High performance perovskite-sensitized mesoscopic solar cells

专利摘要:
The present invention relates to methods for preparing sensitized solar cells using organic-inorganic perovskites as sensitizers.
公开号:ES2579907A2
申请号:ES201590118
申请日:2014-05-05
公开日:2016-08-17
发明作者:Julian Alexander BURSCHKA；Mohammad Khaja Nazeeruddin；Michael Graetzel；Shahzada Ahmad
申请人:Abengoa Research SL；
IPC主号:

专利说明:


SENSITIZED MESOSCOPIC SOLAR CELLS WITH HIGH PERFORMANCE PEROVSKITA
DESCRIPTION
 5 Field of the inventionThe present invention relates to solar cells, in particular to sensitized solar cells, films and / or organic-inorganic perovskite layers, heterojunctions, working electrodes, photo-nodes, and to methods for producing same. The invention also relates to methods of applying organic-inorganic perovskites on a mesoscopic, nanoporous and / or nanostructured surface. BACKGROUND OF THE INVENTION AND PROBLEMS TO BE SOLVED Dye sensitized solar cells (DSC) are one of the 15 most promising third generation photovoltaic (PV) technologies.1 Solid state DSC embodiments have emerged as viable candidates in which the electrolyte is replaced by a material of hole transport (HTM) in the solid state, such as the triarylamine derivative 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9 '-spyrobifluorene (spiro-MeOTAD) 2 or more recently a tin halide perovskite3. Despite achieving remarkable power conversion efficiencies (CPE) of 7% 4 and 8.5% 3 for systems based on spiro-MeOTAD and tin halide perovskite, respectively, the performance of solid state DCS to date it has lagged behind its liquid counterparts that currently reach a PCE of 25 12.3% .5 The differences arise mainly from the recombination of charge carrier 10-100 times faster in the device in solid state compared to the homolog based on liquid electrolyte. In order to collect most of the photogenerated charge carriers, the thickness of the nanocrystalline oxide film is usually kept below 3 μm reducing the light that is collected by the molecular sensitizer and therefore the short-circuit photocurrent (Jsc) and the conversion efficiency of the device.6 Inspired by inorganic thin film photovoltaic devices, many attempts have been made to increase the optical absorption cross section of the light collectors in the solid state DCS. One approach is to replace the molecular sensitizer with quantum dots 35

semiconductors, such as PbS, CdS or Sb2S3, in which semiconductor nanoparticles often assume a double role of light absorption and transport of charge carriers.7 Although the performance of solar cells based on quantum dots has recently progressed an impressive way reaching an ECP of 7.5% 8, still remains below that of other mesoscopic products 5 in solid state. Recently, Kojima et al. introduced organic-inorganic hybrid perovskites that can be processed in solution, of formula CH3NH3PbX3 (X = Br, I) as sensitizers for DSC reaching an ECP of 3.8% in conjunction with mesoporous TiO2 and a liquid electrolyte based on iodide / triiodide. 9 Im et al. 10 subsequently improved the ECP to 6.5% by optimizing the composition of the redox electrolyte.10 In both cases, the photovoltaic devices are affected by poor stability due to the rapid dissolution of the perovskite in the liquid electrolyte. This problem could be overcome by using a configuration in the solid state, using the spiro-MeOTAD mentioned above as a 15-hole conveyor. In this way, Kim et al. achieved a PCE of 9% .11 At the same time, Lee et al. showed that such a device works even better when the mesoporous semiconductor TiO2 film was replaced by an isolating Al2O3 scaffold, indicating rapid electron transport through the perovskite phase.12 Although a high ECP of 10.9% with its highlighted cell, Lee 20 et al. they reported a very poor reproducibility and a large dispersion of the performance of the photovoltaic device. Since the publication of these pioneering studies, several investigations have continued with this concept.13-19 In all this previous work, the perovskite pigment was applied from a solution of the two precursors, PbX2 (X = I, Br or Cl ) and CH3NH3I, in a common solvent, i.e., 25 N, N-dimethylformamide (DMF) or y-butyrolactone (GBL). From the inventors' own experience, it has been found that there is a lack of control of the morphology of the perovskite crystals formed during this kind of processing in solution, it is most likely that this fact is the reason for the poor reproducibility of the performance of the FV cells. The present invention addresses the disadvantages of devices comprising liquid electrolytes, such as the problem of evaporation of the solvent and the penetration of water into the solar cell caused by the difficulty of a long-term sealing especially in cyclic temperature tests.

A further objective of the invention is to provide solar cells, in particular solid state solar cells that have even higher conversion efficiencies than the prior art devices. It was suggested that an efficiency of conversion of light energy into electrical power (η) of approximately 10% is a level necessary for commercial use. The invention seeks to provide an effective solar cell that can be rapidly prepared efficiently, reproducibly, using low cost, readily available materials, using a short manufacturing method based on industrially known manufacturing steps. The present invention addresses the stability problems observed with certain sensitized solar cells. SUMMARY OF THE INVENTION Notably, a novel sequential deposition technique for producing organic-inorganic perovskite films on nanoporous surfaces is reported. In one aspect, the invention provides methods comprising: a step of applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts; and a step of applying and / or depositing one or more ammonium halide salts or inorganic halide salts. The invention provides methods comprising the steps of: a) applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts; and b) applying and / or depositing one or more organic ammonium salts, wherein steps a) and b) can be carried out in any order, and said a) and / or b), said one or more salts of divalent metal or trivalent and / or said one or more organic ammonium salts are applied and / or deposited on a nanoporous surface and / or layer. According to one embodiment, the invention more specifically provides the steps of: c) applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts on a nanoporous layer; D) exposing and / or contacting the film obtained in step a) with a solution comprising one or more organic ammonium salts in a solvent. In one aspect, the invention provides a method for producing a solar cell, the method comprising steps a) and b) of the invention.

In one aspect, the invention provides a method for applying and / or producing a sensitizer on a nanoporous layer and / or surface, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for applying and / or producing a perovskite layer on a nanoporous layer and / or surface, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for coating a nanoporous layer and / or a semiconductor layer, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for producing a photo-anode 10 and / or a working electrode, for example for a solar cell, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for producing a heterojunction, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for producing a nanocrystalline organic-inorganic perovskite layer, the method comprising steps a) and b) of the invention. In one aspect, the invention provides a method for applying and / or producing a perovskite layer on a surface and / or layer having any one or more of the following characteristics: 20 - the layer / surface has a surface area ratio of gram from 20 to 200 m2 / g, preferably from 30 to 150 m2 / g and most preferably from 60 to 120 m2 / g; - the layer / surface comprises and / or is prepared from nanoparticles, such as nanoparticles, nanocolumns and / or nanotubes; - the layer / surface is nanocrystalline; 25 - the layer / surface is mesoporous; - the layer / surface has an overall thickness of from 10 to 3000 nm, preferably from 15 to 1500 nm, more preferably from 20 to 1000 nm, still more preferably from 50 to 800 nm and most preferably from 100 to 500 nm; - the surface has a porosity of 20 to 90%, preferably 50 to 80%; 30 - the surface comprises and / or consists essentially of one or more selected from a metal oxide, a transition metal oxide and a semiconductor material; the method comprising steps a) and b) of the invention. In one aspect, the present invention provides a method for producing a solar cell, the method comprising the steps of:

- provide a current collector and a nanoporous layer; - applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts; - exposing and / or contacting the film obtained in the previous step with a solution comprising one or more organic ammonium salts in a solvent, thereby obtaining a layer comprising an organic-inorganic perovskite; and - providing a counter electrode. In one aspect, the invention provides a method for producing a solar cell, the method comprising the steps of: providing a current collector; - applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts; - applying and / or depositing a layer comprising one or more ammonium salts; and - providing a counter electrode; Wherein said one or more divalent or trivalent metal salts and / or said one or more ammonium salts are deposited on a nanoporous layer, forming an organic-inorganic perovskite layer. In one aspect, the invention provides a method for producing a nanocrystalline organic-inorganic perovskite layer, the method comprising the steps of: - providing a nanoporous layer; - applying and / or depositing a film comprising and / or consisting essentially of one or more divalent or trivalent metal salts on said nanoporous scaffold layer; 25 - exposing the film obtained in the previous step to a solution comprising one or more organic ammonium salts in a solvent, thereby obtaining said organic-inorganic perovskite on said nanoporous scaffold layer. In one aspect, the invention provides a method for producing a nanocrystalline organic-inorganic perovskite layer, the method comprising the steps of: - applying and / or depositing a film comprising one or more divalent or trivalent metal salts; - applying and / or depositing a layer comprising one or more ammonium salts; and, - providing a counter electrode; 35

wherein said one or more divalent or trivalent metal salts and / or said one or more ammonium salts are deposited on a nanoporous layer, forming an organic-inorganic perovskite layer on said nanoporous layer. In one aspect, the invention provides a nanocrystalline organic-inorganic perovskite layer. In additional aspects, the invention provides an organic-inorganic perovskite layer and solar cells obtainable by the methods of the invention. In additional aspects, the present invention provides a solar cell comprising a current collector, a nanoporous layer, a nanoporous scaffolding structure, a perovskite layer and a counter electrode. In one aspect, the invention provides a solar cell comprising a nanoporous layer and an organic-inorganic perovskite layer in contact with said nanoporous layer, wherein said perovskite comprises an organic-inorganic perovskite that forms crystals of a length of <50 nm, preferably <45 nm, more preferably <40 nm. In one aspect, the invention provides a solar cell comprising an organic-inorganic perovskite layer in contact with a nanoporous layer, said solar cell having a power conversion efficiency (PCE) of  12%, preferably of  13% when is exposed to AM 1.5G light. BRIEF DESCRIPTION OF THE FIGURES Figure 1 illustrates the transformation of Pbl2 into CH3NH3PbI3 within the nanopores of a mesoscopic TiO2 film according to an embodiment of the invention described in the examples section. A) SEM of the cross section of a mesoporous TiO2 film 25 infiltrated with PbI2. B) Change in optical density at 550 nm of a film of that type monitored during transformation. C) Change in the emission intensity at 520 nm monitored during the transformation. Excitation at 460 nm. D) Change in emission intensity at 775 nm monitored during transformation. Excitation at 660 nm. E) X-ray diffraction spectra of PbI2 on glass and porous TiO2 / glass before and after the transformation. The immersion time was 60 s in both cases. Figure 2 shows a SEM of the cross section of a complete photovoltaic device of an embodiment of the present invention. Note that the

Thin TiO2 compact layer present between the FTO and the mesoscopic composite is not resolved in the SEM image. Figure 3 shows the characterization of the photovoltaic device and long-term stability of solar cells according to embodiments of the invention. A) JV curves of a photovoltaic device measured at 95.6 mW cm-2 of solar radiation of AM 1.5G 5 simulated (solid line) and in the dark (dashed line). B) Spectrum of IPCE. The right axis indicates the integrated photocurrent that is expected to be generated with 1.5G AM irradiation. C) Spectrum of LHE. D) Spectrum of APCE derived from the IPCE and LHE. E) Evolution of the photovoltaic parameters with constant illumination at approximately 100 mW cm-2 and 45ºC. During aging, the device is maintained at its MPP using MPP tracking. Figure 4 shows the JV characteristics of a highlighted solar cell that reaches 15% PCE according to an embodiment of the invention. The curves of JV were measured at 96.4 mW cm-2 of simulated AM 1.5G solar irradiation (solid line) and in the dark (dashed line). Figure 5 shows MEB photographs of AMX2 perovskite crystals deposited on fluoride-doped tin oxide glass substrate obtained by means of a two-stage procedure (EF) and AMX2 crystals obtained in a single-stage method (FIG. AD) for comparison. Figures 6A and B show the J-V curves of solar cells according to an embodiment of the present invention at 100 MW cm-2 illumination, before (A) and after (B) 500 hours aging. The J-V curves are measured with the same white LED light that was used for the stability test. Figures 7A and 7B show different embodiments of solar cells of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention encompasses the formation of an organic-inorganic perovskite layer. Preferably, the organic-inorganic perovskite layer is provided on a surface and / or on a layer. Preferably, said surface and / or layer is structured, for example structured on a nanoscale. The nanostructured layer can also be referred to as scaffolding, since it preferably forms the support of the perovskite layer to be deposited and / or applied thereto. For example, the nanostructured layer may be referred to as

nanoporous or nanostructured scaffolding or scaffolding layer, for example. In addition, the nanostructured layer preferably has a nanostructured surface. According to one embodiment, said nanostructured layer has a surface area ratio per gram of 20 to 200 m2 / g, preferably 30 to 150 m2 / g and most preferably 60 to 120 m2 / g. According to one embodiment, the nanoporous layer comprises and / or is prepared from nanoparticles, such as spherical nanoparticles, nanoparticles, nanocolumns, nanotubes and / or nanoparticles of any other geometric shape. The nanoparticles preferably have average sizes and / or dimensions in the range of 2 to 10 300 nm, preferably 3 to 200 nm, even more preferably 4 to 150 nm and most preferably 5 to 100 nm. "Dimension" or "size" with respect to the nanoparticles means in the present document extensions in any direction of the space, preferably the maximum average extension of the nanoparticles. In the case of substantially spherical or ellipsoid particles, it preferably refers to the average diameter. In the case of nanosheets, the indicated dimensions refer to the length and thickness. Preferably, the size of the nanoparticles is determined by transmission electron microscopy (MET), scanning electron microscopy (SEM) or surface area analysis of Brunauer-Emmett-Telter (BET) as disclosed by Etgar et al. According to one embodiment, the layer is nanocrystalline. According to one embodiment, the surface is mesoporous. According to one embodiment, the surface is nanoporous. According to one embodiment, the layer has a porosity of 20 to 90%, preferably 50 to 80% as determined by analysis of the surface area of Brunauer-Emmett-Teller (BET). According to one embodiment, the nanoporous layer comprises and / or consists essentially of one or more selected from a metal oxide, a transition metal oxide and a semiconductor material. According to one embodiment, the nanoporous layer or surface has an overall thickness of from 10 to 3000 nm, preferably from 15 to 1500 nm, more preferably from 20 to 1000 30 nm, still more preferably from 50 to 800 nm and most preferably from 100 to 800 nm. 500 nm. According to one embodiment, the nanoporous layer comprises or consists essentially of Si, SiO2, TiO2, Al2O3, Ga2O3, Y2O3, In2O3, ZrO2, HfO2, SnO2, Fe2O3, ZnO, WO3, MoO3, Nb2O5, CdS, ZnS, PbS, Bi2S3, CdSe, CdTe, SrTiO3, GaP, InP, 35

GaAs, CulnS2, CuInSe2, CaTiO3, SrTiO3, BaSnO3, Zn2SnO4 and combinations thereof. According to a preferred embodiment, the nanoporous layer comprises, consists essentially of or consists of one or more selected from Si, TiO2, SnO2, Fe2O3, ZnO, WO3, Nb2O5, CdS, ZnS, PbS, Bi2S3, CdSe, CdTe, SrTiO3, GaP , InP, GaAs, 5 CulnS2, CulnSe2 and combinations thereof. Even more preferred materials of the nanoporous layer are Si, TiO2, SnO2, ZnO, WO3, Nb2O5 and SrTiO3, for example. TiO2 is the most preferred. The skilled person is aware of how to produce layers and / or surfaces having one or more of the characteristics specified above, for example 10 nanoporous or nanostructured surfaces. For example, the layer can be prepared by screen printing or spin coating, for example as is conventional for the preparation of porous semiconductor layers (for example TiO2) in dye-sensitized solar cells, see for example, Thin Solid Films 516, 4613-4619 (2008) or Etgar et al., Adv. Mater. 2012, 24, 2202-2206. 15 layers and nanoporous semiconducting structures have been disclosed, for example, in EP 0333641 and EP 0606453. In the event that a solar cell is to be produced, the scaffolding or the nanostructured layer is preferably provided on a current collector. or on a sublayer, said sublayer being provided on a current collector. Said nanostructured layer and / or said perovskite layer is preferably in electrical contact with said current collector. For the purpose of the present description, the expression "in electrical contact with" means that electrons or holes can pass from one layer to the other layer with which it is in electrical contact, at least in one direction. In particular, considering the flow of electrons in the operating device exposed to electromagnetic radiation, it is considered that the layers through which electrons and / or holes flow are in electrical contact. The expression "in electrical contact with" does not necessarily mean that the electrons and / or voids can move freely in any direction between the layers. According to one embodiment, the solar cell of the invention preferably comprises one or more support layers. The support layer preferably provides the physical support of the device. In addition, the support layer preferably provides protection from physical damage and therefore

it delimits the solar cell with respect to the outside, for example on at least one of the two main sides of the solar cell. According to one embodiment, the solar cell can be constructed by applying the different layers in a sequence of steps, one after another, on the support layer. Therefore, the support layer can also serve as a starting support for the manufacture of the solar cell. Support layers 5 can be provided on only one or both opposite sides of the solar cell. The support layer, if present, is preferably transparent, to allow light to pass through the solar cell. Of course, if the support layer is provided on the side of the solar cell that is not directly exposed to the light to be converted into electrical energy, the support does not necessarily have to be transparent. However, any support layer provided on the side that is designed and / or adapted to be exposed to light for the purpose of energy conversion is preferably transparent. "Transparent" means transparent to at least one part, preferably a major part of the visible light. Preferably, the support layer is substantially transparent at all wavelengths or types of visible light. In addition, the support layer may be transparent to non-visible light, such as for example UV and IR irradiation. Conveniently, and according to a preferred embodiment of the invention, a conductive support layer is provided, said conductive support layer serving as a support as described above as well as a current collector. Therefore, the conductive support layer replaces or contains the support layer and the current collector. The conductive support layer is preferably transparent. Examples of conductive support layers are conductive glass or conductive plastic, which are commercially available. For example, the conductive support layer comprises a material selected from tin oxide doped with indium (ITO), tin oxide with fluorine (FTO), ZnO-Ga2O3, ZnO-Al2O3, tin oxide, tin oxide doped with antimony (ATO), SrGeO3 and zinc oxide, coated on a transparent substrate, such as plastic or glass. According to another embodiment, the current collector can also be provided by a sheet of conductive metal, such as for example a zinc or titanium sheet. Non-transparent conductive materials can be used as current collectors, in particular on the side of the device that is not exposed to the light to be captured by the device. Such metal sheets have been used as current collectors, for example, in flexible devices, such as those disclosed by Seigo Ito et al, Chem. Commun. 2006, 4004-4006. 35

According to a preferred embodiment, the nanoporous layer is provided on a sublayer and / or metal oxide layer. Preferably, the sublayer is provided between the current collector and said nanoporous layer. Preferably, the sublayer is conductive. The sublayer can be prepared from a metal oxide. Preferably, it is preferably prepared from a dense or compact semiconductor material. The sublayer can be prepared from the same materials as the nanoporous scaffold layer, but is usually less porous and more dense. The sublayer can facilitate the application of the surface and / or nanoporous layer. The sublayer preferably has a thickness of 1-120 nm (nanometers). It can be applied, for example, by deposition of atomic layers (ALD). In this case, the thickness of this layer is preferably 1 nm to 25 nm. The sublayer can also be deposited by spray pyrolysis, for example, which normally results in a thickness of preferably 10 nm to 120 nm. The method of the invention preferably comprises the steps of: a) applying and / or depositing a film comprising one or more divalent or trivalent metal salts; and b) applying and / or depositing one or more organic ammonium salts, wherein steps a) and b) can be carried out in any order, and said a) and / or b), said one or more salts of divalent metal or trivalent and / or said one or more organic ammonium salts are applied and / or deposited on said nanoporous surface and / or layer. According to one embodiment, said one or more divalent or trivalent metal salts are selected from salts of formula MX2 or NX3, wherein: M is a divalent metal cation selected from the group consisting of Cu2 +, Ni2 +, Co2 +, Fe2 +, Mn2 +, Cr2 +, Pd2 +, Cd2 +, Ge2 +, Sn2 +, Pb2 +, Eu2 + or Yb2 +; N is selected from the group of Bi3 + and Sb3 +; Any X is independently selected from CI-, Br-, I-, NCS-, CN- and NCO-. Preferably, said metal salt is MX2. According to a preferred embodiment, said metal salt is a metal halide. Preferably, in the case where two or more different metal salts are used, these are different metal halides. According to one embodiment, said organic ammonium salt is selected from AX, AA'X2 and BX2, with independently selected A and A 'of monovalent, organic cations selected from primary, secondary, tertiary or quaternary organic ammonium compounds, including ring systems and hetero-rings containing N, having A and A 'from 1 to 60 carbons and from 1 to 20 heteroatoms; and being B a 35

bivalent, organic cation selected from primary, secondary, tertiary or quaternary organic ammonium compounds having from 1 to 60 carbons and from 2 to 20 heteroatoms and having two nitrogen atoms positively charged. Preferably, said organic ammonium is selected from AX. Preferred embodiments for A, A ', B, M, N and X are disclosed elsewhere in this specification, for example with respect to preferred perovskites of the invention. In the method of the invention, step a) is preferably carried out before step b), but the present invention also encompasses, in other embodiments, that step b) and step a are carried out first. ) after. According to one embodiment, said film of said one or more divalent or trivalent metal salts are applied and / or deposited (step a)) by any one or more selected from: deposition from a solution, deposition from a dispersion , for example, of a colloidal dispersion, deposition by thermal evaporation, deposition by cathodic bombardment, electrodeposition, deposition of atomic layers (ALD) and formation of the metal salt in situ, respectively, in situ. The latter comprises the possibility of applying and / or depositing the divalent or trivalent metal salt in a two- or multi-stage process, for example by depositing a precursor on the surface which is subsequently transformed into the divalent or trivalent metal salt. Examples of deposition from a solution include, for example, drip deposit, spin coating, dip coating, curtain coating, spray coating and ink jet printing for example. According to one embodiment, said film of a divalent or trivalent metal salt is applied and / or deposited by spin coating a solution of one or more of said metal salts at 2000 rpm or more, preferably 3000 rpm or more. Said coating by centrifugation can take place at 4000 rpm or more, preferably 5000 rpm or more and most preferably at 5500 rpm or more, for example 6000 rpm or more. Preferably, said coating by centrifugation takes place for 1 s (second) to 10 minutes, preferably 2 s to 30 s. When more than one divalent metal salt is applied and / or deposited, the two different salts can be applied at the same time. For example, in the case of deposition from a solution, the solution may contain different metal salts. Said different metal salts preferably differ with respect to the

anion. Accordingly, the metal salts MXi2 and MXii2, or for example the metal salts MXi2 and MXii2 and MXiii2 are deposited at the same time, for example they are present in the same solution, M being a defined metal and being Xi, Xii and Xiii different anions selected from the above, preferably different halides. For example, Xi, Xii and Xiii are I-, Cl- and Br-, respectively. According to an embodiment, the method of the invention comprises the steps of applying and / or depositing a film comprising two or more selected from MXi2 MXii2 and MXiii2 in which Xi, Xii and Xiii (load not shown) are each different anions selected from I-, Cl-, Br-, I-, NCS-, CN- and NCO-, preferably from I-, Cl- and Br. A mixed perovskite is obtained if the metal salt film comprising MXi2 and MXii2, or MXi2, MXii2 and MXiii2, for example, can be exposed to an organic ammonium salt according to the invention, which can be selected, independently of any one of AXi, AXii and AXiii. Preferably, if the metal salt film comprises MXi2 and MXii2, the organic ammonium salt is selected from salts comprising one of the anions contained in the metal salt layer, for example from AXi or AXii. According to an embodiment, the method of the invention comprises the step (for example step a)) of applying and / or depositing a film comprising MI2 and one selected from MCl2 and MBr2. For example, MI2 and MCl2 or Ml2 and MBr2, respectively, are deposited from the same solution in which they are dissolved. According to one embodiment, the method of the invention comprises the step (e.g. stage b)) of applying Al to the metal halides obtained in the previous step. Preferably, M is Pb and / or A is CH 3 NH 3 +. According to another embodiment, the method of the invention comprises the step (for example step a)) of applying and / or depositing a film comprising MCl2 and one selected from MI2 and MBr2. For example, MCl2 and MI2 or MCl2 and MBr2, respectively, are deposited from the same solution in which they are dissolved. According to an embodiment, the method of the invention comprises the step (for example step b)) of applying AC1 to the metal halide obtained in the previous step. Preferably, M is Pb 30 and / or A is CH 3 NH 3 +. According to a preferred embodiment, step b) comprises applying and / or depositing a single salt and / or a structurally defined organic ammonium salt. Preferably, a mixture of different organic salts is not applied and / or deposited. Preferably, this is valid regardless of whether a mixture of

different metal salts or a single type of metal salts in the method of the invention. According to an embodiment, in step a) a mixture of MiX2 with MiiX or MiiiX3 can be applied, said MiX2 and one of MiiX and MiiiX3 being preferably applied together / at the same time, for example deposited from the same solution. In this case, 5 Mii and Miii represent monovalent or trivalent cations, which will constitute a doping with a monovalent or trivalent metal salt, respectively. In the result, doped n-type or p-type metal salts, and finally perovskites can be obtained. As mentioned above, said two different metal salts can be applied, which differ from the metal, but which have, for example, identical anions. In this case, metals carrying different charges are preferably applied, resulting in doped perovskites. According to an embodiment, before exposing the applied and / or deposited film of said divalent or trivalent metal salt (for example MX2 or NX3, respectively) to said organic ammonium salt solution, said metal salt is pre-moistened by exposing it to a solvent in the absence of said organic ammonium salt. The solvent used for pre-wetting is preferably the same as the solvent in which said organic ammonium salt is dissolved as disclosed elsewhere in this specification, or is otherwise a solvent in which said salt Metal is not or is not easily soluble. The invention comprises step b) of applying and / or depositing an organic ammonium salt on a nanoporous layer. If step b) is carried out after step a), it preferably comprises or consists essentially of the step of exposing or contacting the film obtained in step a) with a solution comprising one or more ammonium salts organic in a solvent. The solvent for producing the solution comprising said one or more organic ammonium salts is preferably selected from solvents which are good solvents for the organic ammonium salt to be dissolved but a poor solvent for the divalent or trivalent metal salt, in particular MX2 or NX3. Solvent 30 is also preferably a poor solvent (does not dissolve) for the resulting perovskite. The one or more divalent or trivalent metal salts can be exposed to or contacted with said solution comprising the organic ammonium salt by immersing the crystals and / or the metal salt in said solution. For example, layer 35

Nanoporous comprising the deposited metal salt layer (for example MX2 or NX3) can be immersed in said solution of the organic ammonium salt. According to one embodiment, said metal salt film is exposed to or contacted with said solution for 10 minutes or less, preferably 5 minutes or less, even more preferably 1 minute or less, or during the periods of time provided in the paragraph below. According to one embodiment, said organic-inorganic perovskite is formed within <120 s, preferably <60 s after exposure to said solution. More preferably, said organic-inorganic perovskite is formed in the time of <45 s, preferably <30 s after exposure to said solution. In the case of immersion, the nanoporous layer comprising the deposited metal salt layer may be immersed in said solution during the periods of time indicated above (<120 s, etc.). The exposure time (contacting, immersion) is preferably carried out for at least one second, more preferably at least two seconds. Surprisingly, the method of the invention produces metal salt crystals, in particular MX2 or NX3 crystals, and finally perovskite crystals, of smaller sizes, for example of shorter length than that of the respective crystals reported in the art. previous. "Size" or "length", for the purpose of the present specification, refer to the maximum extent along an axis, and is preferably expressed in nanometers (nm). According to one embodiment, the size of the crystals of said metal salt film and / or said organic-inorganic perovskite obtained in the method of the invention are <50 nm, preferably <45 nm, more preferably <40 nm. Still more preferably, said crystals are <35 nm, preferably <30 nm, most preferably <25 nm. Preferably, most of the crystals have the indicated size, more preferably at least 70% of the crystals. Most preferably, crystals that are longer than those indicated above (eg,> 50 or> 45 nm, etc.) are substantially or totally absent, in particular within the pores of said nanoporous layer, but preferably in the layer of perovskita as a whole. According to one embodiment, the layer comprising said perovskite and / or said layer comprising said sensitizer is substantially free of said divalent or trivalent metal salt. In other words, the conversion into perovskite is complete and occurs within the period of time periods indicated above, for example in 35

the time of 25 seconds or 20 seconds. This applies in particular in the case of MX2 contacted with AX, producing the AMX3 perovskite as described elsewhere in this specification. According to one embodiment, the crystals formed during the step of applying and / or depositing said divalent or trivalent metal salt, MX2 or NX3, respectively, comprise 2P polytype crystals on said nanoporous scaffold layer. In addition, said MX2 or NX3 are present in the form of and / or contain additional crystals, which are different from said 2H polytype. Surprisingly, such other crystals are absent when said metal salt is deposited on a flat surface or a surface that is different from the surface and / or nanostructured layer of the invention. According to one embodiment, the organic-inorganic perovskite material that is used and / or obtained in the one or more perovskite layers preferably comprises a perovskite structure of any one of formulas (I), (II), (III), (IV), (V) and / or (VI) below: 15 AA'MX4 (I) AMX3 (II) AA'N2 / 3X4 (III) AN2 / 3X3 (IV) BN2 / 3X4 (V) BMX4 (VI) ) in which A 'is independently selected from the same monovalent organic cations as A, and A and B are as described elsewhere in this specification. In the formulas AA'N2 / 3X4, AN2 / 3X3 and BN2 / 3X4, "2/3" means that each third of the metal cation is missing. In this case, the perovskite is deficient in metal. Preferably, M is Sn2 + or Pb2 +, more preferably Pb2 +. N is preferably selected from the group of Bi3 + and Sb3 +. In the perovskites of formulas (I) to (VI), any X (for example any X in X4) can be independently selected from CI-, Br-, I-, NCS-, CN- and NCO-. Preferably, X is halogen, preferably X is selected from Br- or I-. In accordance with one embodiment, all the anions in "X3" and "X4" are identical. According to a preferred embodiment, "X3" and "X4" contain at least two different anions.

According to a preferred embodiment, "X3" comprises two or more halides, in particular two. Preferably, X3 is Xi2Xii, with Xi2 and Xii being independently selected from halides, preferably from CI-, Br- and I-. Preferably, "X3" is selected from I2CI or I2Br, which form the perovskites AMI2CI and AMI2Br, respectively. According to one embodiment, A and A 'are identical, resulting in perovskite 5 of the formulas A2MX4, A2PbX4, A2SnX4, for the formulas (I), (VIII) and (IX) (see below), for example. Preferably, A and A 'are identical and all X's are identical. According to a preferred embodiment, the perovskite material has the structure selected from one or more of the formulas (I) to (III), preferably (II). According to a preferred embodiment, said organic-inorganic perovskite layer comprises a perovskite structure of any one of formulas (V), (VI), (VII), (VIII), (IX), (X) and (XI) ) below: APbX3 (V) ASnX3 (VI) ABiX4 (VII) AA'PbX4 (VIII) AA'SnX4 (IX) BPbX4 (X) BSnX4 (XI) in which A, A ', B and X are as they are defined elsewhere in this specification. Preferably, X is preferably selected from Br- and I-, most preferably X is I-. According to a preferred embodiment, said organic-inorganic perovskite layer comprises a perovskite structure of the formulas (V) to (IX), more preferably (V) and / or (VI) above. According to one embodiment, A and A ', for example in AX and / or in any one of the formulas (I) to (III), and (V) to (IX), are monovalent cations independently selected from any one of the compounds of the formulas (I) to (8) below:

 wherein, any one of R1, R2, R3 and R4 is independently selected from C1-C15 organic substituents comprising from 0 to 15 heteroatoms. According to one embodiment of said C1-C15 organic substituent, any one, several or all of the hydrogens in said substituent may be replaced by halogen and said organic substituent may comprise up to fifteen (15) N, S or O heteroatoms, and wherein , in any one of the compounds (2) to (8), the two or more of the substituents present (R1, R2, R3 and R4, as applicable) can be covalently connected to each other to form a ring or system of rings replaced or not replaced. Preferably, in a chain of atoms of said C1-C15 organic substituent, any heteroatom is connected to at least one carbon atom. Preferably, neighboring heteroatoms are absent and / or heteroatom-heteroatom bonds are absent in said C1-C15 organic substituent comprising from 0 to 15 heteroatoms. According to an embodiment, any one of R1, R2, R3 and R4 is independently selected from C4 to C15 heteroaromatic or aromatic substituents and C1 to C15 aliphatics, wherein any one, several or all of the hydrogens in said substituent may be replaced by halogen and wherein, in any one of compounds (2) to (8), the two or more of the substituents present may be covalently linked together to form a substituted or unsubstituted ring or ring system.

According to one embodiment, B is a bivalent cation selected from any one of the compounds of formulas (9) and (10) below: wherein, in the compound of formula (9), L is an organic linker structure having from 15 to 10 carbons and from 0 to 5 heteroatoms selected from N, S and / or O, in which any one, several or all of the hydrogens in said L can be replaced by halogen; wherein any one of R1 and R2 is independently selected from any one of substituents (20) to (25) below: wherein the dashed line in the substituents (20) to (25) represents the link by the that said substituent is connected to the linker structure L; wherein R1, R2 and R3 are independently as defined above with respect to the compounds of formulas (1) to (8); Wherein R1 and R2, if both are different from the substituent (20), can be covalently connected to each other by means of their substituents R1, R2 and / or R3, as applicable, and wherein any one of R1, R2 and R3, if present, may be covalently linked to L or the ring structure of compound (10), regardless of whether said substituent is present on R1 or R2; twenty

and wherein, in the compound of formula (10), the circle containing said two positively charged nitrogen atoms represents a substituted or unsubstituted ring or ring system comprising from 4 to 15 carbon atoms and from 2 to 7 heteroatoms, wherein said nitrogen atoms are ring heteroatoms of said ring or ring system, and wherein the rest of said heteroatoms 5 can be independently selected from N, O and S and wherein R5 and R6 are selected independently of H and substituents such as R1 to R4. Halogens that substitute for hydrogens in addition to and / or independently of said 2 to 7 heteroatoms may also be present in whole or in part. Preferably, if the number of carbons that are in L is reduced, the number of heteroatoms is smaller than the number of carbons. Preferably, in the ring structure of formula (10), the number of ring heteroatoms is smaller than the number of carbon atoms. According to one embodiment, L is an aliphatic, aromatic or heteroaromatic linker structure having from 1 to 10 carbons. Preferably, the dotted line in substituents (20) to (25) represents a carbon-nitrogen bond, which connects the nitrogen atom shown in the substituent with a carbon atom of the linker. According to one embodiment, in the compound of formula (9), L is an organic linker structure having from 1 to 8 carbons and from 0 to 4 heteroatoms of N, S 20 and / or O, wherein any one, several or all the hydrogens in said L can be replaced by halogen. Preferably, L is an aliphatic, aromatic or heteroaromatic linker structure having from 1 to 8 carbons, wherein any one, several or all of the hydrogens in said L can be replaced by halogen. According to one embodiment, in the compound of formula (9), L is an organic linker structure having 1 to 6 carbons and from 0 to 3 heteroatoms of N, S and / or O, wherein any one, several or all the hydrogens in said L can be replaced by halogen. Preferably, L is an aliphatic, aromatic or heteroaromatic linker structure having 1 to 6 carbons, wherein any one, several or all of the hydrogens in said L can be replaced by halogen. According to one embodiment, in the compound of formula (9), said linker L is free of any heteroatom of O or S. According to one embodiment, L is free of heteroatoms of N, O and / or S. According to one embodiment, in the compound of formula (10), the circle containing said two positively charged nitrogen atoms represents a ring or system

of substituted or unsubstituted rings comprising from 4 to 10 carbon atoms and from 2 to 5 heteroatoms (including said two ring N atoms). According to one embodiment, said ring or ring system in the compound of formula (10) is free of any heteroatom of O or S. According to one embodiment, said ring or ring system in the compound of formula (10) is free of oxygen. any additional N, O and / or S heteroatom, in addition to said two ring N atoms. This does not exclude the possibility of replacing hydrogens with halogens. As the skilled person will understand, if a ring, substituent, compound or aromatic linker comprises 4 carbons, it comprises at least 1 ring heteroatom, so as to provide an aromatic moiety. According to an embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C8 organic substituents comprising from 0 to 4 heteroatoms of N, S and / or O, in which, independently of said N heteroatoms. , S or O, any one, several or all of the hydrogens in said substituent can be replaced by halogen, and in which two or more of the 15 substituents present in the same cation can be covalently linked together to form a ring or system of rings of substituted or unsubstituted. Preferably, any one of R1, R2, R3 and R4 is independently selected from C1 to C8 aliphatic substituents, C4 to C8 heteroaromatics and C6 to C8 aromatics, wherein said aromatic and heteroaromatic substituents may be further substituted. According to an embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C6 organic substituents comprising from 0 to 3 heteroatoms of N, S and / or O, in which, independently of said N heteroatoms, S or O, any one, several or all of the hydrogens in said substituent may be replaced by halogen, and wherein two or more of the substituents present on the same cation may be covalently linked together to form a ring or ring system replaced or not replaced. Preferably, any one of R1, R2, R3 and R4 is independently selected from C1 to C6 aliphatic substituents, C4 to C6 heteroaromatics and C6 to C8 aromatics, wherein said aromatic and heteroaromatic substituents may be further substituted. According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C4 aliphatic substituents, preferably C1 to C3 and most preferably C1 to C2 in which any one, several or all of the hydrogens

in said substituent can be replaced by halogen and in which two or more of the substituents present in the same cation can be covalently linked together to form a substituted or unsubstituted ring or ring system. According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C10 alkyl, C2 to C10 alkenyl, C2 to C10 alkynyl, C4 to C10 heteroaryl and C6 to C10 aryl, wherein said alkyl, alkenyl and alkynyl, if they comprise 3 or more carbons, they can be linear, branched or cyclic, in which said heteroaryl and aryl can be substituted or unsubstituted, and in which several or all of the hydrogens in R1-R4 can be replaced by halogen . According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C8 alkyl, C2 to C8 alkenyl, C2 to C8 alkynyl, C4 to C8 heteroaryl and C6 to C8 aryl, wherein said alkyl, alkenyl and alkynyl, if they comprise 3 or more carbons, they can be linear, branched or cyclic, wherein said heteroaryl and aryl can be substituted or unsubstituted, and wherein various or all of the hydrogens in R1-R4 can be replaced by halogen According to an embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C6 alkyl, C2 to C6 alkenyl, C2 to C6 alkynyl, C4 to C6 heteroaryl and C6 aryl, wherein said alkyl, alkenyl and alkynyl , if they comprise 3 or more carbons, they can be linear, branched or cyclic, in which said heteroaryl and aryl can be substituted or unsubstituted, and in which several or all of the hydrogens in R1-R4 can be replaced by halogen. According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C4 alkyl, C2 to C4 alkenyl and C2 to C4 alkynyl, wherein said alkyl, alkenyl and alkynyl, if they comprise 3 or more carbons, they can be linear, branched or cyclic, and in which several or all of the hydrogens in R1-R4 can be replaced by halogen. According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C3 alkyl, preferably C1 to C2, C2 to C3 alkenyl, preferably C2 and C2 to C3 alkynyl, preferably C2, wherein said alkyl, Alkenyl and alkynyl, if they comprise 3 or more carbons, can be linear, branched or cyclic, and wherein several or all of the hydrogens in R1-R4 can be replaced by halogen. According to one embodiment, any one of R1, R2, R3 and R4 is independently selected from C1 to C4 alkyl, more preferably C1 to C3 and even more

preferably C1 to C2. Most preferably, any one of R1, R2, R3 and R4 are methyl. Again, said alkyl may be completely or partially halogenated. According to one embodiment, A, A 'and B are monovalent (A, A') and bivalent (B) cations, respectively, selected from substituted and unsubstituted C5 to C6 rings comprising one, two or more nitrogen heteroatoms, in the that one (for A and 5 A ') or two (for B) of said nitrogen atoms is (are) positively charged. Substituents of such halogen rings and C1 to C4 alkyls, C2 to C4 alkenyls and C2 to C4 alkynyls may be selected as defined above, preferably of C1 to C3 alkyls, C3 alkenyls and C3 alkynyls as defined above. Said ring may comprise additional heteroatoms, which may be selected from O, N and S. Bivalent organic cations B comprising two ring-positively charged N-atoms, for example, by the compound of formula (10), are shown by way of example. previously. Such rings can be, for example, aromatic or aliphatic. A, A 'and B may also comprise a ring system comprising two or more rings, at least one of which is ring C5 to C6 substituted and unsubstituted as defined above. The elliptically traced circle in the compound of formula (10) may also represent a ring system comprising, for example, two or more rings, but preferably two rings. In addition, if A and / or A 'comprises two rings, additional ring heteroatoms 20 may be present, which are not preferably charged, for example. However, according to one embodiment, the organic cations A, A 'and B comprise one (for A, A'), two (for B) or more nitrogen atom (s) but are free of any O or S, or any another hetero atom, with the exception of halogens, which can replace one or more nitrogen atoms in cation A and / or B. 25 A and A 'preferably comprise a positively charged nitrogen atom. B preferably comprises two nitrogen atoms positively charged. A, A 'and B can be selected from the rings or ring systems by way of example of formulas (30) and (31) (for A) and from (32) to (34) (for B) below:

 wherein R1 and R2 are, independently, as defined above, and R3, R4, R5, R6, R7, R8, R9 and R10 are independently selected from H, halogen and substituents as defined above for R1 to R4 . Preferably, R3-R10 are selected from H and halogen, most preferably H. In organic cations A, A 'and B, hydrogens can be replaced by halogens, such as F, Cl, I and Br, preferably F or Cl. It is expected that a substitution of this type reduces the hygroscopic properties of the perovskite layer or layers and, therefore, may provide a useful option for the purpose of the present specification. As regards the solar cells of the invention and the production methods thereof, said solar cell preferably comprises an intermediate layer selected from (a) a hole transport material, (b) a protective layer and (c) ) an ionic liquid, said intermediate layer being applied after obtaining said perovskite layer. The intermediate layer is preferably applied after and / or on the perovskite layer. By "void transport material", "material transporting voids", "material transporting loads", "organic void transport material" and "inorganic void transport material", and the like, is meant any material or composition in which charges are transported by movement of holes or 20 electrons (electronic movement) through said material or composition. By

Therefore, the "hole transport material" is an electrically conductive material. Such materials that carry gaps, etc., are different from electrolytes. In the latter, charges are transported by diffusion of molecules. According to a preferred embodiment of the solar cell of the invention, said intermediate layer comprises a hole transport material selected from organic and inorganic void transport materials. According to a preferred embodiment, said intermediate layer comprises an organic hole transport material. Preferably, the solar cell of the invention comprises an intermediate layer, in particular an organic hole transport material, located between said one or more layers of perovskite and a counter electrode. The skilled person is aware of a wide variety of organic void transport materials, such as the conductive polymers disclosed elsewhere in this specification. For example, in WO2007107961, there is disclosed a liquid and non-liquid organic void conductor, which can be used for the purpose of the present invention. In addition, organic void transport materials ("organic electrically conductive agent") are disclosed in EP 1160888 and other 15 publications. Preferred organic void transport materials for the purpose of the present invention are spiro-MeOTAD (2,2 ', 7,7'-tetrakis-N, N-di-p-methoxyphenylamine-9,9'-spirobifluorene) and derivatives of PTAA (poly (triarylamine)) such as (poly [bis (4-20 phenyl) (2,4,6-trimethylphenyl) amine]) or (poly [bis (4-phenyl) (4-butylphenyl) amine]) . US 2012/0017995, which discloses additional hollow transport materials, is fully incorporated herein by reference. It is noted that the term "organic" in the terms "organic void transport material", "organic void transport layer", "organic load transport material" and the like does not exclude the presence of additional components. Additional components may be selected from (a) one or more dopants, (b) one or more solvents, (c) one or more other additives such as ionic compounds, and (d) combinations of the above-mentioned components, for example. In the organic filler material, such additional components may be present in amounts of 0-30% by weight, 0-20% by weight, 0-10% by weight, most preferably 0-5% in weigh. Examples of ionic compounds that may be present in organic void transport materials are TBAPF6, NaCF3SO3, LiCF3SO3, LiClO4 and Li [(CF3SO2) 2N. 35

Examples of other compounds that may be present in organic void transport materials are amines, 4-tert-butylpyridine, 4-nonyl pyridine, imidazole, N-methylbenzimidazole, for example. According to another embodiment, the intermediate layer comprises and / or consists essentially of an inorganic void transport material. A wide variety of inorganic voids transport materials is commercially available. Non-limiting examples of inorganic void transport materials are CuNCS, Cul, MoO3 and WO3. The inorganic void transport material may be doped or not. According to one embodiment, the intermediate layer, for example said organic or inorganic void transport material, removes voids from the perovskite material and / or provides new electrons from the counter electrode to the sensitizer. In other words, the hole transport material transports electrons from the counter electrode to the perovskite material layer. The intermediate layer may comprise and / or consist essentially of a protective layer. According to one embodiment, the protective layer preferably comprises a metal oxide. In particular, the protective layer may comprise or consist essentially of a material selected from Mg oxide, Hf oxide, Ga-oxide, In-oxide, Nb-oxide, Ti-oxide, Ta-oxide, Y-oxide and Zr. Ga-oxide is a preferred material for said protective layer. The protective layer preferably has a thickness of not more than 5 nm, preferably of 4 nm or less, even more preferably of 3 nm or less and most preferably of 2 nm or less. According to preferred embodiments, the protective layer has a thickness of 1.5 nm or less, and even 1 nm or less. Said "protective layer" of metal is preferably a "buffer layer". According to an embodiment of the solar cell and / or heterojunction of the invention, said protective layer is provided by deposition of atomic layers (ALD). For example, 2 to 7 layers are deposited by ALD so that said protective layer is provided. Accordingly, said protective layer is preferably multiple layers of metal oxide. According to one embodiment, the protective layer is as disclosed in the international application PCT / 1132011/055550, filed on December 8, 2011, which is fully incorporated herein by reference.

According to another embodiment, the intermediate layer is absent and said counter electrode and / or metal layer is in direct contact with said perovskite layer and / or is not separated by any additional layer or medium of said perovskite layer. The counter electrode covers the organic-inorganic perovskite layer or, if present, the intermediate layer towards the interior of the cell. The counter electrode can form the outermost layer and therefore one of the outer surfaces of the cell. It is also possible for a substrate or support layer to be present on one side of the counter electrode. The counter electrode generally comprises a catalytically active material, suitable for providing electrons and / or filling gaps into the interior of the device. The counter electrode, for example, may comprise one or more materials selected from (the group consisting of) Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, conductive polymer, conductive oxide such as tin oxide doped with indium (ITO), tin oxide with fluorine (FTO), ZnO-Ga2O3, ZnO-Al2O3, tin oxide, tin oxide doped with antimony (ATO), SrGeO3 and a combination of two or more of those mentioned above, for example. Polymer-conducting polymers comprising polyaniline, polypyrrole, polythiophene, polybenzene, polyethylenedioxythiophene, polypropylenedioxythiophene, polyacetylene, and combinations of two or more of those mentioned above can be selected, for example. Such conductive polymers can be used as void transport materials. The counter electrode can be applied as is conventional, for example by thermal evaporation of the counter electrode material on the perovskite layer or on the intermediate layer, if present. The counter electrode is preferably connected to a current collector, which is then connected to the external circuit. As detailed with respect to the first side of the device, a conductive support such as plastic or conductive glass can be electrically connected to the counter electrode on the second side. The solar cell of the invention is preferably a solar cell in the solid state. The solar cell of the invention is preferably a sensitized solar cell, such as a dye-sensitized solar cell (DSC), wherein said organic-inorganic perovskite is and / or functions as a dye and / or sensitizer. According to one embodiment, a solar cell according to an embodiment of the invention has a power conversion efficiency (PCE) of  13.5%, preferably of  14%, more preferably of  14.5% and most preferably of  15%, 35

when exposed to AM 1.5G light. Preferably, the PCE is  14.2%,  14.4%,  14.6%,  14.8%. The PCE is preferably determined as disclosed in the examples and under the conditions specified therein. The photoanode and / or working electrode of the solar cell of the invention can be formed by the nanoporous layer, optionally together with the perovskite layer. According to one embodiment, the photo-anode and / or working electrode is formed by the perovskite. This applies, for example, if the nanoporous layer is not a semiconductor and / or is not conductive, but fulfills exclusively a surface augmentation function and / or a structural support function for the perovskite. In this case, the perovskite layer is also preferably in direct physical contact with said sublayer and / or is in electrical contact with said current collector. Figures 7 A and B show, by way of example, the solar cells 1 and 1.1. The same layers have the same reference numbers. In the solar cell shown in Figure 7A, the reference number 2 represents a current collector and / or a conductive layer. One side of said current collector 15 is oriented towards the bottom and / or the outside of the cell and thus forms a first side 7 of the solar cell. The nanoporous layer 3 is provided on said current collector 2. Reference number 4 represents the perovskite layer, which is in direct contact with and / or on the nanoporous layer 3. The counter electrode 6, which can be prepared by way of example 20 provides the upper or second side 8 of the solar cell, oriented towards the outside of the cell. Inwards, the counter electrode 6 is in direct contact with the perovskite layer 4. An intermediate layer 5 is absent in the solar cell shown in figure 7 A. The perovskite layer 4 serves as a sensitizer and / or as a transport material of holes. After illumination, electrons are excited in the perovskite layer and injected into the semiconductor material of the nanoporous layer 3. From there, the electrons are pushed by the current collector 2 to an external circuit (not shown). New electrons are taken from the external circuit (not shown) connected to the counter electrode 6, which injects the electrons into the perovskite layer 4, thus closing the electrical circuit. The solar cell 1.1 shown in Figure 7B comprises a transparent support layer 12, which forms a conductive support layer 13 together with the current collector 2. A sublayer 10 and an intermediate layer 5 are present. The intermediate layer comprises preferably an organic hole transport material.

In an exemplary embodiment, the invention is based on the deposition of Pbl2 by solution processing on the nanocrystalline oxide scaffold in a first step and the subsequent transformation of the Pbl2 into the desired nanoscopic perovskite CH3NH3Pbl3 pigment by putting it in contact with a dissolution of CH3NH3I in a solvent that does not readily dissolve PbI2. 5 It is found that the reaction occurs within a few seconds and allows a much better control over the morphology of the perovskite compared to the route previously used. This method is used for the manufacture of solar cells sensitized with perovskite. The use of this new method not only results in excellent reproducibility of the performance of photovoltaic devices, but also allows to achieve a stable performance and a new PCE record of 15.0% using spiro-MeOTAD as a hole conveyor. The present invention will now be illustrated further by means of examples. These examples do not limit the scope of this invention, which is defined by the appended claims. Examples: Preparation of nanocomposite perovskite materials Mesoporous TiO2 (anatase) films were prepared by spin coating a solution of colloidal TiO2 (anatase) particles onto a compact TiO2 sublayer 30 nm thick. The latter was deposited by aerosol spray pyrolysis on a glass substrate coated with transparent conductive oxide (TCO) which acts as an electric front contact of the solar cell. Then PbI2 was introduced into the TiO2 nanopores 25 by spin coating using a 1.0 M solution in DMF maintained at 70 ° C. Using a high PbI2 concentration of this type, it is critical to obtain the high charge of the mesoporous TiO2 films required to produce superior performance solar cells. Additional experimental details are provided in the methods section. Figure 1a shows a photograph of SEM of the cross section of the film thus prepared. The absence of any Pbl2 crystal protruding from the surface of the mesoporous anatase layer shows that the infiltration method leads to a structure in which Pbl2 is contained completely within the nanopores of the TiO2 film. It is found that the composite material 35

The resultant has approximately the same optical absorbance as a compact PbI2 film of 200 nm thickness and is estimated from the optical measurements and the known film porosity of 70% that the fraction of the porous space in the mesoscopic anatase film occupied by nanocrystals of lead iodide is approximately 60%. 5 By immersing the TiO2 / PbI2 composite film in a solution of CH3NH3I in 2-propanol (10 mg ml-1), its color instantaneously changes from yellow to dark brown, indicating the formation of CH3NH3Pbl3. The dynamics of the insertion reaction were monitored by optical emission and absorption as well as X-ray diffraction spectroscopy (XRD). Figure 1b shows that the temporary growth of perovskite uptake at 550 nm is practically complete a few seconds after the exposure of the TiO2 film loaded with PbI2 to the CH3NH3I solution. A small additional increase in absorbance that occurs on a time scale of 100 s that contributes only a small percentage to the total signal increase is attributed to morphological changes that produce an enhanced light scattering. The conversion is accompanied by an extinction of the PbI2 emission at 425 nm (Figure 1c) and a concomitant increase in the luminescence of perovskite at 775 nm (Figure 1d). This last emission passes through a maximum that decreases to a stationary value. This decrease arises from the self-absorption of the luminescence by the perovskite formed during the insertion reaction. The traces were adjusted to a bi-exponential function producing the decay times inserted in the figure. Note that the increase of the emission intensity before extinction in Figure 1c is an optical artifact arising from the opening of the sample compartment for the addition of the CH3NH3I solution. The green and red curves in Figure 1e show X-ray powder diffraction spectra measured before and after contacting the nanocomposite film of TiO2 / Pbl2 with the solution of CH3NH3I, respectively. For comparison, PbI2 was also coated on a flat glass substrate and the resulting film was exposed in the same manner to a solution of CH3NH3I as the nanocomposite material of TiO2 / Pbl2. From a comparison with data from the literature, the Pbl2 deposited by centrifugation coating from a solution in DMF crystallizes in the form of the hexagonal 2H polytype, the most common Pbl2 modification.20 Furthermore, the results show that a flat glass substrate grows crystals in a preferred orientation along the c-axis, hence the appearance of only four diffraction peaks

correspond to the reticular planes (001), (002), (003) and (004) (curve of black color, figure 1e). For PbI2 loaded on a mesoporous TiO2 film (green curve, figure 1e), three additional diffraction peaks are found that do not originate from TiO2, suggesting that the anatase scaffold induces a different orientation for the growth of Pbl2 crystals. Only the peaks marked 5 as (2) and (3) in Figure 1e can be attributed to the lattice planes (110) and (111) of the 2H politic. The peak (1) is assigned to a variant of different Pbl2 whose identification is outside the scope of this report in view of the large number of polyps that have been reported for PbI2.21 During the insertion reaction, the appearance of a series is observed of new diffraction peaks 10 that agree well with the bibliographic data of the tetragonal phase of the perovskite CH3NH3Pbl3.22 However, when Pbl2 is deposited on a flat film (blue curve, figure 1e), the conversion into perovskite after contact with the CH3NH3I solution it is incomplete, a large amount of unreacted Pbl2 being present even after an immersion time of 15 minutes. This is consistent with the observations of Liang et al.23, who reported that the intercalation of CH3NH3I barely advanced beyond the surface of thin Pbl2 films, requiring the complete transformation of the crystal structure several hours. The warning of such long conversion times is that perovskite dissolves in the dissolution of methylammonium iodide over longer periods, restricting the exposure time and making transformation difficult. In striking contrast to the behavior of thin films of lead iodide deposited on a flat support, the conversion of PbI2 nanocrystals in the mesoporous titania film is practically complete on a time scale of seconds as is evident from the disappearance immediately after its most intense diffraction peak (001) and the concomitant appearance of the XRD reflections for the tetragonal perovskite. When the Pbl2 crystals are contained within the scaffold of mesoporous TiO2, their growth is limited to approx. 22 nm for the pore size of the host. Importantly, it is found that limiting the crystals of Pbl2 to such a small size drastically powers its perovskite conversion rate, which is complete within a few seconds of contact with the iodide solution. methylammonium. On the other hand, when deposited on a flat surface, larger PbI2 crystalline units are formed in the 50-200 nm size range as shown by the SEM photographs presented in Figures 5 (e / f). Figure 5 35

it also shows that large crystals of CH3NH3PbI3 are formed with a large size distribution when the perovskite is deposited in a single stage from a solution of CH3NH3I and PbI2 in GBL or DMF. Specifically, Figures 5 AD) show CH3NH3PbI3 deposited by spin coating on a fluoride doped tin oxide glass substrate using a mixed solution of Pbl2 and CH3NH3I (molar ratio 1: 1) in solvent of A, B) and -butyrolactone (GBL) or C, D) N, N-dimethylformamide (DMF). In both cases, the surface coverage is low and the naked FTO is exposed. In Figures E, F), CH3NH3PbI3 is obtained using the sequential deposition method. The immersion time of the PbI2 film in the CH3NH3I / 2-propanol solution was 10 out of 30 s. Compared to the single-step method, sequential deposition produces much smaller crystalline CH3NH3Pbl3 units and full coverage of the FTO surface. A key finding of the present work is that the confinement of PbI2 within the nanoporous network of the TiO2 film greatly facilitates its conversion into the perovskite pigment. In addition, the host's mesoporous scaffolding forces the perovskite to adapt to a similar nanomorphology as the PbI2 precursor. As will be shown below, such composite nanostructures are very effective in collecting sunlight and converting it into electrical energy, opening a new route to produce solar cells with excellent photovoltaic stability and performance. Photovoltaic performance The sequential deposition technique was used to fabricate mesoscopic solar cells using the triarylamine spiro-MeOTAD derivative as void transport material (HTM). Figure 2 shows an SEM image of the cross section of a typical device. The mesoporous TiO2 film had an optimized thickness of about 350 nm and was infiltrated with the perovskite nanocrystals using the two-step procedure mentioned above. The HTM was subsequently deposited by coating by centrifugation. Penetrate at 30 the remaining available pore volume and form a 100 nm thick coating on top of the composite structure. A thin gold layer was vacuum evaporated thermally on the HTM forming the subsequent contact of the device.

The current-voltage characteristics of the solar cells were measured under simulated global air mass (AM) radiation 1.5 (G) and in the dark. Figure 3a shows JV curves measured at a light intensity of 95.6 mW cm-2 for a typical device. From this values are derived for the short-circuit photocurrent (Jsc), the open-circuit voltage (Voc) and the fill factor (FF) of 17.1 5 mA cm-2, 992 mV and 0.73, respectively , producing a PCE of 12.9% (table 1). Table 2 shows statistical data on a larger lot of ten photovoltaic devices. From the average PCE value of 12.0 ± 0.5% and the small standard deviation, it is inferred that photovoltaic products with excellent performance and high reproducibility can be produced using the new method reported in the present document. Figure 3b shows the efficiency spectrum of electron incident photon conversion (IPCE) or external quantum efficiency (EQE) for the perovskite cell. The photocurrent generation starts at 800 nm according to the band gap of the CH3NH3Pbl3, which reaches peak values of more than 90% in the blue region of the spectrum. By integrating the overlap of the IPCE spectrum with the solar photon flux AM 1.5G, a current density of 18.4 mA cm-2 is produced, which is in excellent agreement with the measured photocurrent density, extrapolated to 17.9 mA cm-2 at the conventional solar intensity AM 1,5 of 100 mW cm-2. This confirms that any mismatch between simulated sunlight and conventional AM 1.5G 20 is negligibly small. Comparison with absorbance or light collection efficiency (LHE) shown in Figure 3e reveals that low IPCE values in the range of 600 to 800 nm result from the smaller absorption of perovskite in this spectral region. This is also reflected in the spectrum of internal quantum efficiency (IQE) or electron-absorbed photon conversion efficiency 25 (PACE) that can be deduced from IPCE and LHE and shown in figure 3d. The APCE spectrum presents values above 90% throughout the visible region without correction for reflection losses, which indicates that the device achieves a quantum performance close to unity for the generation and collection of charge carriers. In an attempt to increase the loading of the perovskite absorber on the TiO2 structure and obviate the lack of absorption in the red color region of the spectrum, the conditions for the deposition of the Pbl2 precursor as well as the transformation reaction were slightly modified. . Details are provided in the experimental section. The JV characteristics of a highlighted cell that was manufactured from 35

this way they are represented in figure 4. From these data, values of 20.0 mA cm-2, 993 mV and 0.73 for Jsc Voc, and FF, respectively, are deduced, producing a PCE of 15.0% measured at a light intensity of 96.4 mW cm-2. As far as the inventors are aware, this is the highest power conversion efficiency reported so far for organic or hybrid organic or inorganic solar cells and any photovoltaic device processed in solution. Compared to the data shown in Figure 3a, the device benefits from a significantly higher photocurrent which is attributed to the top loading of the porous titania film with the perovskite pigment which improves the response to the red color of the cell. 10 Long-term Stability In order to test the stability of perovskite-based photovoltaic devices prepared using the aforementioned method, a sealed cell was subjected to long-term light absorption at a light intensity of ca. 100 mW cm-2 and 45ºC. The device was encapsulated in argon and maintained in optimal operating conditions during aging using maximum power point tracking (MPP). A very promising long-term stability is found since the photovoltaic device maintains more than 80% of its initial PCE 20 after a period of 500 h. Even more importantly, no change in the short-circuit photocurrent is observed, indicating that there is no photodegradation of the perovskite light collector. Therefore, the decrease in PCE is due only to a decrease in both the open circuit potential and the FF, while the similar form of both decays suggests that they are both linked to the same degradation mechanism. The change in these two parameters is due to a decrease in the shunt resistance as is evident from Figure 6 in which the JV curves of the device before and after the aging procedure are shown. 30 Conclusions In conclusion, the sequential deposition method for the fabrication of mesoscopic solar cells sensitized with perovskite presented herein provides a means to achieve excellent photovoltaic performance with high reproducibility. The power conversion efficiency of 15% achieved with the 35

The best device is a new record for photovoltaic devices processed in solution and inorganic-organic hybrid or organic solar cells in general. The findings allow entirely new routes for the fabrication of perovskite-based photovoltaic devices since any preformed metal halide structure can be converted to the desired perovskite by this simple insert reaction. A key finding of the research is that the conversion rate is greatly enhanced by confining the metal halide within the nanopores of the metal oxide host acting as scaffolding. The solar cells that were manufactured using this method show not only excellent performance but also show a very promising long-term stability under prolonged test conditions, which gives hope that this new class of mesoscopic solar cells will find extended applications. SUMMARY OF THE METHODS: Manufacture of the device. TCO glass substrates printed with a compact layer of TiO2 were coated by spray pyrolysis in aerosol. A mesoporous TiO2 layer 350 nm thick composed of particles of 20 nm in size was then deposited by spin coating. The mesoporous TiO2 films were infiltrated with PbI2 by spin coating a solution of 1.0 M Pbl2 in DMF which was maintained at 70 ° C and subsequently dried at 70 ° C for 30 min. To form the perovskite, the films were immersed in a solution of CH3NH3I in 2-propanol (10 mg ml-1) for 20 s, rinsed with 2-propanol and dried at 70 ° C for 30 min. The void-transporting material was then deposited by spin coating a solution of spiro-MeOTAD, 4-tert-butylpyridine, 25-lithium bis (trifluoromethylsulfonyl) imide and tris (bis (trifluoromethylsulfonyl) imide) tris (2- (1H) -pyrazol-1-yl) -4-tert-butylpyridine) cobalt (III) in chlorobenzene. 80 nm of gold was thermally evaporated on top of the device to form the subsequent contact. For the fabrication of the highlighted device, slightly modified conditions were used: Firstly, Pbl2 centrifugation was deposited for 5 s instead of 90 s and, secondly, the samples were subjected to a "pre-wetting" by immersion in 2-propanol for 1-2 s before immersion in the solution of CH3NH3I / 2-propanol. Characterization of the device. The current-voltage characteristics were recorded by applying an external potential bias to the cell while recording the voltage.

 photocurrent generated with a digital multimeter. All measurements were carried out using a 0.285 cm 2 metal aperture to define the active area of the device. Long-term stability Devices were sealed in argon using a hot melt polymer and subjected to constant light absorption at about 5 100 mW cm-2. The light source was a series of white LEDs. During the tests, the devices were maintained at their maximum power point (MPP) by electronic control and a temperature of approximately 45 ° C. JV curves were recorded automatically every 2 hours. Optical spectroscopy Mesoporous TiO2 films were deposited on 10 microscopic glass slides and infiltrated with Pbl2 following the procedure mentioned above. The samples were then placed vertically in a cuvette with a length of 10 mm. A solution of CH3NH3I in 2-propanol was then rapidly injected into the cuvette while monitoring either photoluminescence or optical transmission. 15 TABLES: Table 1. PV performance at different light intensities. Intensity JSC VOC FF PCE mW cm-2 mA cm-2 mV -% 9.3 1.7 901 0.77 12.6 49.8 8.9 973 0.75 13.0 95.6 17.1 992 0 , 73 12.9 Table 2. Experimental extension of the PV performance. VOC cell JSC FF PCE - mV mA cm-2 -% 1 990 17.8 0.70 12.2 2 996 17.7 0.72 12.6 3 971 17.11.71 11.7 4 992 17, 9 0.73 12.9 5 978 16.3 0.71 11.4 6 962 16.9 0.73 11.9 7 972 18.1 0.68 12.0 8 986 17.4 0.71 12, 2 9 963 17.5 0.69 11.5 10 959 17.6 0.66 11.2 Average 977  14 17.4 ± 0.5 0.70 0.0212.0 ± 0.5 20

SECTION OF METHODS: Materials. Unless otherwise stated, all materials from Sigma-Aldrich (Switzerland) or Acros Organics (Belgium) were purchased and used as received. Spiro-MeOTAD was purchased from Merck KGaA (Germany). CH3NH3I was synthesized according to a reported procedure.11 5 Manufacture of the device. First, glass substrates coated with fluorinated doped tin oxide (FTO) were cleaned with laser (Tec 15, Pilkington) by ultrasonication in an aqueous alkaline wash solution, rinsed with deionized water, ethanol and acetone and they were treated with O3 / UV for 30 min. A compact layer of TiO2 of 20-40 10 nm thickness was then deposited on the substrates by aerosol pyrolysis at 450 ° C using a commercially available solution of bis (acetylacetonate) titanium diisopropoxide (30% in 2-propanol, Sigma -Aldrich) diluted in ethanol (1:39, ratio in volume) as a precursor and oxygen as a carrier gas. After cooling to room temperature, the substrates were then treated in a 0.02 M aqueous solution of TiCl4 for 30 min. at 70 ° C, washed with deionized water and dried at 500 ° C for 20 min. The mesoporous TiO2 layer composed of particles of 20 nm in size was deposited by spin coating at 5000 rpm for 30 s using a commercial TiO2 paste (Dyesol 18NRT, Dyesol), diluted in ethanol (2: 7, weight ratio) . After drying at 125 ° C, the TiO 2 films were gradually heated to 500 ° C, baked at this temperature for 15 min. and cooled to room temperature. Before use, the films were again dried at 500 ° C for 30 min. PbI2 was dissolved in N, N-dimethylformamide with vigorous stirring and the solution was maintained at 70 ° C during the deposition. The mesoporous TiO2 films were then infiltrated with Pbl2 by spin coating with a 1.0 M Pbl2 solution at 6500 rpm for 90 s and dried at 70 ° C for 30 min. After cooling to room temperature, the films were immersed in a solution of CH3NH3I in 2-propanol (10 mg ml-1) for 20 s, rinsed with 2-propanol and dried at 70 ° C for 30 min. Then the material that carries holes was deposited by spin coating at 4000 rpm for 30 s. The coating formulation was prepared by centrifugation by dissolving 72.3 mg of (2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9-spirobifluorene) (spiro-MeOTAD) , 28.8 μl 4-tert-butylpyridine (TBP), 17.5 μl of a stock solution of lithium bis (trilfluoromethylsulfonyl) imide (LiTFSI) 520 mg ml-1 in acetonitrile and 29 μl of a stock solution of tris ( bis (trifluoromethylsulfonyl) imide) of tris (2- (1H-pyrazol-1-yl) -35

4-tert-butylpyridine) cobalt (III) 300 mg ml-1 in acetonitrile in 1 ml of chlorobenzene. Finally, 80 nm of gold was thermally evaporated on top of the device to form the subsequent contact. The device was manufactured under controlled atmospheric conditions and a humidity of <1%. For the manufacture of the highlighted device that presents a PCE of 15%, 5 slightly modified conditions were used: First, Pbl2 was centrifuged at 6500 rpm for 5 s. Second, the samples were subjected to "pre-wetting" by immersion in 2-propanol for 1-2 s before immersion in the solution of CH3NH3I / 2-propanol. Device characterization The current-voltage characteristics were recorded by applying an external potential bias to the cell while recording the photocurrent generated with a digital multimeter (Keithley model 2400). The light source was a 450 W xenon lamp (Oriel) equipped with a Schott K 113 Tempax sunlight filter (Praezisions Glas & Optik GmbH) in order to adjust the emission spectrum of the lamp to the AM 1, 5G conventional. The 15 electron incident photon conversion efficiency (IPCE) spectra were recorded as a function of the wavelength under a constant white light bias of approximately 5 mW / cm2 supplied by a series of white LEDs. The excitation beam from a 300 W xenon lamp (ILC Technology) was focused through a Gemini-180 double monochromator (Jobin Yvon Ltd.) and stopped at about 2 Hz. Signal was recorded using an amplifier SR830 DSP Lock-In model (Stanford Research Systems). All measurements were carried out using a 0.255 cm2 non-reflective metal aperture to define the active area of the device and to avoid light scattering through the sides. Long-term stability For long-term stability tests, the devices were sealed in argon using a 50 μm thick hot melt polymer and a microscopic cover glass and subjected to constant light absorption at approximately 100 mW cm-2. The light source was a series of white LEDs (LXM3-PW51 4000K, Philips). During testing, the devices were maintained at their maximum power point (MPP) using MPP tracking and a temperature of about 45 ° C. An automatic IV measurement was taken at different light intensities (0%, 1%, 10%, 50% and 100% of the sun) every 2 h. Optical spectroscopy Mesoporous TiO2 films were deposited on microscopic glass slides and infiltrated with Pbl2 following the aforementioned procedure. Then the samples were placed 35

vertically in a conventional cuvette with a length of 10 mm using a Teflon support. A solution of CH3NH3I in 2-propanol was then rapidly injected into the cuvette while monitoring either photoluminescence or optical transmission. The photoluminescence measurements were carried out in a Horiba Jobin Yvon Fluorolog spectrofluorometer. Optical absorption measurements were carried out on a Varian Cary 5 spectrophotometer. X-ray diffraction measurements (XRD). For XRD measurements, nanocomposite TiO2 and TiO2 / Pbl2 materials were deposited on microscopic glass slides using the procedures mentioned above. X-ray powder diagrams were recorded on a 10 PANalytical X'Pert MPD PRO instrument equipped with a ceramic tube (Cu anode, λ = 1.54060 Å), a secondary graphite monochromator (002) and an RTMS X detector 'Celerator, and it was made to work in BRAGG-BRENTANO geometry. The samples were assembled as they were, and the beam mask and the automatic divergence gap were adjusted to the dimensions of the thin films. A stage size of 0.008 ° and a time of acquisition of up to 7.5 min./ ° was chosen. BIBLIOGRAPHY: 1. Hagfeldt, A .; Boschloo, G .; Sun, L .; Kloo, L .; Pettersson, H. Dye-sensitized solar cells. Chem. Rev. 2010, 110, 6595-6663. 20 2. Bach, U. et al. Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon-to-electron conversion efficiencies. Nature 1998, 395, 583-585. 3. Chung, I. Lee, B .; He, J .; Chang, R. P. H .; Kanatzidis, M. G. All-solid-state dye-sensitized solar cells with high efficiency. Nature 2012, 485, 486-489. 4. Burschka, J. et al. Tris (2- (1H-pyrazol-1-yl) pyridine) cobalt (III) as p-type dopant for 25 organic semiconductors and its application in highly efficient solid-state dye-sensitized solar cells. J Am. Chem. Soc. 2011, 133, 18042-18045. 5. Yella, A. et al. Porphyrin-sensitized solar cells with cobalt (II / III) -based redox electrolyte exceed 12 percent efficiency. Science 2011, 334, 629-634. 6. Schmidt-Mende, L .; Zakeeruddin, S. M .; Grätzel, M. Efficiency improvement in solid-30 state-dye-sensitized photovoltaics with an amphiphilic ruthenium-dye. Appl. Phys. Lett. 2005, 86, 013504. 7. Hodes, G .; Cahan, D. All-solid-state, semiconductor-sensitized nanoporous solar cells. Acc. Chem. Res. 2012, 45, 705-713. 8

8. Ning †, D, Zhitomirsky †, D, Adinolfi, V, Sutherland, B, Xu, J, Voznyy, O, Maraghechi, P, Lan, X, Hoogland, S, Yuan, R, Sargent E.H. Graded doping for enhanced colloidal quantum dot photovoltaics. Adv. Mater. 2013, 25,1719-1723. 9. Kojima, A .; Teshima, K .; Shirai, Y .; Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 2009, 131, 6050-6051. 5 10. Im, J.-H. et al. 6.5% efficient perovskite quantum-dot-sensitized solar cell. Nanoscale 2011, 3, 4088-4093. 11. Kim, H.-S. et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep. 2012, 2, 591. 12. Lee, M. M .; Teuscher, J .; Miyasaka, T .; Murakami, T. N .; Snaith, H. J. Efficient 10 hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 2012, 338, 643-647. 13. Etgar, L. et al. Mesoscopic CH3NH3Pbl3 / TiO2 heterjunction solar cells. J Am. Chem. Soc. 2012, 134, 17396-17399. 14. Im, J.-H .; Chung, J .; Kim, S.-J .; Park, N.-G. Synthesis, structure, and photovoltaic 15 property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3) PbI3. Nanoscale Res. Lett. 2012, 7, 353. 15. Edri, E .; Kirmayer, S .; Cahen, D .; Hodes, G. High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite. Phys. Cbem. Lett. 2013, 4, 897-902. 16. Crossland, E. J. W. et al. Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature 2013, 495, 215-219. 17. Noh, J. H .; Im, S. H .; Heo, J. H .; Mandal, T. N .; Seok, S. I. Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. Nano Lett. 2013, DOI: 10.1021 / n1400349b. 25. 18. Cal, B .; Xing, Y .; Yang, Z .; Zhang, W.-H .; Qiu, J. High performance hybrid solar cells sensitized by organolead halide perovskites. Energy Environ. Sci. 2013, DOI: 10.1039 / c3ee40343b. 19. Qui, J. et al. All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO2 nanowire arrays. Nanoscale 2013, 5, 30 3245-3248. 20. ICSD Collection Code 68819, Inorganic Crystal Structure Database (ICSD, http://www.fiz-karlsruhe.com/icsd.html). 21. Beckmann, A. A review of polytypism in lead iodide. Cryst. Res. Technol. 2010, 45, 20 455-460. 35

22. Baikie, T. et al. Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3) Pbl3 for solid-state sensitized solar cell applications. J. Mater. Chem. A 2013, DOI 10.1039 / c3ta10518k. 23. Liang, K .; Mitzi, D. B .; Prikas, M. T. Synthesis and characterization of organic-inorganic perovskite thin films prepared using a versatile two-step dipping technique. 5 Chem. Mater. 1998, 10, 403-411. 

权利要求:
Claims (14)
[1]
CLAIMS 1. Method for producing a solar cell, the method comprising the steps of: 5 - providing a current collector and a nanoporous layer; - applying and / or depositing a film comprising one or more divalent or trivalent metal salts on said nanoporous layer; - exposing and / or contacting the film obtained in the previous step with a solution comprising one or more organic ammonium salts in a solvent, thereby obtaining a layer comprising an organic-inorganic perovskite; and - providing a counter electrode.
[2]
2. Method for producing a nanocrystalline organic-inorganic perovskite layer, the method comprising the steps of: - providing a nanoporous layer; - applying and / or depositing a film of one or more divalent or trivalent metal salts on said nanoporous layer; - exposing and / or contacting the film obtained in the previous step with a solution comprising one or more organic ammonium salts in a solvent, thereby obtaining a layer comprising an organic-inorganic perovskite.
[3]
Method according to any one of the preceding claims, wherein said organic-inorganic perovskite is formed within <120 s, preferably <60 s after exposure to said solution. 25
[4]
A method according to any one of the preceding claims, wherein said metal salt film is exposed for 10 minutes or less to said solution.
[5]
Method according to any one of the preceding claims, wherein said film of said one or more divalent or trivalent metal salts are applied and / or deposited by one or more methods selected from: deposition from a solution, deposition from a dispersion (for example, from a colloidal dispersion), deposition by thermal evaporation or sputtering, electrodeposition, atomic layer deposition (ALD) and formation of said metal salt in situ. 35
[6]
Method according to any one of the preceding claims, wherein said film of said one or more divalent or trivalent metal salts are applied and / or deposited by spin coating of a solution of said metal salt at 3000 rpm or more , preferably 4000 rpm or more. 5
[7]
Method according to any one of the preceding claims, wherein, before exposing the film of said one or more metal salts to said organic ammonium halide solution, said film is previously wetted by exposing it to a solvent in the absence of said organic ammonium halide. 10
[8]
8. Method according to any one of the preceding claims, wherein said nanoporous layer is characterized by one or more of the following characteristics: - it has a surface area ratio per gram of 20 to 200 m2 / g, preferably 30 to 150 m2 / g and most preferably 60 to 120 m2 / g; 15 - comprises and / or is prepared from nanoparticles, such as nanosheets, nanocolumns and / or nanotubes; - is nanocrystalline; - is mesoporous; - has an overall thickness of 10 to 3000 nm, preferably 15 to 1500 nm, more preferably 20 to 1000 nm, still more preferably 50 to 800 nm and most preferably 100 to 500 nm; - it has a porosity of 20 to 90%, preferably 50 to 80%; - It comprises and / or consists essentially of a metal oxide and / or a semiconductor material. 25
[9]
9. Method according to any one of the preceding claims, wherein said one or more divalent or trivalent metal salts, respectively, have the formula MX2 and NX3; wherein M is a divalent metal cation selected from the group consisting of Cu2 +, Ni2 +, Co2 +, Fe2 +, Mn2 +, Cr2 +, Pd2 +, Cd2 +, Ge2 +, Sn2 +, Pb2 +, Eu2 +, or Yb2 +; N is selected from the group of Bi3 + and Sb3 +; any X is independently selected from Cl-, Br-, I-, NCS-, CN- and NCO-; wherein said organic ammonium salt is selected from AX, AA'X2 and BX2, with A and A 'independently selected from monovalent cations,
organics selected from primary, secondary, tertiary, or quaternary organic ammonium compounds, including N-containing ring and hetero-ring systems, A and A 'having from 1 to 60 carbons and from 1 to 20 heteroatoms; and B being a bivalent, organic cation selected from primary, secondary, tertiary, or quaternary organic ammonium compounds having from 1 to 60 carbons and from 2 to 20 heteroatoms and having two positively charged nitrogen atoms.
[10]
10. Solar cell obtainable by claim 1 or any one of claims 3 to 9.
[11]
Solar cell according to claim 10, wherein the organic-inorganic perovskite layer is substantially free of one or more divalent or trivalent metal salts.
[12]
12. Solar cell according to claim 10 comprising polytype 2H crystals of one or more divalent or trivalent metal salts on the nanoporous layer and additional crystals of said one or more metal salts that are different from said polytype 2H.
[13]
A perovskite layer obtainable by any one of claims 2 to 9.
[14]
14. Solar cell comprising a nanoporous layer and a layer of organic-inorganic perovskite in contact with said layer, wherein said perovskite 20 comprises an organic-inorganic perovskite that forms crystals with a length of <50 nm, preferably <45 nm , more preferably <40 nm.

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同族专利:

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公开号 | 公开日

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US20160086739A1|2016-03-24|

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ES2579907B1|2017-10-24|

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MX2015015395A|2016-08-04|

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BR112015028097A2|2017-07-25|

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WO2014180789A1|2014-11-13|

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CN105474421A|2016-04-06|

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ES2579907R1|2017-01-12|

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优先权:

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申请号 | 申请日 | 专利标题

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EP13166720|2013-05-06|

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EP13166720|2013-05-06|

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EP13382181|2013-05-16|

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EP20130382181|EP2804232A1|2013-05-16|2013-05-16|High performance perovskite-sensitized mesoscopic solar cells|

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PCT/EP2014/059124|WO2014180789A1|2013-05-06|2014-05-05|High performance perovskite-sensitized mesoscopic solar cells|

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