DEFECT ENGINEERING IN WIDE BANDGAP PEROVSKITES FOR EFFICIENT AND STABLE FULLY TEXTURED PEROVSKITE-SILICON TANDEM SOLAR CELLS
20250248296 ยท 2025-07-31
Inventors
Cpc classification
H10F77/703
ELECTRICITY
H10K85/111
ELECTRICITY
H10K30/10
ELECTRICITY
H10K85/50
ELECTRICITY
International classification
H10K85/50
ELECTRICITY
H10K30/10
ELECTRICITY
Abstract
Described herein are perovskite ink solutions comprising a composition of Formula I (APbI.sub.3-zBr.sub.z), a tribromide salt, and a solvent, wherein z is defined herein. Further described are perovskite films prepared using the ink solutions, methods for preparing the perovskite films, and use of the films in wide band gap single junction and tandem solar cells. As shown herein, solar cells fabricated using the perovskite films prepared from ink solutions comprising a tribromide salt achieve enhanced efficiency compared to solar cells comprising a perovskite film prepared without the tribromide salt.
Claims
1. An ink solution, comprising: (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), wherein, A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and z is between 0.01 and 1.0; (ii) a tribromide salt; and (iii) a solvent.
2. The ink solution of claim 1, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I.
3. The ink solution of claim 2, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.1 to about 0.5% relative to the composition of Formula I.
4. The ink solution of claim 2 or 3, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.2% relative to the composition of Formula I.
5. The ink solution of claim 1, wherein the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide.
6. The ink solution of claim 1, wherein the tribromide salt is an ammonium tribromide salt.
7. The ink solution of claim 6, wherein the ammonium tribromide salt is trimethylphenylammonium tribromide.
8. The ink solution of claim 1, wherein: A is selected from the group consisting of Cs, FA, and MA, or a combination thereof, and z is between 0.3 and 0.6.
9. The ink solution of claim 8, wherein: A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and z is 0.45.
10. The ink solution of claim 1, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran, -butyrolactone, 2-methoxyethanol, N,N-Dimethylpropyleneurea, N-methyl-2-pyrrolidone, and acetonitrile, or a combination thereof.
11. The ink solution of claim 1, wherein: the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.2% relative to the composition of Formula I.
12. A method for preparing a perovskite film using the ink solution of any one of claims 1-11, comprising: contacting the ink solution of any one of claims 1-11 using a fast coating process onto a substrate to form a film, wherein the fast coating process is selected from the group consisting of blade coating, slot die coating, shear coating, gravure coating, brush coating, syringe coating, and screen printing.
13. The method of claim 12, wherein the fast coating process is blade coating.
14. The method of claim 12, wherein the perovskite film prepared has a thickness of about 300 nm to about 2000 nm.
15. A perovskite film comprising: (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), wherein, A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and z is between 0.01 and 1.0; and (ii) a tribromide salt.
16. The perovskite film of claim 15, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I.
17. The perovskite film of claim 16, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.1 to about 0.5% relative to the composition of Formula I.
18. The perovskite film of claim 16 or 17, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.2% relative to the composition of Formula I.
19. The perovskite film of claim 15, wherein the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide.
20. The perovskite film of claim 15, wherein the tribromide salt is an ammonium tribromide salt.
21. The perovskite film of claim 20, wherein the ammonium tribromide salt is trimethylphenylammonium tribromide.
22. The perovskite film of claim 15, wherein: A is selected from the group consisting of Cs, FA, and MA, or a combination thereof; and z is between 0.3 and 0.6.
23. The perovskite film of claim 22, wherein: A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and z is 0.45.
24. The perovskite film of claim 15, wherein: the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the film at a molar ratio of about 0.2% relative to the composition of Formula I.
25. The perovskite film of any one of claims 15-24, wherein the film has a thickness of about 300 nm to about 2000 nm.
26. A wide band gap perovskite solar cell, comprising the perovskite film of any one of claims 15-25.
27. A solar cell comprising: one or more transparent conductive oxide layers; one or more conductive electrode layers; and one or more active layers, wherein at least one of said one or more active layers is a wide band gap material comprising the perovskite film of any one of claims 15-25.
28. The solar cell of claim 27 further comprising: one or more hole transport layers; and one or more electron transport layers.
29. The solar cell of claim 28, comprising: one transparent conductive oxide layer; one conductive electrode layer; one hole transport layer; one electron transport layer; and one active layer, wherein the active layer is a wide band gap material comprising the perovskite film of any one of claims 15-25.
30. The solar cell of claim 29, wherein: the hole transport layer is disposed on the transparent conductive oxide layer; the active layer comprising the perovskite film is disposed on the hole transport layer; the electron transport layer is disposed on the active layer; and the conductive electrode layer is disposed on the electron transport layer.
31. The solar cell of claim 29, wherein: the electron transport layer is disposed on the transparent conductive oxide layer; the active layer comprising the perovskite film is disposed on the electron transport layer; the hole transport layer is disposed on the active layer; and the conductive electrode layer is disposed on the hole transport layer.
32. The solar cell of claim 30, wherein: the transparent conductive oxide layer is ITO; the hole transport layer is PTAA optionally doped with TPFB; the electron transport layer is C.sub.60; and the conductive electrode layer is Cu or Ag; and wherein the solar cell further comprises a buffer layer of BCP or SnO.sub.2 disposed between the electron transport layer and the conductive electrode layer.
33. The solar cell of claim 32, wherein the perovskite film has a thickness of about 1000 nm.
34. The solar cell of claim 32 or 33, having a Power Conversion Efficiency of at least 21%.
35. The solar cell of claim 27, wherein said solar cell is a tandem solar cell, comprising two active layers; wherein a first sub cell comprises a first active layer, wherein the first active layer is the wide band gap material comprising the perovskite film of any one of claims 15-25; and a second sub cell comprises a second active layer, wherein the second active layer comprises silicon; wherein the first sub cell is disposed on the second sub cell; and a recombination layer is disposed between the first sub cell and the second sub cell.
36. The solar cell of claim 35, wherein the silicon is textured silicon.
37. The solar cell of claim 36, wherein the textured silicon is characterized by a truncated pyramid shape.
38. The solar cell of any one of claims 35-37, wherein the perovskite film has a thickness of about 1000 nm.
39. The solar cell of any one of claims 35-38, further comprising: one or more electron transport layers; one or more hole transport layers; and one or more interlayers.
40. The solar cell of claim 39, wherein: a first hole transport layer is disposed on the recombination layer; an interlayer is disposed on the first hole transport layer; and the perovskite film is disposed on the interlayer.
41. The solar cell of claim 40, wherein the interlayer is LiF or MgF.sub.2.
42. The solar cell of any one of claims 35-41, wherein the second sub cell is a silicon heterojunction cell.
43. The solar cell of claim 35, wherein the recombination layer is ITO.
44. The solar cell of any one of claims 35-43, having a PCE of at least 26%.
45. The solar cell of any one of claims 35-43, having a PCE of at least 27%.
46. The solar cell of any one of claims 35-43, capable of sustaining about 90% of its initial efficiency after about 500 hours.
47. The solar cell of any one of claims 27-43, wherein the wide band gap material has a band gap of about 1.50 eV to about 2.4 eV.
48. The solar cell of claim 47, wherein the wide band gap material has a band gap of about 1.65 eV.
49. A method of improving the efficiency of a wide band gap solar cell, comprising: incorporating an enhanced perovskite film into a wide band gap solar cell; wherein the enhanced perovskite film comprises: (i) a composition of Formula I
APbI.sub.3-zBr.sub.z(I), wherein, A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and z is between 0.01 and 1.0; and (ii) a tribromide salt; wherein the tribromide salt is present in the enhanced perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula (I); and wherein the efficiency of the wide band gap solar cell is improved relative to a wide band gap solar cell comprising a perovskite film of Formula I that lacks the tribromide salt.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
[0065] Perovskite-silicon tandem cells with double side textured silicon can achieve higher efficiency with less optical loss. However, there are several challenges to obtaining such high efficiency. For one, wide bandgap (WBG) mixed halide perovskite materials are characterized as having a very short charge-carrier diffusion length. Additionally, a thick perovskite layer is typically needed to fully cover the textured silicon to avoid shunting. As shown herein, WBG perovskite materials with partial iodide sites replaced by bromide have increased deep charge trap concentrations induced by iodine interstitials, which limit the performance of WBG perovskite cells. However, as described herein, perovskite films prepared using an ink solution comprising an ammonium tribromide salt endows perovskite-silicon tandem solar cells containing the films with enhanced efficiency. In particular, the tribromide ions in the perovskite suppress iodine interstitial formation and therefore reduce charge recombination in bladed WBG perovskite solar cells.
[0066] Perovskite solar cells (PSCs) exhibited unprecedented progress in recent years with the highest certified efficiency reaching over 25% (1). To further improve the efficiency of PSCs and overcome the detailed balance theory limit for single-junction solar cells, tandem solar cells are generally applied by integrating wide-bandgap (WBG) perovskites with mature photovoltaic (PV) technologies, such as crystalline silicon, Cu (In, Ga) Se.sub.2 (CIGS) (2-4) or with another low bandgap perovskites (5-7). Among these perovskite-based tandem PV technologies, the perovskite-silicon tandem solar cell has emerged as a mainstream PV technology that can deliver a certified efficiency over 29% (8). Currently, monolithic two-terminal perovskite-silicon tandem devices fabricated by solution processes are still predominately based on front-side polished and rear-side textured crystalline silicon (c-Si), which experience a large loss of photocurrent due to light reflection (9). Double-side textured crystalline silicon with increased light-trapping properties has been shown to deliver a high efficiency upper limit for perovskite/silicon tandem devices (10-12).
[0067] The first fully textured perovskite-silicon tandem cells had a front texture size of up to 6 micrometers (m), in which the WBG perovskite on textured silicon was conformally formed by a combination of evaporation and solution coating (10). Recently, a much smaller texture structure of one micrometer or less on the front surface of silicon has been shown to have comparable anti-reflection capabilities as the large texture structure, enabling the fabrication of fully textured perovskite-silicon tandem devices using much simpler one-step solution-based blade-coating or spin coating methods (11, 12). However, the efficiencies of the reported perovskite-silicon tandem solar cells only reached 25-26%, which does not demonstrate the full potential of the double side textured silicon structure. The low PCEs of the tandem cells were predominately limited by the much smaller open-circuit voltage (V.sub.OC) and fill factor (FF) than those made on flat silicon (11-14).
[0068] It is still difficult to deposit a perovskite layer to conformally cover textured silicon by solution-based methods, even when the texture size is as small as one micrometer. Thus, the deposited WBG perovskite layer still needs to be thick enough (>1 m) to avoid shunting and afford both high efficiency and manufacturing viability. In this context, it is useful to deposit high-quality thick WBG perovskite films with long carrier diffusion length and low non-radiative recombination to enable efficient charge collection for efficient tandem devices on double-side-textured c-silicon. This imposes a greater requirement for WBG perovskite films made on textured silicon than those made on flat silicon. The WBG perovskite solar cell efficiency generally decreases quickly when the perovskite film thickness increases beyond 600 nm. In addition, mixed-halide IBr perovskites, which are often used to obtain an optimum bandgap for tandem solar cells, typically fail to exhibit an expected V.sub.OC increase with bandgap broadening. Even for regular WBG perovskite devices fabricated on flat substrates, the V.sub.OC deficits are still much larger than those with optimized pure iodide perovskites (15). The V.sub.OC deficits of pure iodide perovskites has been reported to be as small as 0.3 V (16); however, the V.sub.OC is usually larger than 0.5 V in mixed halide WBG perovskite devices. Studies indicate that such a large V.sub.OC loss in WBG perovskites is caused by photo-induced halide segregation (17, 18). Mahesh et al. identified, however, that the dominant V.sub.OC loss mechanism in WBG perovskite cells is a result of relatively low radiative efficiency caused by higher defect density within WBG films, though these compositions might not show clear light induced phase segregation (19). No insight into the chemical nature of these defects was provided in Mahesh's investigation, however.
[0069] As described herein, it was identified that positive iodine interstitials (I.sub.i.sup.+) are the dominant, deep charge-trapping defects in WBG perovskites, and which increase with the incorporation of bromide. Further described is an effective way to reduce bulk deep trap density in WBG perovskite films by adding trimethylphenylammonium tribromide (TPABr.sub.3), which dramatically elongates the carrier diffusion length. Mixed halide perovskite Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 with an ideal bandgap of 1.65 eV was used for fabricating monolithic tandem solar cells on textured silicon. Single-junction perovskite devices with over 1-m-thick WBG perovskite films showed an increased PCE of 21.9% with an impressive V.sub.OC of 1.25 V and FF of 0.830. As shown herein, the perovskite ink formulation and solar cell fabrication strategy resulted in an efficiency of 28.6% for fully textured perovskite-silicon tandem cells.
[0070] The presently disclosed subject matter will now be described more fully hereinafter. However, many modifications and other embodiments of the presently disclosed subject matter set forth herein will come to mind to one skilled in the art to which the presently disclosed subject matter pertains having the benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that the presently disclosed subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. In other words, the subject matter described herein covers all alternatives, modifications, and equivalents. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in this field. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In the event that one or more of the incorporated literature, patents, and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls.
I. Definitions
[0071] As used herein, and/or refers to and encompasses any and all possible combinations of one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative (or).
[0072] As used herein, the term about, when referring to a measurable value such as an amount of a compound or agent of the current subject matter, dose, time, temperature, and the like, is meant to encompass variations of 20%, 10%, 5%, 1%, 0.5%, or even 0.10% of the specified amount.
[0073] As used herein, conditional language used herein, such as, among others, can, could, might, may, e.g., and the like, unless specifically stated otherwise or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without author input or prompting, whether these features, elements and/or steps are included or are to be performed in any particular embodiment. The terms comprising, including, having, and the like are synonymous and are used inclusively, in an open-ended fashion, and do not exclude additional elements, features, acts, operations, and so forth. Also, the term or is used in its inclusive sense (and not in its exclusive sense) so that when used, for example, to connect a list of elements, the term or means one, some, or all of the elements in the list.
[0074] As used herein, PSC refers to perovskite solar cell.
[0075] As used herein, PCE refers to power conversion efficiency. The terms power conversion efficiency, PCE, photovoltaic efficiency, and solar cell efficiency, may be used interchangeably and refer to the ratio of energy output from the photovoltaic device to the energy input to the photovoltaic device. The energy output is in the form of electrical energy and energy input is in the form of electromagnetic radiation (e.g., sunlight). Unless otherwise indicated, the photovoltaic efficiency refers to terrestrial photovoltaic efficiency, corresponding to AM1.5 conditions, where AM is Air Mass. PCE may be measured by one or more techniques conventionally known to one of ordinary skill in the art.
[0076] As used herein, photoactive device refers to (i) a device capable of and configured to convert electromagnetic radiation (e.g., X-ray, infrared, ultraviolet, and/or visible light) to electrical energy and/or converting electrical energy to electromagnetic radiation. A photoactive device may be configured to both convert light to electrical energy (e.g., as a solar cell) and convert electrical energy to light (e.g., via electroluminescence), for example depending on the direction of electrical current in the device (e.g., depending on whether electrical power is withdrawn from or supplied to the device). Exemplary photoactive devices include, but are not limited to, a photovoltaic cell (also referred to as a solar cell), a photodiode, and a light emitting diode (LED). In certain embodiments, a photoactive device can also refer to a device configured to change its optical, physical, and/or electrical properties with change in its exposure to electromagnetic radiation and/or a device configured to change its optical properties in response to a change in input of electrical energy. Exemplary photoactive devices can also include, but are not limited to, a photoresistor, phototransistor, photomultiplier, photoelectric cell, and an electrochromic cell.
[0077] As used herein, active layer refers to a photoactive layer in a device, such as a solar cell, and/or it may include a photoactive material. Furthermore, it should be noted that the use of the term active layer is in no way meant to restrict or otherwise define, explicitly or implicitly, the properties of any other layer in the device.
[0078] As used herein, the term defect refers to a defective site in a crystal lattice where the local crystal structure does not correspond to the crystal structure of the bulk material. Non-limiting examples of defective sites include point defects, line defects, and planar defects. Point defects include vacancy defects (the absence of an ion), interstitial defects (the interstitial inclusion of an additional ion), Frenkel defects (a closely located pair of defects consisting of an interstitial defect and a vacancy defect) and the presence of an impurity ion. Planar defects include grain boundaries and stacking faults.
II. Perovskite Films
[0079] In one aspect, the subject matter described herein is directed to a perovskite film comprising: [0080] (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), [0081] wherein, [0082] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and [0083] z is between 0.01 and 1.0; and [0084] (ii) a tribromide salt.
[0085] In certain embodiments of the perovskite film, A may comprise an ammonium, an organic cation of the general formula [NR.sub.4].sup.+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: methyl, ethyl, propyl, butyl, pentyl group or isomer thereof; any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., pyridine, pyrrole, pyrrolidine, piperidine, tetrahydroquinoline); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (e.g., acetic acid, propanoic acid); and ester or amide derivatives thereof; any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, seine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments, A is methylammonium, (CH.sub.3NH.sub.3.sup.+). In certain embodiments, A is methylammonium. In certain embodiments, A is tetramethylammonium, ((CH.sub.3).sub.4N.sup.+). In certain embodiments, A is butylammonium, which may be represented by (CH.sub.3(CH.sub.2).sub.3NH.sub.3.sup.+) for n-butylammonium, by ((CH.sub.3).sub.3CNH.sub.3.sup.+) for t-butylammonium, or by (CH.sub.3).sub.2CHCH.sub.2NH.sub.3) for iso-butylammonium. In certain embodiments, A is phenethylammonium, which may be represented by C.sub.6H.sub.5(CH.sub.2).sub.2NH.sub.3.sup.+ or by C.sub.6H.sub.5CH(CH.sub.3)NH.sub.3*. In certain embodiments, A comprises phenylammonium, C.sub.6H.sub.5NH.sub.3.sup.+.
[0086] In certain embodiments of the perovskite film, A may comprise a formamidinium, an organic cation of the general formula [R.sub.2NCHNR.sub.2].sup.+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: hydrogen, methyl, ethyl, propyl, butyl, pentyl or an isomer thereof; any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., imidazole, benzimidazole, dihydropyrimidine, (azolidinylidenemethyl)pyrrolidine, triazole); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof, any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments A is a formamidinium ion represented by (H.sub.2NCHNH.sub.2.sup.+).
[0087] In certain embodiments of the perovskite film, A may comprise a guanidinium, an organic cation of the general formula [(R.sub.2N).sub.2CNR.sub.2].sup.+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: hydrogen, methyl, ethyl, propyl, butyl, pentyl group or isomer thereof, any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., octahydropyrimido[1,2-a]pyrimidine, pyrimido[1,2-a]pyrimidine, hexahydroimidazo[1,2-a]imidazole, hexahydropyrimidin-2-imine); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments, A is a guanidinium ion of the type (H.sub.2NC(NH.sub.2).sub.2.sup.+).
[0088] In certain embodiments of the perovskite film, A may comprise an alkali metal cation, such as Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, or Cs.sup.+.
[0089] Pb in the composition of Formula I of the perovskite film, refers to lead.
[0090] I refers to iodide and Br to bromide.
[0091] In certain embodiments of the perovskite film, z is between 0.05 and 1.0. In certain embodiments of the perovskite film, z is 0.01, 0.02, 0.03, 0.04, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 1. In certain embodiments of the perovskite film, z is between 0.01 and 0.05, 0.01 and 0.03, 0.01 and 0.15, 0.02 and 0.10, 0.01 and 0.5, 0.01 and 0.75, 0.3 and 0.6, 0.2 and 0.7, 0.1 and 0.8, 0.3 and 0.5, 0.4 and 0.9, or 0.4 and 0.6.
[0092] In certain embodiments of the perovskite film, the tribromide salt is present in the perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I. In certain embodiments of the perovskite film, the tribromide salt is present in the perovskite film at a molar ratio of about 0.1 to about 0.5%, 0.05 to about 3%, about 0.05 to 2%, about 0.10 to about 0.8%, about 0.3 to about 0.7%, about 0.5 to about 0.9%, or about 0.4 to about 0.8% relative to the composition of Formula I. the tribromide salt is present in the perovskite film at a molar ratio of about 0.05%, 0.1%, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2% relative to the composition of Formula I.
[0093] In certain embodiments of the perovskite film, the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide. In certain embodiments of the perovskite film, the tribromide salt is an ammonium tribromide salt. In certain embodiments of the perovskite film, the ammonium tribromide salt is trimethylphenylammonium tribromide.
[0094] In certain embodiments of the perovskite film, A is selected from the group consisting of Cs, FA, and MA, or a combination thereof; and z is between 0.3 and 0.6. In certain other embodiments of the perovskite film, A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and z is 0.45.
[0095] In certain embodiments of the perovskite film, the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the film at a molar ratio of about 0.2% relative to the composition of Formula I.
[0096] In certain embodiments of the perovskite film, the perovskite film has a thickness of about 300 nm to about 2000 nm. In certain embodiments, the perovskite film has a thickness of about 300 nm to about 1000 nm, about 300 nm to about 500 nm, about 400 nm to about 800 nm, about 500 nm to about 1500 nm, about 600 nm to about 1800 nm, about 300 nm to about 900 nm, about 1000 nm to about 1500 nm, about 1000 nm to about 2000 nm, about 400 nm to about 1100 nm, about 1200 nm to about 1500 nm, about 1300 nm to about 1800 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, about 900 nm to about 1000 nm, about 1000 nm to about 1100 nm, about 1100 nm to about 1200 nm, about 1200 nm to about 1300 nm, about 1300 nm to about 1400 nm, about 1400 nm to about 1500 nm, about 1500 nm to about 1600 nm, about 1600 nm to about 1700 nm, about 1700 nm to about 1800 nm, about 1800 nm to about 1900 nm, or about 1900 nm to about 2000 nm.
III. Ink Solutions
[0097] In certain embodiments, the subject matter disclosed herein is directed to an ink solution, comprising: [0098] (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), [0099] wherein, [0100] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof, and [0101] z is between 0.01 and 1.0; [0102] (ii) a tribromide salt;
and [0103] (iii) a solvent.
[0104] In certain embodiments of the ink solution, A may comprise an ammonium, an organic cation of the general formula [NR.sub.4]+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: methyl, ethyl, propyl, butyl, pentyl group or isomer thereof, any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., pyridine, pyrrole, pyrrolidine, piperidine, tetrahydroquinoline); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (e.g., acetic acid, propanoic acid); and ester or amide derivatives thereof; any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments, A is methylammonium, (CH.sub.3NH.sub.3.sup.+). In certain embodiments, A is methylammonium. In certain embodiments, A is tetramethylammonium, ((CH.sub.3).sub.4N.sup.+). In certain embodiments, A is butylammonium, which may be represented by (CH.sub.3(CH.sub.2).sub.3NH.sub.3.sup.+) for n-butylammonium, by ((CH.sub.3).sub.3CNH.sub.3.sup.+) for t-butylammonium, or by (CH.sub.3).sub.2CHCH.sub.2NH.sub.3.sup.+) for iso-butylammonium. In certain embodiments, A is phenethylammonium, which may be represented by C.sub.6H.sub.5(CH.sub.2).sub.2NH.sub.3.sup.+ or by C.sub.6H.sub.5CH(CH.sub.3)NH.sub.3*. In certain embodiments, A comprises phenylammonium, C.sub.6H.sub.5NH.sub.3.sup.+.
[0105] In certain embodiments of the ink solution, A may comprise a formamidinium, an organic cation of the general formula [R.sub.2NCHNR.sub.2].sup.+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: hydrogen, methyl, ethyl, propyl, butyl, pentyl or an isomer thereof; any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., imidazole, benzimidazole, dihydropyrimidine, (azolidinylidenemethyl)pyrrolidine, triazole); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments A is a formamidinium ion represented by (H.sub.2NCHNH.sub.2.sup.+).
[0106] In certain embodiments of the ink solution, A may comprise a guanidinium, an organic cation of the general formula [(R.sub.2N).sub.2CNR.sub.2].sup.+ where the R groups can be the same or different groups. Suitable R groups include, but are not limited to: hydrogen, methyl, ethyl, propyl, butyl, pentyl group or isomer thereof; any alkane, alkene, or alkyne C.sub.xH.sub.y, where x=1-20, y=1-42, cyclic, branched or straight-chain; alkyl halides, C.sub.xH.sub.yX.sub.z, x=1-20, y=0-42, z=1-42, X=F, Cl, Br, or I; any aromatic group (e.g., phenyl, alkylphenyl, alkoxyphenyl, pyridine, naphthalene); cyclic complexes where at least one nitrogen is contained within the ring (e.g., octahydropyrimido[1,2-a]pyrimidine, pyrimido[1,2-a]pyrimidine, hexahydroimidazo[1,2-a]imidazole, hexahydropyrimidin-2-imine); any sulfur-containing group (e.g., sulfoxide, thiol, alkyl sulfide); any nitrogen-containing group (nitroxide, amine); any phosphorous containing group (phosphate); any boron-containing group (e.g., boronic acid); any organic acid (acetic acid, propanoic acid) and ester or amide derivatives thereof; any amino acid (e.g., glycine, cysteine, proline, glutamic acid, arginine, serine, histindine, 5-ammoniumvaleric acid) including alpha, beta, gamma, and greater derivatives; any silicon containing group (e.g., siloxane); and any alkoxy or group, OC.sub.xH.sub.y, where x=0-20, y=1-42. In certain embodiments, A is a guanidinium ion of the type (H.sub.2NC(NH.sub.2).sub.2.sup.+).
[0107] In certain embodiments of the ink solution, A may comprise an alkali metal cation, such as Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+, or Cs.sup.+. Pb in the composition of Formula I of the perovskite film, refers to lead.
[0108] I refers to iodide and Br to bromide.
[0109] In certain embodiments of the ink solution, z is between 0.05 and 1.0. In certain embodiments of the ink solution, z is 0.01, 0.02, 0.03, 0.04, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 1. In certain embodiments of the ink solution, z is between 0.01 and 0.05, 0.01 and 0.03, 0.01 and 0.15, 0.02 and 0.10, 0.01 and 0.5, 0.01 and 0.75, 0.3 and 0.6, 0.2 and 0.7, 0.1 and 0.8, 0.3 and 0.5, 0.4 and 0.9, or 0.4 and 0.6.
[0110] In certain embodiments of the ink solution, the tribromide salt is present in the ink solution at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I. In certain embodiments of the ink solution, the tribromide salt is present in the ink solution at a molar ratio of about 0.1 to about 0.5%, 0.05 to about 3%, about 0.05 to 2%, about 0.10 to about 0.8%, about 0.3 to about 0.7%, about 0.5 to about 0.9%, or about 0.4 to about 0.8% relative to the composition of Formula I. the tribromide salt is present in the ink solution at a molar ratio of about 0.05%, 0.1%, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2% relative to the composition of Formula I.
[0111] In certain embodiments of the ink solution, the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide. In certain embodiments of the ink solution, the tribromide salt is an ammonium tribromide salt. In certain embodiments of the ink solution, the ammonium tribromide salt is trimethylphenylammonium tribromide.
[0112] In certain embodiments of the ink solution, A is selected from the group consisting of Cs, FA, and MA, or a combination thereof; and zis between 0.3 and 0.6. In certain other embodiments of the ink solution, A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and z is 0.45.
[0113] In certain embodiments of the ink solution, the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.2% relative to the composition of Formula I.
[0114] In certain embodiments of the ink solution, the solvent is selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran, -butyrolactone, 2-methoxyethanol, N,N-Dimethylpropyleneurea, N-methyl-2-pyrrolidone, and acetonitrile, or a combination thereof. In certain embodiments, the solvent is selected from one or more of dimethyl sulfoxide, dimethylformamide, 2-methoxyethanol, acetonitrile, methanol, propanol, butanol, tetrahydrofuran, pyridine, alkylpyridine, pyrrolidine, chlorobenzene, dichlorobenzene, dichloromethane, 1-methoxypropan-2-ol, 2-methoxy-1-methylethyl acetate, 2-butoxyethanol, 2-butoxyethyl acetate, 2-(propyloxy)ethanol, ethyl 3-ethoxypropionate, glycol ethers, dimethylacetamide, acetone, N,N-Dimethylpropyleneurea, and chloroform.
IV. Methods for Preparing Perovskite Films
[0115] In certain embodiments, the subject matter disclosed herein is directed to a method for preparing a perovskite film using the ink solutions disclosed herein, comprising: [0116] contacting an ink solution disclosed herein using a fast coating process onto a substrate to form a film, wherein the fast coating process is selected from the group consisting of blade coating, slot die coating, shear coating, gravure coating, brush coating, syringe coating, and screen printing.
[0117] In certain embodiments of the above method, the fast coating process is blade coating. In certain embodiments, a device is used in the fast coating process for contacting the ink solution onto the substrate. In the blade coating process, a blade coater may be used. As used herein, blade coater is synonymous with doctor blade. In certain embodiments, doctor blade coating techniques are used to facilitate formation of the perovskite film during the fabrication process.
[0118] In certain embodiments of the above method, the perovskite film prepared has a thickness of about 300 nm to about 2000 nm. In certain embodiments, the perovskite film prepared has a thickness of about 300 nm to about 1000 nm, about 300 nm to about 500 nm, about 400 nm to about 800 nm, about 500 nm to about 1500 nm, about 600 nm to about 1800 nm, about 300 nm to about 900 nm, about 1000 nm to about 1500 nm, about 1000 nm to about 2000 nm, about 400 nm to about 1100 nm, about 1200 nm to about 1500 nm, about 1300 nm to about 1800 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, about 900 nm to about 1000 nm, about 1000 nm to about 1100 nm, about 1100 nm to about 1200 nm, about 1200 nm to about 1300 nm, about 1300 nm to about 1400 nm, about 1400 nm to about 1500 nm, about 1500 nm to about 1600 nm, about 1600 nm to about 1700 nm, about 1700 nm to about 1800 nm, about 1800 nm to about 1900 nm, or about 1900 nm to about 2000 nm.
V. Devices
[0119] The perovskite films described herein are useful in a variety of photoactive and photovoltaic applications. The perovskite films can be integrated into, for example, photoluminescent devices, photoelectrochemical devices, thermoelectric devices, and photocatalytic devices. Some non-limiting examples in which the polycrystalline perovskite films can be applied include solar cells, solar panels, solar modules, light-emitting diodes, lasers, photodetectors, x-ray detectors, batteries, hybrid PV batteries, field effect transistors, memristors, or synapses. In a preferred embodiment, the perovskite films described herein are useful in a wide band gap perovskite solar cell.
[0120] In certain embodiments, the subject matter disclosed herein is directed to a solar cell, comprising: [0121] one or more transparent conductive oxide layers; [0122] one or more conductive electrode layers; and [0123] one or more active layers, wherein at least one of said one or more active layers is a wide band gap material comprising a perovskite film described herein.
[0124] In certain embodiments of the above solar cell, the solar cell further comprises: [0125] one or more hole transport layers; and [0126] one or more electron transport layers.
[0127] In certain embodiments of the above solar cell, the solar cell comprises [0128] one transparent conductive oxide layer; [0129] one conductive electrode layer; [0130] one hole transport layer; [0131] one electron transport layer; and [0132] one active layer, wherein the active layer is a wide band gap material comprising a perovskite film described herein.
[0133] In certain embodiments of the above solar cell, [0134] the hole transport layer is disposed on the transparent conductive oxide layer; [0135] the active layer comprising the perovskite film is disposed on the hole transport layer; [0136] the electron transport layer is disposed on the active layer; and [0137] the conductive electrode layer is disposed on the electron transport layer.
[0138] In certain embodiments of the above solar cell, [0139] the electron transport layer is disposed on the transparent conductive oxide layer; [0140] the active layer comprising the perovskite film is disposed on the electron transport layer; [0141] the hole transport layer is disposed on the active layer; and [0142] the conductive electrode layer is disposed on the hole transport layer.
[0143] In certain embodiments of the above solar cell, [0144] the transparent conductive oxide layer is ITO; [0145] the hole transport layer is PTAA optionally doped with TPFB; [0146] the electron transport layer is C.sub.60; and [0147] the conductive electrode layer is Cu or Ag; and wherein the solar cell further comprises a buffer layer of BCP or SnO.sub.2 disposed between the electron transport layer and the conductive electrode layer.
[0148] In certain embodiments of the above solar cell, the perovskite film has a thickness of about 1000 nm. In certain other embodiments, the perovskite film has a thickness of about 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, or 2000 nm. In certain other embodiments, the perovskite film has a thickness of about 300 to about 2000 nm, 300 nm to about 1000 nm, about 300 nm to about 500 nm, about 400 nm to about 800 nm, about 500 nm to about 1500 nm, about 600 nm to about 1800 nm, about 300 nm to about 900 nm, about 1000 nm to about 1500 nm, about 1000 nm to about 2000 nm, about 400 nm to about 1100 nm, about 1200 nm to about 1500 nm, about 1300 nm to about 1800 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, about 900 nm to about 1000 nm, about 1000 nm to about 1100 nm, about 1100 nm to about 1200 nm, about 1200 nm to about 1300 nm, about 1300 nm to about 1400 nm, about 1400 nm to about 1500 nm, about 1500 nm to about 1600 nm, about 1600 nm to about 1700 nm, about 1700 nm to about 1800 nm, about 1800 nm to about 1900 nm, or about 1900 nm to about 2000 nm.
[0149] In certain embodiments of the above solar cell, the solar cell has a Power Conversion Efficiency (PCE) of at least 21%, 22%, 23%, 24%, or 25%.
[0150] In certain other embodiments, the subject matter described herein is directed to a tandem solar cell, comprising two active layers; [0151] wherein a first sub cell comprises a first active layer, wherein the first active layer is the wide band gap material comprising the perovskite film disclosed herein; and [0152] a second sub cell comprises a second active layer, wherein the second active layer comprises silicon; [0153] wherein the first sub cell is disposed on the second sub cell; and a recombination layer is disposed between the first sub cell and the second sub cell.
[0154] In certain embodiments of the above tandem solar cell, the silicon is textured silicon. In certain embodiments of the above tandem solar cell, the textured silicon is characterized by a truncated pyramid shape.
[0155] In certain embodiments of the above tandem solar cell, the perovskite film has a thickness of about 1000 nm. In certain other embodiments, the perovskite film has a thickness of about 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, 1600 nm, 1700 nm, 1800 nm, 1900 nm, or 2000 nm. In certain other embodiments, the perovskite film has a thickness of about 300 to about 2000 nm, 300 nm to about 1000 nm, about 300 nm to about 500 nm, about 400 nm to about 800 nm, about 500 nm to about 1500 nm, about 600 nm to about 1800 nm, about 300 nm to about 900 nm, about 1000 nm to about 1500 nm, about 1000 nm to about 2000 nm, about 400 nm to about 1100 nm, about 1200 nm to about 1500 nm, about 1300 nm to about 1800 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, about 900 nm to about 1000 nm, about 1000 nm to about 1100 nm, about 1100 nm to about 1200 nm, about 1200 nm to about 1300 nm, about 1300 nm to about 1400 nm, about 1400 nm to about 1500 nm, about 1500 nm to about 1600 nm, about 1600 nm to about 1700 nm, about 1700 nm to about 1800 nm, about 1800 nm to about 1900 nm, or about 1900 nm to about 2000 nm.
[0156] In certain embodiments of the above tandem solar cell, the tandem solar cell further comprises: [0157] one or more electron transport layers; [0158] one or more hole transport layers; and [0159] one or more interlayers layers.
[0160] In certain embodiments of the above tandem solar cell, [0161] a first hole transport layer is disposed on the recombination layer; [0162] an interlayer is disposed on the first hole transport layer; and [0163] the perovskite film is disposed on the interlayer.
[0164] In certain embodiments of the above tandem solar cell, the interlayer is LiF or MgF.sub.2.
[0165] In certain embodiments of the above tandem solar cell, the second sub cell is a silicon heterojunction cell.
[0166] In certain embodiments of the above tandem solar cell, the recombination layer comprises a conductive oxide material. In certain embodiments of the above tandem solar cell, the recombination layer comprises graphene oxide, gold, or mixtures thereof. In certain embodiments of the above tandem solar cell, the recombination layer comprises ITO.
[0167] In certain embodiments of the above tandem solar cell, the tandem solar cell has a Power Conversion Efficiency (PCE) of at least 26%, 27%, 28%, or 29%.
[0168] In certain embodiments of the above tandem solar cell, the tandem solar cell is capable of sustaining about 90%, 91%, 92%, 93%, 94%, or 95% of its initial efficiency after about 500 hours.
[0169] In certain embodiments of the above solar cell (tandem or single junction), the wide band gap material has a band gap of about 1.50 eV to about 2.4 eV. In certain other embodiments, the wide band gap material has a band gap of about 1.6 eV to 2.2 eV, 1.6 eV to 1.8 eV, 1.7 eV to 1.9 eV, or 1.8 eV to 2.1 eV. In certain other embodiments, the wide band gap material has a band gap of about 1.6 eV, 1.61 eV, 1.62 eV, 1.63 eV, 1.64 eV, 1.65 eV, 1.66 eV, 1.67 eV, 1.68 eV, 1.69 eV, or 1.7 eV.
[0170] The transparent conductive oxide layer and the conductive electrode layer comprise the anode and cathode (or vice versa) in the solar cell. In certain embodiments, the cathode and anode each comprise at least one of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, boron, aluminum, gallium, indium, thallium, tin, lead, flerovium, bismuth, antimony, tellurium, polonium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, indium, platinum, gold, mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, copernicium, samarium, neodymium, ytterbium, an alkali metal fluoride, an alkaline-earth metal fluoride, an alkali metal chloride, an alkaline-earth metal chloride, an alkali metal oxide, an alkaline-earth metal oxide, a metal carbonate, a metal acetate, carbon nanowire, carbon nanosheet, carbon nanorod, carbon nanotube, graphite, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum doped zinc oxide (AZO), antimony-tin mixed oxide (ATO), network of metal/alloy nanowire, or a combination of two or more of the above materials. In an embodiment, the positive electrode is a cathode. In an embodiment, the negative electrode is an anode. In an embodiment, the negative electrode is a terminal for connection to an external circuit. In an embodiment, the positive electrode is a terminal for connection to an external circuit.
[0171] In certain embodiments, the transparent conductive oxide layer is selected from the group consisting of ITO, FTO, ZITO, and AZO. In certain embodiments, the metal electrode is selected from the group consisting of Al, Au, Cu, Cr, Ca, Mg, Bi, Ag, and Ti.
[0172] In certain embodiments, the solar cell or module described herein contains two transparent conductive oxide layers, each independently selected from the group consisting of ITO, FTO, ZITO, and AZO.
[0173] In certain embodiments, the hole transport layer comprises at least one of poly(3,4-ethylene dioxithiophene) (PEDOT) doped with poly(styrene sulfon icacid) (PSS), Spiro-OMeTAD, pm-spiro-OMeTAD, po-spiro-OMeTAD, dopants in spiro-OMeTAD, 4,4-biskptrichlorosilylpropylphenyl)pheny laminoThiphenyl (TPD-Si2), poly(3-hexyl-2,5-thienylene vinylene) (P3HTV), C60, carbon, carbon nanotube, graphene quantum dot, graphene oxide, copper phthalocyanine (CuPc), Polythiophene, poly(3,4-(1hydroxymethyl)ethylenedioxythiophene (PHMEDOT), n-dodecylbenzenesulfonic acid/hydrochloric acid doped poly(aniline) nanotubes (a-PANIN)s, poly(styrene sulfonic acid)-graft-poly(aniline) (PSSA-g-PANI), poly(9,9-dioctylfluorene)-co-N-(4-(1-methylpropyl)phenyl) diphenylamine (PFT), 4,4-bis(p-trichlorosilylpropylphenyl) phenylaminobiphenyl (TSPP), 5,5-bis(p-trichlorosilylpropylphenyl) phenylamino-2,20 bithiophene (TSPT), N-propyltriethoxysilane, 3,3,3-trifluo ropropyltrichlorosilane or 3-aminopropyltriethoxysilane, Poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) (PTAA), (Poly[[(2,4-dimethylphenyl)imino]-1,4-phenylene(9,9-dioctyl-9H-fluorene-2,7-diyl)-1,4phenylene], (PF8-TAA)), (Poly [[(2,4-dimethylphenyl)imino]-1,4-phenylene (6,12-dihydro-6,6,12,12tetraoctylindeno[1,2-b]fluorene-2,8-diyl)-1,4-phenylene]) (PIF8-TAA), poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB7), poly[N-90-heptadecanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothiadiazole)](PCDTBT), Poly[2,5-bis(2-decyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-(E)-1,2-di(2,20-bithiophen-5-yl) ethene](PDPPDBTE), 4,8-dithien-2-yl-benzo[1,2-d;4,5-d]bistriazole-alt-benzo[1,2-b:4,5b]dithiophenes (pBBTa-BDTs), pBBTa-BDT1, pBBTa-BDT2 polymers, poly(3-hexylthiophene) (P3HT), poly(4,4-bis(N-carbazolyl)-1,1-biphenyl) (PPN), triarylamine (TAA) and/or thiophene moieties, Paracyclophane, Triptycene, and Bimesitylene, Thiophene and Furan-based hole transport materials, Dendrimer-like and star-type hole transport materials, VO, VOX, MoC, WO, ReO, NiOx, AgOx, CuO, Cu2O, V2O5, CuI, CuS, CuInS2, colloidal quantum dots, lead sulphide (PbS), CuSCN, Cu2ZnSnS4, Au nanoparticles and their derivatives. Thiophene derivatives, Triptycene derivatives, Triazine derivatives, Porphyrin derivatives, Triphenylamine derivatives, Tetrathiafulvalene derivatives, Carbazole derivatives and Phthalocyanine derivatives. As used herein, when a material is referred to a derivate or as derivatives, such as Triphenylamine derivatives, the material contains Triphenylamine in its backbone structure. In certain embodiments, the hole transport layer is selected from the group consisting of PTAA, Spiro-OMeTAD, PEDOT:PSS, NiO, MoO.sub.3, V.sub.2O.sub.5, Poly-TPD, EH44, P3HT, and a combination thereof.
[0174] In certain embodiments, the electron transport layer comprises at least one of LiF, CsP, LiCoO, CsCO, TiOx, TiO, nanorods (NRs), ZnO, ZnO nanorods (NRs), ZnO nanoparticles (NPs), ZnO, AlO, CaO, bathocuproine (BCP), copper phthalocyanine (CuPc), pentacene, pyronin B, pentadecafluorooctyl phenyl-C60-butyrate (F-PCBM), C60, C60/LiF, ZnO NRS/PCBM, ZnO/cross-linked fullerene derivative (C-PCBSD), single walled carbon nanotubes (SWCNT), poly(ethylene glycol) (PEG), poly(dimethylsi loxane-block-methyl methacrylate) (PDMS-b-PMMA), polar polyfluorene (PF-EP), polyfluorene bearing lateral amino groups (PFN), polyfluorene bearing quaternary ammonium groups in the side chains (WPF-oxy-F), polyfluorene bearing quaternary ammonium groups in the side chains (WPF-6-oxy-F), fluorene alternating and random copolymer bearing cationic groups in the alkyl side chains (PFNBr DBT15), fluorene alternating and random copolymer bearing cationic groups in the alkyl side chains (PFPNBr), poly (ethylene oxide) (PEO), and fullerene derivatives. In certain embodiments, the electron transport layer is selected from the group consisting of C60, BCP, TiO.sub.2, SnO.sub.2, PCBM, ICBA, ZnO, ZrAcac, LiF, TPBI, PFN, Nb.sub.2O.sub.5, and a combination thereof.
[0175] In any of the embodiments above, the solar cell can further comprise a buffer layer. In certain embodiments, the buffer layer is disposed between the electron transport layer and said conductive electrode layer In certain embodiments, the buffer layer is selected from the group consisting of PDI, PDINO, PFN, PFNBr, SnO.sub.2, ZnO, ZrAcac, TiO.sub.2, BCP, LiF, PPDIN6, and TPBi. In certain embodiments, the buffer layer is BCP.
[0176] In certain embodiments, the back of the solar cell is encapsulated with a polymer. The polymer can be any polymer sheet sealed by encapsulant, or ethylene-vinyl acetate copolymer (EVA), polypropylene, polyolefin (POE), ethylene-propylene-diene monomer (EPDM), or cross-linkable encapsulants that can be laminated to the back of solar the cell.
[0177] In certain embodiments the conductive electrode layer has a thickness of about 1 nm to about 1000 m, about 100 nm to about 500 nm, about 1 m to about 500 m, about 250 m to about 1000 m, or about 250 nm to about 250 m. In certain embodiments, the conductive electrode has a thickness of about 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 550 nm, 1 m, 10 m, 20 m, 30 m, 40 m, 50 m, 60 m, 70 m, 80 m, 100 m, 150 m, 200 m, 250 m, 300 m, 350 m, 400 m, 450 m, 500 m, 550 m, 600 m, 700 m, 800 m, 900 m, or 100 m.
[0178] In certain embodiments, the transparent conductive oxide layer has a thickness of about 1 nm to about 1000 m, about 100 nm to about 500 nm, about 1 m to about 500 m, about 250 m to about 1000 m, or about 250 nm to about 250 m. In certain embodiments, the transparent conductive layer has a thickness of about 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 300 nm, 400 nm, 500 nm, 550 nm, 1 m, 10 m, 20 m, 30 m, 40 m, 50 m, 60 m, 70 m, 80 m, 100 m, 150 m, 200 m, 250 m, 300 m, 350 m, 400 m, 450 m, 500 m, 550 m, 600 m, 700 m, 800 m, 900 m, or 100 m.
[0179] In certain embodiments, the hole transport layer and electron transport layer each individually has a thickness of about 0.1 nm to about 10 m, about 0.5 nm to about 100 nm, about 10 nm to about 500 nm, about 300 nm to about 700 nm, about 100 nm to about 1 m, about 1 m to about 10 m, or about 800 nm to about 5 m. In certain embodiments, the hole transport layer and electron transport layer each individually has a thickness of about 0.1 nm, 0.5 nm, 1.0 nm, 2.0 nm, 5.0 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 1 m, 2 m, 3 m, 4 m, 5 m, 6 m, 7 m, 8 m, 9 m, or 10 m.
VI. Methods for Improving the Efficiency of a Wide Band Gap Solar Cell
[0180] In certain embodiments, the subject matter disclosed herein is directed to a method of improving the efficiency of a wide band gap solar cell, comprising: [0181] incorporating an enhanced perovskite film into a wide band gap solar cell; [0182] wherein the enhanced perovskite film comprises: [0183] (i) a composition of Formula I
APbI.sub.3-zBr.sub.z(I), [0184] wherein, [0185] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and [0186] z is between 0.01 and 1.0; [0187] and [0188] (ii) a tribromide salt; [0189] wherein the tribromide salt is present in the enhanced perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula (I); and [0190] wherein the efficiency of the wide band gap solar cell is improved relative to a wide band gap solar cell comprising a perovskite film of Formula I that lacks the tribromide salt.
[0191] As used herein, improving the efficiency of a wide band gap solar cell refers to increasing the power conversion efficiency (PCE) of a solar cell (which, in certain embodiments, can be a tandem solar cell) through modifications in a perovskite film active layer, as discussed in the methods and compositions described herein. In certain embodiments, such as discussed in the Examples, the above method results in an improvement in a wide band gap solar cell's efficiency (PCE), by 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99% compared to a wide band gap solar cell comprising a perovskite film of Formula I that lacks the tribromide salt.
[0192] In certain embodiments of the above method, z is between 0.05 and 1.0. In certain embodiments of the above method, z is between 0.05 and 1.0. In certain embodiments of the above method, z is 0.01, 0.02, 0.03, 0.04, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, or 1. In certain embodiments of the above method, z is between 0.01 and 0.05, 0.01 and 0.03, 0.01 and 0.15, 0.02 and 0.10, 0.01 and 0.5, 0.01 and 0.75, 0.3 and 0.6, 0.2 and 0.7, 0.1 and 0.8, 0.3 and 0.5, 0.4 and 0.9, or 0.4 and 0.6.
[0193] In certain embodiments of the above method, the tribromide salt is present in the enhanced perovskite film at a molar ratio of about 0.2% relative to the composition of Formula I.
[0194] The subject matter described herein is directed to the following embodiments: [0195] 1. An ink solution, comprising: [0196] (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), [0197] wherein, [0198] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), [0199] or a combination thereof; and [0200] z is between 0.01 and 1.0; [0201] (ii) a tribromide salt; [0202] and [0203] (iii) a solvent. [0204] 1A. The ink solution of embodiment 1, wherein z is between 0.05 and 1.0. [0205] 2. The ink solution of embodiment 1, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I. [0206] 3. The ink solution of embodiment 2, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.1 to about 0.5% relative to the composition of Formula I. [0207] 4. The ink solution of embodiment 2 or 3, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.2% relative to the composition of Formula I. [0208] 5. The ink solution of embodiment 1, wherein the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide. [0209] 6. The ink solution of embodiment 1, wherein the tribromide salt is an ammonium tribromide salt. [0210] 6a. The ink solution of embodiment 6, wherein the ammonium tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, and benzyltrimethylammonium tribromide. [0211] 7. The ink solution of embodiment 6 or 6a, wherein the ammonium tribromide salt is trimethylphenylammonium tribromide. [0212] 8. The ink solution of embodiment 1, wherein: [0213] A is selected from the group consisting of Cs, FA, and MA, or a combination thereof; and [0214] z is between 0.3 and 0.6. [0215] 9. The ink solution of embodiment 8, wherein: [0216] A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and [0217] z is 0.45. [0218] 10. The ink solution of embodiment 1, wherein the solvent is selected from the group consisting of dimethyl sulfoxide, dimethylformamide, dichloromethane, tetrahydrofuran, -butyrolactone, 2-methoxyethanol, N,N-Dimethylpropyleneurea, N-methyl-2-pyrrolidone, and acetonitrile, or a combination thereof. [0219] 11. The ink solution of embodiment 1, wherein: [0220] the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and [0221] the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the ink solution at a molar ratio of about 0.2% relative to the composition of Formula I. [0222] 12. A method for preparing a perovskite film using the ink solution of any one of embodiments 1-11, comprising: [0223] contacting the ink solution of any one of embodiments 1-11 using a fast coating process onto a substrate to form a film, wherein the fast coating process is selected from the group consisting of blade coating, slot die coating, shear coating, gravure coating, brush coating, syringe coating, and screen printing. [0224] 13. The method of embodiment 12, wherein the fast coating process is blade coating. [0225] 14. The method of embodiment 12, wherein the perovskite film prepared has a thickness of about 300 nm to about 2000 nm. [0226] 15. A perovskite film comprising: [0227] (i) a composition of Formula I:
APbI.sub.3-zBr.sub.z(I), [0228] wherein, [0229] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and [0230] z is between 0.01 and 1.0; and [0231] (ii) a tribromide salt. [0232] 15A. The perovskite film of embodiment 15, wherein z is between 0.05 and 1.0. [0233] 16. The perovskite film of embodiment 15, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula I. [0234] 17. The perovskite film of embodiment 16, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.1 to about 0.5% relative to the composition of Formula I. [0235] 18. The perovskite film of embodiment 16 or 17, wherein the tribromide salt is present in the perovskite film at a molar ratio of about 0.2% relative to the composition of Formula I. [0236] 19. The perovskite film of embodiment 15, wherein the tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, hexamethylenetetramine tribromide, pyridinium tribromide, 4-(dimethylamino)pyridinium tribromide, boron tribromide, phosphorus tribromide, aluminum tribromide, and benzyltrimethylammonium tribromide. [0237] 20. The perovskite film of embodiment 15, wherein the tribromide salt is an ammonium tribromide salt. [0238] 20a. The perovskite film of embodiment 20, wherein the ammonium tribromide salt is selected from the group consisting of tetrabutylammonium tribromide, tetramethylammonium tribromide, trimethylphenylammonium tribromide, and benzyltrimethylammonium tribromide. [0239] 21. The perovskite film of embodiment 20 or 20a, wherein the ammonium tribromide salt is trimethylphenylammonium tribromide. [0240] 22. The perovskite film of embodiment 15, wherein: [0241] A is selected from the group consisting of Cs, FA, and MA, or a combination thereof; and [0242] z is between 0.3 and 0.6. [0243] 23. The perovskite film of embodiment 22, wherein: [0244] A is Cs, FA, and MA, wherein the molar ratio of Cs to FA to MA is about 0.1:0.2:0.7; and [0245] z is 0.45. [0246] 24. The perovskite film of embodiment 15, wherein: [0247] the composition of Formula I is Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.2.55Br.sub.0.45; and [0248] the tribromide salt is trimethylphenylammonium tribromide, wherein the tribromide salt is present in the film at a molar ratio of about 0.2% relative to the composition of Formula I. [0249] 25. The perovskite film of any one of embodiments 15-24, wherein the film has a thickness of about 300 nm to about 2000 nm. [0250] 26. A wide band gap perovskite solar cell, comprising the perovskite film of any one of embodiments 15-25. [0251] 27. A solar cell comprising: [0252] one or more transparent conductive oxide layers; [0253] one or more conductive electrode layers; and [0254] one or more active layers, wherein at least one of said one or more active layers is a wide band gap material comprising the perovskite film of any one of embodiments 15-25. [0255] 28. The solar cell of embodiment 27 further comprising: [0256] one or more hole transport layers; and [0257] one or more electron transport layers. [0258] 29. The solar cell of embodiment 28, comprising: [0259] one transparent conductive oxide layer; [0260] one conductive electrode layer; [0261] one hole transport layer; [0262] one electron transport layer; and [0263] one active layer, wherein the active layer is a wide band gap material comprising the perovskite film of any one of embodiments 15-25. [0264] 30. The solar cell of embodiment 29, wherein: [0265] the hole transport layer is disposed on the transparent conductive oxide layer; [0266] the active layer comprising the perovskite film is disposed on the hole transport layer; [0267] the electron transport layer is disposed on the active layer; and [0268] the conductive electrode layer is disposed on the electron transport layer. [0269] 31. The solar cell of embodiment 29, wherein: [0270] the electron transport layer is disposed on the transparent conductive oxide layer; [0271] the active layer comprising the perovskite film is disposed on the electron transport layer; [0272] the hole transport layer is disposed on the active layer; and [0273] the conductive electrode layer is disposed on the hole transport layer. [0274] 32. The solar cell of embodiment 30, wherein: [0275] the transparent conductive oxide layer is ITO; [0276] the hole transport layer is PTAA optionally doped with TPFB; [0277] the electron transport layer is C.sub.60; and [0278] the conductive electrode layer is Cu or Ag; and wherein the solar cell further comprises a buffer layer of BCP or SnO.sub.2 disposed between the electron transport layer and the conductive electrode layer. [0279] 33. The solar cell of embodiment 32, wherein the perovskite film has a thickness of about 1000 nm. [0280] 34. The solar cell of embodiment 32 or 33, having a Power Conversion Efficiency of at least 21%. [0281] 35. The solar cell of embodiment 27, wherein said solar cell is a tandem solar cell, comprising two active layers; [0282] wherein a first sub cell comprises a first active layer, wherein the first active layer is the wide band gap material comprising the perovskite film of any one of embodiments 15-25; and [0283] a second sub cell comprises a second active layer, wherein the second active layer comprises silicon; [0284] wherein the first sub cell is disposed on the second sub cell; and a recombination layer is disposed between the first sub cell and the second sub cell. [0285] 36. The solar cell of embodiment 35, wherein the silicon is textured silicon. [0286] 37. The solar cell of embodiment 36, wherein the textured silicon is characterized by a truncated pyramid shape. [0287] 38. The solar cell of any one of embodiments 35-37, wherein the perovskite film has a thickness of about 1000 nm. [0288] 39. The solar cell of any one of embodiments 35-38, further comprising: [0289] one or more electron transport layers; [0290] one or more hole transport layers; and [0291] one or more interlayers. [0292] 40. The solar cell of embodiment 39, wherein: [0293] a first hole transport layer is disposed on the recombination layer; [0294] an interlayer is disposed on the first hole transport layer; and [0295] the perovskite film is disposed on the interlayer. [0296] 41. The solar cell of embodiment 40, wherein the interlayer is LiF or MgF.sub.2. [0297] 42. The solar cell of any one of embodiments 35-41, wherein the second sub cell is a silicon heterojunction cell. [0298] 43. The solar cell of embodiment 35, wherein the recombination layer is ITO. [0299] 44. The solar cell of any one of embodiments 35-43, having a PCE of at least 26%. [0300] 45. The solar cell of any one of embodiments 35-43, having a PCE of at least 27%. [0301] 46. The solar cell of any one of embodiments 35-43, capable of sustaining about 90% of its initial efficiency after about 500 hours. [0302] 47. The solar cell of any one of embodiments 27-43, wherein the wide band gap material has a band gap of about 1.50 eV to about 2.4 eV. [0303] 48. The solar cell of embodiment 47, wherein the wide band gap material has a band gap of about 1.65 eV. [0304] 49. A method of improving the efficiency of a wide band gap solar cell, comprising: [0305] incorporating an enhanced perovskite film into a wide band gap solar cell; [0306] wherein the enhanced perovskite film comprises: [0307] (i) a composition of Formula I
APbI.sub.3-zBr.sub.z(I), [0308] wherein, [0309] A is a cation selected from the group consisting of methylammonium (MA), tetramethylammonium (TMA), formamidinium (FA), cesium (Cs), rubidium (Rb), potassium (K), sodium (Na), butylammonium (BAH), phenethylammonium (PEA), phenylammonium (PHA), and guanidinium (GU), or a combination thereof; and [0310] z is between 0.01 and 1.0; [0311] and [0312] (ii) a tribromide salt; [0313] wherein the tribromide salt is present in the enhanced perovskite film at a molar ratio of about 0.05 to about 1.0% relative to the composition of Formula (I); and [0314] wherein the efficiency of the wide band gap solar cell is improved relative to a wide band gap solar cell comprising a perovskite film of Formula I that lacks the tribromide salt. [0315] 49A. The method of embodiment 49, where z is between 0.05 and 1.0.
[0316] The following examples are offered by way of illustration and not by way of limitation.
EXAMPLES
Materials and Methods
[0317] Formamidinium iodide (FAI), Formamidinium bromide (FABr), Methylammonium iodide (MAI), methylammonium bromide (MABr), and n-octylammonium iodide were purchased from Greatcell Solar company. PTAA (number-averaged molecular mass, Mn=7,000-10,000), Lead iodide (PbI.sub.2), lead bromide (PbBr.sub.2), cesium iodide (CsI), BCP, dimethyl sulfoxide, 2-methoxyethanol (2-ME), and toluene were purchased from Sigma-Aldrich. Trimethylphenylammonium tribromide (TPABr.sub.3) and 4-Isopropyl-4-methyldiphenyliodonium Tetrakis(pentafluorophenyl)borate (TPFB) were purchased from TCI chemicals. C.sub.60 was purchased from NANO-C company. Lithium fluoride (LiF) was purchased from Alfa Aesar. Copper and silver for thermal evaporation were obtained from Kurt J. Lesker company. Tetrakis(dimethylamino)tin(IV) was purchased from Strem Chemicals.
Perovskite Single-Junction Cells Fabrication
[0318] Patterned ITO-glass substrates were washed with isopropanol and acetone sequentially and then treated with UV/ozone for 15 min before use. The PTAA doped with 15 wt % TPFB dissolved in toluene with a concentration of 3 mg/mL was blade-coated on an ITO-glass substrate at 20 mm/s with a 200 m coating gap at room temperature. For blade coating Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 films, 1.6 M of Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 precursor dissolved in 2-ME with methylammonium hypophosphite (0.15 wt %), 1--phosphatidylcholine (0.05 wt %), n-octylammonium iodide (0.1 wt %), phenylethylammonium chloride (0.05 wt %), TPABr.sub.3 (0.1, 0.2, and 0.5 mol) and 25 mol % of DMSO (compared to Pb) was blade-coated on a PTAA-coated ITO substrate using N.sub.2 knife (20 psi) with a coating speed of 20 mm/s and a coating gap of 200 m. Then, the as-coated solid perovskite films were annealed at 120 C. in air for 4 min. For opaque devices, 18 nm of C.sub.60, 6 nm of BCP, and 80 nm of Cu were sequentially deposited by thermal evaporation. For semitransparent devices, the WBG perovskite films were thermally evaporated with 18 nm of C.sub.60, followed by coating 15 nm of SnO.sub.2 buffer layer by atomic layer deposition (ALD) using a Ultratech/Cambridge Nanotech Savannah S200 system under a base pressure of 0.05 torr. During SnO.sub.2 deposition, the substrate temperature was maintained at 85 C., and the Tetrakis(dimethylamino)tin(IV) (TDMASn) and water precursor temperatures were maintained at 60 C. and room temperature, respectively. To deposit a 15-nm-thick SnO.sub.2 layer, the following processing sequence was used for 2000 cycles: dosing sequences t1, t2, t3 and t4, where t1 and t3 refer to the times of precursor and oxidant-dosing and t2 and t4 refer to the times for purging, were 0.02, 10, 0.1 and 10 s, respectively. Then, 60 nm of ITO was sputtered from a 4-inch ITO target with 100 W power in a Kurt J. Lesker PVD 75 Pro Line tool on top of the SnO.sub.2. 500 nm of Ag fingers were thermally evaporated on top of the ITO. Finally, a PDMS layer with a negative silicon wafer's random pyramid texture (2-5 m pyramid size) was used as the antireflective coating.
Silicon Cells Fabrication
[0319] The silicon heterojunction (SHJ) bottom cell was fabricated with an n-type, 170-m-thick, double-side textured, monocrystalline czochralski silicon. The texturing process was completed in accordance with the procedures discussed in B. Chen et al., Joule 4, 850-864 (2020). Once the texturing process was complete, the wafers were cleaned in piranha, RCA-B, and buffered oxide etchant solutions prior to deposition of amorphous silicon (a-Si:H) layers. Intrinsic and p-type a-Si:H films (6 and 15 nm thick, respectively) were first deposited by plasma-enhanced chemical vapor deposition on the rear side of the wafer, and intrinsic and n-type a-Si:H films (6 and 8 nm thick, respectively) were then deposited on the front side. A 20-nm-thick ITO layer was sputtered from a 90/10 In.sub.2O.sub.3/SnO.sub.2 target in an MRC 944 tool on the front side of the wafer through a shadow mask to define 10.5 mm10.5 mm square cells. A 70-nm-thick ITO layer was also sputtered on the textured rear surface through the same shadow mask, followed by a 300-nm-thick silica layer spray coated through a stainless-steel mesh to define local contact openings, and finally, a 200-nm-thick sputtered silver layer. The silicon cells were then annealed at 200 C. for 20 min before fabricating the perovskite cells on top.
Perovskite/Silicon Tandem Cells Fabrication
[0320] The blade coating parameter of the doped PTAA on textured silicon was the same as that on the glass substrate, except a higher doped PTAA concentration was used (4 mg/mL). The WBG perovskite layer, top interface layer, and electrode were identical to the semitransparent device fabrication.
Device Characterization
[0321] The J-V characteristics of solar cells were recorded using a Keithley 2400 source meter with a Xenon lamp-based solar simulator (Oriel Sol3A, Class AAA Solar Simulator). The intensity of simulated light was calibrated to 100 mW cm.sup.2 by a silicon reference cell (Newport 91150 V-KG5). All devices were measured with a scan rate of 0.1 V/s in air at room temperature, and the delay time was 10 ms. For single-junction perovskite devices, the working area was defined by a photomask with an aperture area of 6.08 mm.sup.2. For tandem devices, the working area was defined by a photomask with an aperture area of 1 cm.sup.2.
PL, TRPL, and PL Mapping
[0322] The PL and TRPL spectra were measured by a PicoQuant Flue Time 300 instrument at room temperature. The excitation source was a 640 nm pulsed laser with a repetition frequency of 5 MHz. The PL mapping was conducted on a PicoQuant MT100 FLIM System at room temperature. A 640 nm laser pulsed at 2 MHz with an intensity of 0.7 sun per pulse was coupled into the confocal microscope and focused 2020 m onto the sample. The PL mapping was conducted over a region, and the PL intensity was recorded by a hybrid PMT detector.
Long-Term Operational Stability Test
[0323] Single-junction and tandem devices were encapsulated with a coating of CYTOP thin layer first (followed by annealing at 60 C. for 20 min), and then deposited with epoxy to create a seal over the active area covered with a glass. Encapsulated solar cells were kept in ambient environment and continuously illuminated under a xenon-lamp-based solar simulator (SF300A, Sciencetech) with 1-sun light intensity. During stability tests, the encapsulated devices under resistive load (determined from maximum power point) were coupled to a cooling stage maintained at 25 C.
Ion Migration Measurements
[0324] Activation energy for ion migration can be extracted from the temperature-dependent electrical conductivity by the Nernst-Einstein relation: (T)=(.sub.0/T)exp(E.sub.a/KT), where k is the Boltzmann constant, Go is a constant, and T is temperature.
[0325] Activation energy measurements were performed in a probe station under vacuum below 10 Pa with white light through a quartz window. The samples were placed on a metal plate with its temperature being controlled by a heater and injected with liquid N.sub.2. For conductivity, the current through the devices was stabilized for 5 min when an objective temperature was reached, before the current measurement was performed. A semiconductor analyzer (Keithley 2400) was used for current measurements with an applied bias of 10 V
Time-Resolved Microwave Conductivity (TRMC) Measurements
[0326] WBG perovskite films were deposited by blade coating on 25111.1 mm quartz plates identical to device films, and excited with 650 nm laser excitation at 10 Hz over a fluence range of 2 orders of magnitude to verify the data was collected in an intensity-independent regime of photoresponse kinetics. Samples were sealed within the microwave cavity and flushed continuously with dry N.sub.2 during all measurements. The relative change in microwave power, P, was recorded. This change in microwave power, P, results from the absorption of microwaves by photoinduced free electrons and holes in the sample, and is related to photoconductivity through the following equation: P/P=KG, where the calibration factor K is experimentally determined individually for each sample. Considering holes and electrons are created in equal pairs, the quantum generation efficiency multiplied by the sum of carrier mobilities is related to photoconductivity through: G=qF.sub.AI.sub.0(), where q is the elementary charge, =2.2 is the geometric factor for the X-band waveguide used, I.sub.0 is the incident photon flux, FA the fraction of light absorbed at the excitation wavelength, f is the quantum efficiency of free carrier generation per photon absorbed and Pm the sum of the mobilities of electrons and holes. Bi-exponential fits of the photoconductivity decay transients were weighted to calculate the average carrier lifetime using the equation: .sub.avg=(A.sub.0.sub.0+A.sub.1.sub.1)/(A.sub.0+A.sub.1).
External Quantum Efficiency (EQE) Measurements
[0327] Perovskite solar cells: EQE measurements were conducted with a Newport quantum efficiency measurement kit by focusing a monochromatic light beam with a wavelength from 300 to 900 nm onto the device.
[0328] Tandem solar cells: EQE measurements were performed via a PV Measurements QE-X10 tool. Bias lighting of a white light equipped with a long pass (>800 nm) filter and green light were applied to measure the EQE of the perovskite and silicon sub cells, respectively.
DFT Calculations
[0329] DFT calculations were performed using the CASTEP package. Perdew-Burke-Ernzerhof (PBE) correlation exchange functional at the generalized gradient approximation (GGA) level and ultrasoft pseudopotentials with a plane wave basis set energy cut-off of 500 eV were adopted. The geometric optimization of each periodic cell was carried out until the change in energy and force in each atom were less than 110-5 eV/atom and 0.03 eV/, respectively. The formation energy of an interstitial iodide was calculated by E_f=(defect)E(perf)_I+qE_F, where E(defect) and E(perf) were the total energy of the perovskite crystal with and without an interstitial iodide, I was the chemical potential of I which was chosen to be of the energy of an iodine molecule, q was the charge state of the interstitial iodide which was 1 and EF was the Fermi level of the perovskite.
Example 1: Trap Distribution in WBG Perovskite Solar Cells
[0330] Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.1-xBr.sub.x).sub.3 (x=0, 5%, 10%, 15%, 20%) perovskite devices with various amounts of bromide content were fabricated by air knife-assisted blade-coating (11, 20). All other conditions were kept unchanged to determine the influence of bromide incorporation on defect properties in WBG perovskites. The bromide ratio was intentionally controlled to be or below 20% to avoid the notable light induced phase segregation in WBG perovskites (17). The typical J-V curves of p-i-n structure Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.1-xBr.sub.x).sub.3 devices are shown in
[0331] Previous studies on pure iodide perovskites elucidated that the two main deep trap bands are induced by negative halide interstitials (I.sub.i.sup.) or positive halide interstitials (I.sub.i*). To further verify whether these deep traps in Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.1-xBr.sub.x).sub.3 are still iodine interstitial related defects, a small amount of CsI was added to Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 and the trap density change was measured. As shown in inset E of
[0332] Adding Br to the iodide perovskites increased the concentration of the I.sub.i.sup.+ defect band. A larger depth of I.sub.i.sup.+ can be explained by the slightly enlarged bandgap by Br incorporation. The increased I.sub.i.sup.+ density in WBG perovskites indicates a lower formation energy for these defects with Br incorporation. The Fermi level dependent formation energy of I.sub.i.sup.+ in MAPbI.sub.3 and MAPb(I.sub.0.85Br.sub.0.2).sub.3 was calculated, showing a lower formation energy of I.sub.i.sup.+ across the bandgap in MAPb(I.sub.0.85Br.sub.0.2).sub.3(
TABLE-US-00001 TABLE 1 Photovoltaic parameters of Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.1xBr.sub.x).sub.3 solar cells with and without TPABr.sub.3. With or Bandgap without V.sub.OC J.sub.SC PCE Composition (eV) TPABr.sub.3 (V) (mA/cm.sup.2) FF (%) Cs.sub.0.1FA.sub.0.2MA.sub.0.7PbI.sub.3 1.56 w/o 1.15 22.9 0.821 21.6 w/ 1.16 22.9 0.823 21.8 Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.95Br.sub.0.05).sub.3 1.59 w/o 1.16 22.4 0.801 20.8 w/ 1.18 22.4 0.809 21.4 Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.90Br.sub.0.10).sub.3 1.63 w/o 1.16 21.8 0.817 20.6 w/ 1.21 21.9 0.815 21.6 Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 1.65 w/o 1.17 20.9 0.786 19.3 w/ 1.23 21.2 0.813 21.2 Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.80Br.sub.0.20).sub.3 1.69 w/o 1.18 20.1 0.782 18.5 w/ 1.25 20.2 0.818 20.7
Example 2: Thick WBG Perovskite Single Junction Solar Cells
[0333] The influence of TPABr.sub.3 additive on thick perovskite device performance was examined. Triple-cation WBG perovskite Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 with a bandgap of 1.65 eV was used as an example. TPABr.sub.3 addition (0.2 mol %) did not significantly change the WBG perovskite film morphology as shown by the scanning electron microscopy (SEM) images in
TABLE-US-00002 TABLE 2 J-V characteristics of opaque perovskite solar cells (with and without TPABr.sub.3) with different perovskite thicknesses. Thickness J.sub.SC (nm) Device V.sub.OC (V) (mA/cm.sup.2) FF PCE (%) 450 Control 1.17 20.18 0.78 18.32 With TPABr.sub.3 1.23 20.66 0.81 20.58 660 Control 1.17 20.60 0.77 18.59 With TPABr.sub.3 1.23 20.91 0.81 20.91 820 Control 1.16 19.77 0.76 17.62 With TPABr.sub.3 1.23 20.83 0.82 21.02 1100 Control 1.15 19.60 0.75 16.87 With TPABr.sub.3 1.23 21.23 0.80 20.89
[0334] The J-V characteristics of 1-m-thick WBG perovskite devices with different concentrations of TPABr.sub.3 (0.1, 0.2, 0.5 mol % with respect to Pb) were also measured, the results for which are shown in
TABLE-US-00003 TABLE 3 SCAPS simulation parameters used for WBG perovskite solar cells. Parameters PTAA Perovskite C.sub.60 Thickness (nm) 10 1000 25 Bandgap (eV) 3.6 1.65 1.9 Electron affinity (eV) 1.8 3.93 4.1 Relative dielectric permittivity 3 31 5 CB effective DOS (1/cm.sup.3) 5.00E18 2.00E18 2.00E18 VB effective DOS (1/cm.sup.3) 5.00E18 2.00E18 2.00E18 Electron mobility (cm.sup.2/Vs) 1.00E3 1.00E1 1.00E2 Hole mobility (cm.sup.2/Vs) 1.00E3 1.00E1 1.00E2 Shallow donor density ND (1/cm.sup.3) 0.00 1.00E11 2.00E18 Shallow acceptor density NA (1/cm.sup.3) 2.00E17 1.00E13 0.00 Radiative recombination coefficient (cm.sup.3/s) 0.00 1.00E12 0.00 Note: Trap distributions in WBG perovskites determined from DLCP measurements.
Example 3: Transport and Recombination Property Changes
[0335] To understand the impact of TPABr.sub.3 on the charge transport and recombination dynamics of the WBG perovskites, a series of measurements was carried out. First, a transient photovoltage (TPV) measurement was used to compare the charge carrier recombination lifetime of the control and TPABr.sub.3-based devices with one-sun light bias. The carrier recombination lifetime obtained from TPV decay curves increased from 0.57 s to 1.24 s upon TPABr.sub.3 incorporation. Light intensity-dependent V.sub.OC measurements were performed, which can present key correlations between diode ideality factor (n.sub.id) and charge recombination behavior. As shown in inset B in
[0336] To understand which type of charge traps was reduced, the photoconductivity of the perovskite films was measured with charge transport layers, either PTAA or PCBM, to extract one charge type. Inset E in
[0337] The charge carrier diffusion length of electrons and holes in WBG perovskite films was obtained using a PL quenching study, in which C.sub.60 and PTAA were again used as electron and hole quenchers (insets G and H in
Example 4: Monolithic Perovskite/Silicon Tandem Cells
[0338] To evaluate the WBG perovskites for perovskite/silicon tandem solar cells, single-junction opaque and semitransparent devices were developed (
[0339] Perovskite/silicon tandem solar cells were then fabricated by blade coating optimized 1.65-eV WBG perovskites on fully textured silicon bottom cells with a mean texture size of 0.43 m(11, 31). The architecture of the perovskite/silicon tandem cells is shown in inset A of
[0340] The photostability of WBG perovskite films and devices was also examined. The PL stability of WBG perovskite films was monitored with and without TPABr.sub.3 at continuous 10-sun equivalent 640-nm laser illumination (
[0341] The operational stability of encapsulated semitransparent devices was then investigated at maximum power point under 1-sun illumination in ambient air (temperature: 25 C., humidity: 30-60%) (27). The evolution of corresponding device photovoltaic parameters is shown in
[0342] Provided in Tables 4 and 5 are summaries of the performance characteristics of the solar cells disclosed herein compared to those of the art.
TABLE-US-00004 TABLE 4 Performance summary of single-junction WBG perovskite solar cells reported in perovskite-silicon tandems V.sub.OC Bandgap V.sub.OC deficit J.sub.SC PCE Composition (eV) (V) (V) FF (mA/cm.sup.2) (%) Ref [Cs.sub.0.22FA.sub.0.78Pb(I.sub.0.85Br.sub.0.15).sub.3].sub.0.97(MAPbCl.sub.3).sub.0.03 1.67 1.22 0.45 0.832 20.20 20.4 (2a) Cs.sub.0.05(FA.sub.0.77MA.sub.0.23).sub.0.95Pb(I.sub.0.77Br.sub.0.23).sub.3. 1.68 1.224 0.466 0.82 20.70 20.8 (3a) Cs.sub.0.1MA.sub.0.9Pb(I.sub.0.9Br.sub.0.1).sub.3 1.63 1.167 0.463 0.82 21.00 20.1 (4a) (FA.sub.0.65MA.sub.0.2Cs.sub.0.15)Pb(I.sub.0.8Br.sub.0.2).sub.3 1.68 1.20 0.48 n/a n/a 20.7 (5a) Cs.sub.0.15(FA.sub.0.83MA.sub.0.17).sub.0.85Pb(I.sub.0.8Br.sub.0.2).sub.3 1.64 1.15 0.49 0.804 20.90 19.3 (6a) Cs.sub.0.1FA.sub.0.2MA.sub.0.7Pb(I.sub.0.85Br.sub.0.15).sub.3 1.65 1.25 0.43 0.83 21.1 21.9 This work
TABLE-US-00005 TABLE 5 Comparison of reported high-efficiency perovskite/silicon tandem solar cells Si Method for V.sub.OC J.sub.SC PCE architecture perovskite deposition (V) (mA/cm.sup.2) FF (%) Ref Flat Spin coating 1.90 19.26 0.795 29.15 (3a) Flat Spin coating 1.886 19.12 0.753 27.13 (2a) Flat Spin coating 1.756 19.2 0.792 26.7 (5a) Textured Vacuum deposition 1.788 19.53 0.731 25.24 (7a) Textured Blade coating 1.82 19.2 0.753 26.2 (4a) Textured Spin coating 1.78 19.1 0.756 25.71 (8a) Textured Vacuum deposition 1.735 19.8 0.731 25.1 (9a) Textured Blade coating 1.92 18.95 0.786 28.56 This work
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[0384] Efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental errors and deviations should be accounted for.
[0385] One skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which could be used in the practicing the subject matter described herein. The present disclosure is in no way limited to just the methods and materials described.
[0386] Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter belongs.
[0387] Throughout this specification and the claims, the words comprise, comprises, and comprising are used in a non-exclusive sense, except where the context requires otherwise. It is understood that embodiments described herein include consisting of and/or consisting essentially of embodiments.
[0388] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of the range and any other stated or intervening value in that stated range, is encompassed. The upper and lower limits of these small ranges which may independently be included in the smaller rangers is also encompassed, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.
[0389] Many modifications and other embodiments set forth herein will come to mind to one skilled in the art to which this subject matter pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the subject matter is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.