Photovoltaic devices containing cyclobutane-based hole transport materials

Abstract

The teachings herein relate to hole transport compounds containing a cyclobutyl moiety, which can be made into organic hole conductors and hole transport materials. Furthermore, optoelectronic and photoelectrochemical devices, in particular photovoltaic devices, organic-inorganic perovskite films, layered photovoltaic devices, p-n heterojunctions, dye-sensitized solar cells, organic solar cells, and solid-state solar cells comprising such hole transport materials or hole transport compounds are described. Notably, perovskite solar cell modules fabricated using the disclosed HTM compounds exhibit record efficiencies exceeding 19.0% for an active area of 30.24 cm 2 .

Description

Technical Field

[0001] This invention relates to hole transport compounds containing a central cyclobutyl moiety, organic hole conductors, and hole transport materials comprising such compounds, as well as optoelectronic or optochemical devices comprising such hole transport materials or hole transport compounds, particularly photovoltaic devices, pn heterojunctions, dye-sensitized solar cells, organic solar cells, and solid-state solar cells. The invention also relates to methods for preparing such organic hole conductors, layers, and optochemical devices. Background Technology

[0002] In recent decades, there has been a great deal of interest in renewable energy, especially the most powerful of them – the sun. Over the past two decades, the conversion of solar energy into electricity using thin-film third-generation photovoltaics (PV) has been extensively explored. Sandwich / monocell PV devices, consisting of a mesoporous photoanode with an organic / inorganic light collector, a redox electrolyte / solid hole conductor, and a counter electrode, have gained significant attention due to their ease of fabrication, flexibility in material selection, and low production costs.

[0003] In recent years, organic-inorganic hybrid perovskite solar cells (PSCs) have attracted widespread attention worldwide due to their low cost and ease of manufacture. [1] Since 2009, Miyasaka and colleagues have reported a power conversion efficiency (PCE) of 3.8% for the PSC. [2] Since then, the performance of these photovoltaic devices has improved significantly, with PCE now exceeding 25%.

[0004] Hole transport materials are one of the essential components for high-efficiency PV devices. These materials are responsible for transporting photogenerated carriers from the absorber to the electrodes. Hole transport materials should exhibit sufficient charge transport properties, sufficient energy levels, especially their highest occupied molecular orbital (HOMO) energy levels, and good thermal stability. [3] These materials are the weakest link in the entire PV device. Despite efforts to develop new hole transport materials, the field still uses 2,2',7,7'-tetra-(N,N-di-p-methoxyaniline)-9,9'-spirodifluorene (Spiro-OMeTAD) as the organic hole transport material (HTM). Unfortunately, the synthesis of this HTM is a lengthy and complex process, requiring expensive Pd catalysts, sensitive (n-butyllithium) Grignard reagents, corrosive (Br2) reagents, and low temperatures (-78°C). [4] Furthermore, to ensure optimal performance, Spiro-MeOTAD must be purified via sublimation, which inevitably increases the cost of the material.

[0005] Due to the high cost of synthesizing Spiro-OMeTAD, developing low-cost and efficient HTMs remains a key challenge for large-scale applications. Synthetic work replacing Spiro-MeOTAD has yielded several groups of HTM molecules that have exhibited good charge mobility and comparable performance in PV devices; however, the vast majority of these derivatives still require expensive catalysts and multi-step synthetic processes.

[0006] The synthesis of previously discovered hole transport materials involves expensive starting compounds that are not commercially available, require very low reaction temperatures, use corrosive reagents, and involve complex reaction steps (e.g., the five steps of the Spiro-OMetTAD synthesis). Therefore, the synthesis process is lengthy, time-consuming, and expensive, and has a significant environmental impact. This invention provides a hole transport material that can be used in high-efficiency solar cells, prepared using a minimal number of industrially scalable steps and readily available or low-cost materials, resulting in very low material cost and environmental impact.

[0007] Carbazole is known to be a promising core unit for molecular design because it can be substituted with a variety of desired groups, thereby enabling fine-tuning of optical and electrochemical properties. [5] Various carbazole-containing supports are commonly used as peripheral electron donor units to adjust HOMO energy levels and are applied to PSCs, exhibiting considerable photovoltaic performance. [6–8] This includes the star-shaped SGT series, [9,10] benzodithiazol

[11] Dimethylbenzene, [12,13] Examples of bipyridine and pyrene groups. Photodimeric carbazole is an attractive structural unit due to its simple, elegant, and green synthesis, and has been studied in early work as a material with no excimers and high hole carrier mobility. [16–18]

[0008] In this paper, we disclose the development of a novel hexamethylenetetramine (HTM) containing cyclobutane as a novel structural core component, with two differently substituted photodimeric carbazole arms branched to the sides. The specific arrangement of the carbazole groups on the cyclobutane core may also facilitate carrier transport processes. Furthermore, the large volume and sterically hindered rigid trans configuration create a competition between planarization and repulsive steric hindrance, resulting in a pseudo-spiral arrangement and diverse torsion angles. The effects of different peripheral carbazole substituents on various properties of the newly synthesized molecule have been systematically investigated. The novel cyclobutane-based HTM has been successfully applied to PSCs, showing a PCE up to 21% higher than spiro-OMeTAD and improved long-term stability under atmospheric conditions. Most importantly, to obtain the novel HTM, we applied a green chemistry-inspired protocol, proposing for the first time the synthesis of an HTM for PSCs that eliminates the use of hazardous substances, thereby reducing adverse environmental impacts without sacrificing efficiency. Summary of the Invention

[0009] The purpose of this invention is to provide novel hole-transporting organic compounds with suitable energy levels that do not require a sublimation step for purification after synthesis, as in the case of the synthesis of Spiro-OMeTAD.

[0010] The present invention also provides novel hole transport materials that provide higher power conversion efficiency (PCE) for photovoltaic devices containing perovskite, organic or organometallic dyes as sensitizers. Attached Figure Description

[0011] Figure 1 Microscopic images showing cross-sectional views of sample photovoltaic cells containing FTO / SnO2 / perovskite / Spiro-OMeTAD / Au (left) and FTO / SnO2 / perovskite / cyclobutyl-HTM / Au (right).

[0012] Figure 2 The current-voltage curves of the photovoltaic cell are shown, in which compounds 1, 5 and 7 corresponding to compounds V1244, V1366 and V1321, as well as Spiro-OMeTAD, are explored as hole transport materials. Figure 3 The current-voltage curves of the photovoltaic cell are shown, in which compounds 2, 3, 4 and 6, corresponding to compounds V1296, V1297, V1361 and V1367, were explored as hole transport materials. Detailed Implementation

[0013] The primary aim of these teachings is to introduce new compounds of formula (I) containing a cyclobutane moiety:

[0014] (I)

[0015] in,

[0016] R, R 1 It is a monocyclic or polycyclic system containing at least one pair of conjugated double bonds (-C=C=C-), wherein the polycyclic system comprises fused aromatic rings or monocyclic aromatic rings that are bonded to N, O, S, Se, or Si heteroatoms via covalent bonds or heterocyclic ring systems. The monocyclic or polycyclic system may be composed of H, halogen, cyano, C1-C20 cyanoalkyl, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkoxyalkyl, C1-C20 haloalkyl, or C1-C20 haloalkoxyalkyl, wherein the cyanoalkyl, alkyl, alkoxy, alkoxyalkyl, haloalkyl, haloalkoxyalkyl, C4-C20 aryl, C4-C20 alkylaryl, C4-C20 alkoxyaryl, C4-C20 alkenylarylalkyl, C4-C20 alkoxyarylalyl, or C4-C20 diekoxyarylalyl, and if they contain three or more carbons, they may be straight-chain, branched, or cyclic; and wherein the halogen is selected from Cl, F, Br, or I.

[0017] According to another embodiment, the hole-transporting compound of formula (I) containing a cyclobutyl moiety is selected from, but not limited to, compounds according to any one of formulas (1) to (52):

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026] In yet another embodiment, the present invention provides a hole transport material comprising at least one molecule having hole transport properties and a combination of two or more compounds selected from formula (I). The compounds of formula (I) are used as organic nonpolymer semiconductors. More specifically, the present invention provides a hole transport material of at least one compound selected from formula (I).

[0027] In another embodiment, the present invention also provides a photoelectric and / or photochemical device comprising a compound of formula (I). The photoelectric and / or photochemical device comprises a hole transport material, wherein the hole transport material comprises a compound of formula (I).

[0028] Photoelectric and / or photochemical devices are selected from the group consisting of: organic photovoltaic devices, photovoltaic solid-state devices, pn heterojunctions, organic solar cells, dye-sensitized solar cells, or solid-state solar cells.

[0029] In a preferred embodiment, the photoelectric and / or photochemical device, particularly a photovoltaic solid-state device, comprises a conductive support layer, a surface-enhancing support structure or electron transport layer, a sensitizer or sensitizer layer, a hole transport layer, a cyclobutyl-based compound of formula (I), a counter electrode, and / or a metal layer. Furthermore, the photoelectric and / or photochemical device is a photovoltaic solid-state device, which is a solid-state solar cell comprising an organic-inorganic perovskite as a sensitizer.

[0030] According to another embodiment, the photoelectric and / or photochemical device is a solar cell selected from organic solar cells, dye-sensitized solar cells, or solid-state devices.

[0031] In yet another embodiment, the hole transport layer of the optoelectronic and / or optochemical device, particularly the photovoltaic solid-state device, is made of a hole transport material comprising at least one small molecule hole transport material selected from compounds of formula (I).

[0032] The conductive support layer is preferably substantially transparent. "Transparent" means transparent to at least a portion, preferably the main portion, of visible light. Preferably, the conductive support layer is substantially transparent to visible light of all wavelengths or types. Furthermore, the conductive support layer may be transparent to invisible light (e.g., UV and IR radiation).

[0033] The conductive support layer preferably functions and / or contains a current collector to collect the current obtained from the photovoltaic solid-state device. The conductive support layer may comprise materials selected from indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), ZnO-Ga2O3, ZnO-Al2O3, tin oxide, antimony-doped tin oxide (ATO), SrGeO3, and zinc oxide, preferably coated on a transparent substrate (e.g., plastic or glass). In this case, the plastic or glass provides the supporting structure of the layer, while the referenced conductive material provides conductivity. Such support layers are commonly referred to as conductive glass and conductive plastic, respectively, and are preferred conductive support layers according to the invention.

[0034] According to another embodiment, the surface-area-enhancing scaffold structure is nanostructured and / or nanoporous. Therefore, the scaffold structure is preferably structured at the nanoscale. Compared to the surface area of ​​the conductive support, the structure of the scaffold increases the effective surface area. The scaffold structure is made of metal oxide and / or contains metal oxide as an electron transport material. For example, the material of the scaffold structure is selected from semiconductor materials such as Si, TiO2, SnO2, Fe2O3, ZnO, WO3, Nb2O5, CdS, ZnS, PbS, Bi2S3, CdSe, CdTe, GaP, InP, GaAs, CuInS2, CuInSe2, or combinations thereof.

[0035] According to one embodiment, the sensitizer layer of a photovoltaic solid-state device comprises at least one pigment selected from the group consisting of organic, inorganic, organometallic, organic-inorganic pigments, or combinations thereof. The sensitizer is preferably a light-absorbing compound or material. Preferably, the sensitizer is a pigment, and most preferably, the sensitizer is an organic-inorganic pigment. The sensitizer layer may comprise one or more pigments selected from the group consisting of: organometallic sensitizing compounds, metal-free organic sensitizing compounds, inorganic sensitizing compounds such as quantum dots, aggregates of organic pigments, nanocomposites, particularly organic-inorganic perovskites, and combinations thereof. For the purposes of this invention, any type of dye or sensitizer can be used in principle, including combinations of different types of dyes or different dyes of the same type.

[0036] According to a preferred embodiment, the sensitizer layer of the photovoltaic solid-state device is coated with a layer comprising a compound of formula (I). Preferably, the sensitizer layer comprises an organic-inorganic perovskite.

[0037] According to a preferred embodiment, the sensitizer or sensitizer layer comprises, is composed of, or is made of organic-inorganic perovskite. The organic-inorganic perovskite is provided under a film of a perovskite pigment, a mixture of perovskite pigments, or a perovskite pigment mixed with other dyes or sensitizers.

[0038] According to a further embodiment, the sensitizer layer contains another pigment besides the organic-inorganic perovskite pigment, said other pigment being selected from organic pigments, organometallic pigments, or inorganic pigments.

[0039] According to another embodiment, the photoelectric and / or photochemical device is a dye-sensitized solar cell (DSC) comprising a compound of formula (I) as a hole transport material and a pigment as a sensitizer, the pigment being selected from organic pigments, organometallic pigments, inorganic pigments, or combinations thereof.

[0040] For the purposes of this specification, the term "perovskite" refers to "perovskite structure" and not specifically to the perovskite material CaTiO3. For the purposes of this specification, "perovskite" encompasses and preferably refers to any material having a crystal structure of the same type as perovskite oxides, and materials in which a divalent cation is replaced by two separate monovalent cations. The perovskite structure has a general stoichiometry of AMX3, where "A" and "M" are cations and "X" is an anion. The "A" and "M" cations can carry multiple charges; for example, in the original perovskite mineral (CaTiO3), the A cation is divalent and the M cation is tetravalent.

[0041] In a further embodiment, the organic-inorganic perovskite layer material comprises a perovskite structure of formula (II):

[0042] AMX3 (II)

[0043] in

[0044] -A is an alkali metal ion, preferably Li. + Na + K + 、Rb + Cs + Ammonium or amidonium ions, wherein one or more hydrogen atoms are substituted with alkyl or acyl groups. The ammonium ions include mono-, di-, tri-, and tetraalkylammonium ions, wherein one or more hydrogen atoms are substituted with alkyl groups. Preferably, the substituent is an alkyl group or a group independently selected from C1-C6, preferably methyl or ethyl. The ammonium ions, N-alkylamidonium, and immidinium ions, wherein one or more hydrogen atoms are substituted with alkyl groups. Preferably, the amidonium or immidinium ions are selected from C1-C6 formamide groups, preferably formamidonium or acetamium groups. The hydrogen atoms in organic cation A may be substituted with halogens selected from F, Cl, I, and Br, preferably F or Cl.

[0045] Preferably, A is Cs + or methylammonium ion (MA) + ), or formamidinium ion (FA + ).

[0046] -M is a divalent metal cation selected from the following group: Cu 2+ Ni 2+ Co 2+ Fe 2+ Mn 2+ Cr 2+ Pd 2+ Cd 2+ 、Ge 2+ Sn 2+ Pb 2+ Eu 2+ or Yb2+ Pb is preferred 2+ Sn 2+ .

[0047] -X is a monovalent anion, independently selected from the following groups: Cl - ,Br - I - NCS - CN - and NCO - Preferred Cl - ,Br - Or I - X can be the same or different.

[0048] According to preferred embodiments, examples of organic-inorganic perovskites are: methyl ammonium lead halide, such as methyl ammonium lead iodide (CH3NH3PbI3); methyl mixed halide ammonium lead, such as CH3NH3PbClI2; lead formamidinium halide, such as HC(NH2)2PbI3, HC(NH2)2PbBr3 or HC(NH2)2PbCl2I; cesium lead iodide (CsPbI3) and cesium tin iodide (CsSnI3).

[0049] In a further embodiment, the organic-inorganic perovskite layer material comprises a mixed perovskite structure, wherein A is a mixture of two or more cations as defined above, and X is a mixture of two or more anions as defined above. Preferably, A is a mixture of two cations, M is Pb, and X is a mixture of two anions. Formula (II) can be expressed as formula (III):

[0050] A 1 1-y A 2 y PbX 1 3-z X 2 z (III)

[0051] in,

[0052] A 1 and A 2 It is an organic monovalent cation as defined above;

[0053] X 1 and X 2 The groups can be the same or different, and are composed of the following: Cl - ,Br - I - NCS - CN - and NCO - ;

[0054] y is in the interval between 0.1 and 0.9;

[0055] z is in the interval between 0.2 and 2;

[0056] General synthetic schemes for compounds of formula (I).

[0057] Hole-transporting compounds corresponding to general formula (I) containing cyclobutane moieties were prepared via a three-step synthetic route as shown in Scheme 1. According to the reference, the first step was the photochemical cyclodimerization of commercially available 9H-vinylcarbazole (Sigma-Aldrich) (J. Polym. Science A 1987, 25, 1463). Then, precursor A was brominated (Monatshefte Für Chemie-Chemical Monthly. 1971, 102, 711) to give 1,2-bis(3,6-dibromo-9H-carbazole-9-yl)cyclobutane (B). The final step was a Buchwald-Hartwig cross-coupling reaction of intermediate B with bis(4-methoxyphenyl)amine, bis(4-methylphenyl)amine, or diphenylamine to give target compounds 1-3. Compounds 4-6 were synthesized according to this method. Therefore, in the cases of compounds 4, 5 and 6, N-(4-methoxyphenyl)-9,9-dimethyl-9H-fluorene-2-amine, 9-ethyl-N-(4-methoxyphenyl)-9H-carbazole-3-amine and bis(9-ethyl-9H-carbazole-3-yl)amine are used instead of diphenylamine derivatives in the final step.

[0058]

[0059] For example, in the presence of palladium(II) acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide, via Suzuki cross-coupling between intermediate B and 4-methoxy-N-(4-methoxyphenyl)-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxoboronyl-2-yl)phenyl]-aniline (TCI Europe Ltd), a hole-transporting compound 7 (Scheme 2) containing a cyclobutyl moiety and corresponding to general formula (I) was synthesized:

[0060]

[0061]

[0062] General preparation procedure for perovskite solar cells

[0063] As the substrate for the device, etched fluorine-doped tin oxide (FTO) was used and cleaned prior to assembly. The cleaned FTO was then spin-coated with a solution of SnO2 and water, dried, and briefly heated to 190°C. The remaining steps were performed under nitrogen atmosphere. A perovskite precursor solution was prepared using a standard stock solution in DMSO / DMF and then spin-coated onto the substrate. The resulting perovskite film was annealed at 100°C. A solution of hole transport material was prepared using the hole transport compound of interest, chlorobenzene, and any additives. An HTM layer was applied to the perovskite film via spin-coating, followed by the deposition of gold electrodes via thermal evaporation. Figure 1 A cross-sectional view of a photovoltaic cell obtained using a cyclobutyl-based hole transport material, compound 5 (V1366), is shown.

[0064] Example

[0065] The following provides information on embodiments of actual implementations, describing the preparation and properties of compounds (1-7) of the present invention. This information is provided for illustrative purposes and does not limit the scope of the invention.

[0066] Synthesis of intermediates A and B

[0067] 1,2-Bis(9H-carbazole-9-yl)cyclobutane (A):

[0068]

[0069] Irradiate a solution of 9-vinylcarbazole (12 g, 62 mmol) in 125 mL of acetone for 15 hours at room temperature. Air is continuously bubbled through the solution. Filter the precipitate and recrystallize with acetone. Recover the precipitate as creamy crystals (8.5 g, 70.8% yield).

[0070] 1 H NMR (400MHz,THF-d6)δ8.02(d,J=8.0Hz,4H),7.72(d,J=8.0Hz,4H),7.34(t,J=7.6Hz,4 H),7.13(t,J=7.6Hz,4H),6.53–6.29(m,2H),3.22–2.99(m,2H),2.80–2.63(m,2H).

[0071] 13 C NMR (101MHz,THF)138.27,123.59,121.69,118.15,117.15,107.88,52.48,18.59.

[0072] 1,2-Bis(3,6-dibromo-9H-carbazole-9-yl)cyclobutane (B)

[0073]

[0074] Compound (A) (1.9 g, 4.9 mmol) was dissolved in THF (50 mL). Then, 20% H₂SO₄ (50 mL) solution was added. Next, KBr and KBrO₃ solution (69 mL H₂O, KBr 4.1 g, KBrO₃ 1.15 g) was slowly added dropwise at a rate of 10 mL / min, and the mixture was stirred at room temperature for 72 hours. The precipitate was collected by filtration, washed with water, and then washed three times with hot methanol. The precipitated product was recovered as white crystals of product B (3.1 g, 88.6% yield).

[0075] 1 H NMR (400MHz,THF-d6)δ8.26(s,4H),7.65(d,J=8.8Hz,4H),7.50(d,J=8.8Hz,4H),6.41–6.13(m,2H),3.14–2.96(m,2H),2.85–2.64(m,2H).

[0076] 13 C NMR (101MHz,THF)δ139.05,129.02,124.33,123.45,112.47,111.59,54.51,20.75.

[0077] Example 1

[0078] 1,2-Bis[3,6-bis(4,4'-dimethoxy)diphenylamino-9H-carbazole-9-yl]cyclobutane (see Scheme 1, Compound 1 or V1244):

[0079]

[0080] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and 4,4'-dimethoxydiphenylamine (0.98 g, 4.3 mmol, 6 equivalents) in anhydrous toluene (7 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalents), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalents), and sodium tert-butoxide (6 equivalents) were added, and the solution was refluxed under an argon atmosphere for 5 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was purified by column chromatography using a 3:9.5 v / v THF / n-hexane eluent. The resulting product was precipitated from acetone into 15 times excess ethanol. The precipitate was filtered off and washed with ethanol to collect product V1244. The precipitated product was recovered as a pale green solid (0.52 g, 56.3% yield).

[0081] 1 H NMR (400MHz,THF-d6)δ7.66–7.51(m,8H),7.08(d,J=8.8,1.7Hz,4H),6.88(d,J=8.8Hz,16H),6. 71(d,J=8.8Hz,16H),6.34–6.18(m,2H),3.69(s,24H),3.03–2.91(m,2H),2.70–2.60(m,2H).

[0082] 13 C NMR (101MHz,THF)δ154.95,142.47,141.24,137.03,124.27,124.13,123.92,116.39,114.17,110.55,54.75,54.54,20.62.

[0083] Composition analysis: Calculation, %: C 77.88; H 5.76; N 6.49.C 84 H 74 N6O8 was found to have the following properties: %C 77.97; H 5.72; N 6.41.

[0084] Example 2

[0085] 1,2-Bis[3,6-bis(4,4'-dimethyl)diphenylamino-9H-carbazole-9-yl]cyclobutane (V1296)

[0086] (See Scheme 1, Compound 2 or VV1296):

[0087]

[0088] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and 4,4'-dimethoxydiphenylamine (0.84 g, 4.3 mmol, 6 equivalents) in anhydrous toluene (7 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalents), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalents), and sodium tert-butoxide (6 equivalents) were added, and the solution was refluxed under an argon atmosphere for 22 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was recrystallized from ethanol / toluene 1:1 to give pale green crystals of V1296 (0.46 g, 55.4% yield). 1 H NMR (400MHz,THF-d6)δ7.67(s,4H),7.66(d,J=8.8Hz,4H),7.12(d,J=8.8Hz,4H),6.93(d,J=8.4Hz,16 H),6.85(d,J=8.4Hz,16H),6.39–6.25(m,2H),3.09–2.92(m,2H),2.79–2.59(m,2H),2.22(s,24H).

[0089] 13 C NMR (101MHz,THF)δ144.59,138.67,135.70,128.59,127.45,123.16,122.52,120.71,116.07,108.91,52.89,18.84,17.92.

[0090] Composition analysis: Calculations, %: C 86.41; H 6.39; N 7.20. C 84; H 74; N 6. Found, % C 86.24; H 6.45; N 7.31.

[0091] Example 3

[0092] 1,2-Bis(3,6-bisdiphenylamino-9H-carbazole-9-yl)cyclobutane (see Scheme 1, Compound 3 or V1297):

[0093]

[0094] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and diphenylamine (0.72 g, 4.3 mmol, 6 equivalent) in anhydrous toluene (7 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalent), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalent), and sodium tert-butoxide (6 equivalent) were added, and the solution was refluxed under an argon atmosphere for 27 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was purified by column chromatography using a 1:9 v / v THF / n-hexane eluent. The resulting product was precipitated from THF into 15 times excess n-hexane. The precipitate was filtered off and washed with hexane to collect product V1297. The precipitated product was recovered as a pale green solid (0.44 g, 58.7% yield).

[0095] 1 H NMR (400MHz, DMSO-d6) δ7.89(d,J=9.2Hz,4H),7.83(d,J=2.0Hz,4H),7.27–7.05(m,2 0H),6.97–6.79(m,24H),6.39–6.24(m,2H),2.93–2.75(m,2H),2.70–2.55(m,2H).

[0096] 13 C NMR (101MHz, DMSO) δ148.42,139.76,138.02,129.65,126.33,124.09,122.46,122.02,119.67,112.27,54.24,21.65.

[0097] Composition analysis: Calculations, %: C 86.50; H 5.54; N 7.96. C 76; H 58; N 6. Found, % C 86.65; H 5.50; N 7.85.

[0098] Example 4

[0099] 1,2-Bis{3,6-Bis[N-(9,9-dimethylfluoren-2-yl)-N-(4-methoxyphenyl)amino]-9H-carbazole-9-yl}cyclobutane (compound 4 or V1361):

[0100]

[0101] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and N-(4-methoxyphenyl)-9,9-dimethyl-9H-fluorene-2-amine (1.35 g, 4.3 mmol, 6 equivalents) in anhydrous toluene (10 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalents), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalents), and sodium tert-butoxide (6 equivalents) were added, and the solution was refluxed under argon atmosphere for 5 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was purified by column chromatography using 5.5:19.5 v / v THF / n-hexane as eluent. The resulting product was precipitated from THF into 15 times excess n-hexane. The precipitate was filtered off and washed with hexane, and V1361 was collected as a yellow-green solid. (0.67g, 57.3% yield).

[0102] 1 H NMR (400MHz, DMSO-d6) δ7.88(d,J=8.4Hz,4H),7.78(s,4H),7.55(d,J=7.8Hz,4H),7.4 9(d,J=7.8Hz,4H),7.28(d,J=7.2Hz,4H),7.24–7.16(m,8H),7.11(t,J=7.4Hz,4H), 7.00(d,J=8.6Hz,8H),6.93(s,4H),6.80(d,J=8.6Hz,8H),6.69(d,J=8.4Hz,4H),6. 42–6.23(m,2H),3.64(s,12H),2.92–2.77(m,2H),2.76–2.56(m,2H),1.17(s,24H).

[0103] 13 C NMR (101MHz, DMSO)δ155.83,154.82,153.15,149.03,141.15,140.42,139.09,137.50,131.40,127.37,126.76,126.35,1 25.32,123.94,122.86,121.12,119.41,119.19,118.17,115.27,114.25,111.87,55.55,53.96,46.56,27.29,27.25.

[0104] Composition analysis: Calculation, %: C 84.95; H 6.02; N 5.12.C 116 H 98 N6O2 was found to have the following properties: %C 84.85; H 6.06; N 5.15.

[0105] Example 5

[0106] 1,2-Bis{3,6-Bis[N-(9-ethylcarbazole-3-yl)-N-(4-methoxyphenyl)amino]-9H-carbazole-9-yl}cyclobutane (compound 5 or V1366):

[0107]

[0108] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and 9-ethyl-N-(4-methoxyphenyl)-9H-carbazole-3-amine (1.35 g, 4.3 mmol, 6 equivalents) in anhydrous toluene (10 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalents), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalents), and sodium tert-butoxide (6 equivalents) were added, and the solution was refluxed under argon atmosphere for 5 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was purified by column chromatography using 4.5:8 v / v THF / n-hexane as eluent. The resulting product was precipitated from THF into 15 times excess n-hexane. The precipitate was filtered off and washed with hexane, and V1366 was collected as a yellow-green solid. (0.71g, 60.7% yield).

[0109] 1 H NMR (400MHz,THF-d6)δ7.84(d,J=8.0Hz,4H),7.75(s,4H),7.69–7.58(m,8H),7.37( d,J=8.4Hz,4H),7.33–7.25(m,8H),7.19–7.11(m,8H),6.97(t,J=7.4Hz,4H),6. 92(d,J=8.8Hz,8H),6.68(d,J=8.8Hz,8H),6.38–6.26(m,2H),4.31(q,J=7.0Hz, 8H),3.65(s,12H),3.08–2.93(m,2H),2.71–2.58(m,2H),1.33(t,J=7.0Hz,12H).

[0110] 13 C NMR(101MHz,THF)δ154.55,143.30,141.94,141.50,140.44,136.86,136.20,125.19,124.98 124.35,123.79,123.69,123.56,122.77,120.21,118.13,116.09,115. 97,114.11,110.49,108.88,108.19,54.74,54.52,37.04,20.57,13.14.

[0111] Composition analysis: Calculation, %: C 81.82; H 5.76; N 8.52. 112 H 94 N 10 O4. Found: %C 81.91; H 5.70; N 7.50.

[0112] Example 6

[0113] 1,2-Bis{3,6-Bis[N-(9-ethylcarbazole-3-yl)-amino]-9H-carbazole-9-yl}cyclobutane

[0114] (Compound 6 or V1367):

[0115]

[0116] A solution of intermediate B (0.5 g, 0.7 mmol, 1 equivalent) and bis(9-ethyl-9H-carbazole-3-yl)amine (1.72 g, 4.3 mmol, 6 equivalent) in anhydrous toluene (12 mL) was purged with argon for 30 min. Then, palladium(II) acetate (0.02 equivalent), tri-tert-butylphosphonium tetrafluoroborate (0.027 equivalent), and sodium tert-butoxide (6 equivalent) were added, and the solution was refluxed under argon atmosphere for 6 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The resulting solid precipitate was filtered off. The crude product was purified by column chromatography using 4.5:8 v / v THF / n-hexane as eluent. The resulting product was precipitated from THF into 15 times excess ethanol. The precipitate was filtered off and washed with ethanol, and V1367 was collected as a yellow-green solid (0.62 g, 43.7% yield).

[0117] 1 H NMR(400MHz,THF-d6)δ7.92–7.50(m,24H),7.38–7.10(m,36H),6.93(t,J=7.4Hz,8H),6.46–6.29 (m,2H),4.24(q,J=6.8Hz,16H),3.11–2.94(m,2H),2.70–2.57(m,2H),1.28(t,J=6.8Hz,24H).

[0118] 13 C NMR (101MHz,THF)δ142.76,142.40,140.41,136.70,135.94,128.72,127.96,125.07,124.46,123.66 ,123.32,122.85,120.24,118.04,115.74,115.44,110.45,108.83,108.10,54.73,37.01,13.17.

[0119] Component analysis Calculation, %: C 84.39; H 5.77; N 9.84. C 140; H 114; N 14. Found, % C 84.28; H 5.83; N 9.89.

[0120] Example 7

[0121] 1,2-Bis|3,6-Bis{4-[N,N-(-bis(4-methoxyphenyl)amino]phenyl}-9H-carbazole-9-yl|cyclobutane

[0122] (See Scheme 2, Compound 7 or VV1321):

[0123]

[0124] A solution of intermediate B (0.1 g, 0.14 mmol, 1 equivalent) and 4-methoxy-N-(4-methoxyphenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)phenyl)aniline (0.61 g, 1.4 mmol, 10 equivalent) in anhydrous toluene (10 mL) was purged with argon for 10 min. Then, tetrakis(triphenylphosphine)palladium (0) (0.115 equivalent) and 2 M K₂CO₃ (4 mL) were added, and the solution was heated at 90 °C for 3 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and extracted with ethyl acetate and distilled water. The organic layer was dried over anhydrous Na₂SO₄, filtered, and the solvent was evaporated. The crude product was purified by column chromatography using a 4:8.5 v / v THF / n-hexane eluent. The resulting product was precipitated from THF into 15 times excess n-hexane. The precipitate was filtered off and washed with hexane, and V1321 was collected as a pale yellow-green solid (0.1 g, 43.9% yield).

[0125] 1 H NMR (400MHz,THF-d6)δ8.34(s,4H),7.76(d,J=8.8Hz,4H),7.59(d,J=8.8Hz,4H),7.51(d,J=8.6Hz,8H),7.02(d,J=8.8Hz,16 H),6.97(d,J=8.6Hz,8H),6.82(d,J=8.8Hz,16H),6.50–6.35(m,2H),3.74(s,24H),3.19–3.02(m,2H),2.86–2.68(m,2H).

[0126] 13 C NMR (101MHz,THF)δ154.17,145.70,139.26,137.80,132.26,130.62,125.34,12 4.20,122.65,122.48,119.37,115.94,112.55,108.21,52.85,52.74,18.86.

[0127] Component analysis Calculation, %: C 81.08; H 5.67; N 5.25.C 108 H 90 N6O8 was found to have the following properties: %C 81.35; H 5.54; N 5.23.

[0128] Example 8

[0129] Ionization potential measurement

[0130] The solid-state ionization potential (I) of the layers of compounds of formulas (1) to (7) pMeasurements were performed using electron emission in air (E. Miyamoto, Y. Yamaguchi, M. Masaaki, Electrophotography, 1989, Vol. 28, p. 364). Samples for ionization potential measurement were prepared by dissolving the material in THF and coating it onto an aluminum plate pre-coated with a methyl methacrylate and methacrylic acid copolymer adhesive layer approximately 0.5 μm thick. The thickness of the transport material layer was 0.5 μm. -1 μm. Photoelectric emission experiments are conducted in a vacuum, and high vacuum is one of the main requirements for these measurements. If the vacuum level is not high enough, sample surface oxidation and gas adsorption will affect the measurement results. However, in our case, the organic material studied is sufficiently stable to oxygen, and measurements can be performed in air. The sample is illuminated with monochromatic light from a quartz monochromator equipped with a deuterium lamp. The power of the incident beam is (2-5)·10 -8 W. A negative voltage of –300V is supplied to the sample substrate. The illumination component has a diameter of 4.5 × 15 mm. 2 The counter electrode of the slit is placed 8 mm from the sample surface. The counter electrode is connected to the input terminal of a BK2-16 electrometer and operates in open input mode for photocurrent measurement. A 10 -15 -10 -12 A strong photocurrent, I, flows in a circuit under illumination. The photocurrent I is strongly dependent on the incident photon energy, hυ. The plot of I is... 0.5 =dependence of f(hν). Typically, the dependence of photocurrent on the energy of the incident light quantum can be expressed by I. 0.5 The linear relationship between hν and the threshold is well described. The linear part of this dependency is extrapolated to the hν axis, and I p The value was determined to be the photon energy at the intercept point. p The results are shown in Table 1.

[0131] Example 9

[0132] Hole drift mobility measurement

[0133] Samples for hole mobility measurement were prepared as follows: A 1:1 THF solution of synthetic compounds 1-7, or a composition of the synthetic compounds with bisphenol-Z polycarbonate (PC-Z) (Iupilon Z-200 from Mitsubishi Gas Chemical), was spin-coated onto a polyester film with a conductive Al layer. THF was used for compounds 1-7. The layer thickness was in the range of 5-10 μm. Hole drift mobility was measured using electrostatic copying time-of-flight (XTOF) technology (Vaezi-Nejad, SM, Int. J. Electronics, 1987, 62, No. 3, 361-384). An electric field was generated by positive corona charging. Charge carriers were generated by irradiating the layer surface with a nitrogen laser pulse (pulse duration 2 ns, wavelength 337 nm). The surface potential drop due to pulse irradiation was as high as 1-5% of the initial potential before irradiation. The rate of surface potential drop, dU / dt, was measured using a capacitive probe connected to a broadband electrometer. The kink on the transient curve of dU / dt in a double logarithmic scale determines the passage time t. t Drift mobility is expressed by the formula μ = d 2 / U0t t The calculations were performed, where d is the layer thickness and U0 is the surface potential at the irradiation time. The results are shown in Table 1.

[0134] Table 1 Ionization potentials (I0.05) of hole transport compounds 1-7 and Spiro-OMeTAD p ) and charge mobility value (μ)

[0135]

[0136]

[0137]

[0138] Estimated synthesis of compounds 1, 5 and 6 I p The values ​​are in the range of 4.77 eV to 5.03 eV, and are close to the value of Spiro-OMeTAD (5.0 eV). Meanwhile, the I values ​​of compounds 2-4 and 7... p The values ​​are slightly higher, in the range of 5.28–5.48 eV. The measured charge mobility values ​​of synthesized compounds 1 and 3–7 are also comparable to those measured by Spiro-OMeTAD, while the charge mobility of compound 2 increases by about an order of magnitude under a weak electric field (μ0 = 10). -4 cm 2 V -1 S -1 ).

[0139] Example 10

[0140] Photovoltaic cell manufacturing and performance measurement

[0141] The performance of hole transport compounds 1-7 was tested in a mixed perovskite-based solar cell using a mesoporous TiO2 photoanode and an Au cathode (FTO / dense TiO2 / mesoporous dense TiO2 / mixed perovskite / V1244 / gold).

[0142] The fabrication of perovskite solar cells is as follows: Chemically etched FTO glass (Nippon Sheet Glass) was cleaned with a cleaning solution, acetone, and isopropanol. A thin film of SnO2 nanoparticles in a commercially available aqueous solution was applied at 1500 rpm·s. -1 The SnO2 solution was spin-coated onto the substrate at 3000 rpm for 30 seconds; the weight ratio of SnO2 solution to water was 1:3. Immediately after spin-coating, the substrate was dried on a hot plate at 80°C, and then heated at 190°C for 30 minutes. After cooling, PbI2, PbBr2, MABr, and FAI were mixed in a DMSO / DMF mixed solvent (1 / 8) to prepare 1.5M (FAPbI3). 0.85 (MAPbBr3) 0.15 Perovskite precursor solution. The perovskite solution was then continuously spin-coated onto the substrate at 1000 rpm for 10 seconds and 5000 rpm for 30 seconds, respectively. 1 mL of diether was added dropwise at 5000 rpm over 10 seconds. The perovskite film was annealed at 100 °C for 40 minutes. A reference solution was prepared by dissolving 91 mg Spiro-OMeTAD (Merck) and additives in 1 mL of chlorobenzene. As additives, 21 μL of lithium bis(trifluoromethanesulfonylimide) (520 mg in 1 mL acetonitrile), 16 μL of FK209 [tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III)tris(bis(trifluoromethanesulfonyl)imide] (375 mg in 1 mL acetonitrile), and 36 μL of 4-tert-butylpyridine were added from the stock solution. Solutions based on cyclobutyl hole-transporting compounds 1-7 were prepared by dissolving the synthesized compounds at an optimized concentration of 40 mM and additives in 1 mL of chlorobenzene. As additives, 15 μL of lithium bis(trifluoromethanesulfonylimide), 10 μL of FK209, and 26 μL of 4-tert-butylpyridine were added from the stock solution. HTM layers were formed by spin-coating the solutions at 4000 rpm for 20 seconds, followed by thermal evaporation deposition of a 70 nm thick gold electrode. All perovskite and HTM deposition preparations were performed in a nitrogen-filled glove box to minimize the influence of moisture.

[0143] Current-voltage characteristics were recorded by applying an external bias voltage to the battery, while the generated photocurrent was recorded using a digital source meter (Keithley Model 2400). The light source was a 450W xenon lamp (Oriel) equipped with a Schott K113 Tempax sunlight filter (PraezisionsGlas&Optik GmbH) to ensure the lamp's emission spectrum conformed to the AM1.5G standard. Accurate light intensity was determined using a calibrated silicon reference diode equipped with an infrared cutoff filter (KG-3, Schott) before each measurement. The voltage scan rate was 100 mV·s. -1 No prolonged light irradiation or forward bias was applied as pretreatment of the device before the measurement began. A 0.891cm... 2 The effective area is used to mask the battery in order to fix the effective area and reduce the impact of scattered light on small devices.

[0144] The performance characterization results are shown in Table 2. Figure 2 Typical current density-voltage (JV) curves (reverse scan) for PSCs of compounds 1 (V1244), 7 (V1321), and 5 (V1366) are shown with reference to spiro-OMeTAD. Devices with cyclobutyl-based HTMs exhibit photoelectric conversion performance comparable to spiro-OMeTAD, particularly compound 5 (V1366), which shows a higher photocurrent. However, devices with compounds 2 (V1296), 3 (V1297), 4 (V1361), and 6 (V1367) as cyclobutyl-based HTMs exhibit relatively low PCE (Power Consumption Efficiency). Figure 3 The degraded properties of compounds 2 (V1296) and 3 (V1297) can be explained by their fairly deep HOMO levels, which may lead to a mismatch with the perovskite valence band, while compound 6 (V1367) has one of the lowest hole drift mobilities in the series. On the other hand, compared with spiro-OMeTAD (with 24.17 mA·cm⁻¹), -2 J SC 1.114V of V OC Compared to 21.64% for 80.3% FF, a 21% PCE (by 24.38 mA·cm⁻²) was achieved for compound 5 (V1366) based devices. SC The composition of the side arm (1.092V open-circuit voltage and 79.1% FF) indicates that the molecular engineering of the side arm completely determines the performance of the final device.

[0145] Table 2 Photovoltaic cell performance compounds 1-7 and Spiro-OMeTAD

[0146]

[0147]

[0148] Example 11

[0149] Perovskite solar cell module manufacturing and performance measurement

[0150] The performance of hole transport compound 5 (V1366) as the HTM in a perovskite solar cell module was compared with that of a module using the standard HTM Spiro-OMeTAD.

[0151] A module consisting of eight cells connected in series was patterned using a Newport YAG laser. For the fabrication of the solar module, a 6.5cm × 7cm FTO substrate was patterned using a 1500mW laser with a scribing width of 80μm. A thin film of SnO2 nanoparticles in a commercially available aqueous solution was then applied at 1500 rpm. -1 The SnO2 solution was spin-coated onto the substrate at 3000 rpm for 30 seconds; the weight ratio of SnO2 solution to water was 1:3. After spin-coating, the substrate was immediately dried on a hot plate at 80°C, and then heated at 190°C for 30 minutes. After cooling, PbI2, PbBr2, MABr, and FAI were mixed in a DMSO / DMF mixed solvent (1 / 4) to prepare a 1M (FAPbI3)0.85 (MAPbBr3)0.15 perovskite precursor solution. Then, the perovskite solution was continuously spin-coated onto the substrate at 1000 rpm for 10 seconds and 4000 rpm for 30 seconds, respectively. 600 μL of chlorobenzene was added dropwise at 4000 rpm over 10 seconds. The perovskite film was annealed at 100°C for 40 minutes. A solution of compound 5 (V1366)HTM was prepared by dissolving 40 mM V1366 and additives in 1 mL of chlorobenzene. As additives, 15 μL of lithium bis(trifluoromethanesulfonylimide), 10 μL of FK209, and 26 μL of 4-tert-butylpyridine were added from the stock solution. An HTM layer was formed by spin-coating the solution at 4000 rpm for 30 seconds, followed by thermal evaporation deposition of a 70 nm thick gold electrode. Next, the SnO2 / perovskite / HTM layer was scribed using a 1000 mW laser with a scribing width of 500 μm. Finally, a gold electrode was deposited by thermal evaporation, and the gold layer was scribed using a 1000 mW laser with a scribing width of 100 μm.

[0152] Similar to photovoltaic cells, the modules were characterized, but with the following modifications. The effective area of ​​each module was calculated using Nano Measurer 1.2. The IPCE spectrum was recorded at approximately 10 mW·cm², provided by an array of white light-emitting diodes. -2The wavelength function under constant white light bias. The excitation beam from a 300W xenon lamp (ILC technology) was focused by a Gemini-180 dual monochromator (Jobin Yvon Ltd) and chopped at approximately 2Hz. The signal was recorded using an SR830 DSP lock-in amplifier (Stanford Research Systems). All measurements were characterized in air at room temperature.

[0153] To characterize the scale-up performance of the cyclobutyl-based HTM, we fabricated a 6.5 × 7 cm perovskite module based on compound 5 (V1366). This module exhibited a PCE of 19.06%, where J... SC 2.99 mA·cm⁻², V OC The voltage is 8.275V and the FF is 77%. To the best of our knowledge, over 19% of the highest PCE values ​​are based on perovskite modules that are not based on spiro-OMeTAD.

[0154] References

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Claims

1. A photovoltaic cell, comprising a conductive support layer, a surface-enhancing support layer, a sensitizer layer, a hole transport layer, and a counter electrode, wherein, The hole transport layer comprises a cyclobutane-based hole transport compound, wherein the cyclobutane-based hole transport compound is selected from the group consisting of: 1,2-Bis[3,6-bis(4,4'-dimethoxy)diphenylamino-9H-carbazole-9-yl]cyclobutane; 1,2-Bis{3,6-Bis[N-(9-ethylcarbazole-3-yl)-N-(4-methoxyphenyl)amino]-9H-carbazole-9-yl}cyclobutane; 1,2-Bis[3,6-Bis{4-[N,N-(-bis(4-methoxyphenyl)amino]phenyl}-9H-carbazole-9-yl]cyclobutane.

2. The photovoltaic cell according to claim 1, wherein, The battery is an organic photovoltaic cell, a photovoltaic solid-state cell, or a dye-sensitized solar cell.

3. The photovoltaic cell according to claim 1 further comprises organic-inorganic perovskite as a sensitizer.

4. The photovoltaic cell according to claim 3, wherein, The organic-inorganic perovskite has a perovskite-type structure of formula (II): AMX3 (II) in, A is selected from the following organic monovalent cations: Li + Na + K + 、Rb + Cs + Ammonium or amidon ions; wherein one or more hydrogen atoms of the ammonium or amidon ion are substituted with alkyl or acyl groups or halogens; wherein the ammonium ion is a mono-, di-, tri-, or tetraalkylammonium ion; and wherein the alkyl group is independently selected from C1-C6; M is a divalent metal cation selected from the following group: Cu 2+ Ni 2+ Co 2+ Fe 2+ Mn 2+ Cr 2+ Pd 2+ Cd 2+ 、Ge 2+ Sn 2+ Pb 2+ Eu 2+ or Yb 2+ ,and X is a monovalent anion, independently selected from the following: Cl - ,Br - I - NCS - CN - and NCO - .

5. The photovoltaic cell according to claim 3, wherein, The organic-inorganic perovskite has a mixed perovskite structure according to formula (III): A 1 1-y A 2 y PbX 1 3-z X 2 z(III) in, A 1 and A 2 It is selected from the following organic monovalent cations Li+, Na+, etc. + K + 、Rb + Cs + Ammonium or amidon ions; wherein one or more hydrogen atoms of the ammonium or amidon ion are substituted by an alkyl group, an acyl group, or a halogen; wherein the ammonium ion is a mono-, di-, tri-, or tetraalkylammonium ion; wherein the alkyl group is independently selected from C1-C6; X 1 and X 2 They are the same or different monovalent anions selected from the following: Clˉ, Brˉ, Iˉ, NCSˉ, CNˉ and NCOˉ; y lies in the interval between 0.1 and 0.9; and z is in the interval between 0.2 and 2.

6. The photovoltaic cell according to claim 4, wherein, A is a methylammonium ion or a formamide ion, and X is a Br₂. - Or I - .

7. The photovoltaic cell according to claim 5, wherein, A 1 A is a methylammonium ion. 2 For formamide ions, X 1 For Br - And X 2 For I - .

8. The photovoltaic cell according to claim 1, wherein, The surface enhancement support layer comprises Si, TiO2, SnO2, Fe2O3, ZnO, WO3, Nb2O5, CdS, ZnS, PbS, Bi2S3, CdSe, CdTe, SrTiO3, GaP, InP, GaAs, CuInS2, CuInSe2, or combinations thereof.

9. The photovoltaic cell according to claim 1, wherein, The hole transport layer also includes lithium bis(trifluoromethanesulfonylimide), [tris(2-(1H-pyrazole-1-yl)-4-tert-butylpyridine)-cobalt(III), tris(bis(trifluoromethanesulfonyl)imide) and 4-tert-butylpyridine].

10. The photovoltaic cell according to claim 1, wherein, The conductive support layer comprises a conductive material selected from the following: indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), ZnO-Ga2O3, ZnO-Al2O3, tin oxide, antimony-doped tin oxide (ATO), SrGeO3, and zinc oxide.

11. The photovoltaic cell according to claim 10, further comprising a transparent substrate on which the conductive material is applied.

12. The photovoltaic cell according to claim 1, wherein, Each layer is configured to have a planar structure.

13. The photovoltaic cell according to claim 1, wherein, The conductive support layer is adjacent to the surface-enhancing support layer. The support layer is located between the conductive support layer and the sensitizer layer. The sensitizer layer is located between the surface-enhancing support layer and the hole transport layer. The hole transport layer is located between the sensitizer layer and the counter electrode layer.

14. A photovoltaic device comprising two or more photovoltaic cells as described in claim 1, wherein, The photovoltaic cells are connected in series or in parallel.

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