength for HC(NH.sub.2).sub.2SnIX.sub.2 phases for the second emission wavelength.

(122) FIG. 18 shows PL emission vs. wavelength for CH.sub.3NH.sub.3PbIX.sub.2 phases for the first emission wavelength.

(123) FIG. 19 shows PL emission vs. wavelength for CH.sub.3NH.sub.3PbIX.sub.2 phases for the second emission wavelength.

(124) Sample Synthetic Process 7:

(125) CH.sub.3NH.sub.3I or HC(NH.sub.2).sub.2I (1 equivalent), SnI.sub.2 or PbI.sub.2 or mixtures of them (1 equivalent), where X is a group 17 element, were ground finely at room temperature. The resulting solids were then tested for photoluminescence.

Example 6

(126) This Example provides some illustrative examples of Type IV materials and processes for their synthesis. The Type IV materials of this example include those comprising the phase designated (F) in the description that follows.

(127) The phase of type (F) includes germanium iodides having the formulas: GeI.sub.2, GeI.sub.4, AGeI.sub.5 and A.sub.2GeI.sub.6, where A is a Group 1 metal or an organic cation. Specific examples include: (ρ) GeI.sub.1 and GeI4; (σ) AGeI.sub.5; and (τ) A.sub.2GeI.sub.6.

(128) FIG. 20 shows PL emission vs. wavelength for germanium iodide phases.

(129) Sample Synthetic Process 8:

(130) An alkali metal iodide or an organic iodide salt (1 or 2 equivalents) and GeI.sub.4 (1 equivalent) were ground finely at room temperature. The resulting solids were then tested for photoluminescence.

Example 6

(131) This Example provides some illustrative examples of Type V materials and processes for their synthesis. The Type V materials of this example include those comprising two phases, designated categories (G), (H) and (I) in the description that follows.

(132) In this family of materials are incorporated all possible combinations of the materials described as Types I-IV. It is possible to mix i) the halide, X, ii) the octahedrally coordinated metal, M, iii) the cation, A, and iv) it is possible to add another phase to alloy or dope the material (as described in type I), to prepare materials of the general formula (AMX.sub.3).sub.1-x(M′O.sub.z).sub.x, (AMX.sub.3).sub.1-x(AM′F.sub.6).sub.x, (alloying) and (AM.sub.1-zX.sub.3-z)(M′X.sub.z) doping. A denotes any cation, M=Ge, Sn or Pb, M′ any element described in type I and X is any halide, as described in Type I-IV materials.

(133) Type V materials of category (G) have the formula ASnIX.sub.2xMO.sub.z: where M=an element described above as a Type I material. Specific examples include: (υ) (AMX.sub.3).sub.1-x(M′O.sub.z).sub.x, where A denotes any cation described above, M=Ge, Sn or Pb, M′ any element described above as a Type I material, and X is any halide; and (φ) (AMX.sub.3).sub.1-x(AM′F.sub.6).sub.x, where A denotes any cation described above, M=Ge, Sn or Pb, M′ any element described above as a Type I material, and X is any halide.

(134) FIG. 21 shows PL emission vs. wavelength for CsSnF.sub.2I+ borosilicate and CsSnF.sub.2I+ alumina.

(135) Sample Synthetic Process 9:

(136) A pyrex ampule or an α-alumina crucible placed inside a pyrex crucible was loaded with CsI (1 equivalent) and SnF.sub.2 (1 equivalent). The ampule was sealed under a 10.sup.−4 mbar vacuum and heated up to 350° C. and cooled. The resulting solids were tested for photoluminescence.

(137) Sample Synthetic Process 10:

(138) CH.sub.3NH.sub.3I or HC(NH.sub.2).sub.2I (1 equivalent), SnI.sub.2 or PbI.sub.2 or mixtures of them (1 equivalent), where X is a group 17 element, and a variable amount of CH.sub.3NH.sub.3zM′F.sub.6 or HC(NH.sub.2).sub.2zM′F.sub.6 were ground finely at room temperature. The resulting solids were tested for photoluminescence, or first were annealed at elevated temperatures and cooled and then tested for photoluminescence.

(139) Type V materials of category (H) have the formula AM.sub.1-xM′.sub.xX.sub.3: where M, M′=Ge, Sn, or Pb. Mixing of the metals leads to a shift in the emission wavelength. Specific examples include: (χ) (AMX.sub.3).sub.1-x(A′M′X′.sub.3).sub.x, where A denotes any cation described above, M=M′=Ge, Sn or Pb, and X is any halide.

(140) FIG. 22 shows PL emission vs. wavelength for CH.sub.3NH.sub.3Sn.sub.1-xPb.sub.xI.sub.3 for different values of x.

(141) Sample Synthetic Process 11:

(142) CH.sub.3NH.sub.3I or HC(NH.sub.2).sub.2I (1 equivalent), SnI.sub.2 or PbI.sub.2 or mixtures of them (1 equivalent), where X is a Group 17 element, were ground finely at room temperature. The resulting solids were annealed at an elevated temperature and tested for photoluminescence.

(143) Type V materials of category (I) have the formula (AM.sub.1-zX.sub.3-z)(M′X.sub.z): where A is any cation discussed above, M=Ge, Sn, or Pb, M′=a transition metal and X=any halide.

(144) FIG. 23 shows PL emission vs. wavelength for CH.sub.3NH.sub.3SnCl.sub.2I and CH.sub.3NH.sub.3Sn.sub.0.9CO.sub.0.1Cl.sub.2I.

(145) Sample Synthetic Process 12:

(146) An alkali metal or an organic iodide salt (1 equivalent), SnX.sub.2 or PbX.sub.2 and a transition metal halide, where X is a Group 17 element, in a ratio that the total metal content is 1 equivalent, were ground finely at room temperature. The resulting solids were annealed at elevated temperatures and cooled and then tested for photoluminescence.

(147) Unless otherwise specified, the x (or z) values provided in the chemical formulas herein are 0.01<x (or z)<0.99.

Example 7

(148) This Example illustrates methods of making a DSC comprising CsSnBr.sub.3 and CsSnI.sub.2Br as HTMs.

(149) Materials and Methods.

(150) Preparation of CsSnBr.sub.3 and Other A/M/X Compounds.

(151) Pure CsSnBr.sub.3 is prepared by reaching a stoichiometric mixture of CsBr and SnBr.sub.2 in an evacuated pyrex or fused silica tube at an elevated temperature for 1 h, followed by quenching or cooling for 1-3 h to room temperature (˜23° C.) (RT). The reaction of the stoichiometric mixture of CsBr and SnBr.sub.2 is carried out at a temperature in the range of 400°-700° C. The CsSnI.sub.2Br compound (i.e., with Br doping) and the compound doped with SnF.sub.2 are made using a procedure analogous to that for F doping and SnF.sub.2 doping described in Example 1.

(152) TiO.sub.2 Electrode Preparation.

(153) The TiO.sub.2 electrode was prepared using the method described in Example 1.

(154) DSC Assembly.

(155) The DSC is assembled according to the process described in Example 1. The structure of the solar cell is the same as that shown in FIG. 1.

(156) JV Characteristics.

(157) The JV characteristics of the solar cell are measured according to the techniques described in Example 1.

(158) TABLE-US-00012 TABLE 12 J-V characteristics of the DSCs comprising HTMs of CsSnI.sub.2Br, CsSnBr.sub.3 and each of these doped with 5% SnF.sub.2 using an F-etched TiO.sub.2 photoanode under irradiation of 100 mWcm.sup.−2 simulated AM 1.5 sunlight. JV characteristics Area FF η (cm.sup.2) V.sub.OC (V) J.sub.SC (mA/cm.sup.2) (%) (%) CsSnBr.sub.3 0.298 0.705 6.68 62.4 2.94 CsSnI.sub.2Br 0.239 0.700 17.0 68.3 8.12 CsSnBr.sub.3 + 5% SnF.sub.2 0.279 0.705 17.96 63.4 8.03 CsSnI.sub.2Br + 5% SnF.sub.2 0.249 0.659 12.5 69.8 5.74

(159) As shown in the table above the CsSnBr.sub.(3-x)I.sub.x materials showed improved V.sub.oc and J.sub.sc compared to the CsSnI.sub.3 system.

(160) FIG. 25 shows the photocurrent density-voltage (J-V) characteristics of the solar cell devices under irradiation of 100 mWcm.sup.−2 simulated AM 1.5 sunlight.

Example 8

(161) This Example illustrates the fabrication of pn-junction type solar cells that use A/M/X compounds as hole transport materials, but do not include a photosensitive dye.

(162) FIG. 26 provides a schematic diagram of the solar cell. As shown in panel (D) of FIG. 26, the cell includes a back electrode 2402 comprising a transparent conducting oxide (e.g., FTO), a front electrode comprising and electrically conducting film (e.g., Pt) 2404 disposed on a transparent conducting oxide 2406. Disposed between and electrical communication with electrodes 2402 and 2404/2406 are a layer comprising an n-type TiO.sub.2 nanoparticle film 2408 and a layer comprising a A/M/X compound 2410, either CsSnI.sub.3 or CsSnI.sub.(3-x)F.sub.x.

(163) The pn-junction cells were fabricated as follows. The A/M/X compounds (synthesized as described previously) were dispersed in dimethylformamide (DMF) and dropped on the n-type doped TiO.sub.2 nanoparticle film (FIG. 26, panels (i) and (ii)). After being drop coated, the films were heated at 150˜200° C. until the A/M/X compounds turned black (panel (iii)). And then, the active sides of the resulting film and platinized electrode were mechanically contacted and sealed by Amosil 4 sealant (panel (iv)). The detailed photovoltaic properties (measured as described above) are given in Table 13 and the J-V characteristics are shown in FIG. 27.

(164) TABLE-US-00013 TABLE 13 TiO.sub.2 JV characteristics Area Thickness J.sub.sc FF EFF (cm.sup.2) (μm) V.sub.OC (V) (mA/cm.sup.2) (%) (%) (a) CsSnI.sub.3 0.306 12.1 0.205 0.923 41.5 0.078 (b) CsSnI.sub.3−xF.sub.x 0.282 12.3 0.467 0.809 59.3 0.224

(165) The word “illustrative” is used herein to mean serving as an example, instance, or illustration. Any aspect or design described herein as “illustrative” is not necessarily to be construed as preferred or advantageous over other aspects or designs. Further, for the purposes of this disclosure and unless otherwise specified, “a” or “an” means “one or more”. Still further, the use of “and” or “or” is intended to include “and/or” unless specifically indicated otherwise.

(166) The foregoing description of illustrative embodiments of the invention has been presented for purposes of illustration and of description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiments were chosen and described in order to explain the principles of the invention and as practical applications of the invention to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.