method for formulating perovskite solar cell materials

专利摘要:
It is a method for preparing photoactive perovskite materials. The method comprises the step of preparing a lead halide precursor paint. The preparation of a lead halide precursor paint comprises the steps of: introducing a lead halide into a vessel, introducing a first solvent into the vessel and bringing the lead halide into contact with the first solvent to dissolve the lead halide . The method further comprises depositing the lead halide precursor paint on a substrate, drying the lead halide precursor paint to form a thin film, annealing the thin film and rinsing the thin film with a second solvent and a salt.
公开号:BR112017002107B1
申请号:R112017002107-2
申请日:2015-07-30
公开日:2020-10-27
发明作者:Michael D. Irwin；Jerred A. Chute；Vivek V. Dhas
申请人:Hee Solar, L.L.C；
IPC主号:

专利说明:

BACKGROUND
[1] The use of photovoltaics (PVs) to generate electrical power from radiation or solar energy can include many benefits, including, for example, a power source, low or no emissions, power production independent of the grid. energy, durable physical structures (without moving parts), reliable and stable systems, modular construction, relatively quick installation, safe use and manufacture and satisfactory public opinion and acceptance of use.
[2] The particularities and advantages of the present invention will be readily apparent to those skilled in the art. Although numerous changes can be made by those skilled in the art, such changes are within the spirit of the invention. BRIEF DESCRIPTION OF THE DRAWINGS
[3] Figure 1 is a design illustration of DSSC representing several layers of DSSC according to some of the modalities of the present disclosure.
[4] Figure 2 is another illustration of a DSSC design representing several layers of the DSSC according to some of the modalities of the present disclosure.
[5] Figure 3 is an exemplary illustration of the BHJ device design in accordance with some of the modalities of the present disclosure.
[6] Figure 4 is a schematic view of a typical photovoltaic cell that includes an active layer in accordance with some of the modalities of the present disclosure.
[7] Figure 5 is a schematic of a typical solid state DSSC device according to some embodiments of the present disclosure.
[8] Figure 6 is a stylized diagram that illustrates components of an exemplary PV device in accordance with some embodiments of the present disclosure.
[9] Figure 7 is a stylized diagram showing components of an exemplary PV device in accordance with some embodiments of the present disclosure.
[10] Figure 8 is a stylized diagram showing components of an exemplary PV device in accordance with some embodiments of the present disclosure.
[11] Figure 9 is a stylized diagram showing components of an exemplary PV device in accordance with some embodiments of the present disclosure. DETAILED DESCRIPTION OF PREFERENTIAL MODALITIES
[12] Improvements in various aspects of PV technologies compatible with organic, non-organic and / or hybrid PVs promise to further reduce the cost of both OPVs and other PVs. For example, some solar cells, such as solar cells sensitized by solid-state dye, can take advantage of innovative low-cost, high-stability alternative components, such as solid-state charge transport materials (or, colloquially, “state electrolytes solid"). In addition, various types of solar cells can advantageously include interface and other materials, which can, among other advantages, be more durable and less costly than the conventional options currently in existence.
[13] The present disclosure refers, in general, to compositions of matter, apparatus and methods of using materials in photovoltaic cells in the creation of electrical energy from solar radiation. More specifically, this disclosure refers to photoactive compositions and other compositions of matter, as well as apparatus, methods of use, and formation of those compositions of matter.
[14] Examples of such compositions of matter may include, for example, gap transport materials and / or materials that may be suitable for use such as, for example, interface layers, dyes and / or other elements of PV devices. Such compounds can be distributed in a variety of PV devices, such as heterojunction cells (for example, bilayer and volume), hybrid cells (for example, organic with CHsNHsPbh, ZnO nanobonds or quantum dots of PbS), and DSSCs (solar cells sensitized by dye). The latter, DSSCs, exist in three forms: solvent-based electrolytes, ionic liquid electrolytes, and solid-state gap carriers (or solid-state DSSCs, that is, SS-DSSCs). SS-DSSC structures according to some modalities can be substantially free of electrolyte, containing, instead, gap transport materials such as spiro-OMeTAD, CsSnh and other active materials.
[15] Some or all of the materials according to some of the modalities of the present disclosure can also be advantageously used in any organic or other electronic device, with some examples that include, without limitation: battery, field effect transistors (FETs), diodes light emitters (LEDs), non-linear optical devices, memristors, capacitors, rectifiers and / or rectifying antennas.
[16] In some embodiments, the present disclosure may provide PV and other similar devices (for example, batteries, hybrid PV batteries, multi-function PVs, FETs, LEDs, etc.). These devices may, in some embodiments, include enhanced active material, interface layers and / or one or more perovskite materials. A perovskite material can be incorporated into several of one or more aspects of a PV or other device. A perovskite material according to some modalities can be of the general formula CMX3, in which: C comprises one or more cations (for example, an amine, ammonium, a Group 1 metal, a Group 2 metal, and / or others cations or cation-like compounds); M comprises one or more metals (examples including Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti and Zr); and X comprises one or more anions. Perovskite materials according to various modalities are discussed in more detail below. PHOTOVOLTAIC CELLS AND OTHER ELECTRONIC DEVICES
[17] Some PV modalities can be described by reference to various representations of solar cells, as shown in Figures 1, 3, 4 and 5. For example, an exemplary PV architecture according to some modalities can be substantially of substrate-anode-IFL-active layer-IFL-cathode forms. The active layer of some modalities can be photoactive and / or can include photoactive material. Other layers and materials can be used in the cell, as is known in the art. In addition, it should be noted that the use of the term “active layer” is in no way intended to restrict or otherwise define, explicitly or implicitly, the properties of any other layer - for example, in some modalities, either or both IFLs can also be active as they can also be semiconductors. In particular, referring to Figure 4, a stylized generic PV cell 2610 is depicted, illustrating the highly interfacial nature of some layers within the PV. PV 2610 represents a generic architecture applicable to various PV devices, such as DSSC PV modalities. The PV cell 2610 includes a transparent layer 2612 of glass (or material similarly transparent to solar radiation) which allows solar radiation 2614 to be transmitted through the layer. The transparent layer of some embodiments can also be referred to as a substrate (for example, as with the substrate layer 1507 of Figure 1), and can comprise any or more of a variety of rigid or flexible materials such as: glass, polyethylene, PET , Kapton, quartz, aluminum foil, gold or steel foil. Photoactive layer 2616 is composed of material type p or electron donor 2618 and material type n or electron acceptor 2620. The active layer or, as shown in Figure 4, photoactive layer 2616, is sandwiched between two electrode layers electrically conductive 2622 and 2624. In Figure 4, electrode layer 2622 is an ITO material. As noted earlier, an active layer of some modalities need not necessarily be photoactive, although, in the device shown in Figure 4, it is. The 2624 electrode layer is an aluminum material. Other materials can be used as is known in the art. Cell 2610 also includes an interface layer (IFL) 2626, shown in the example in Figure 4 as a PEDOTPSS material. IFL can assist in load separation. In some embodiments, IFL 2626 may comprise a photoactive organic compound according to the present disclosure as a self-assembled monolayer (SAM) or as a thin film. In other embodiments, IFL 2626 may comprise a thin-layered bilayer, which is discussed in more detail below. There may also be an IFL 2627 on the aluminum cathode side of the device. In some embodiments, IFL 2627 on the aluminum cathode side of the device may also comprise or comprise instead a photoactive organic compound according to the present disclosure as a self-assembled monolayer (SAM) or as a thin film. In other embodiments, IFL 2627 on the aluminum cathode side of the device may also comprise or comprise a thin-coated bilayer instead (again, discussed in greater detail below). An IFL according to some modalities can be semiconductor in character, and can be of type p or type n. In some embodiments, the IFL on the cathode side of the device (for example, IFL 2627 as shown in Figure 4) can be of type p, and the IFL on the anode side of the device (for example, IFL 2626 as shown in Figure 4 ) can be type n. In other embodiments, however, the cathode-side IFL can be type n and the anode-side IFL can be type p. Cell 2610 is attached to leads 2630 and a discharge unit 2632, like a battery.
[18] Still other modalities can be described with reference to Figure 3, which represents a stylized BHJ device design, and includes: glass substrate 2401; ITO electrode (tin doped indium oxide) 2402; interface layer (IFL) 2403; photoactive layer 2404; and LiF / AI 2405 cathodes. BHJ building materials referred to as mere examples; any other BHJ constructs known in the art can be used consistent with the present disclosure. In some embodiments, the photoactive layer 2404 can comprise any one or more materials that the active or photoactive layer 2616 of the device of Figure 4 can comprise.
[19] Figure 1 is an illustration of DSSC PVs simplified according to some modalities, referred to in the present context for purposes of illustrating the assembly of such exemplary PVs. An exemplary DSSC as shown in Figure 1 can be constructed according to the following: electrode layer 1506 (shown as fluorine-doped tin oxide, FTO) is deposited on a layer of substrate 1507 (shown as glass). The ML 1505 mesoporous layer (which in some embodiments may be TIO 2) is deposited on the electrode layer 1506 and then the photoelectrode (until now comprising substrate layer 1507, electrode layer 1506 and mesoporous layer 1505) is embedded in a solvent (not shown) and dye 1504. This leaves dye 1504 attached to the ML surface. A separate counter electrode is produced comprising the substrate layer 1501 (also shown as glass) and the electrode layer 1502 (shown as Pt / FTO). The photoelectrode and counterelectrode are combined, sandwiching the various layers 1502 - 1506 between the two layers of substrate 1501 and 1507 as shown in Figure 1 and allowing the electrode layers 1502 and 1506 to be used as a cathode and anode, respectively. A layer of electrolyte 1503 is deposited directly on the complete photoelectrode after the dye layer 1504 or through an opening in the device, typically a sandblasted pre-drilled gap in the counter electrode substrate 1501. The cell can also be attached to taps and a discharge unit, such as a battery (not shown). Substrate layer 1507 and electrode layer 1506, and / or substrate layer 1501 and electrode layer 1502 must be sufficiently transparent to allow solar radiation to pass through to photoactive dye 1504. In some embodiments, the counter electrode and / or photoelectrode can be rigid, while in others either or both can be flexible. The substrate layers of various modalities can comprise any or more of: glass, polyethylene, PET, Kapton, quartz, aluminum foil, gold leaf and steel. In certain embodiments, a DSSC may additionally include a collection layer taken 601, as shown in Figure 2, to diffuse the incident light in order to increase the length of the light path through the photoactive layer of the device (thus increasing the likelihood that the light to be absorbed into the photoactive layer).
[20] In other embodiments, the present disclosure provides solid-state DSSCs. Solid state DSSCs according to some modalities can provide advantages such as lack of leakage and / or corrosion problems, which can affect DSSCs that comprise liquid electrolytes. In addition, a solid-state charge carrier can provide faster device physics (for example, faster cargo transport). In addition, solid-state electrolytes can, in some embodiments, be photoactive and therefore contribute to power derived from a solid-state DSSC device.
[21] Some of the examples of solid-state DSSCs can be described by reference to Figure 5, which is a stylized scheme of a typical solid-state DSSC. As with the exemplificative solar cell represented, for example, in Figure 4, an active layer comprised of first and second active material (for example, conductor and / or semiconductor) material (2810 and 2815, respectively) is sandwiched between electrodes 2805 and 2820 (shown in Figure 5 as Pt / FTO and FTO, respectively). In the embodiment shown in Figure 5, the first active material 2810 is the p-type active material, and comprises a solid state electrolyte. In certain embodiments, the first active material 2810 may comprise an organic material such as spiro-OMeTAD and / or poly (3-hexylthiophene), a binary, ternary, inorganic quaternary or major complex, any solid semiconductor material or any combination thereof. In some embodiments, the first active material may comprise, instead, or in addition, an oxide and / or a sulfide, and / or a selenide and / or an iodide (e.g., CsSnh). Therefore, for example, the first active material of some embodiments may comprise solid-state p-type material, which may comprise indium and copper sulphide, and, in some embodiments, may comprise gallium, indium and copper selenide. The second active material 2815 shown in Figure 5 is active material of type n, and comprises TiO2 coated with a dye. In some embodiments, the second active material may likewise comprise an organic material, such as spiro-OMeTAD, a binary, ternary, quaternary, or major inorganic complex or any combination thereof. In some embodiments, the second active material may comprise an oxide, such as alumina, and / or may comprise a sulfide, and / or the same may comprise a selenide. Therefore, in some embodiments, the second active material may comprise indium and copper sulphide, and in some embodiments, it may comprise gallium, indium and copper selenide. The second active material 2815 of some embodiments may constitute a mesoporous layer. In addition to being active, any one or both of the first and second active materials 2810 and 2815 can be photoactive. In other embodiments (not shown in Figure 5), the second active material can comprise an electrolyte solid. In addition, in embodiments in which any of the first and second active materials 2810 and 2815 comprise a solid electrolyte, the PV device may lack an effective amount of liquid electrolyte. Although shown and referred to in Figure 5 as a p-type solid state layer (e.g., first active material comprising electrolyte solid) it may in some embodiments instead be a n-type semiconductor. In these embodiments, then, the second active material (for example, TiO2 (or other mesoporous material) as shown in Figure 5) coated with a dye can be type p semiconductor (as opposed to type n semiconductor shown and discussed in relation to Figure 5).
[22] The substrate layers 2801 and 2825 (both shown in Figure 5 as glass) form the respective outer bottom and top layers of the exemplary cell in Figure 5. These layers can comprise any material of sufficient transparency to allow solar radiation to pass through. for the active / photoactive layer comprising dye, first and second active and / or photoactive materials 2810 and 2815, such as glass, polyethylene, PET, Kapton, quartz, aluminum foil, gold leaf and / or steel. In addition, in the modality shown in Figure 5, electrode 2805 (shown as Pt / FTO) is the cathode and electrode 2820 is the anode. As with the exemplary solar cell shown in Figure 4, solar radiation passes through the substrate layer 2825 and electrode 2820 to the active layer, over which at least a portion of the solar radiation is absorbed for the purpose of producing one or more excites to enable electrical generation.
[23] A solid state DSSC according to some modalities can be constructed substantially similar to that described above in relation to the DSSC represented as stylized in Figure 1. In the embodiment shown in Figure 5, active material of type p 2810 corresponds to the electrolyte 1503 of Figure 1; active material of type n 2815 corresponds to both dyes 1504 and ML 1505 of Figure 1; electrodes 2805 and 2820 respectively correspond to electrode layers 1502 and 1506 of Figure 1; and substrate layers 2801 and 2825 respectively correspond to substrate layers 1501 and 1507.
[24] Various modalities of the present disclosure provide improved materials and / or designs in various aspects of solar cell and other devices, which include, among other things, active materials (which include gap transport layers and / or electron transport), layers interface and general device design. INTERFACE LAYERS
[25] The present disclosure in some embodiments provides advantageous materials and designs of one or more layers of interface within a PV, which includes thin-coated IFLs. Thin-coated IFLs can be used in one or more IFLs of a PV in accordance with various modalities discussed in this document in this document.
[26] First, as noted earlier, one or more IFLs (for example, either or both IFLs 2626 and 2627 as shown in Figure 4) may comprise a photoactive organic compound of the present disclosure as a self-assembled monolayer (SAM) or like a thin film. When a photoactive organic compound of the present disclosure is applied as a SAM, it can comprise a linking group through which it can be covalently or otherwise bonded to the surface of either or both of the anode and cathode. The linking group of some modalities may comprise any one or more of COOH, SIXX (where X may be any chemical moiety suitable to form a ternary silicon compound, such as Si (OR) if SiCh), SO3, PO4H, OH, CH2X (where X may comprise a Group 17 halide), and O. The linking group may be covalently or otherwise linked to an electron-removing chemical moiety, an electron donor chemical moiety and / or a chemical portion of the nucleus. The bonding group can attach to the electrode surface to form a directional layer of a single molecule (or, in some embodiments, multiple molecules) in thickness (for example, in which multiple photoactive organic compounds are attached to the anode and / or cathode). As noted, SAM can be fixed by means of covalent interactions, but in some modalities it can be fixed by means of ionic hydrogen bonding and / or dispersion force interactions (ie, Van Der Waals). In addition, in certain modalities, upon exposure to light, the SAM can enter an excited zwiterionic state, thus creating a highly polarized IFL, which can directly charge the carriers of an active layer on an electrode (for example, the anode or cathode). This improved load carrier injection can, in some modalities, be performed by electronically polarizing the cross section of the active layer and thus increasing the load carrier drift speeds towards its respective electrode (for example, gap to anode; electrons to cathode). Molecules for anode applications of some embodiments may comprise adjustable compounds that include a primary electron donor chemical moiety attached to a chemical nucleus moiety, which in turn is linked to an electron removing chemical moiety, which, in turn, it is linked to a link group. In cathode applications according to some modalities, the IFL molecules can comprise an adjustable compound comprising an electron-deficient chemical moiety attached to a chemical nucleus moiety, which in turn is linked to a chemical donor moiety electron, which, in turn, is linked to a bonding group. When a photoactive organic compound is used as an IFL in accordance with such modalities, it may retain the photoactive character, although, in some modalities, it need not be photoactive.
[27] In addition to or instead of a photoactive organic compound SAM IFL, a PV according to some modalities may include a thin interface layer (a "thin-coated interface layer" or "thin-coated IFL" ) coated in at least a portion of the first or second active material of these modalities (for example, first or second active material 2810 or 2815 as shown in Figure 5). And, in turn, at least a portion of the thin-coated IFL can be coated with a dye. The thin-coated IFL can be of the n or p type; in some embodiments, it may be of the same type as the underlying material (for example, TiO or other mesoporous material, such as TiO2 of the second active material 2815). The second active material may comprise TiO2 coated with a thin-coated IFL comprising alumina (e.g., AI2O3) (not shown in Figure 5), which in turn is coated with a dye. References in this document to TiO2 and / or titania are not intended to limit the ratios of tin and oxide in those oxide-tin compounds described herein. That is, a titania compound can comprise titanium in any one or more of its various oxidation states (e.g., titanium I, titanium II, titanium III, titanium IV), and therefore, various modalities may include stoichiometric amounts and / or not stoichiometric titanium and oxide. Therefore, several modalities can include (instead of or in addition to TÍO2) TixOy, where x can be any value, integer or non-integer, between 1 and 100. In some modalities, x can be between approximately 0.5 and 3. Likewise, y can be between approximately 1.5 and 4 (and, again, it does not have to be an integer). Therefore, some modalities may include, for example, TiO2 and / or TiOO3. In addition, titania in any ratio or combination of ratios between titanium and oxide can be of any one or more crystal structures in some modalities, including any one or more among anatase, rutile and amorphous.
[28] Other exemplary metal oxides for use in thin-coated IFL of some modalities may include semiconductor metal oxides, such as ZnO, ZrO2, NÓ2O3, SrTiOs, Ta2θs, NiO, WO3, V2O5, or MOO3. The exemplary embodiment in which the second (e.g., type n) active material comprises TiO2 coated with a thin-coated IFL comprising AI2O3 could be formed, for example, with a precursor material such as AI (NO3) 3 * xH2O, or any another material suitable for depositing AI2O3 in TiO2, followed by thermal annealing and dye coating. In exemplary embodiments in which a coating of MOO3 is used instead, the coating can be formed with a precursor material such as Na2Mθ4 * 2H2θ; whereas a V2O5 coating according to some modalities can be formed with a precursor material such as NaVOs; and a WO3 coating according to some embodiments can be formed with a precursor material such as NaWCU'FhO. The concentration of precursor material (for example, AI (Nθ3) 3 * xH2θ) can affect the final film thickness (here, of AI2O3) deposited on 0 TiO2 or other active material. Therefore, modifying the concentration of the precursor material can be a method by which the final film thickness can be controlled. For example, greater film thickness can result from a higher concentration of precursor material. Increased film thickness may not necessarily result in greater PCE in a PV device that comprises a metal oxide coating. Therefore, a method of some modalities may include coating a layer of TiO2 (or another mesoporous) with the use of a precursor material that has a concentration in the range of approximately 0.5 to 10.0 mM; other embodiments may include coating the layer with a precursor material that has a concentration in the range of approximately 2.0 to 6.0 mM; or, in other embodiments, approximately 2.5 to 5.5 mM.
[29] In addition, although referred to in this document as AI2O3 and / or alumina, it should be noted that various aluminum and oxygen ratios can be used in the formation of alumina. Therefore, although some modalities discussed in this document in this document are described with reference to AI2O3, this description is not intended to define a necessary ratio of aluminum to oxygen. Instead, the modalities can include any one or more aluminum oxide compounds, where each has an aluminum oxide ratio according to AlxOy, where x can be any value, integer or non-integer, between approximately 1 and 100. In some modalities, x can be between approximately 1 and 3 (and, again, it does not have to be an integer). Likewise, y can be any value, integer or non-integer, between 0.1 and 100. In some embodiments, y can be between 2 and 4 (and, again, it doesn't have to be an integer). In addition, several crystalline forms of AlxOy can be present in several modalities, such as alpha, gamma and / or amorphous forms of alumina.
[30] Likewise, although referred to herein as MoOs, WO3, θ V2O5, these compounds can instead, or additionally, be represented as MoxOy, WxOy, and VxOy, respectively. With respect to each of MoxOy and WxOy, x can be any value, integer or non-integer, between approximately 0.5 and 100; in some modalities, it can be between approximately 0.5 and 1.5. Likewise, y can be any value, integer or non-integer, between approximately 1 and 100. In some embodiments, y can be any value between approximately 1 and 4. With respect to VxOy, x can be any value , integer or non-integer, between approximately 0.5 and 100; in some modalities, it can be between approximately 0.5 and 1.5. Likewise, y can be any value, integer or non-integer, between approximately 1 and 100; in certain embodiments, it can be an integer or non-integer value between approximately 1 and 10.
[31] Similarly, references in some exemplary embodiments in this document to CsSnh are not intended to limit the component element ratios in cesium tin-iodine compounds according to various modalities. Some modalities may include stoichiometric and / or non-stoichiometric amounts of tin and iodide, and thus these modalities may include, instead, or in addition, various ratios of cesium, tin and iodine, such as any one or more cesium- tin-iodine, where each has a CsxSnylz ratio. In these modalities, x can be any value, integer or non-integer, between 0.1 and 100. In some modalities, x can be between approximately 0.5 and 1.5 (and, again, it does not have to be an integer ). Likewise, y can be any value, integer or non-integer, between 0.1 and 100. In some embodiments, y can be between approximately 0.5 and 1.5 (and, again, it doesn't have to be a number all). Likewise, z can be any value, integer or non-integer, between 0.1 and 100. In some embodiments, z can be between approximately 2.5 and 3.5. In addition, CsSnh can be doped or composed with other materials, such as SnF2, in CsSnh: SnF2 ratios that are in the range of 0.1: 1 to 100: 1, including all values (integer or non-integer) between them.
[32] In addition, a thin-coated IFL can comprise a bilayer. Therefore, returning to the example where the thin-coated IFL comprises a metal oxide (such as alumina), the thin-coated IFL can comprise TiO2-plus-metal oxide. This thin-coated IFL may have a greater ability to withstand charge recombination compared to mesoporous TIO2 or other active material alone. In addition, in forming a layer of TiO2 layer, a coating of secondary TiO2 is often necessary to provide sufficient physical interconnection of TiO2 particles, according to some embodiments of the present disclosure. The coating of a thin-layered IFL bilayer in mesoporous TiO2 (or other mesoporous active material) may comprise a coating combination with the use of a compound comprising both metal oxide and TiCU, resulting in a thin-layered IFL bilayer that comprises a combination of metal oxide and secondary TiO2 coating, which can provide performance improvements over the use of any material alone.
[33] Thin-coated IFLs and the method of coating them on TIO2 previously discussed again can, in some embodiments, be used in DSSCs that comprise liquid electrolytes. Therefore, returning to the example of a thin-coated IFL and referring again to Figure 1 for an example, the DSSC of Figure 1 could further comprise a thin-coated IFL as described above coated in the mesoporous layer 1505 (i.e., IFL thin coating would be inserted between the mesoporous layer 1505 and the dye 1504).
[34] In some embodiments, the thin-coated IFLs previously discussed in the context of DSSCs can be used at any interface layer of a semiconductor device, such as a PV (for example, a hybrid PV or other PV), transistor effect transistor. field, light emitting diode, non-linear optical device, memristor, capacitor, rectifier, rectifying antenna, etc. In addition, thin-coated IFLs of some embodiments may be employed in any of several devices in combination with other compounds discussed in the present disclosure, which include, without limitation, any one or more of the following of the various embodiments of the present disclosure: solid gap transport material such as active material and additives (such as, in some embodiments, chenodeoxycholic acid or 1,8-diiodooctane). ADDITIONS
[35] As noted earlier, PV and other devices according to some modalities may include additives (which may be, for example, any one or more among acetic acid, propanoic acid, trifluoroacetic acid, chenodeoxycholic acid, deoxycholic acid, 1.8 -diiodooctane and 1,8-dithiooctane). These additives can be used as pre-treatments directly before dye soaking or mixed in various ratios with a dye to form the soaking solution. These additives can, in some cases, work, for example, to increase the dye solubility, avoid the dye molecule clustering, blocking open active sites, and inducing molecular ordering among the dye molecules. They can be used with any suitable dye, including a photoactive compound according to various modalities of the present disclosure as discussed in this document. PEROVSKITA MATERIAL
[36] A perovskite material can be incorporated into several of one or more aspects of a PV or other device. A perovskite material according to some modalities can be of the general formula CMX3, in which: C comprises one or more cations (for example, an amine, ammonium, a Group 1 metal, a Group 2 metal, and / or others cations or cation-like compounds); M comprises one or more metals (examples including Fe, Co, Ni, Cu, Sn, Pb, Bi, Ge, Ti and Zr); and X comprises one or more anions. In some embodiments, C may include one or more organic cations.
[37] In certain embodiments, C may include an ammonium, an organic cation of the general formula [NRψ where the R groups can be the same or different groups. Suitable R groups include, without limitation: methyl, ethyl, propyl, butyl, pentyl or isomer group; any alkane, alkene, or CxHy alkaline, where x = 1 - 20, y = 1 - 42, cyclic, branched or straight chain; alkyl halides, CxHyXz, x = 1 - 20, y = 0 - 42, z = 1 - 42, X = F, Cl, Br, or I; any aromatic group (for example, phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in which at least one nitrogen is contained within the ring (pyridine, pyrrole, pyrrolidine, piperidine, tetrahydroquinoline); any sulfur-containing group (for example, sulfoxide, thiol, alkyl sulfide); any group that contains nitrogen (nitroxide, amine); any group that contains phosphorus (phosphate); any group that contains boron (for example, boronic acid); any organic acid (for example, acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (for example, glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniovaleric acid) that includes alpha, beta, gamma and major derivatives; any group containing silicon (for example, siloxane); and any alkoxide or group, - OCxHy, where x = 0 - 20, y = 1 - 42.
[38] In certain embodiments, C may include a formamidium, an organic cation of the general formula [(R2NCHNR2] + where the R groups can be the same groups or different groups. Suitable R groups include, without limitation: hydrogen group, methyl, ethyl, propyl, butyl, pentyl or isomer thereof; any alkane, alkene, or CxHy alkaline, where x = 1 - 20, y = 1 - 42, cyclic, branched or straight chain; alkyl halides, CxHyXz, x = 1 - 20, y = 0 - 42, z = 1 - 42, X = F, Cl, Br, or I; any aromatic group (eg phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in that at least one nitrogen is contained within the ring (for example, imidazole, benzimidazole, dihydropyrimidine, (azolidinulidenemethyl) pyrrolidine, triazole); any sulfur-containing group (for example, sulfoxide, thiol, alkyl sulfide); any group that contains nitrogen (nitroxide, amine); any group containing phosphorus (phosphate); any group containing boron (for example, boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (for example, glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniovaleric acid) that includes alpha, beta, gamma and major derivatives; any group containing silicon (for example, siloxane); and any alkoxide or group, -OCxHy, where x = 0 - 20, y = 1 - 42.
[39] In certain embodiments, C may include a guanidinium, an organic cation of the general formula [(R2N) 2C = NR2] + where the R groups can be the same or different groups. Suitable R groups include, without limitation: hydrogen, methyl, ethyl, propyl, butyl, pentyl or isomer groups; any alkane, alkene, or CxHy alkaline, where x = 1 - 20, y = 1 - 42, cyclic, branched or straight chain; alkyl halides, CxHyXz, x = 1 - 20, y = 0 - 42, z = 1 - 42, X = F, Cl, Br, or I; any aromatic group (for example, phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in which at least one nitrogen is contained within the ring (for example, octahidropyrimido [1,2a] pyrimidine, pyrimido [2,3-a] pyrimidine, hexahidroimidazo [2,3-a] imidazole, hexahydropyrimidin2, 3-imine); any sulfur-containing group (for example, sulfoxide, thiol, alkyl sulfide); any group that contains nitrogen (nitroxide, amine); any group that contains phosphorus (phosphate); any group that contains boron (for example, boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (for example, glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniovaleric acid) that includes alpha, beta, gamma and major derivatives; any group containing silicon (for example, siloxane); and any alkoxide or group, - OCxHy, where x = 0 - 20, y = 1 - 42.
[40] In certain embodiments, C may include an ethylene tetramine cation, an organic cation of the general formula [(R2N) 2C = C (NR2) 2] + where the R groups can be the same or different groups. Suitable R groups include, without limitation: hydrogen, methyl, ethyl, propyl, butyl, pentyl or isomer groups; any alkane, alkene, or CxHy alkaline, where x = 1 - 20, y = 1 - 42, cyclic, branched or straight chain; alkyl halides, CxHyXz, x = 1 - 20, y = 0 - 42, z = 1 - 42, X = F, Cl, Br, or I; any aromatic group (for example, phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes in which at least one nitrogen is contained within the ring (for example, 2-hexahydropyrimidin-2-ylidenohexahydropyrimidine, octahidropyrazine [2,3-b] pyrazine, pyrazine [2,3-b] pyrazine, quinoxaline [2,3 - b] quinoxaline); any sulfur-containing group (for example, sulfoxide, thiol, alkyl sulfide); any group that contains nitrogen (nitroxide, amine); any group that contains phosphorus (phosphate); any group that contains boron (for example, boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (for example, glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniovaleric acid) that includes alpha, beta, gamma and major derivatives; any group containing silicon (for example, siloxane); and any alkoxide or group, -OCxHy, where x = 0 - 20, y = 1 - 42.
[41] In some embodiments, X may include one or more halides. In certain embodiments, X may include a Group 16 anion instead or additionally. In certain embodiments, the Group 16 anion may be sulfide or selenide. In some embodiments, each organic cation C may be larger than each metal M, and each anion X may have the ability to bond with either a cation C or a metal M. Examples of perovskite materials according to various modalities include CsSnh (previously discussed in this document) and CsxSnylz (with x, y and z varying according to the previous discussion). Other examples include compounds of the general formula CsSnXs, where X can be any one or more of: I3, I2.95F0.05; I2CI; ICI2; and CI3. In other embodiments, X can comprise any one or more of I, Cl, F, and Br in quantities so that the total ratio of X to Cs and Sn results in the general stoichiometry of CsSnXs. In some embodiments, the combined stoichiometry of the elements that make up X may follow the same rule as lz as discussed earlier in relation to CsxSnylz. Still other examples include compounds of the general formula RNHsPbXs, where R can be CnFhn + i, where n is in the range 0 to 10, and X can include any or more of F, Cl, Br, and I in amounts of so that the total ratio of X in comparison to the cation RNH3 and metal Pb results in the general stoichiometry of RNFhPbXs. In addition, some specific examples of R include H, alkyl chains (for example, CH3, CH3CH2, CH3CH2CH2, and so on), and amino acids (for example, glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammonium valeric acid) which include alpha, beta, gamma, and major derivatives. COMPOSITE PEROVSKITA MATERIAL DEVICE DESIGN
[42] In some embodiments, the present disclosure may provide composite PV design and other similar devices (for example, batteries, hybrid PV batteries, FETs, LEDs, etc.) that include one or more perovskite materials. For example, one or more perovskite materials can serve as either or both of the first and the second active materials of some modalities (for example, active materials 2810 and 2815 in Figure 5). More generally, some embodiments of the present disclosure provide PV or other devices that have an active layer comprising one or more perovskite materials. In these embodiments, the perovskite material (that is, the material that includes any one or more perovskite materials) can be used in active layers of various architectures. In addition, the perovskite material can act on the function (or functions) of any one or more components of an active layer (for example, cargo transport material, mesoporous material, photoactive material and / or interface material, each of which are discussed in more detail below). In some embodiments, the same perovskite materials can act in multiple such functions, although in other modalities, a plurality of perovskite materials can be included in a device, with each perovskite material acting in one or more of these functions. In certain embodiments, regardless of the role that a perovskite material may have, it can be prepared and / or be present in a device in several states. For example, it can be substantially solid in some embodiments. In other embodiments, it can be a solution (for example, perovskite material can be dissolved in liquid and present in said liquid in its individual ionic subspecies); or it can be a suspension (for example, of particles of perovskite material). A solution or suspension may be coated or otherwise deposited within a device (for example, on another component of the device, such as a mesoporous, interfacial, charge-carrying, photoactive or other layer and / or on an electrode ). Perovskite materials in some embodiments can be formed in situ on a surface of another component of a device (for example, by vapor deposition as a thin film solid). Any other suitable means to form a solid or liquid layer comprising perovskite material can be employed.
[43] In general, a perovskite material device may include a first electrode, a second electrode and an active layer comprising a perovskite material, the active layer being at least partially arranged between the first and the second electrodes. In some embodiments, the first electrode can be one of an anode and a cathode, and the second electrode can be the other of an anode and cathode. An active layer according to certain modalities can include any one or more active layer components, which includes any one or more of: cargo transport material; liquid electrolyte; mesoporous material; photoactive material (for example, a dye, silicon, cadmium telluride, cadmium sulfide, cadmium selenide, gallium selenide, indium and copper, gallium arsenide, germanium and germanium phosphite, semiconductor polymers, other photoactive materials)); and interface material. Any one or more of these active layer components can include one or more perovskite materials. In some embodiments, some or all of the active layer components may be completely or partially arranged in sublayers. For example, the active layer can comprise any one or more of: an interface layer that includes interface material; a mesoporous layer that includes mesoporous material; and a cargo transport layer that includes cargo transport material. In some embodiments, the photoactive material, such as a dye, can be coated over, or otherwise disposed of, any one or more of these layers. In certain embodiments, any one or more layers can be coated with a liquid electrolyte. In addition, an interface layer can be included between any two or more other layers of an active layer according to some modalities, and / or between a layer and a coating (such as between a dye and a mesoporous layer), and / or between two coatings (such as between a liquid electrolyte and a dye), and / or between an active layer component and an electrode. Reference to the layers in this document may include a final provision (for example, substantially distinct portions of each separately definable material within the device), and / or reference to a layer may mean provision during the construction of a device, regardless of the possibility of subsequent intermixing of the material (or materials) in each layer. The layers may, in some embodiments, be distinct and comprise substantially contiguous material (for example, layers may be as stylized in Figure 1). In other embodiments, the layers can be substantially intermediate (as in the case of, for example, BHJ, hybrid, and some DSSC cells), whose example is shown by the first and second active materials 2618 and 2620 within the photoactive layer 2616 in the Figure 4. In some embodiments, a device may comprise a mixture of these two types of layers, as also shown by the device in Figure 4, which contains separate contiguous layers 2627, 2626, and 2622, in addition to a photoactive layer 2616 comprising intermediate layers of the first and second active materials 2618 and 2620. In any case, any two or more layers of any type can, in certain modalities, be arranged adjacent to each other (and / or in an intermediate way with each other) in order to achieve a high contact surface area. In certain embodiments, a layer comprising perovskite material can be arranged adjacent to one or more other layers in order to achieve high contact surface area (for example, where a perovskite material exhibits low charge mobility). In other embodiments, the high contact surface area may not be necessary (for example, where a perovskite material exhibits high charge mobility).
[44] A perovskite material device according to some modalities can optionally include one or more substrates. In some embodiments, either or both of the first and the second electrodes can be coated or otherwise arranged on a substrate, so that the electrode is disposed substantially between a substrate and the active layer. The materials of the composition of the devices (for example, substrate, electrode, active layer and / or active layer components) can be completely or partially rigid or flexible in various modalities. In some embodiments, an electrode can act as a substrate, thus negating the need for a separate substrate.
[45] In addition, a perovskite material device according to certain modalities may optionally include light collection material (for example, in a light collection layer, such as the Light Collection Layer 1601 as represented in the exemplary PV represented in Figure 2). In addition, a perovskite material device may include any one or more additives, such as any one or more of the additives discussed above in relation to some embodiments of the present disclosure.
[46] The description of some of the various materials that can be included in a perovskite material device will be made in part with reference to Figure 7. Figure 7 is a stylized diagram of a 3900 perovskite material device according to some modalities. Although various components of the 3900 device are illustrated as separate layers comprising contiguous material, it should be understood that Figure 7 is a stylized diagram; therefore, the modalities according to it may include such distinct layers and / or substantially intermediate non-contiguous layers consistent with the use of "layers" previously discussed in the present document. The 3900 device includes the first and second substrates 3901 and 3913. A first electrode 3902 is disposed on an internal surface of the first substrate 3901, and a second electrode 3912 is disposed on an internal 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 3910 cargo transport layer, and several interface layers. In addition, Figure 7 illustrates an exemplary device 3900 according to modalities in which the sublayers of the active layer 3950 are separated by the interface layers, and, additionally, in which the interface layers are arranged over each electrode 3902 and 3912. In In particular, the second, third and fourth interface layers 3905, 3907, and 3909 are respectively arranged between each of the mesoporous layer 3904, the first photoactive material 3906, the second photoactive material 3908 and the cargo transport layer 3910. A first and fifth interface layers 3903 and 3911 are respectively arranged between (i) the first electrode 3902 and the mesoporous layer 3904; and (si) the load transport layer 3910 and second electrode 3912. Therefore, the architecture of the exemplary device represented in Figure 7 can be distinguished as: substrate — electrode — active layer — electrode — substrate. The architecture of the active layer 3950 can be distinguished as: interface layer — mesoporous layer — interface layer — photoactive material — interface layer — photoactive material — interface layer — cargo transport layer — interface layer. As noted earlier, in some embodiments, the interface layers do not need to be present; or, one or more interface layers can be included only between certain, but not all, components of an active layer and / or components of a device.
[47] A substrate, like either or both of the first and second substrates 3901 and 3913, can be flexible or rigid. If two substrates are included, at least one must be transparent or translucent to electromagnetic radiation (EM) (such as UV, visible or IR radiation). If a substrate is included, it can be similarly transparent or translucent, although it need not be, as long as a portion of the device allows EM radiation to contact the active layer 3950. Suitable substrate materials include any or more of: glass; sapphire; magnesium oxide (MgO); mica; polymers (for example, PET, PEG, polypropylene, polyethylene, etc.); ceramics; cloths (for example, cotton, silk, wool); wood; plaster wall; metal; and combinations thereof.
[48] As noted earlier, an electrode (for example, one of electrodes 3902 and 3912 in Figure 7) can be an anode or a cathode. In some embodiments, one electrode may function as a cathode, and the other may function as an anode. Either or both of the 3902 and 3912 electrodes can be coupled to leads, cables, wires or other means that enable charge transportation to and / or from the 3900 device. An electrode can be any conductive material, and at least one electrode it must be transparent or translucent for EM radiation, and / or be arranged in a way that allows EM radiation to contact at least a portion of the active layer 3950. Suitable electrode materials may include any one or more of: tin and indium or tin doped indium oxide (ITO); fluorine doped tin oxide (FTO); cadmium oxide (CdO); tin, indium and zinc oxide (ZITO); zinc and aluminum oxide (AZO); aluminum (Al); gold (Au); calcium (Ca); magnesium (Mg); titanium (Ti); steel; carbon (and allotropies thereof); and combinations thereof.
[49] The mesoporous material (for example, the material included in the mesoporous layer 3904 of Figure 7) can include any material that contains pore. In some embodiments, the pores can have diameters that are in the range of about 1 to about 100 nm; in other embodiments, the pore diameter can be in the range of about 2 to about 50 nm. Suitable mesoporous material includes any one or more of: any interface material and / or mesoporous material discussed elsewhere in this document; aluminum (Al); bismuth (Bi); Indian (In); molybdenum (Mo); niobium (Nb); nickel (Ni); silicon (Si); titanium (Ti); vanadium (V); zinc (Zn); zirconium (Zr); an oxide of any one or more of the foregoing metals (for example, alumina, ceria, titania, zinc oxide, zircona, etc.); a sulfide from any one or more of the foregoing metals; a nitride from any one or more of the foregoing metals; and combinations thereof.
[50] The photoactive material (for example, first or second photo material 3906 or 3908 of Figure 7) can comprise any photoactive compound, such as any or more of silicon (in some cases, monocrystalline silicon), cadmium telluride, sulfide cadmium, cadmium selenide, gallium selenide, indium and copper, gallium arsenide, indium and germanium phosphite, one or more semiconductor polymers and combinations thereof. In certain embodiments, the photoactive material may comprise instead or additionally comprise a dye (for example, N719, N3, other dyes based on ruthenium). In some embodiments, a dye (of any composition) can be coated over another layer (for example, a mesoporous layer and / or an interface layer). In some embodiments, the photoactive material may include one or more perovskite materials. The photoactive substance that contains perovskite material may be in a solid form, or in some embodiments it may take the form of a dye that includes a suspension or solution that comprises perovskite material. This solution or suspension can be coated over other device components in a similar way to other dyes. In some embodiments, material containing solid perovskite can be deposited by any suitable means (for example, vapor deposition, solution deposition, direct placement of the solid material, etc.). Devices according to various modalities may include one, two, three, or more photoactive compounds (for example, one, two, three, or more perovskite materials, dyes, or combinations thereof). In certain embodiments that include multiple dyes or other photoactive materials, each of the two or more dyes or other photoactive materials can be separated by one or more layers of interface. In some embodiments, multiple dyes and / or photoactive compounds can be, at least in part, intermixed.
[51] The cargo transport material (for example, cargo transport material of the 3910 cargo transport layer in Figure 7) can include solid state cargo transport material (ie, a colloquially identified solid state electrolyte) ), or may include a liquid electrolyte and / or ionic liquid. Any of the liquid electrolyte, ionic liquid and solid-state charge-carrying material can be referred to as the charge-carrying material. As used herein, "cargo transport material" refers to any material, solid, liquid or otherwise capable of collecting cargo carriers and / or transporting cargo carriers. For example, in PV devices according to some modalities, a charge carrier material may have a capacity to transport charge carriers to an electrode. Charge carriers can include gaps (the transport of which could produce charge transport material as well as properly identified “gap transport material”) and electrons. Gaps can be transported towards an anode, and electrons towards a cathode, depending on the placement of the charge transport material in relation to a cathode or anode in a PV or other device. Suitable examples of cargo-carrying material according to some embodiments may include any one or more of: perovskite material; I7h '; Co complexes; polythiophenes (for example, poly (3-hexylthiophene) and derivatives thereof, or P3HT); carbazole-based copolymers, such as polyheptadecanylcarbazole dithienylbenzothiadiazole and derivatives thereof (for example, PCDTBT); other copolymers such as polycyclopentadithiophene — benzothiadiazole and derivatives thereof (for example, PCPDTBT); poly (triarylamine) compounds and derivatives thereof (for example, PTAA); Spiro-OMeTAD; fullerene and / or fullerene derivatives (for example, C60, PCBM); and combinations thereof. In certain embodiments, the cargo transport material can include any material, solid or liquid, with the ability to collect charge carriers (electrons or gaps), and / or with the ability to carry charge carriers. The load-carrying material of some embodiments can therefore be semiconductor and / or active material of type n or p. The load carrying material can be disposed near one of the electrodes of a device. The same can, in some modalities, be arranged adjacent to an electrode, although in other modalities an interface layer can be arranged between the charge transport material and an electrode (as shown, for example, in Figure 7 with the fifth layer 3911 interface). In certain embodiments, the type of cargo transport material can be selected based on the electrode it is close to. For example, if the cargo transport material collects and / or transports gaps, it may be close to an anode for the purpose of transporting gaps in the anode. However, the charge-carrying material can instead be placed next to a cathode, and be selected or constructed for the purpose of transporting electrons to the cathode.
[52] As noted earlier, devices according to various modalities can optionally include an interface layer between any two other layers and / or materials, although devices according to some modalities need not contain any interface layers. So, for example, a perovskite material device can contain zero, one, two, three, four, five or more layers of interface (like the example device in Figure 7, which contains five layers of interface 3903, 3905, 3907, 3909, and 3911). An interface layer may include a thin-coated interface layer according to modalities discussed earlier in this document (for example, comprising alumina and / or other metal oxide particles, and / or a metal oxide / titania bilayer) and / or other compounds according to thin-coated interface layers as discussed elsewhere in this document). An interface layer according to some modalities can include any material suitable for improving the collection and / or transportation of cargo between two layers or materials; it can also help to avoid or reduce the likelihood of cargo recombination once a cargo has been transported away from one of the materials adjacent to the interface layer. Suitable interface materials may include any one or more of: any mesoporous material and / or interface material discussed elsewhere in this document; Al; Bi; In; Mo; Ni; platinum (Pt); Si; You; V; Nb; Zn; Zr; oxides of any of the foregoing metals (for example, alumina, silica, titania); a sulfide from the previous metals; a nitride from any of the foregoing metals; functionalized or non-functionalized alkyl silyl groups; graphite; graphene; fullerenes; carbon nanotubes; and combinations thereof (which includes, in some modalities, bilayers of combined materials). In some embodiments, an interface layer may include perovskite material.
[53] A device according to the stylized representation of Figure 7 may, in some embodiments, be a PV, such as a DSSC, BHJ, or hybrid solar cell. In some embodiments, the devices according to Figure 7 may constitute serial or parallel multicellular PVs, batteries, hybrid PV batteries, FETs, LEDS and / or any other device discussed in this document. For example, a BHJ of some modalities may include two electrodes corresponding to electrodes 3902 and 3912, and an active layer comprising at least two materials in a heterojunction interface (for example, any two of the materials and / or layers of the active layer 3950 ). In certain embodiments, other devices (such as hybrid PV batteries, serial or parallel multicellular PVs, etc.) may comprise an active layer that includes a perovskite material, corresponding to the active layer 3950 in Figure 7. Briefly, the stylized nature of the representation of the exemplary device of Figure 7 in no way limit the permissible structure or architecture of the devices of various modalities according to Figure 7.
[54] Additional more specific exemplary modalities of perovskite devices will be discussed in terms of additional stylized representations of the exemplary devices. The stylized nature of these representations, Figures 11 and 12, is not similarly intended to restrict the type of device that can, in some embodiments, be constructed according to any one or more of Figures 11 and 12. This is , the architectures shown in Figures 11 and 12 can be adapted to provide BHJs, batteries, FETs, hybrid PV batteries, serial multicellular PVs, parallel multicellular PVs and other similar devices in other embodiments of the present disclosure, in accordance with any suitable means (which includes both those discussed expressly elsewhere in this document, and other suitable means, which will be evident to those skilled in the art with the benefit of this disclosure).
[55] Figure 8 represents an exemplary 4100 device according to various modalities. Device 4100 illustrates modalities that include first and second glass substrates 4101 and 4109. Each glass substrate has an FTO electrode disposed on its inner surface (first electrode 4102 and second electrode 4108, respectively), and each electrode has a layer interface deposited on its internal surface: The first TiCMIOS interface layer is deposited on the first electrode 4102, and the second interface layer of Pt 4107 is deposited on the second electrode 4108. They are sandwiched between the two interface layers: one mesoporous layer 4104 (which comprises THO2); photoactive material 4105 (which comprises the MAPbls perovskite material); and a cargo transport layer 4106 (which here comprises CsSnh).
[56] Figure 9 represents an exemplary 4300 device that omits a mesoporous layer. Device 4300 includes a photoactive compound of perovskite material 4304 (comprising MAPbla) sandwiched between the first and second interface layers 4303 and 4305 (comprising titania and alumina, respectively). The titania interface layer 4303 is coated on a first electrode of FTO 4302, which, in turn, is placed on an internal surface of a 4301 glass substrate. A spiro-OMeTAD 4306 charge transport layer is coated on an alumina interface layer 4305 and disposed on an internal surface of a second gold electrode 4307.
[57] As will be apparent to an individual of ordinary skill in the art with the benefit of this disclosure, several other modalities are possible, such as a device with multiple photoactive layers (as exemplified by photoactive layers 3906 and 3908 of the example device in Figure 7). In some embodiments, as discussed above, each photoactive layer can be separated by an interface layer (as shown by the third interface layer 3907 in Figure 7). In addition, a mesoporous layer can be disposed on an electrode as shown in Figure 7 by the mesoporous layer 3904 being disposed on the first electrode 3902. Although Figure 7 represents an intervening interface layer 3903 disposed between the two, in some embodiments a mesoporous layer can be placed directly on an electrode. EXAMPLES OF ADDITIONAL PEROVSKITA MATERIAL DEVICE
[58] Other exemplary perovskite material device architectures will be evident to those skilled in the art with the benefit of this disclosure. Examples include, without limitation, devices that contain active layers that have any of the following architectures: (1) liquid electrolyte — perovskite material — mesoporous layer; (2) perovskite material — dye — mesoporous layer; (3) first perovskite material — second perovskite material — mesoporous layer; (4) first perovskite material — second perovskite material; (5) first perovskite material — dye — second perovskite material; (6) solid-state cargo transport material — perovskite material; (7) solid state cargo transport material — dye— perovskite material — mesoporous layer; (8) solid state cargo transport material — perovskite material — dye — mesoporous layer; (9) solid state cargo transport material — dye— perovskite material — mesoporous layer; and (10) solid-state cargo transport material — perovskite material — dye — mesoporous layer. The individual components of each exemplary architecture (eg, mesoporous layer, cargo transport material, etc.) may be in accordance with the above discussion for each component. In addition, each example architecture is discussed in more detail below.
[59] As a particular example of some of the aforementioned active layers, in some embodiments, an active layer can include a liquid electrolyte, perovskite material and a mesoporous layer. The active layer of certain of these modalities can substantially have the architecture: liquid electrolyte — perovskite material — mesoporous layer. Any liquid electrolyte can be suitable; and any mesoporous layer (for example, TiO2) may be suitable. In some embodiments, the perovskite material can be deposited on the mesoporous layer, and on it coated with liquid electrolyte. The perovskite material of some of these modalities can act at least in part as a dye (therefore, it can be photoactive).
[60] In other exemplary embodiments, an active layer can include perovskite material, a dye and a mesoporous layer. The active layer of certain of these modalities can substantially have the architecture: perovskite material - dye - mesoporous layer. The dye can be coated on the mesoporous layer and the perovskite material can be placed on the mesoporous layer coated with dye. The perovskite material can function as the gap transport material in certain of these modalities.
[61] In yet other exemplary embodiments, an active layer can include the first perovskite material, the second perovskite material and a mesoporous layer. The active layer of certain of these modalities can substantially have the architecture: first perovskite material - second perovskite material - mesoporous layer. The first and second perovskite materials may each comprise the same perovskite material or they may comprise different perovskite materials. Any of the first and second perovskite materials can be photoactive (for example, a first and / or second perovskite material of these modalities can function at least in part as a dye).
[62] In certain exemplary embodiments, an active layer can include the first perovskite material and the second perovskite material. The active layer of certain of these modalities can have substantially the architecture: first perovskite material - second perovskite material. The first and second perovskite materials may each comprise the same perovskite material (or materials) or they may comprise different perovskite materials. Any of the first and second perovskite materials can be photoactive (for example, a first and / or second perovskite material of these modalities can function at least in part as a dye). In addition, any of the first and second perovskite materials may have the ability to function as a gap transport material. In some embodiments, one of the first and second perovskite materials works as an electron transport material, and the other of the first and second perovskite materials works as a dye. In some embodiments, the first and second perovskite materials can be arranged within the active layer so that it reaches a highly interfacial area between the first perovskite material and the second perovskite material, as in the arrangement shown for the first and second materials assets 2810 and 2815, respectively, in Figure 5 (or as shown similarly by pen2618 and 2620 type material, respectively, in Figure 4).
[63] In additional exemplary embodiments, an active layer can include the first perovskite material, a dye and the second perovskite material. The active layer of certain of these modalities can have substantially the architecture: first perovskite material - dye - second perovskite material. Any one of the first and second perovskite materials can function as a cargo-carrying material, and the other of the first and second perovskite materials can function as a dye. In some embodiments, both the first and the second perovskite materials can, at least in part, serve overlapping, similar and / or identical functions (for example, both can serve as a dye and / or both can serve as a carrier material gap).
[64] In some other exemplary embodiments, an active layer can include a solid-state charge-carrying material and a perovskite material. The active layer of certain of these modalities can substantially have the architecture: solid state cargo transport material - perovskite material. For example, the perovskite material and solid-state cargo transport material can be arranged within the active layer so that it reaches a high interface area, as in the arrangement shown for the first and second active materials 2810 and 2815, respectively , in Figure 5 (or as shown similarly by the pen2618 and 2620 type material, respectively, in Figure 4).
[65] In other exemplary embodiments, an active layer may include a solid-state charge-carrying material, a dye, perovskite material and a mesoporous layer. The active layer of certain of these modalities can substantially have the architecture: solid-state cargo transport material — dye— perovskite material — mesoporous layer. The active layer of certain others among these modalities can substantially have the architecture: solid state cargo transport material - perovskite material - dye - mesoporous layer. Perovskite material can, in some embodiments, serve as a second dye. Perovskite material can, in these modalities, increase the amplitude of the spectrum of visible light absorbed by a PV or other device that includes an active layer of these modalities. In certain embodiments, the perovskite material may also serve or serve instead as an interface layer between the dye and the mesoporous layer and / or between the dye and the cargo transport material.
[66] In some exemplary embodiments, an active layer may include a liquid electrolyte, a dye, a perovskite material and a mesoporous layer. The active layer of certain of these modalities can substantially have the architecture: solid-state cargo transport material — dye — perovskite material — mesoporous layer. The active layer of certain others among these modalities can substantially have the architecture: solid state cargo transport material — perovskite material — dye — mesoporous layer. The perovskite material can serve as a photoactive material, an interface layer and / or a combination thereof.
[67] Some modalities provide BHJ PV devices that include perovskite materials. For example, a BHJ of some embodiments may include a photoactive layer (for example, photoactive layer 2404 in Figure 3), which may include one or more perovskite materials. The photoactive layer of such BHJ may also include or include instead any or more of the exemplary discussed components listed above in relation to active DSSC layers. Additionally, in some embodiments, the BHJ photoactive layer may have an architecture in accordance with any of the exemplary modalities of the active DSSC layers discussed above.
[68] In some embodiments, any PV or other similar device may include an active layer in accordance with any one or more of the compositions and / or architectures discussed above. As another exemplary embodiment, an active layer that includes perovskite material can be included in a multi-layer PV cell, as or both the first and second photoactive layers 3701 and 3705 of the example cell shown in the stylized diagram in Figure 6. Such a PV cell multi-active layer that includes an active layer with perovskite material could, moreover, be incorporated within a series of electrically coupled multi-layer PV cells.
[69] In some embodiments, any of the active layers that include perovskite materials incorporated in PVs or other devices, as discussed in this document, may additionally include any of the various additional materials also discussed in this document as appropriate for inclusion in a active layer. For example, any active layer that includes perovskite material can additionally include an interface layer according to various modalities discussed in the present document (such as, for example, a thin-coated interface layer). As an additional example, an active layer that includes perovskite material may additionally include a light collection layer, such as the Light Collection Layer 1601 as depicted in the example PV shown in Figure 2. FORMULATION OF THE ACTIVE LAYER OF PEROVSKITA MATERIAL
[70] As discussed earlier, in some embodiments, a perovskite material in the active layer may have the formulation CMXβ-yX'y (0> y> 3), where: C comprises one or more cations (for example, an amine , ammonium, a Group 1 metal, a Group 2 metal, and / or other cations or cation-like compounds); M comprises one or more metals (for example, Fe, Cd, Co, Ni, Cu, Hg, Sn, Pb, Bi, Ge, Ti, Zn and Zr); and X and X 'comprise one or more anions. In one embodiment, the perovskite material may comprise CPbh-yCly. In certain embodiments, the perovskite material can be deposited as an active layer in a PV device through, for example, drop scattering, rotary scattering, extrusion printing, screen printing, or inkjet printing on a substrate layer using the steps outlined below.
[71] First, a lead halide precursor paint is formed. A quantity of lead halide can be agglomerated in a clean, dry ampoule inside a glove box (ie, a controlled atmosphere box with glazed portholes that allows material to be handled in an air-free environment). Suitable lead halides include, without limitation, lead (II) iodide, lead (II) bromide, lead (II) chloride and lead (II) fluoride. The lead halide may comprise a single species of lead halide or may comprise a mixture of lead halide in an exact ratio. In certain embodiments, the lead halide mixture may comprise any binary, ternary or quaternary ratio from 0.001 to 100 mol% of iodide, bromide, chloride or fluoride. In one embodiment, the lead halide mixture can comprise lead (II) chloride and lead (II) iodide in a ratio of about 10:90 mokmol. In other embodiments, the lead halide mixture may comprise lead (II) chloride and lead (II) iodide in a ratio of about 5:95, about 7.5: 92.5, or about 15: 85 mokmol.
[72] A solvent can then be added to the ampoule to dissolve the lead solids to form the lead halide precursor paint. Suitable solvents include, without limitation, dry dimethylformamide, dimethyl sulfoxide (DMSO), methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, pyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform and combinations thereof. In one embodiment, the lead solids are dissolved in dry dimethylformamide (DMF). Lead solids can be dissolved at a temperature between about 20 ° C to about 150 ° C. In one embodiment, the lead solids are dissolved at about 85 ° C. Lead solids can be dissolved for as long as necessary to form a solution, which can occur over a period of time up to about 72 hours. The resulting solution forms the basis of the lead halide precursor paint. In some embodiments, the lead halide precursor paint can have a lead halide concentration between about 0.001 M and about 10 M. In one embodiment, the lead halide precursor paint has a lead halide concentration of about of 1 M. In some embodiments, the lead halide precursor paint may additionally comprise an amino acid (eg, 5-aminovaleric acid, histidine, glycine, licine), an amino acid hydrohalide (eg, 5-hydrochloride -aminovaleric), an IFL surface modifying agent (SAM) (such as those discussed earlier in the specification), or a combination thereof.
[73] Lead halide precursor paint can then be deposited on the desired substrate. Suitable substrate layers can include any of the substrate layers identified earlier in this disclosure. As noted above, lead halide precursor ink can be deposited through a variety of means, which include, without limitation, droplet spreading, rotary spreading, extrusion printing, screen printing, or inkjet printing. In certain embodiments, the lead halide precursor paint can be coated by spinning on the substrate at a speed of about 500 rpm to about 10,000 rpm for a period of time from about 5 seconds to about 600 seconds. In one embodiment, the lead halide precursor paint can be coated by spinning the substrate at about 3,000 rpm for about 30 seconds. Lead halide precursor paint can be deposited on the substrate in an ambient atmosphere in a humidity range of about 0% relative humidity to about 50% relative humidity. The lead halide precursor paint can then be left to dry in an atmosphere substantially free of water, that is, less than 20% relative humidity, to form a thin film.
[74] The thin film can then be thermally annealed for a period of time up to about 24 hours at a temperature of about 20 ° C to about 300 ° C. In one embodiment, the thin film can be thermally annealed for about ten minutes at a temperature of about 50 ° C. The active layer of perovskite material can then be completed by a conversion process in which the precursor film is submerged or rinsed with a solution comprising a solvent or mixture of solvents (eg DMF, isopropanol, methanol, ethanol, butanol, chlorobenzene chloroform, dimethylsulfoxide, water) and salt (for example, methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide, 5-aminovaleric acid iodide) in a concentration between 0.001 M and 10 M. In certain embodiments, thin films can also be thermally post-annealed in the same way as in the first line of this paragraph. AMMONIUM IODIDE PURIFICATION
[75] As discussed earlier, in some embodiments, the precursor film for the active layer of perovskite material can be submerged or rinsed with a solution comprising a solvent or mixture of solvents that includes, without limitation, methylammonium iodide, sodium iodide formamidinium, guanidinium iodide. A synthetic procedure for methylammonium iodide (MAI) is now described. A similar procedure can be applied to guanidinium iodide (GAI), formamidinium iodide (FAI), amino acid iodide, or any halide salt (for example, iodine, bromine, chlorine or fluorine) thereof.
[76] A molar excess of methyl amine in methanol is added to an aqueous iodoid solution (Hl) in a vessel. In one embodiment, the methyl amine has a concentration of about 9.8 M, although suitable concentrations can be in the range of about 0.001 M to about 12 M. In one embodiment, the Hl solution has a concentration of about 57%, although the appropriate concentrations can be in the range of about 1% to about 100%. Any suitable vessel may be used, which includes, without limitation, a flask, beaker, Erlenmeyer flask, Schlenk flask or any glass vessel. The reaction is carried out under an inert oxygen-free atmosphere with addition of drops with stirring. In one embodiment, the reaction occurs at a temperature of about 0 ° C, although the reaction can also occur at a temperature as low as about -196 ° C or as high as about 100 ° C. After the completion of the addition of methyl amine, the solution is left to mix and warm to room temperature over a period of 2 hours. In some embodiments, the solution can be warmed to room temperature in as little as 1 minute or as much as about 72 hours. Upon completion of the reaction, the solvent is removed using a vacuum. A solid remains, which can be red or orange in color. This solid is an impure form of methylammonium iodide, in particular a mixture comprising methylammonium iodide, excess starting materials and / or reaction residues.
[77] A non-polar or slightly polar solvent (eg, diethyl ether) is then added to the impure methylammonium iodide, and the mixture is sonicated for about 30 minutes in the dark before decanting the liquid. In some embodiments, the solution can be sonicated for any length of time up to about 12 hours. This washing step of diethyl ether can be repeated countless times until the solid becomes colorless or slightly yellow. In one embodiment, the washing step of diethyl ether is repeated a total of three times. This produces a purer form of methylammonium iodide.
[78] Methylammonium iodide is then dissolved in a volume of minimal solvent ethanol in a sonicator at a temperature between about 20 ° C to about 150 ° C. In one embodiment, the temperature is about 60 ° C. Suitable solvents include methanol, ethanol, propanol, butanol or other polar solvents. In one embodiment, the solvent comprises ethanol. Once completely dissolved, the solution is cooled to room temperature over a period of about 30 minutes, and then layered with an equal volume (for ethanol) of diethyl ether. In other embodiments, a ratio between ethanol and diethyl ether can be in the range of about 1:10 to about 10: 1 by volume. The vessel is then purged with an inert gas (for example, argon or nitrogen), and then placed in a dark, cold place. In some embodiments, the pot can be placed in an environment with a temperature of about -196 ° C to about 25 ° C. In one embodiment, the vessel can be placed in a refrigerator. The pot can be left in the dark, cold place for a period of time from about 1 hour to about 168 hours. In one embodiment, the vase can be left in the dark, cold place for about 14 hours. The resulting colorless crystalline solid is recovered by a suitable method (for example, vacuum filtration, gravity filtration, or centrifuge), and subsequently washed with a cold or slightly polar non-polar solvent (for example, diethyl ether) and dried. In some embodiments, the crystalline solid can be washed once, twice or more times. The lens can be dried in room air or by any suitable equipment, which includes, without limitation, a vacuum oven, a convection oven, a furnace, a vacuum desiccator or a vacuum line. In one embodiment, the solid is dried for about 14 hours at about 40 ° C. However, the solid can be dried for a period of time from about 1 hour to about 168 hours and at a temperature of about 20 ° C to about 200 ° C.
[79] Therefore, the present invention is well adapted to achieve the purposes and advantages as well as those that are inherent in it. The particular modalities disclosed above are only illustrative, as the present invention can be modified and practiced in different, but equivalent, apparent ways to those skilled in the art that have the benefit of the teachings in this document. In addition, none of the limitations are intended for the details of construction or design shown in this document, other than those described in the claims below. Therefore, it is evident that the particular illustrative modalities disclosed above can be altered or modified, and all such variations are considered within the scope and spirit of the present invention. In particular, each range of values (of the form, “from about aa to b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately ab”) disclosed in this document must be understood to refer to the power set (the set of all subsets) of the respective ranges of values, and to present each range encompassed within the broadest range of values. Also, the terms in the claims have their common meaning of plan unless otherwise explicitly and clearly defined by the patent.

权利要求:
Claims (15)
[0001]
1. Method characterized by the fact that it comprises the steps of: preparing a lead halide precursor paint, in which the preparation of a lead halide precursor paint comprises the steps of: introducing a lead halide into a vessel; wherein the lead halide comprises a mixture of lead (II) chloride and lead (II) iodide; introducing a first solvent into the vessel; and bringing the lead halide into contact with the first solvent to dissolve the lead halide to form the lead halide precursor solution. deposit the lead halide precursor paint on a substrate; drying the lead halide precursor paint to form a thin film; annealing the thin film; and rinse the thin film with a second solvent and a salt selected from the group consisting of methylammonium iodide, formamidinium iodide, guanidinium iodide, 1,2,2-triaminovinylammonium iodide and 5-aminovaleric acid ihydrate.
[0002]
2. Method according to claim 1, characterized by the fact that the mixture of lead (II) chloride and lead (II) iodide is mixed in a ratio of 10 mol of lead (II) chloride to 90 mol of lead (II) iodide.
[0003]
3. Method, according to claim 1, characterized by the fact that the first solvent is selected from the group consisting of dry dirnetylformamide, dimethyl sulfoxide (DMSO), methanol, ethanol, propanol, butanol, tetrahydrofuran, formamide, pyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, chloroform and combinations thereof.
[0004]
4. Method according to claim 1, characterized by the fact that the placing of the lead halide in contact with the solvent to dissolve the lead halide occurs between 20 ° C to 150 ° C.
[0005]
5. Method according to claim 1, characterized by the fact that the placement of the lead halide in contact with the solvent to dissolve the lead halide occurs at 85 ° C.
[0006]
6. Method according to claim 1, characterized by the fact that the lead halide precursor paint has a lead halide concentration between 0.001 Me and 10 M.
[0007]
7. Method, according to claim 1, characterized by the fact that the deposition of lead halide precursor ink on the substrate occurs by droplet spreading, rotary spreading, extrusion printing, silkscreen or inkjet printing.
[0008]
8. Method according to claim 1, characterized by the fact that the annealing of the thin film occurs for up to 24 hours at a temperature between 20 ° C to 300 ° C.
[0009]
9. Method according to claim 1, characterized by the fact that annealing of the thin film takes place for ten minutes at a temperature of 50 ° C.
[0010]
10. Method according to claim 1, characterized by the fact that the second solvent is selected from the group consisting of dimethylformamide, isopropanol, methanol, ethanol, butanol, chloroform, chlorobenzene, dimethylsulfoxide, water and combinations thereof.
[0011]
11. Method according to claim 1, characterized by the fact that the salt comprises formamidinium iodide.
[0012]
12. Method according to claim 10, characterized by the fact that the salt is dissolved in the second solvent in a concentration between 0.001 Me and 10 M.
[0013]
13. Method according to claim 11, characterized by the fact that the salt comprises methylammonium iodide.
[0014]
14. Method according to claim 1, characterized in that the thin film rinse comprises at least partial submergence in the second solvent.
[0015]
15. Method, according to claim 1, characterized by the fact that the annealing of the thin film takes place between 5 to 30 minutes at a temperature between 40 ° C to 60 ° C.

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法律状态:
2018-02-06| B25A| Requested transfer of rights approved|Owner name: HEE SOLAR, L.L.C. (US) |

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2019-12-17| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-05-19| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-10-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-07-06| B25F| Entry of change of name and/or headquarter and transfer of application, patent and certif. of addition of invention: change of name on requirement|Owner name: HEE SOLAR, L.L.C. (US) Free format text: A FIM DE ATENDER A(S) ALTERACAO(OES) DE NOME REQUERIDA(S) ATRAVES DA PETICAO NO870210053129 DE 14/06/2021, DE ALTERACAO DE NOME, E NECESSARIO APRESENTAR : LEGALIZACAOCONSULAR OU APOSTILLE E TRADUCAO JURAMENTADA. |

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2021-12-07| B25E| Requested change of name of applicant rejected|Owner name: HEE SOLAR, L.L.C. (US) Free format text: INDEFERIDO O PEDIDO DE ALTERACAO DE NOME CONTIDO NA PETICAO 870210053129 DE 14/06/2021, POR AUSENCIA DE CUMPRIMENTO DA EXIGENCIA PUBLICADA NA RPI NO 2635, DE 06/07/2021. |

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2022-01-04| B25D| Requested change of name of applicant approved|Owner name: HUNT PEROVSKITE TECHNOLOGIES, L.L.C. (US) |

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