Process of forming a photoactive layer of an optoelectronic device

Abstract

A process of forming a thin film photoactive layer of an optoelectronic device comprising: providing a substrate having a surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In; and converting the metal surface or metal coating of the substrate to a perovskite layer.

Claims

1. A process of forming a thin film photoactive layer of an optoelectronic device comprising: providing a substrate having a metallic surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In; and converting the metallic surface of the substrate to a perovskite layer comprising an organo-metal halide perovskite, wherein the converting comprises: applying onto the surface of the substrate at least one perovskite precursor comprising at least one compound having a formula AX, or at least one reaction constituent for forming at least one compound having the formula AX, to form the perovskite layer, wherein A comprises a nitrogen-containing organic cation and X is selected from at least one of F, Cl, Br or I.

2. A process according to claim 1, further comprising, prior to the converting step, providing the substrate with a metallic coating comprising the metal M to form the metallic surface.

3. A process according to claim 2, wherein the coating comprising metal M is provided by a process comprising at least one of: a deposition method including at least one of electrodeposition, electrophoretic deposition, electroplating, or electroless deposition; a physical coating method including at least one of sputter, cold spray; or application of solid film or layer to the substrate; or an evaporative coating method.

4. A process according to claim 2, wherein the metal coating comprising the metal M has a thickness between 25 and 200 nm.

5. A process according to claim 3, wherein the coating comprising metal M is deposited on the substrate with a metal deposition rate of between 0.1 and 2 Angstrom/second.

6. A process according to claim 1, wherein the converting step comprises: contacting the metallic surface with a vapor X selected from a halide vapor comprising at least one of F, Cl, Br or I, or an acetic acid vapor, to form a coating comprising metal compound MX.sub.2 on the substrate; and thereafter applying at least one perovskite precursor to the substrate to form the perovskite layer.

7. A process according to claim 6, wherein the metallic surface is contacted with a vapor X at between 50 and 200? C.

8. A process according to claim 1, wherein the perovskite precursor comprises at least one perovskite precursor vapor and the converting step includes forming the perovskite layer by vapor deposition.

9. A process according to claim 8, wherein the perovskite vapor deposition process comprises: exposing the substrate to a perovskite precursor vapor comprising the perovskite precursor or one or more reactants for producing said perovskite precursor; and allowing deposition of the perovskite precursor vapor onto the metal compound MX.sub.2 coating on the substrate, to produce the perovskite layer thereon.

10. A process according to claim 9, wherein the perovskite vapor deposition is allowed to continue until a solid layer of perovskite is formed with a thickness of from 100 nm to 100 ?m.

11. A process according to claim 1, wherein the perovskite precursor is a perovskite precursor solution comprising at least one perovskite precursor dissolved in a coating solvent.

12. A process according to claim 1, wherein A in the perovskite precursor AX comprises an organic cation having a formula R.sub.1R.sub.2R.sub.3R.sub.4N, wherein: R.sub.1 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; R.sub.2 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; R.sub.3 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; and R.sub.4 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

13. A process according to claim 1, wherein A in the perovskite precursor AX comprises an organic cation having a formula R.sub.5R.sub.6N?CHNR.sub.7R.sub.8, and wherein: R.sub.5 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; R.sub.6 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; R.sub.7 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; and R.sub.8 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

14. A process according to claim 1, wherein the perovskite layer comprises at least one of CH.sub.3NH.sub.3MX.sub.3 or HC(NH.sub.2).sub.2MX.sub.3, in which, M is selected from Pb, Sn, Tl, Bi, or In; and X is selected from at least one of F, Cl, Br or I.

15. A process according to claim 1, wherein the perovskite layer comprises at least one of CH.sub.3NH.sub.3PbX.sub.3 or HC(NH.sub.2).sub.2PbX.sub.3, in which X is selected from at least one of F, Cl, Br or I.

16. A process according to claim 1, wherein the perovskite layer comprises CH.sub.3NH.sub.3MCl.sub.xI.sub.3-x, in which M is selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In, preferably M is Pb.

17. A process according to claim 1, wherein the nitrogen containing organic cation comprises an ammonium group.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The present invention will now be described with reference to the figures of the accompanying drawings, which illustrate particular preferred embodiments of the present invention, wherein:

(2) FIG. 1 provides a schematic illustration of the layers comprising a solar cell incorporating a photoactive layer according to the present invention in (A) a conventional solar cell structure; and (B) an inverted solar cell structure.

(3) FIG. 2 provides schematic illustrations of: (a) the generic structure of an embodiment of the optoelectronic device of the present invention; and (b) a layer structure of a photovoltaic cell according to one embodiment of the present invention.

(4) FIG. 3 provides a process flow diagram of a process of forming a photoactive layer according to a first process (one step) embodiment of the present invention.

(5) FIG. 4 provides a process flow diagram of a process of forming a photoactive layer according to a second process (two step) embodiment of the present invention.

(6) FIG. 5 provides a graph of typical chronoamperometric deposition data for electrochemical deposition of a lead (Pb) seed layer.

(7) FIG. 6 provides an I-V curve for the planar perovskite solar cell prepared via electrochemical deposition of a lead (Pb) seed layer.

(8) FIG. 7 provides I-V curves of the evaporated Pb on ZnO/ITO embodiment.

(9) FIG. 8 provides XRD analysis of the evaporated Pb seed layer, converted to the active CH.sub.3NH.sub.3PbI.sub.3 material.

(10) FIG. 9 shows (a) SEM image of PbCl.sub.2 formed by the Pb seed layer (b) SEM image of subsequent formed CH.sub.3NH.sub.3PbI.sub.3, and c) surface topology AFM of PbCl.sub.2 following conversion.

(11) FIG. 10 provides an I-V curve of the evaporated Pb on TiO.sub.2IFTO embodiment.

(12) FIG. 11 shows cross-section SEM depicting the thin-layer of TiOx deposited on the surface of FTO glass.

(13) FIG. 12 shows SEM topographic images showing that the deposition of TiOx results in a uniform coating on FTO, comprising (a) FTO (no coating); (b) as a 10 nm coating; (c) as a 20 nm coating; (d) as a 30 nm coating; (e) as a 40 nm coating and (f) or a 50 nm coating.

(14) FIG. 13 depicts a calibration plot of evaporated Pb seed thickness against the final perovskite active film thickness as a function of deposited Pb thickness.

(15) FIG. 14 shows an AFM topography of the layers of a perovskite active film formed from the thermally-evaporated Pb seed layer.

(16) FIGS. 15(a) to (d) show SEM of Perovskite grains after direct conversion of Pb films to CH.sub.3NH.sub.3PbI.sub.3 via vapour treatment with CH.sub.3NH.sub.3I vapour under 200 mBar vacuum at the indicated temperatures.

(17) FIG. 16XRD pattern of thermally-evaporated Pb film.

(18) FIG. 17 provides a typical XRD pattern of a PbI.sub.2 film formed via vapour treatment of a thermally-evaporated Pb film with I.sub.2 vapour

(19) FIG. 18A provides an XRD pattern of final perovskite films, (a) formed from thermally-evaporated Pb converted to perovskite via vapour treatment with subsequent I.sub.2 and CH.sub.3NH.sub.3I vapour treatments, (b) pattern of a typical spin-coated perovskite sample.

(20) FIG. 18B represents surface profilimetry data depicting the relative difference in surface uniformity for (a) FTO glass as a substrate; (b) solution derived spin-cast PbI.sub.2 film; and (c) PbI.sub.2 made from Pb thermally evaporated on FTO converted to PbI.sub.2 with I.sub.2 vapour.

(21) FIG. 19 provides a plot of the Typical UV visible spectrum of a perovskite film formed from a 75 nm Pb seed layer.

(22) FIG. 20 provides a Typical Tauc plot from UV-visible reflectance data illustrating the 1.54 eV bandgap of final perovskite active layer from a thermally evaporated Pb seed layer.

(23) FIG. 22 shows a Pb film deposited on TiO.sub.2IFTO substrate at ?1.0 V vs Ag/AgCl for 30 s. The electrolyte was 10 mM Pb(NO.sub.3).sub.2+0.1 M NH.sub.4NO.sub.3 supporting electrolyte.

(24) FIG. 23 shows (A) SEM morphology of a typical Pb deposit; (B) Energy-dispersive X-ray analysis of the deposit. Blue=Sn (from FTO conducting glass); Yellow=Pb (deposits).

(25) FIG. 24 provides Examples of control of electrodeposition process on final Pb seed layer, in which A is 10 seconds at 0.6V, B is 30 seconds at 0.6 V, C is 10 seconds at 0.7 V, D is 30 seconds at 0.7 V.

DETAILED DESCRIPTION

(26) Optoelectronic device such as photovoltaic cells, particularly thin film and flexible solar cells are formed as a multilayer coating on a substrate. As shown in FIG. 1, this multilayer coating structure can be arranged on the substrate in at least two different arrangements termed in the art as (A) a conventional structure, or (M) as an inverted structure (FIG. 1(B)).

(27) As shown in FIG. 1(A), a conventional structure is formed on a substrate having the following layers successively layered on a surface thereof: a transparent conductive oxide (TCO) layer, followed by a hole transporting layer; followed by the photoactive layer; followed by an electron transporting layer, and followed by a conductor layer (typically a metal).

(28) As shown in FIG. 1(B), an inverted structure is formed on a substrate having the following layers successively layered on a surface thereof: a transparent conductive oxide (TCO) layer, followed by an electron transporting layer; followed by the photoactive layer; followed by a hole transporting layer, and followed by a conductor layer (typically a metal).

(29) Each layer can be formed by one of a number of coating techniques known in the art including evaporation, deposition, electrodeposition, electroless deposition, electrophoretic deposition, vapour deposition, sputter coating, casting, doctor blading, screen printing, inkjet printing, pad printing, knife coating, meniscus coating, slot die coating, gravure coating, reverse gravure coating, kiss coating, micro-roll coating, curtain coating, slide coating, spray coating, flexographic printing, offset printing, rotatory screen printing, dip coating, direct or physical application or the like. It should be appreciated that a person skilled in the art would be able to adopt a suitable technique to apply each layer based on techniques known in the art.

(30) The various layers can comprise a number of suitable components currently known in the art. Examples include: Suitable transparent conductive oxides (TCO) include tin doped indium oxide (ITO), fluoride-doped tin oxide (FTO), doped zinc oxide such as aluminium doped zinc oxide(AZO), or indium doped cadmium-oxide; Suitable hole transporting layers include a transparent conducting polymer such as at least one of Poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxythiophene and polystyrene sulfonate mixture (PEDOT:PSS), poly(4,4-dioctylcyclopentadithiophene); doped P3HT (Poly(3-hexylthiophene-2,5-diyl)) or the like; Suitable electron transporting layers include zinc oxide, titanium dioxide, tungsten trioxide or the like; Suitable conductor layers comprise aluminium, silver, magnesium, copper or suitable alloys thereof or the like; and Suitable substrates include metals, polymers, ceramics or glasses.

(31) A generic schematic of the optoelectronic device structure is shown in FIG. 2a. This device can be mounted on any solid substrate material (glass, plastic, metal foil, metal mesh etc.). In FIG. 2a at least one of the metallic electrodes must be transparent/semitransparent (for example: doped or undoped metal oxide, perovskite, polymer, thin metal, metal mesh etc.) whereas the opposite electrode can be transparent/semitransparent or reflective. The light absorbing perovskite, which can be n-type, p-type or intrinsic, is sandwiched between one n-type and one p-type semiconducting layer (organic, inorganic, amorphous-Si, perovskite, hybrid organic/inorganic etc.) for selective electron and hole extraction respectively. The structure shown can be inverted.

(32) Multijunction cells can also be produced using the process of the present invention. Multijunction cells can be produced by layering a series of perovskite structures (for instance, successive halide substitution in the series I, Cl, Br, F or combinations thereof) which vary in bandgap and hence spectral sensitivity to facilitate broader spectral response within the device. In the embodiment of the optoelectronic device as a photovoltaic cell, these may be formed from multiple junctions of perovskite materials or top-cell junctions with common semiconductors used by those knowledgeable in the art, for instance monocrystalline silicon or polycrystalline silicon.

(33) Certain embodiments of the optoelectronic device of the invention have the specific structure shown in FIG. 2b.

(34) The present invention provides method of forming a photoactive layer and a photoactive layer of the optoelectronic devices shown in FIGS. 1 and 2 and an intermediate which can be used in that method to form optoelectronic devices. The photoactive layer is in a photoactive region of that device. As shown in FIGS. 1 and 2a, the photoactive region typically comprises: an electron-transporting (n-type region) comprising at least one n-type layer; a hole-transporting (p-type) region comprising at least one p-type layer; and, disposed between the electron-transporting region and the hole-transporting region: a layer of a perovskite semiconductor.

(35) The term photoactive region, as used herein, refers to a region in the optoelectronic device which (i) absorbs light, which may then generate free charge carriers; or (ii) accepts charge, both electrons and holes, which may subsequently recombine and emit light.

(36) The skilled person will appreciate that a perovskite material can be represented by the formula [A][M][X].sub.3, wherein [A] is at least one cation, [M] is at least one cation and [X] is at least one anion. When the perovskite comprise more than one A cation, the different A cations may distributed over the A sites in an ordered or disordered way. When the perovskite comprises more than one M cation, the different M cations may distributed over the M sites in an ordered or disordered way. When the perovskite comprise more than one X anion, the different X anions may be distributed over the X sites in an ordered or disordered way. The symmetry of a perovskite comprising more than one A cation, more than one M cation or more than one X cation, will be lower than that of CaTiO.sub.3. A perovskite is a crystalline compound. Thus, the layer of the perovskite semiconductor without open porosity typically consists essentially of crystallites of the perovskite.

(37) As mentioned in the preceding paragraph, the term perovskite, as used herein, refers to (a) a material with a three-dimensional crystal structure related to that of CaTiO.sub.3 or (b) a material comprising a layer of material, wherein the layer has a structure related to that of CaTiO.sub.3. Although both of these categories of perovskite may be used in the devices according to the invention, it is preferable in some circumstances to use a perovskite of the first category, (a), i.e. a perovskite having a three-dimensional (3D) crystal structure. Such perovskites typically comprise a 3D network of perovskite unit cells without any separation between layers. Perovskites of the second category, (b), on the other hand, include perovskites having a two-dimensional (2D) layered structure. Perovskites having a 2D layered structure may comprise layers of perovskite unit cells that are separated by (intercalated) molecules; an example of such a 2D layered perovskite is [2-(I-cyclohexenyl)ethylammonium]2PbBr.sub.4. 2D layered perovskites tend to have high exciton binding energies, which favours the generation of bound electron-hole pairs (excitons), rather than free charge carriers, under photoexcitation. The bound electron-hole pairs may not be sufficiently mobile to reach the p-type or n-type contact where they can then transfer (ionise) and generate free charge. Consequently, in order to generate free charge, the exciton binding energy has to be overcome, which represents an energetic cost to the charge generation process and results in a lower voltage in a photovoltaic cell and a lower efficiency. In contrast, perovskites having a 3D crystal structure tend to have much lower exciton binding energies (on the order of thermal energy) and can therefore generate free carriers directly following photoexcitation. Accordingly, the perovskite semiconductor employed in the devices and processes of the present invention is preferably a perovskite of the first category, (a), i.e. a perovskite which has a three-dimensional crystal structure. This is particularly preferable when the optoelectronic device is a photovoltaic device.

(38) In order to provide highly efficient photovoltaic devices, the absorption of the absorber/photoactive region should ideally be maximised so as to generate an optimal amount of current. Consequently, when using a perovskite as the absorber in a solar cell, the thickness of the perovskite layer should ideally be in the order of from 300 to 600 nm, in order to absorb most of the sun light across the visible spectrum. In particular, in a solar cell the perovskite layer should generally be thicker than the absorption depth (which is defined as the thickness of film required to absorb 90% of the incident light of a given wavelength, which for the perovskite materials of interest is typically above 100 nm if significant light absorption is required across the whole visible spectrum (400 to 800 nm)), as the use of a photoactive layer in photovoltaic devices with a thickness of less than 100 nm can be detrimental to the performance of the device.

(39) In contrast, electroluminescent (light-emitting) devices do not need to absorb light and are therefore not constrained by the absorption depth. Moreover, in practice the p-type and n-type contacts of electroluminescent devices are typically chosen such that once an electron or hole is injected on one side of the device it will not flow out of the other (i.e. they are selected so as to only inject or collect a single carrier), irrespective of the thickness of the photoactive layer. In essence, the charge carriers are blocked from transferring out of the photoactive region and will thereby be available to recombine and generate photons, and can therefore make use of a photoactive region that is significantly thinner.

(40) As used herein, the term thickness refers to the average thickness of a component of an optoelectronic device. Typically, therefore, when the optoelectronic device is a photovoltaic device, the thickness of the perovskite layer is greater than 100 nm. The thickness of the perovskite layer in the photovoltaic device may for instance be from 100 nm to 100 ?m, or for instance from 100 nm to 700 nm. The thickness of the perovskite layer in the photovoltaic device may for instance be from 200 nm to 100 ?m, or for instance from 200 nm to 700 nm.

(41) In a perovskite type photoactive device, such as a photovoltaic cell, the photoactive layer comprises an organic-inorganic perovskite-structured semiconductor. The present invention provides a process of forming a photoactive layer of a perovskite type photoactive device. The photoactive layer formed by the present invention can be formed using two distinct method steps:

(42) Step One

(43) Step one involves the provision of a suitable intermediate comprising a substrate which comprises the required metal M or has a metal coating M applied thereto, in which the metal M is selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In. Where the substrate comprises the metal M, it is typically a thin film of that metal.

(44) In some embodiments, the process can also include the application of the metal to a suitable substrate, thereby forming an intermediate suitable for the process of the present invention. In this step, at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In is applied to a substrate to form a coated substrate. The substrate can be any suitable layer from the photoactive device, such as a metal layer, stainless steel, Ti, Ni mesh, FTO/ITO glass, glass with deposited conductor, PET/polymer, Carbons/nanocarbons or the like. The metal is applied to a layer of that substrate using a suitable metal deposition technique. Suitable techniques include at least one of: a deposition method such as electrodeposition, electrophoretic deposition, electroplating, or electroless deposition; a physical coating method such as sputter coating, cold spray; or application of solid film or layer to the substrate; or an evaporative coating method.

(45) Evaporation or evaporative deposition is a method of thin-film deposition in which the source material, in the case of the present invention metal M, is evaporated in a vacuum or reduced pressure. Ideally vapours other than the source material are almost entirely removed before the process begins. The vacuum allows vapour particles to travel directly to the target substrate surface, where the metal particles condense back to a solid state. All evaporation systems include a vacuum pump and energy source that evaporates the material to be deposited. Energy sources include heated semimetal (ceramic) evaporators in which a pool of melted metal forms and evaporates into a cloud above the source; radiatively heated crucible; molecular beam epitaxy; electron beam heating; flash evaporation, in which a fine wire of source material is fed continuously onto a hot ceramic bar, and evaporates on contact; resistive evaporation accomplished by passing a large current through a resistive wire or foil containing the material to be deposited; or the like. It is to be understood that a variety of suitable evaporative deposition equipment is commercially available and could be used for the metal application/coating step of the process of the present invention.

(46) Sputter deposition is a physical vapour deposition (PVD) method involving ejecting material from a source onto a substrate housed in a vacuum chamber to form a thin film of the sputter material on a target surface of the substrate. For the present invention, the sputtered atoms would comprise metal atom M, as defined above. Sputtered atoms ejected from the target have a wide energy distribution, typically up to tens of eV (100,000 K). The sputtered ions (typically only a small fractionin the order of 1%of the ejected particles are ionized) can ballistically fly from the target in straight lines and impact energetically on the substrates or vacuum chamber (causing resputtering). Alternatively, at higher gas pressures, the ions collide with the gas atoms that act as a moderator and move diffusively, reaching the substrates or vacuum chamber wall and condensing after undergoing a random walk. As can be appreciated, a number of parameters (gas pressure, temperature, pressure, voltage and the like) can be varied to control sputter deposition. However, this technique can provide a large degree of control over the growth and microstructure of the film. It is to be understood that a variety of suitable sputter deposition equipment is commercially available and could be used for the metal application/coating step of the process of the present invention.

(47) Electrodeposition or electroplating uses electric current to reduce dissolved metal cations so that they form a coherent metal coating on an electrode. The conducting substrate to be plated forms the cathode of the circuit. The anode can be made of the metal to be plated on the substrate, or another conducting material. The anode and cathode (substrate) are immersed in an electrolyte solution containing one or more dissolved metal salts (typically metal salts of the desired metal M to be coated on the substrate) as well as other ions that permit the flow of electricity. A power supply supplies a direct current to the anode, oxidizing the metal atoms that it comprises and allowing them to dissolve in the solution. At the cathode, the dissolved metal ions in the electrolyte solution are reduced at the interface between the solution and the cathode, such that they plate out onto the cathode. The rate at which the anode is dissolved is equal to the rate at which the cathode is plated, vis-a-vis the current through the circuit. In this manner, the ions in the electrolyte bath are continuously replenished by the anode. It is to be understood that a variety of suitable electrodeposition equipment is commercially available and could be used for the metal application/coating step of the process of the present invention.

(48) Furthermore, it should be appreciated that selected additives and surfactants can significantly influence the morphology in electrodeposition. It should be appreciated that any electrodeposition process used in the present invention may use of such additives to obtain optimal metal coating layers. For example in some embodiments, the electrolyte will contain a metal precursor for deposition including simple salts (for instance, Pb(BF.sub.4).sub.2, Pb(acetate).sub.2 or Pb(NO.sub.3).sub.2 and the like) or coordination compounds of the desired metal (lead gluconate and the like) dissolved in solution. In addition to the dissolved metal precursor, a supporting electrolyte consisting of a soluble inert salt (KNO.sub.3, NH.sub.4NO.sub.3, NH.sub.4(acetate) and the like) to avoid large electrolyte resistance or other ionic species such as a strong acid or base (e.g., HNO.sub.3, KOH and the like). Where concentrations of metal precursor are used are sufficiently high to minimise resistance losses in the solution, the metal precursor itself may simultaneously act as the supporting electrolyte.

(49) In addition to the metal precursor and supporting electrolyte, the electrolyte may contain certain additives to promote deposition of seed morphologies with favourable structures. For instance, the use of surface-active agents (surfactants) including neutral surfactants (poly-ethylene glycol, Triton X-100 and the like) cationic head group (cetyltrimethylammonium bromide and the like), or anionic head group (sodium dodecyl sulphate and the like). Other additives include H.sub.3B0.sub.3 and its various conjugate bases, NH.sub.4F, NaF, H.sub.3PO.sub.4 or other phosphate salts and the like may be included to induce favourable seed morphology. Furthermore, the control of solution pH with acids, bases and buffers may be used to modify the deposition of the seed deposit.

(50) For example, in one exemplary embodiment, electrodeposition is used to coat a layer of metal on a substrate. Here the substrate is used as a cathode in an electrodeposition arrangement. The substrate must be conducting substrate to form an electrode, for example a metal substrate or a metal coated substrate, for example TiO.sub.2-coated FTO glass. The conductive substrate is placed in a lead or other suitable metal containing solution, with a corresponding anode spaced apart from the cathode, resulting in Pb (or other metal) deposition. Persons skilled in the art will know there are many options for solution composition, pH, deposition potential or current, temperature, surface-active additives, metal compounds etc. which can influence the optimisation of an electrodeposition process. The electrodeposited layer provides a suitable mesoporous template for conversion to a photoactive perovskite layer.

(51) Electrophoretic deposition (EPD) involves submerging the substrate (in this case a conducting substrate) into a container or vessel which holds a coating bath or solution and applying direct current electricity through the coating bath using electrodes. The conductive substrate is one of the electrodes, and a set of counter-electrodes are used to complete the circuit. Typically voltages of 25-400 volts DC are used in electrocoating or electrophoretic applications. The bath typically is formed from colloidal particles suspended in a liquid medium migrate under the influence of an electric field (electrophoresis) and are deposited onto the substrate. The materials which are being deposited are the major determining factor in the actual processing conditions and equipment which may be used.

(52) Electroless deposition or electroless plating uses a redox reaction to deposit metal on a substrate without the passage of an electric current. The technique involves reduction of a complexed metal using a mild reducing agent, such as formaldehyde. Electroless deposition allows a constant metal ion concentration to bathe all parts of the substrate, thereby depositing metal evenly on the substrate. It is to be understood that a variety of suitable electroless deposition is commercially available and could be used for the metal application/coating step of the process of the present invention.

(53) Cold spray coating involves the acceleration of solid powders in a supersonic gas jet and subsequent impact with the substrate, to plastically deform and adheres those particles to the surface of that substrate. Subsequent particle impacts cause the particles to adhere to each other and form an overlap deposit comprising the coating over the surface of the substrate. The coating comprises a plurality of particles forming a distinct layer over the surface of the particle. Adhesion of the coating is by mechanical bonding or local fusion to the substrate surface. For the present invention, a surface of the substrate would be coated using solid powders of the requisite metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In accelerated at that surface using suitable cold spray coating equipment. It is to be understood that a variety of suitable cold spray coating equipment is commercially available and could be used for the metal application/coating step of the process of the present invention.

(54) In yet other embodiments, a thin metal film of the requisite metal M can be adhered to, melted or otherwise applied onto a suitable surface of a substrate.

(55) Step Two

(56) Step two involves converting the metal surface/layer of the intermediate (i.e. the comprising metal surface or coated metal layer) to a perovskite layer. In step two, a perovskite precursor is applied to the metal surface or a converted form of the metal layer to convert the metal layer to a photoactive perovskite layer.

(57) Conversion of the metal surface of the intermediate may involve: (i) direct reaction of the metal layer into the photoactive Perovskite layer; and/or (ii) one or more intermediate steps in which the metal layer is converted into different species (oxidation or halogenation or the like) which in turn can be reacted with a perovskite precursor to form a photoactive perovskite layer.

(58) FIG. 3 illustrates a first embodiment (one step) of the conversion process in which the coated metal layer 110 of a coated substrate (the intermediate) 100 is converted into a perovskite layer. In this process, a substrate 100 undergoes the coating deposition step 105 as described above to deposit a metal coating layer 110 thereon. The substrate 100 includes a film layer 102 (for example plastic) and functional layers 104 such as a transparent conductive oxide (TCO) layer and either a hole transporting layer(s) or electron transporting layer(s) prior to coating with the metal layer 110. Subsequently, that metal coating layer 110 is directly reacted with a perovskite precursor solution or vapour in conversion step 112 to form the photoactive Perovskite layer 120.

(59) Where a solution is used, the perovskite precursor compound is dissolved in a coating solvent. The coating solvent for the AX perovskite precursor salts preferably comprise solvents in which PbI.sub.2 is insoluble, such as isopropanol or other alcohols, alcohol blends or similar.

(60) For example, in one embodiment, the metal deposited layer, for example Pb, is immersed or otherwise coated with a perovskite precursor solution, such as CH.sub.3NH.sub.3I and CH.sub.3NH.sub.3Cl dissolved in a solvent (for example anhydrous isopropanol or other alcohol blends) to form the photoactive Perovskite layer (CH.sub.3NH.sub.3)PbI.sub.3-xCl.sub.x. In a second embodiment, the metal deposited layer, for example Pb, is immersed in a solution of CH.sub.3NH.sub.3I and CH.sub.3NH.sub.3Cl in a solvent (for example anhydrous isopropanol or other alcohol blends) together with a low concentration of an acid such as acetic acid to facilitate transition via decreased pH and formation of the acetate conjugate base as an iodo salt.

(61) The perovskite precursor solution can be applied to the metal coated substrate by any number of suitable application techniques. Suitable techniques for applying the applied coating to the substrate include, but should not be limited to, at least one of: casting, doctor blading, screen printing, inkjet printing, pad printing, knife coating, meniscus coating, slot die coating, gravure coating, reverse gravure coating, kiss coating, micro-roll coating, curtain coating, slide coating, spray coating, flexographic printing, offset printing, rotatory screen printing, slip coating or dip coating.

(62) In some embodiments, the perovskite precursor solution is applied by spin-coating followed by thermal annealing.

(63) The perovskite precursor may alternatively or also be applied using a vapour deposition process in which a perovskite precursor vapour is reacted directly with the metal coating of the coated substrate. The precursor vapour typically comprises at least one perovskite precursor or one or more reactants for producing said perovskite precursor. This process is described in more detail below.

(64) FIG. 4 illustrates a second embodiment (two step) of the conversion process in which the coated metal layer 210 of a coated substrate (i.e. the intermediate) 200 is converted into a perovskite layer. In this process, a substrate 200 undergoes the coating deposition step 205 as described above to deposit a metal coating layer 210 thereon. Again, the substrate 200 includes a film layer 202 (for example plastic) and functional layers 204 such as a transparent conductive oxide (TCO) layer and either a hole transporting layer(s) or electron transporting layer(s) prior to coating with the metal layer 210. The metal coating layer 210 of the substrate 200 is then reacted with a halide vapour 211 (for example selected from at least one of F, Cl, Br or I) to form a metal halide MX.sub.2 coating 215 on the coated substrate 200. Subsequently, that metal halide coating layer 215 is reacted with a perovskite precursor solution or vapour in a final conversion step 218 to form the photoactive Perovskite layer 220 on the substrate 200.

(65) As shown in FIG. 4, halogenation of the metal layer occurs in a reactor, such as a bomb type reactor halide between 50 and 200? C., preferably between 75 and 150? C. It is noted that the pressure in the bomb reaction would typically be greater than ambient pressure. Halide vapour results from halide containing solution such as KCl, KI, HCL, HBr; halide salts such as (add); CH.sub.3NH.sub.3X; Eutectic melts; RTIL eutectic melts, or halide solids such I.sub.2, CH.sub.3NH.sub.3X contact and react with the metal layer to form a metal halide layer.

(66) The metal halide layer can then be reacted with a perovskite precursor solution, such as CH.sub.3NH.sub.3I and CH.sub.3NH.sub.3Cl dissolved in a solvent (for example anhydrous isopropanol or other alcohol blends) to form the photoactive Perovskite layer (CH.sub.3NH.sub.3)PbI.sub.3-xCl.sub.x.

(67) In other embodiments, the metal layer is reacted with acetic acid vapour thereby forming a metal acetate intermediate layer (for example Pb(CH.sub.3COO).sub.2 when the metal M is lead), which can then be converted to the active perovskite film, for example via a solution/vapour diffusion process.

(68) Alternatively, the perovskite layer can be formed by vapour deposition process in which the metal halide layer is exposed to a perovskite precursor vapour, thereby allowing deposition of the perovskite precursor vapour onto the metal halide MX.sub.2 coating on the coated substrate, to produce a perovskite layer thereon. The perovskite precursor vapour typically comprises least one perovskite precursor or one or more reactants for producing said perovskite precursor vapour deposition is typically allowed to continue until the solid layer of perovskite has a thickness of from 100 nm to 100 ?m, and preferably from 100 nm to 700 nm.

(69) Vapour deposition is a well understood process, and has been previously used for forming perovskite layers from metal halide layers, for example as taught in WO2014045021A1 the contents of which should be understood to be incorporated into this specification by this reference. In this process, generally comprises producing the perovskite precursor vapour by evaporating said perovskite or evaporating said one or more reactants for producing said perovskite. In this step the perovskite or the one or more reactants for producing the perovskite can be transferred to an evaporation chamber which is subsequently evacuated. The perovskite or the one or more reactants for producing the perovskite are then heated. The resulting vapour is then exposed to the metal coating of the coated substrate and thereby deposited therein, to produce a solid layer of said perovskite thereon. If reactants are used, these react together in situ to produce the perovskite on the substrate. Vapour deposition is allowed to continue until the solid layer of perovskite has a desired thickness, for instance a thickness of from 10 nm to 100 ?m, or more typically from 10 nm to 10 ?m.

(70) Deposition methods of inorganic perovskite have been well researched, such as pulsed-laser deposition and chemical solution deposition. The hybrid inorganic-organic perovskite, such as (C.sub.6H.sub.5C.sub.2H.sub.4NH.sub.3).sub.2PbI.sub.4 or (C.sub.6H.sub.5C.sub.2H.sub.4NH.sub.3).sub.2PbBr.sub.4, have been successfully evaporated through single source thermal deposition. However, since the deposition methods of the hybrid inorganic-organic perovskite were rarely mentioned because of the significant difference in physical and chemical properties between the inorganic and organic materials, the dual-source thermal deposition was applied to evaporate the organic source and inorganic source simultaneously but with independent control (V. K. Dwivedi, J. J. Baumberg, and G. V. Prakash, Direct deposition of inorganic-organic hybrid semiconductors and their template-assisted microstructures, Materials Chemistry and Physics, vol. 137, no. 3, pp. 941-946, January 2013).

(71) As discussed previously, a large number of perovskite precursors can be used in the present invention for forming the perovskite layer. The perovskite precursor (for solution treatment, vapour deposition or the like as detailed above) generally comprises at least one compound having the formula AX, or at least one reaction constituent for forming at least one compound having the formula AX, in which A comprises an ammonium group or other nitrogen containing organic cation and X is selected from at least one of F, Cl, Br or I. Suitable examples are broadly detailed above in the summary of invention section. In exemplary embodiments, the perovskite precursor comprises an organo-lead Iodide and/or Chloride perovskite precursor. As discussed above, A can be selected from a large number of ammonium or nitrogen containing organic cations. In some embodiments, A comprises cations having the general formula RCH.sub.2NH.sub.3.sup.+, RC(NH.sub.2).sub.2.sup.+, R.sub.aR.sub.bCH.sub.1NH.sub.3.sup.+, R.sub.aR.sub.bR.sub.cCNH.sub.3.sup.+, R.sub.aR.sub.bNH.sub.2.sup.+, or R.sub.aR.sub.bR.sub.cNH.sup.+, where R, R.sub.a, R.sub.b, R.sub.c comprises H or a substituted or unsubstituted alkyl group or groups, preferably a C.sub.1 to C.sub.6 substituted or unsubstituted alkyl or aryl group or groups.

(72) Whilst a number of organo-metal halide perovskite are possible, preferably A comprises at least one of CH.sub.3NH.sub.3.sup.+, or HC(NH.sub.2).sub.2.sup.+. Thus, in some embodiments the perovskite precursor AX is selected from the group consisting of CH.sub.3NH.sub.3X and HC(NH.sub.2).sub.2X, and wherein X is selected from at least one of F, Cl, Br or I. For example, perovskite precursor may comprise a mixture of CH.sub.3NH.sub.3Cl and CH.sub.3NH.sub.3I. Accordingly, in preferred embodiments AX comprises CH.sub.3NH.sub.3X.

(73) Whilst FIGS. 3 and 4 show the process of the present invention using a coated substrate, it should be appreciated that the process could equally be used on a selected surface of a thin metal substrate, preferably thin film metal substrate formed from the requisite metal M.

EXAMPLES

Example 1Electrochemical Deposition of Pb Thin Film Seed Layer for Planar Perovskite Solar Cells

(74) In this example, a thin metallic Pb seed layer is electrochemically deposited on an n-type compact blocking layer, in this case TiO.sub.2, as a precursor for a perovskite solar cell. The deposited Pb seed layer is then chemically converted to the photoactive perovskite material.

(75) It should be appreciated that whist demonstrated for planar perovskite solar cells, the method and techniques exemplified can equally be applied to non-planar perovskite solar cells configurations for example the inclusion of a mesoscopic thin-film of nanoparticles for example TiO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2 or the like.

(76) 1.1 Electrochemical Deposition of Pb

(77) The electrochemical deposition equipment included the following:

(78) An electrolyte consisting of a 0.01 mol/L solution of Pb(NO.sub.3).sub.2 as Pb source and 0.1 mol/L KNO.sub.3 as inert conducting electrolyte (also known as supporting electrolyte.

(79) A working electrode (that where the reaction of interest takes placePb electrodeposition) consisting of a TiO.sub.2-modified fluorine-doped tin oxide (FTO) substrate. The FTO pattern of the electrode was previously modified with a laser ablation system to give a defined area for Pb deposition. The TiO.sub.2 modification forms the compact hole-blocking layer in the completed cell. In our example, the TiO.sub.2 is deposited by spin coating a solution of 0.5 mol/L titanium(IV) tetraisopropoxide precursor in 1-butanol acidified with 0.35 mol/L glacial acetic acid. The deposition is carried out at 4000 rpm for 15 seconds. The titanium isopropoxide is cleaned from the FTO electrical contact areas by removal with a pen filled with 1-butanol solvent. The substrate is then heated to 120? C. for 1 h, before being sintered at 500? C. for 30 min.

(80) A counter electrode comprising a catalytic Pt-modified FTO sample. It is noted that the counter electrode material must be catalytic, and so any other metal inert to corrosion could also be used.

(81) A reference electrode was used to provide a fixed reference potential point from which the potential of the working electrode can be modified in order to bring about the desired electrochemical deposition. In this example, a commercial saturated calomel electrode (SCE) was used. The potentials defined will be referenced to this potential.

(82) In our electrochemical cell the distance between the working and counter electrodes was ca. 3 cm. The reference electrode was situated midway between the two electrodes, with care taken to not block ionic transport between the electrodes.

(83) The technique of chronoamperometry (literally, time-current or measure current vs time at a fixed potential) was used to deposit the Pb film seed layer. The electrochemical deposition of Pb was carried out at room temperature at ?0.85 V vs. SCE for 100 seconds. FIG. 5 provides a plot of typical chronoamperometric deposition data for this electrochemical deposition of Pb.

(84) 1.2 Conversion to CH.sub.3NH.sub.3PbI.sub.3 Photoactive Perovskite Material

(85) The Pb seed layer was chemically converted to the perovskite layer through application (dipping) the Pb coated substrate in a solution of CH.sub.3NH.sub.3I (10 mg/mL), Acetic acid (2?10.sup.?3 mol/L) in anhydrous isopropanol for 1 min to convert to CH.sub.3NH.sub.3PbI.sub.3. It should be appreciated that alternative cations (CH.sub.3NH.sub.3.sup.+, Cs.sup.+, formamidinium etc) and anions (Br.sup.?, Cl.sup.? etc) are also possible. Substrates were removed and rinsed with isopropanol.

(86) 1.3 Photovoltaic Cell Fabrication

(87) Under glovebox conditions (<1 ppm O.sub.2 and H.sub.2O) a solution of 0.068 mol/L spiro-OMeTAD hole transport material, 0.055 M 4-tertbutyl pyridine and 9?10.sup.?3 mol/L Li TFSI additives was prepared and spun cast at 2000 rpm for 30 seconds. To complete the cell, a 90 nm gold cathode and contact were thermally evaporated under high vacuum.

(88) 1.4 Cell Performance

(89) FIG. 6 provides the I-V curve for the planar perovskite solar cell prepared via electrochemical deposition of a lead seed layer.

Example 2Thermal Evaporation of Thin Pb Film as Perovskite Seed Layer for Planar Perovskite Solar Cells

(90) In the following two examples (2.1 and 2.2), a thin metallic Pb seed layer is formed by thermal evaporation of Pb and condensation onto an n-type compact blocking layer (in this example either ZnO or TiO.sub.2) as a precursor for a perovskite solar cell. The seed layer once deposited is then chemically converted to the photoactive perovskite material.

(91) 2.1 ZnO Blocking Layer on Indium-Doped Tin Oxide (ITO) Substrate Embodiment

(92) 2.1.1 Substrate Preparation

(93) The ITO substrate was cleaned by successive sonication treatments in detergent (Hellmanex, 1% in milli-W water), pure milli-Q water and isopropanol.

(94) ZnO blocking layer was applied by spin casting a suspension of ZnO nanoparticles in 1-butanol onto the cleaned ITO substrate. The film was annealed at 100? C. After annealing, the ZnO film was treated by plasma treatment for 1 hour. This was necessary for film stability.

(95) 2.1.2 Pb Seed Layer Deposition

(96) Metallic Pb was deposited by thermal evaporation under high vacuum conditions. 75 nm of Pb was deposited at 0.5 nm/s.

(97) 2.1.3 Conversion to PbI.sub.2.

(98) The PbI.sub.2 film was treated to an iodine vapour/nitrogen atmosphere at 70? C. for 1 hour to tarnish the Pb film to PbI.sub.2. Films were removed and washed with isopropanol to remove residual I.sub.2.

(99) 2.1.4 Conversion to Photoactive Perovskite.

(100) In a glovebox atmosphere, a solution of CH.sub.3NH.sub.3I in isopropanol was spun-cast to deposit a layer of the solid atop the PbI.sub.2/CH.sub.3NH.sub.3PbI.sub.3 film. The film was then annealed at 80? C. for 15 min to complete the conversion to perovskite. The film was rinsed with isopropanol to remove residual CH.sub.3NH.sub.3I.

(101) 2.1.5 Photovoltaic Cell Fabrication

(102) In a glovebox atmosphere, a solution of 20 mg/mL P3HT polymer hole transport material in chlorobenzene was spun cast atop the perovskite film at 2000 rpm. The contacts were cleaned, before evaporation of a 80 nm thick layer of Ag as the cathode.

(103) 2.1.6 Performance

(104) FIG. 7 provides that I-V curves of the evaporated Pb on ZnO|ITO embodiment. Note the Y-axis of this printout is mA/cm.sup.2 (current density) and not mA (raw current).

(105) 2.2 TiO.sub.2 Blocking Layer on FTO Substrate Embodiment

(106) 2.2.1 Substrate Preparation

(107) The FTO substrate was cleaned by successive sonication treatments in detergent (Hellmanex, 1% in milli-W water), pure milli-Q water and isopropanol.

(108) TiO.sub.2 blocking layer was applied by screen printing a commercial Ti-containing blocking layer solution (BL-1; Dyesol) onto the cleaned FTO substrate. The film was dried at 90? C. before being sintered at 500? C. for 30 min. The film was then treated to a solution of TiCl.sub.4 (0.02 mol/L in milli-Q water) for 30 min at 70? C. The film was subsequently sintered again using the same process.

(109) 2.2.2 Pb Seed Layer Deposition

(110) Metallic Pb was deposited by thermal evaporation a under high vacuum conditions. 50 nm of Pb was deposited at 0.5 nm/s.

(111) 2.2.3 Conversion to PbI.sub.2

(112) The PbI.sub.2 film was treated to an iodine vapour/nitrogen atmosphere at 70? C. for 1 hour to tarnish the Pb film to PbI.sub.2. Films were removed and washed with isopropanol to remove residual I.sub.2.

(113) 2.2.4 Conversion to Photoactive Perovskite

(114) In a glovebox atmosphere, a solution of CH.sub.3NH.sub.3I in isopropanol was spun-cast to deposit a layer of the solid atop the PbI.sub.2/CH.sub.3NH.sub.3PbI.sub.3 film. The film was then annealed at 100? C. for 15-30 min to complete the conversion to perovskite. The film was rinsed with isopropanol to remove residual CH.sub.3NH.sub.3I.

(115) FIG. 8 provides an XRD analysis of the evaporated Pb seed layer, converted to the active CH.sub.3NH.sub.3PbI.sub.3 material. Grazing incidence X-ray diffraction (FIG. 8) of deposited thin films demonstrates the preparation of the desired perovskite photoactive CH.sub.3NH.sub.3PbI.sub.3 material. Two methods can be used for the conversion of PbI.sub.2 to perovskite: (1) vapour deposition/intercalation of CH.sub.3NH.sub.3I into PbI.sub.2 film. (2) spin-coating and thermal annealing of a CH.sub.3NH.sub.3I material in anhydrous isopropanol. The crystallite size was determined using a calibration of a Si standard to be (1) 273 nm and (2) 128 nm based on the 28.4 degrees 2-theta diffraction peak.

(116) FIG. 9 provides SEM images of (a) PbCl.sub.2 formed by the Pb seed layer (b) subsequent CH.sub.3NH.sub.3PbI.sub.3, and (c) surface topology AFM of PbCl.sub.2 following conversion. The regularity of the Pb seed layer is evident in the conversion to PbCl.sub.2. SEM of PbCl.sub.2 layer (FIG. 9a) reveals sub-100 nm crystallites which are readily converted to the active CH.sub.3NH.sub.3PbI.sub.3 (FIG. 9b) with larger domain sizes which provide fewer grain boundaries in the final device. The surface topology was investigated using atomic force microscopy mapping of the solar cell layers, depicted in FIG. 9c. The analysis reveals the evaporated Pb seed layer and subsequent PbI.sub.2 layer to be highly planar and smooth (12.8 and 28.3 nm roughness RMS, respectively).

(117) 2.2.5 Photovoltaic Cell Fabrication.

(118) In a glovebox atmosphere, a solution of 20 mg/mL P3HT polymer hole transport material in chlorobenzene was spun cast atop the perovskite film at 2000 rpm. The contacts were cleaned, before evaporation of a 80 nm thick layer of Ag as the cathode.

(119) 2.2.6 Performance

(120) FIG. 10 provides the I-V curve of the evaporated Pb on TiO.sub.2/FTO embodiment.

Example 3Embodiment of TiOx Blocking Layer Formation

(121) A device was produced following the method outlined in Example 1. However, in this example prior to a thin metallic Pb seed layer being electrochemically deposited onto the substrate, the substrate requires a thin-layer to reduce electrical recombination and hence a blocking layer is deposited prior to deposition of the Pb seed layer. For large area embodiments, typical spray-cast or screen-printed TiO.sub.2 thin-films can be replaced by the use of an evaporated thin-film of Ti, introduced under an oxidising environment using DC magnetron sputtering. This results in a controlled thickness of film of semi-amorphous TiO.sub.x.

(122) A cross-section SEM depicting the thin-layer of TiO.sub.x deposited on the surface of FTO glass by sputtering is shown in FIG. 11. This SEM topographic images shows that the deposition of TiOx results in a uniform coating on FTO. The series of coating thickness are shown in FIG. 12 which confirms a thin-film results that conforms to the underlying substrate morphology.

Example 4Embodiment of Evaporated Pb Seed Layer

(123) In the following example, a thin metallic Pb seed layer was formed by thermal evaporation of Pb and condensation onto an n-type compact blocking layer (in this example either ZnO or TiO.sub.2) as a precursor for a perovskite solar cell. The seed layer once deposited is then chemically converted using I.sub.2 vapour treatment and subsequent exposure to CH.sub.3NH.sub.3I vapour in a 2-step treatment to form a photoactive perovskite material following the same method outline in Example 2.

(124) FIG. 13 depicts a calibration plot of evaporated Pb seed thickness against the final perovskite active film thickness as a function of deposited Pb thickness.

(125) FIG. 14 shows an AFM topography of the layers of a perovskite active film formed from the thermally-evaporated Pb seed layer. This demonstrates that the thin-film maintains the morphology of the FTO substrate from Pb seed layer, to PbI.sub.2 and the final CH.sub.3NH.sub.3PbI.sub.3, substantially matching the surface roughness of the substrate to which the layer is applied.

(126) Surface roughness was determined on two different lateral scales: i) for regions <30 micron Atomic Force Microscopy (AFM) in scanning mode was used to scan an area equivalent to 20?20 micron using Root Mean Square (RMS) as the quantity of merit to represent standard deviation of surface height as a function of changes in spatial and/or temporal surface roughness; ii) Surface Profilometry was used for lengths >30 mm and up to 2 mm by drawing a stylus across the surface in hills and valleys mode and a planar region of the scan, no less than 500 mm, allowed the determination of the maximum and minimum of surface features where the range from maximum to minimum defines the surface barrier height, for these purposes. It should be noted that the minimum and maximum is measured relative to a baseline of the stylus.

(127) In FIG. 14, the following properties apply to the AFM topography:

(128) TABLE-US-00001 TABLE 1 Sample properties for AFM shown in FIG. 14 Sample Properties A Bare FTO RMS roughness = 27.1 nm B Pb thermally evaporated on FTO RMS roughness = 23.9 nm C Pbl.sub.2 made from Pb thermally evaporated on FTO Converted to Pbl.sub.2 with l.sub.2 vapour RMS roughness = 24.0 nm D CH.sub.3NH.sub.3Pbl.sub.3 Perovskite from thermally evaporated Pb seed on FTO Pbl.sub.2 formed with l.sub.2 vapour Perovskite formed from Pbl.sub.2 with CH.sub.3NH.sub.3l vapour RMS roughness = 24.9 nm

(129) Table 1 and FIG. 9 indicate that the surface roughness of the intermediate is lower than the surface roughness of the substrate. This difference is preferably at least 2 nm and more preferably at least 3 nm. It should be appreciated that the roughness parameters in Table 1 are Root Mean Squared Surface Roughness R.sub.RMS values. The Root Mean Square of surface roughness represents the standard deviation of surface heights and is used to compare spatial and temporal changes in a surface.

(130) FIG. 15 provides a series of SEM images that depict the direct conversion of the Pb seed film through the introduction of CH.sub.3NH.sub.3I (MEAI) in the presence of atmospheric O.sub.2 in trace amounts in a sealed chamber. This series of SEM images demonstrates that conversion to the active perovskite film morphology can be activated and controlled through variation of temperature of furnace. It should be noted that the black specks in the images are a result of sputtering conductive coating (Au) to stablise sample for analysis.

(131) Using different depths of grazing angle to examine the surface film formed in this example in the absence of the underlying substrate (FTO on glass), XRD pattern of thermally-evaporated Pb film indicates that the seed deposit is amorphous as shown in FIG. 16.

(132) FIG. 17 provides a Typical XRD pattern of a PbI.sub.2 film formed via vapour treatment of a thermally-evaporated Pb film with I.sub.2 vapour (as formed in this example) representing complete conversion of the Pb to the intermediate PbI.sub.2 film.

(133) FIG. 18A provides an XRD pattern of final perovskite films, (a) formed from thermally-evaporated Pb converted to perovskite via vapour treatment with subsequent I.sub.2 and CH.sub.3NH.sub.3I vapour treatments, (b) pattern of a typical spin-coated perovskite sample. The crystallite size from the Scherrer equation gives 273 nm for our method vs 128 nm for the spin-coated sample. Instrument broadening was calibrated with a Si standard.

(134) FIG. 18B represents surface profilimetry data depicting the relative difference in surface uniformity for (a) FTO glass as a substrate; (b) solution derived spin-cast PbI.sub.2 film; and (c) PbI.sub.2 made from Pb thermally evaporated on FTO converted to PbI.sub.2 with I.sub.2 vapour. As detailed above, Surface Profilometry is used to determine surface roughness (RMS roughness) for lengths >30 mm and up to 2 mm by drawing a stylus across the surface in hills and valleys mode and a planar region of the scan, no less than 500 mm, allowed the determination of the maximum and minimum of surface features where the range from maximum to minimum defines the surface barrier height, for these purposes. For FIG. 18B, the films were examined for hills and valleys over a distance of 600 ?m where (a) gave a minimum ?11.97 nm/maximum 182.8 nm and a barrier height of 194.8 nm; (b) gave a minimum ?15.48 nm/maximum 28.74 nm and a barrier height of 44.22 nm; (c) gave a minimum ?8.12 nm/maximum 28.87 nm and a barrier height of 36.99 nm representing an approx. 20% improvement in surface roughness for this process over conventional solution derived spin cast/coating deposition methods. It is further noted that the minimum or valleys of the three samples provide (a) the original substrate (?11.97 nm); (b) cast spun increasing to ?15.48 nm; and (c) the thermal evaporation of Pb coating decreases to ?8.12 nm. Thus, for the thermal evaporation of Pb coating, the decrease in minimum (valley) depth provides an indication of improvement on surface roughness (decrease) as the coating process fills these regions, improving the surface topography and thus roughness compared to the original substrate. In contrast, the cast coating resulted in increased roughness compared to the original substrate.

(135) FIG. 19 provides a plot of the typical UV visible spectrum of a perovskite film formed from a 75 nm Pb seed layer. Similarly, FIG. 20 provides a Typical Tauc plot from UV-visible reflectance data illustrating the 1.54 eV bandgap of final perovskite active layer from a thermally evaporated Pb seed layer.

(136) FIG. 21(A) and FIG. 21(B) provide an example of operating device from evaporated Pb layer: (left) current-voltage response; (right) incident photon to current efficiency. PbI.sub.2 formed by vapour treatment with I.sub.2. CH.sub.3NH.sub.3PbI.sub.3 formed by interdiffusion with CH.sub.3NH.sub.3I in isopropanol and subsequent annealing.

Example 5Embodiment of Evaporated Pb Seed Layer

(137) In the following example, a thin metallic Pb seed layer was again formed by thermal evaporation of Pb and condensation onto an n-type compact blocking layer (in this example either ZnO or TiO.sub.2) as a precursor for a perovskite solar cell. The seed layer once deposited is then chemically converted using I.sub.2 vapour treatment and subsequent exposure to CH.sub.3NH.sub.3I vapour in a 2-step treatment to form a photoactive perovskite material following the same method outline in Example 2.

(138) FIG. 22 shows a Pb film deposited on TiO.sub.2IFTO substrate at ?1.0 V vs Ag/AgCl for 30 s. The electrolyte was 10 mM Pb(NO.sub.3).sub.2+0.1 M NH4NO.sub.3 supporting electrolyte.

(139) FIG. 23 shows (A) SEM morphology of a typical Pb deposit; (B) Energy-dispersive X-ray analysis of the deposit. Blue=Sn (from FTO conducting glass); Yellow=Pb (deposits).

(140) Finally, FIG. 24 provides examples of control of electrodeposition process on final Pb seed layer, in which A is 10 seconds at 0.6V, B is 30 seconds at 0.6 V, C is 10 seconds at 0.7 V, D is 30 seconds at 0.7 V. Sample A image deliberately includes open space to depict the underlying FTO substrate.

(141) Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is understood that the invention includes all such variations and modifications which fall within the spirit and scope of the present invention.

(142) Where the terms comprise, comprises, comprised or comprising are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other feature, integer, step, component or group thereof.

(143) Clauses

(144) The clauses defining the breath and scope of the present invention are as follows:

(145) C1. A process of forming a thin film photoactive layer of an optoelectronic device comprising:

(146) providing a substrate having a surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In; and

(147) converting the metal surface or metal coating of the substrate to a perovskite layer.

(148) C2. A process according to clause 1, wherein the substrate is coated with a metal M prior to the converting step by:

(149) applying at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to a substrate to form a coated substrate.

(150) C3. A process according to clause 2, wherein the at least one coating of a metal M is applied to the substrate by a deposition method.

(151) C4. A process according to clause 3, wherein the deposition method includes at least one of electrodeposition, electrophoretic deposition, electroplating, or electroless deposition.

(152) C5. A process according to clause 2, wherein the at least one coating of a metal M is applied to the substrate by a physical coating method.

(153) C6. A process according to clause 5, wherein the physical coating method includes at least one of sputter, cold spray; or application of solid film or layer to the substrate.

(154) C7. A process according to clause 2 and 5, wherein the at least one coating of a metal M is applied to the substrate by an evaporative coating method.

(155) C8. A process according to any one of clauses 5 or 7, wherein the metal layer is formed with a metal deposition rate on the substrate of between 0.1 and 2 Angstrom/second, preferably between 0.5 and 1.0 Angstrom/second.

(156) C9. A process according to clause 8, wherein the deposition time is between 5 and 30 mins, preferably between 10 and 20 mins.

(157) C10. A process according to any one of clauses 2 to 7, wherein the metal layer on the coating substrate is between 25 and 200 nm.

(158) C11. A process according to any preceding clause, wherein the converting step comprises:

(159) applying at least one perovskite precursor to the metal coating of the coated substrate to form the perovskite layer.

(160) C12. A process according to any one of clauses 1 to 10, wherein the converting step comprises:

(161) contacting the at least one coating of the metal coated substrate with a vapour X selected from a halide vapour comprising at least one of F, Cl, Br or I, or acetic acid vapour to form a metal compound MX.sub.2 coating on the coated substrate; and thereafter

(162) applying at least one perovskite precursor to the coated substrate to form the perovskite layer.

(163) C13. A process according to clause 12, wherein the halide vapour results from vapour from at least one of: halide containing solution; or halide solids.

(164) C14. A process according to clause 12 or 13, wherein the at least one coating of the metal coated substrate is contacted with a vapour X at between 50 and 200? C., preferably between 75 and 150? C.

(165) C15. A process according to clause 12, 13 or 14, wherein the at least one coating of the metal coated substrate is contacted with a vapour X in a reduced pressure, preferably in a vacuum.

(166) C16. A process according to any one of clauses 11 to 15, wherein the at least one coating of the metal coated substrate is contacted with a vapour X in a bomb type reactor.

(167) C17. A process according to any one of clauses 11 to 16, wherein the perovskite precursor comprises at least one perovskite precursor vapour.

(168) C18. A process according to clause 17, wherein the converting step includes forming the perovskite layer by vapour deposition.

(169) C19. A process according to clause 18, wherein the vapour deposition process comprises:

(170) exposing the coated substrate to a perovskite precursor vapour comprising the perovskite precursor or one or more reactants for producing said perovskite precursor; and

(171) allowing deposition of the perovskite precursor vapour onto the metal halide MX.sub.2 coating on the coated substrate, to produce a perovskite layer thereon.

(172) C20. A process according to clause 18 or 19, wherein the vapour deposition is allowed to continue until the solid layer of perovskite has a thickness of from 100 nm to 100 ?m, preferably from 100 nm to 700 nm.

(173) C21. A process according to any one of clauses 11 to 20, wherein the perovskite precursor is a perovskite precursor solution comprising at least one perovskite precursor dissolved in a coating solvent.

(174) C22. A process according to clause 21, wherein the coating solvent comprises an alcohol based solvent, preferably isopropanol.

(175) C23. A process according any one of clauses 21 or 22, wherein the perovskite precursor is applied to the substrate using at least one of:

(176) casting, doctor blading, screen printing, inkjet printing, pad printing, knife coating, meniscus coating, slot die coating, gravure coating, reverse gravure coating, kiss coating, micro-roll coating, curtain coating, slide coating, spin coating, spray coating, flexographic printing, offset printing, rotatory screen printing, or dip coating.

(177) C24. A process according to any one of clauses 21 or 22, wherein the perovskite precursor is applied by dipping the coated substrate into the perovskite precursor solution.

(178) C25. A process according to any one of clauses 11 to 24, wherein the perovskite precursor comprises at least one compound having the formula AX, or at least one reaction constituent for forming at least one compound having the formula AX, in which A comprises an ammonium group or other nitrogen containing organic cation and X is selected from at least one of F, Cl, Br or I.
C26. A process according to clause 25, wherein A in the perovskite precursor AX comprises an organic cation having the formula (R.sub.1R.sub.2R.sub.3R.sub.4N), wherein:

(179) R.sub.1 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl;

(180) R.sub.2 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl;

(181) R.sub.3 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; and

(182) R.sub.4 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

(183) C27. A process according to any one of clauses 25 or 26, wherein A in the perovskite precursor AX comprises an organic cation having the formula (R.sub.5R.sub.6N?CHNR.sub.7R.sub.8), and wherein:

(184) R.sub.5 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl;

(185) R.sub.6 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl;

(186) R.sub.7 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl; and

(187) R.sub.8 is hydrogen, unsubstituted or substituted C1-C20 alkyl, or unsubstituted or substituted aryl.

(188) C28. A process according to any one of clauses 25 to 27, wherein the perovskite precursor AX is selected from the group consisting of CH.sub.3NH.sub.3X and HC(NH.sub.2).sub.2X, and wherein X is selected from at least one of F, Cl, Br or I.

(189) C29. A process according to clause 28, wherein perovskite precursor comprises a mixture of CH.sub.3NH.sub.3Cl and CH.sub.3NH.sub.3I

(190) C30. A process according to any preceding clause, wherein the perovskite layer comprises an organo-metal halide perovskite.

(191) C31. A process according to clause 30, wherein the perovskite layer comprises at least one of CH.sub.3NH.sub.3MX.sub.3 or HC(NH.sub.2).sub.2MX.sub.3, in which, M is selected from Pb, Sn, Tl, Bi, or In; and X is selected from at least one of F, Cl, Br or I.

(192) C32. A process according to any preceding clause, wherein the perovskite layer comprises an organo-lead halide perovskite, preferably comprising at least one of CH.sub.3NH.sub.3PbX.sub.3 or HC(NH.sub.2).sub.2PbX.sub.3, in which X is selected from at least one of F, Cl, Br or I.

(193) C33. A process according to any preceding clause, wherein the perovskite layer comprises CH.sub.3NH.sub.3MCl.sub.xI.sub.3-x or CH.sub.3NH.sub.3MI.sub.3-xCl.sub.x, in which M is selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In, preferably M is Pb.

(194) C34. A process according to any preceding clause, wherein the substrate comprises a conductive substrate.

(195) C35. A process according to any preceding clause, wherein the substrate comprises at least one of a polymer, metal, ceramic or glass, preferably a polymer film.

(196) C36. A process according to any preceding clause, wherein the substrate comprises at least one of: metal, preferably selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, In, Ni, Fe, stainless steel; FTO/ITO glass; glass with a conductive layer; polymer or plastic; or carbons/nanocarbons based substrates.
C37. A process according to any preceding clause, wherein the substrate includes one or more layers or coatings selected from at least one of:

(197) at least one coating of a transparent conductive oxide (TCO);

(198) at least one electrode screening layer;

(199) at least one hole blocking layer;

(200) at least one electron blocking layer;

(201) at least one hole transporting layer; or

(202) at least one electron transporting layer.

(203) C38. A process according to any preceding clause, wherein the substrate includes the following coatings:

(204) at least one coating of a transparent conductive oxide (TCO) and at least one hole transporting layer applied to the TCO; or

(205) at least one coating of a TCO and at least one electron transporting layer applied to the TCO.

(206) C39. A thin film photoactive layer formed using a process according to any one of the preceding clauses.

(207) C40. An optoelectronic device including a photoactive layer formed using a process according to any one of the preceding clauses.

(208) C41. A multi-junction solar cell including a photoactive layer formed using a process according to any one of the preceding clauses.

(209) C42. An optoelectronic device according to clause 40 or 41 comprising a photoactive device, preferably comprising at least one of a photovoltaic cell, a photoactive sensor or a light emitting device.

(210) C43. An optoelectronic device including a photoactive region which comprises:

(211) a n-type region comprising at least one n-type layer;

(212) a p-type region comprising at least one p-type layer; and

(213) a photoactive layer formed by a process according to any one of clauses 1 to 38 disposed between the n-type region and the p-type region.

(214) C44. An optoelectronic device comprising:

(215) a negative electrode comprising a current collector and a negative electrode material;

(216) a positive counter electrode comprising a current collector and a positive electrode material; and

(217) a charge transporting material between the positive electrode and negative electrode;

(218) wherein one or both of the positive electrode material and negative electrode material comprises a composite electrode material comprising:

(219) a conductive substrate;

(220) an electrode-screening layer; and

(221) a photoactive layer formed by a process according to any one of clauses 1 to 38.

(222) C45. An optoelectronic device according to clause 44, wherein the electrode-screening layer comprises

(223) at least one hole blocking layer; or

(224) at least one electron blocking layer.

(225) C46. A process of forming a thin film photoactive layer of an optoelectronic device can comprise the steps of:

(226) applying at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to a substrate to form a coated substrate; and

(227) converting the metal coating of the coated substrate to a perovskite layer.

(228) C47. Use of a substrate having a surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to form a thin film photoactive layer comprising:

(229) converting the metal surface or metal coating of the substrate to a perovskite layer.

(230) C48. A process of forming a thin film photoactive layer of an optoelectronic device can comprise the steps of:

(231) applying at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to a substrate to form a coated substrate; and

(232) converting the metal coating of the coated substrate to a perovskite layer,

(233) wherein the at least one coating of a metal M is applied to the substrate by a deposition method comprising at least one of electrodeposition, electrophoretic deposition, electroplating, or electroless deposition.

(234) C49. A process of forming a thin film photoactive layer of an optoelectronic device can comprise the steps of:

(235) applying at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to a substrate to form a coated substrate; and

(236) converting the metal coating of the coated substrate to a perovskite layer, wherein the at least one coating of a metal M is applied to the substrate by a physical coating method comprising at least one of an evaporative coating method, sputter, or cold spray.

(237) C50. An intermediate for use in forming a thin film photoactive layer of an optoelectronic device comprising a substrate having a surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In,

(238) wherein the metal surface or metal coating of the substrate is convertible to a perovskite layer by applying at least one perovskite precursor thereto.

(239) C51. An intermediate according to clause 50, wherein the substrate is coated with a metal M having a thickness of between 25 and 200 nm.

(240) C52. An intermediate according to clause 51, wherein the variation in thickness of metal M on the substrate is no more than 10 nm, preferably no more than 7 nm.

(241) C53. An intermediate according to any one of clauses 50 to 52, wherein the substrate comprises a conductive substrate coated with a metal M.

(242) C54. An intermediate according to clause 53, wherein the substrate comprises at least one of a polymer, metal, ceramic or glass, preferably a polymer film.

(243) C55. An intermediate according to clause 53 or 54, wherein the substrate comprises at least one of: metal, preferably selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, In, Ni, Fe, stainless steel; FTO/ITO glass; glass with a conductive layer; polymer or plastic; or carbons/nanocarbons based substrates.
C56. An intermediate according to any one of clauses 50 to 55, wherein the surface roughness of the intermediate is lower than the surface roughness of the substrate and preferably this difference is at least 2 nm and more preferably at least 3 nm.
C57. An intermediate according to any one of clauses 50 to 55, wherein the substrate includes one or more layers or coatings selected from at least one of:

(244) at least one coating of a transparent conductive oxide (TCO);

(245) at least one electrode screening layer;

(246) at least one hole blocking layer;

(247) at least one electron blocking layer;

(248) at least one hole transporting layer; or

(249) at least one electron transporting layer.

(250) C58. An intermediate according to any one of clauses 50 to 56, wherein the substrate includes the following coatings:

(251) at least one coating of a transparent conductive oxide (TCO) and at least one hole transporting layer applied to the TCO; or

(252) at least one coating of a TCO and at least one electron transporting layer applied to the TCO.

(253) C59. An intermediate comprising a metal compound MX.sub.2 coating on a substrate for use in forming a thin film photoactive layer of an optoelectronic device comprising a substrate having a surface formed from a metal M coating selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In contacted with a vapour X selected from a halide vapour comprising at least one of F, Cl, Br or I, or acetic acid vapour,

(254) wherein the metal compound MX2 coating on the coated substrate comprises crystallite having a size of less than 100 nm, preferably between 1 nm and 100 nm, more preferably between 10 nm and 90 nm, and

(255) wherein the metal compound MX.sub.2 coating on the substrate is convertible to a perovskite layer by applying at least one perovskite precursor thereto.

(256) C60. An organo-metal halide perovskite layer according to clause 59, wherein the minimum value in a surface profilometry measurement of the substrate is less than the minimum value in a surface profilometry measurement of metal compound MX.sub.2 coating on a substrate by at least 3 nm, preferably at least 5 nm, more preferably at least 7 nm.
C61. An organo-metal halide perovskite layer produced from an intermediate comprising a substrate having a surface comprising or coated with a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In, wherein the metal surface or metal coating of the substrate is converted to the perovskite layer by applying at least one perovskite precursor thereto.
C62. An organo-metal halide perovskite layer having a roughness substantially matching the roughness of the substrate to which the layer is applied.
C63. An organo-metal halide perovskite layer according to clause 62, wherein the RMS (root mean squared) roughness is less than 10 nm and preferably less than 5 nm and even more preferably less than 3 nm.
C64. A method of monitoring the quality of a thin film photoactive layer of an optoelectronic device, comprising the steps of:

(257) applying at least one coating of a metal M selected from at least one of Pb, Sn, Ge, Si, Ti, Bi, or In to a substrate by a deposition method comprising at least one of electrodeposition, electrophoretic deposition, electroplating, or electroless deposition to form a coated substrate; and

(258) converting the metal coating of the coated substrate to a perovskite layer,

(259) wherein the deposition method includes a deposition quality control sensor.

(260) C65. A method according to clause 64, wherein the deposition quality control sensor comprises at least one of applied electrical current or voltage, frequency of the applied electrical signal or measured impedance of the final deposited product.