METHOD FOR PRODUCING A LIGHT ABSORBING FILM WITH A PEROVSKITE-LIKE STRUCTURE

Abstract

The invention relates to methods for producing a light-absorbing material with a perovskite-like structure, and can be used to form a light-absorbing layer in the production of photovoltaic cells for saving the materials and increasing the allowable size of converters. These advantages are achieved by forming a uniform layer of component B on the substrate, preparing a mixture of reagents that react with component B under predetermined conditions, and a reaction inhibitor that suppresses this reaction under these conditions; the prepared mixture is applied in stoichiometric amount or greater than stoichiometric on the layer of component B and the reaction inhibitor is removed from the mixture, ensuring activation of the chemical reaction between the mixture of reagents and component B to form films of perovskite-like material.

Claims

1-20. (canceled)

21. A method for producing a film of a light-absorbing material having a perovskite-like structure and a structural formula of ABX.sub.3, comprising the following steps: a) forming a uniform layer of a component B on a substrate, b) applying a mixture of reagents AX, X.sub.2 and an inhibitor on the layer of the component B, wherein this mixture does not react with the component B under first predetermined conditions, and AX, X.sub.2 reagents are applied in a stoichiometric amount or more than stoichiometric amount regarding to the component B; c) forming liquid reactive polyhalide melts having general composition structure AX.sub.n (n2.5) by removing the inhibitor, and uniformly distributing said formed melts over the layer of the component B, followed by a reaction between the component B and the reactive polyhalide melts under second predetermined conditions; wherein the reaction of the melts AX.sub.n with the component B produce the highly homogeneous film of a perovskite-like material having the structural formula of ABX.sub.3, wherein CH.sub.3NH.sub.3.sup.+ (MA.sup.+), (NH.sub.2).sub.2CH.sup.+ (FA.sup.+), Cs.sup.+, Rb.sup.+, or a mixture thereof is used as component A; Cl.sup. or Br.sup. or I.sup. or a mixture thereof is used as component X, and Pb, Sn or a mixture thereof is used as the component B.

22. The method according to claim 21, characterized in that the inhibitor is removed under conditions that differ from the first predetermined conditions.

23. The method according to claim 21, characterized in that the inhibitor is removed from the mixture by evaporation or freezing or sublimation.

24. The method according to claim 21, characterized in that a solvent is used as an inhibitor to dissolve at least one of the reagents in the solvent.

25. The method according to claim 21, characterized in that as the inhibitor, uses a liquid is used that is not miscible with at least one of the reagents.

26. The method according to claim 21, characterized in that the inhibitor is removed by washing the substrate with a solvent, in which insoluble components of the film of the perovskite-like material are not soluble.

27. The method according to claim 21, wherein to obtain the film of a perovskite-like light-absorbing material having a structural formula ABX.sub.3, the mixture of reagents AX and X.sub.2 is applied to the substrate in a solution of the inhibitor, wherein the inhibitor is an organic solvent that slows down a reaction of AX and X.sub.2 with the reagent B, and said organic solvent is further removed to ensure the following reaction occurs: B+AX+X.sub.2=ABX.sub.3.

28. The method according to claim 27, wherein the reagents AX and X.sub.2 are dissolved in the organic solvent, but component B is not dissolved.

29. The method according to claim 27, wherein the component B is applied on the substrate in an amount per unit area that provides a final film of the perovskite-like compound ABX.sub.3 of a given thickness.

30. The method according to claim 21, wherein the component B is applied by a vacuum deposition or electrochemical deposition or by contacting a wave of the melted component B with a cooled substrate or by chemical vapor deposition from gas phase.

31. The method according to claim 21, wherein the mixture is applied by spraying through a nozzle, or ultrasonic spraying, or inkjet printing, or spin coating, or electrospraying, or printing, or dip coating.

32. The method according to claim 27, wherein surplus of reagents AX and X.sub.2 after completion of the reaction is removed by washing with a solvent that does not interact with the film of the perovskite-like material.

33. The method according to claim 27, wherein surplus of reagents AX and X.sub.2, after completion of the reaction, is removed by dropping a solvent that does not interact with the film of the perovskite-like material on the substrate.

34. The method according to claim 27, wherein surplus of reagents AX and X.sub.2, after completion of the reaction, is removed by calcination at an elevated temperature.

35. The method according to claim 27, wherein surplus of reagents AX and X.sub.2, after completion of the reaction, is removed by evaporation under reduced pressure.

36. The method according to claim 30, wherein deposition is carried out using a carrier gas, which is dry air or argon or nitrogen.

37. The method according to claim 21, wherein isopropyl alcohol or ethyl alcohol is used as the inhibitor.

38. The method according to claim 32, wherein a prepared mixture is applied under conditions that remove surplus components that are not involved in the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0018] The reaction mixture, in the application, refers to one or more reagents that react with component B, as well as a mixture of them with a reaction inhibitor.

[0019] The inhibitor, in the application, in general, refers to a chemical compound or a mixture of several compounds, where adding the inhibitor to the reaction mixture suppresses the chemical reaction between two or more reagents. In the particular case, the solvent may act as an inhibitor, reducing the chemical activity of one or more reagents. In the particular case, the inhibitor inhibits a chemical reaction between some component of the reaction mixture and component B.

[0020] The technical result is achieved by forming a uniform layer of component B on the substrate, preparing a mixture of reagents that react with component B under predetermined conditions, and a reaction inhibitor that suppresses this reaction under these conditions, applying the mixture in the stoichiometric amount or more than stoichiometric amount on the layer of component B and removing the reaction inhibitor from the mixture to activate the chemical reaction between the reaction mixture and component B to form a perovskite-like material. That is, upon receiving a film of light-absorbing material with a perovskite-like structure, a uniform layer of component B is formed on the substrate, a mixture is prepared from reactants that react with component B under predetermined conditions, and a reaction inhibitor that suppresses this reaction under these conditions, the prepared mixture is applied in stoichiometric amount or more than stoichiometric amount on the layer of component B and the reaction inhibitor is removed from the mixture, while ensuring activation of the chemical reaction between the mixture of the reagents and component B to form a perovskite-like film material.

[0021] In particular cases, the implementation of the invention, the reaction inhibitor is removed from the reaction mixture by evaporation from the reaction mixture or freezing the specified reagents from the mixture or sublimation of the reaction inhibitor.

[0022] In the particular case of the invention, a solvent is used as an inhibitor of the reaction, which can dissolve at least one of the reagents in or a liquid that cannot be mixed with at least one of the reagents is used as an inhibitor of the reaction.

[0023] In the particular case of the invention, the reaction inhibitor is removed by washing the carrier substrate with a solvent in which the components of the final functional layer (film of perovskite-like material) are insoluble.

[0024] In the particular case of the invention, upon producing a layer (or film) of a light-absorbing material with a perovskite-like structure having the structural formula ABX.sub.3, according to the technical solution, a layer of reagent B is applied to the substrate, which is a film of elementary Pb or Sn or a mixture of them, and then a solution of the mixture of reagents AX and X.sub.2 in an organic solvent is applied on the substrate, wherein an organic solvent slows down the reaction between AX and X.sub.2 with reagent B, conditions for the removal of the solvent are provided that step ensure proper conditions for proceeding the reaction B+AX+X.sub.2=ABX.sub.3. In this case, CH.sub.3NH.sub.3.sup.+ or (NH.sub.2).sub.2CH.sup.+ or C(NH.sub.2).sub.3.sup.+ or Cs.sup.+ or Rb.sup.+ or a mixture of them is used as component A; Cl.sup. or Br.sup. or I.sup. or a mixture of them is used as component X.

[0025] In the particular implementation of the invention, an organic solvent is used as the inhibitor in which the reagents AX and X.sub.2 are dissolved, but component B is not dissolved in the organic solvent. Component B is applied per unit area in an amount that provides a given thickness of the final film of the perovskite-like compound ABX.sub.3. Component B can be applied by vacuum deposition, electrochemical deposition, contact of a molten metal with a cooled substrate, by chemical deposition from the gas phase or by other methods. A solution of the mixture of reagents AX and X.sub.2 is applied by spraying, or printing or dripping. Surplus reagents AX and X.sub.2 upon completion of the reaction, if necessary, can be removed by washing in a solvent that does not interact with the perovskite layer, dripping the solvent onto the surface, calcinating at elevated temperature, evaporating under reduced pressure. Gases such as, for example, dry air, argon and nitrogen can act as a carrier gas during spraying. Solvents such as isopropyl alcohol, ethyl alcohol and other organic solvents can be used as solvents for the AX and X.sub.2 reagents, as well as for washing the substrates after the completion of the reaction.

[0026] In the particular case of the implementation of the invention, the application of the reaction mixture is carried out under conditions in which a surplus of components of the reaction is removed in a natural way (the autodosing of the components of the reaction mixture occurs) due to their evaporation or sublimation during application.

[0027] With the invention, it is possible to control the stoichiometry of the formation of a film of light-absorbing material reaction due to preliminary controlled deposition of component B on the substrate and further controlled deposition of the AX and X.sub.2 reagents solution, carried out by inkjet, spraying or other methods, ensuring uniform application of the mixture on the substrate. After applying the solution of reagents AX and X.sub.2 on the surface of the film of component B, the solvent removal takes place followed by the formation of liquid polyhalide reaction melts consisting of a mixture of reagents AX and X.sub.2 of the general composition structure AX.sub.n (n2.5), which are uniformly distributed over the surface of the film of component B and react with this component with the formation of a perovskite-like compound with an ABX.sub.3 structure, which makes it possible to achieve a high homogeneity of films over a large area by methods that are scalable and realizable under industrial production conditions.

[0028] Component B is considered to be metals, a mixture of them, alloys, as well as compounds where in the elemental composition presents corresponding metal.

[0029] The uniform distribution of the reaction melt over the surface of the component B is achieved by the so-called Reactive wetting of the film surface of component B with polyhalide melts of composition AX.sub.n, the mechanism of which is to change the nature of wetting as a result of the reaction on the surface of component B due to their high reactivity with respect to component B.

[0030] With the proposed method, the achievement of a technical result, namely, obtaining a single-phase, highly homogeneous large area film of a light absorbing material, is achieved by uniformly distributing AX.sub.n (n2.5) reaction melts over the surface of the B component film, as well as controlling the stoichiometry of the reaction to form a film of light absorbing material. The main parameters affecting the achievement of the technical result are the thickness and uniformity of the B film applied to the substrate, the uniform distribution of the AX and X.sub.2 mixture solution over the surface of the B film, the concentration of the AX and X.sub.2 reagents, the amount of the B component applied to the film, the composition of the solvent used, the temperature of the film of the component B, the presence of modifying additives in the solution of reagents AX and X.sub.2 and/or in the film of component B.

[0031] The proposed method allows to obtain continuous single-phase films of compounds with a perovskite structure of a wide range of compositions (ABX.sub.3, where CH.sub.3NH.sub.3.sup.+ (MA.sup.+), (NH.sub.2).sub.2CH.sup.+ (FA.sup.+), Cs.sup.+, Rb.sup.+, or a mixture of them are usually used as A.sup.+, B.sup.2+ Pb2+, Sn2+ or a mixture of them; as X.sup. are used I.sup., Br.sup., Cl.sup. or a mixture of them) which can be used to create solar cells, large-area solar cells, photodetectors, LEDs and other semiconductor devices.

[0032] In addition, using the proposed method it is possible to obtain thin films of semiconductors, including those ones based on the usage of materials with a structure different from perovskite-like and made from elements or their sources other than Pb, Sn.

[0033] In an illustrative implementation, to obtain a hybrid organo-inorganic perovskite composition CH.sub.3NH.sub.3PbI.sub.3 (MAPbI.sub.3), a solution of iodine (I.sub.2) and methyl ammonium iodide (MAI) in isopropanol (i-PrOH) was sprayed onto a substrate heated to 120 C. and pre-coated with a layer of metallic lead (Pb) on it. Upon contact of the sprayed aerosol with a heated lead film, isopropanol evaporated to form a polyiodide composition on the surface of lead and MAI-nI2 (n1), which reacted with lead, as a result was achieved the formation of a film of CH.sub.3NH.sub.3PbI.sub.3. The reaction takes place with a time delays, where the solvent removal stage determines the time delay and is crucial because when the metal lead film is immersed in the solution used for spraying (in a certain concentration range), the conversion of metal lead into perovskite is retarded. The formation of perovskite in the proposed method occurs in the process of drying the droplets deposited on the surface of metallic lead, as a result of which a polyiodide composition is formed, which reacts with lead. Since the reaction starts before the complete evaporation of isopropanol, and the reaction rate is determined, including the concentration of isopropanol in the composition, it is possible to control the rate of the reaction, for example, by changing the substrate temperature or the content of isopropanol in the original composition. Below are the parameters of the synthesis, which may be used in the preparation of continuous single-phase films by the proposed method with the achievement of the technical result, as well as the effect of influence of features on the parameters of the synthesis.

[0034] The composition of the used halides that make up the solution, directly affects the morphology and composition of the perovskite obtained. Any combination of AX is possible. The following combinations were tested when implementing the method: MAI, MAI/MABr, which resulted in the use of MAPbI.sub.3, MAPbI.sub.xBr.sub.3-x; MAI/FAI, the use of which was obtained MA.sub.xFA.sub.1-xPbI.sub.3.

[0035] The total ratio of the content of halides in a solution to the content of I.sub.2, or the ratio AX-I.sub.2 in reactions with metals, produces a direct impact on the morphology, phase composition and other properties of the final product. Since iodine and various halides sublimate (evaporate) during sputtering and subsequent annealing at different rates, the final composition of the melt on the surface of the substrate will be determined not only by the composition of the applied solution, but also by temperature and pressure of the process. Using the example of obtaining MAPbI.sub.3, the following relationships were tested: MAI:I.sub.1=1:1 and MAI:I.sub.1=1:1.5. Primary results showed that in the designated range it is possible to obtain single-phase MAPbI.sub.3 films, while films obtained using the 1:1.5 solution demonstrate the best functional properties, due to the fact that some of the iodine evaporates from heating and, if for the reaction requires MAI:I.sub.2=1:1, and for the implementation of the method the composition is used, where MAI:I.sub.1=1:1, then the actual content of iodine participating in the reaction is less, that is, there exists a lack of iodine in the system.

[0036] To improve the functional properties and stability of the final films, it is possible to introduce into the initial solution other halides that do not form the target perovskite structure, for example, aminovaleric acid hydroiodide, butylammonium iodide (in general, CH.sub.3(CH.sub.2).sub.nNH.sub.3I), phenylethylammonium iodide, BiI.sub.3 and others. HI, CH.sub.3NH.sub.3Cl and (NH.sub.2).sub.2CHCl can also be used as modifying additives.

[0037] When implementing the method it is possible to use different concentrations of reagents. The method showed good results in terms of improving the homogeneity and quality of perovskite films in the range of total concentrations of iodides from 2 to 10 mg/ml.

[0038] An important factor determining the functional properties of films of semiconductor materials obtained by the claimed method is the molar ratio of component B and the reagents applied to it. The inventive method allows to choose such conditions of application of the reaction mixture, under which the removal of surplus components of this mixture, i.e. their autodosing is achieved. In the particular case of usage the MAI-nI2 reaction mixture (nl) in isopropanol, autodosing can be achieved by spraying the reaction mixture onto the surface of metallic lead, heated to a temperature of 150-250 C., which leads to evaporation and/or sublimation of surplus components of the reaction mixture.

[0039] When using metal films as a layer containing metal, deposition of such films on a substrate is possible by vacuum thermal sputtering, magnetron sputtering, electrodeposition, chemical reduction from solutions or gaseous compounds. When checking the possibility of implementing the proposed method, thin films of metallic lead, tin, PbSn alloys, as well as alloys with alloying additives, for example, Cu and Bi, were tested.

[0040] In addition, layer-by-layer deposition of various metals suitable for the formation of a perovskite layer may be used to form a metal-containing layer.

[0041] As a specific example of implementation, a film of metallic copper was used as a film of component B, where MAI:I.sub.2=1:3 solution was applied at a substrate temperature of 100 C., after which surplus MAI was removed by washing with isopropyl alcohol.

[0042] To form a layer containing component B, lead compounds can also be used, for example, PbI.sub.2 and PbO, which can be deposited on a substrate by various methods, for example, by applying a solution of lead salts on a rotating substrate.

[0043] For the synthesis of MAPbI.sub.3, MAPbI.sub.xBr.sub.3-x, MA.sub.xFA.sub.1-xPbI.sub.3, a temperature of 120 C. was used. In addition, the method showed the possibility of using at least temperatures from 20 to 150 C. for MAPbI.sub.3 and from 20 to 400 C. for CsPbI.sub.3. Optimal for the implementation of the method is to maintain the substrate temperature above the melting temperature of the corresponding polyiodide. It is also possible to use a preheated substrate, as well as gradual cooling or gradual heating of the substrate after the application of the reactants. Preheating for 0-10 min was tested.

[0044] The substrate can be subjected to further processing after applying a solution to it and completing the reaction to form a perovskite layer. For example, washing with the use of various solvents or a mixture of them, for example, isopropanol, ethanol, diethyl ether, chlorobenzene, toluene, can be used.

[0045] Annealing can also be carried out at elevated temperatures. In particular, annealing was tested at 100 C. for 1-10 min, an increase in the annealing time to 60 minutes and longer has not led to a deterioration in the properties of the perovskite layer. In this case, the choice of the temperature of the annealing is determined by the chemical composition of a particular compound and for MAPbI.sub.3 usually does not exceed 150 C., for CsPbI.sub.3350 C. Annealing can also be carried out in a special atmosphere, for example, in an atmosphere of humid air, dry air, in an atmosphere of argon, and also in an atmosphere containing solvent vapors, for example, methylamine, dimethylformamide or dimethyl sulfoxide.

[0046] Annealing in vapors of the corresponding iodides AX is possible at temperatures limited from below by the evaporation temperature of the corresponding halide, and from above by the temperature of its decomposition. For example, for MAI, the typical temperature range is 150-200 C.

[0047] The mixture of reagents and solvent (solution) can be applied to the substrate by the following tested methods: classical spraying through a nozzle, ultrasonic spraying, inkjet printing, spin coating, electrospray, aerosol jet printing, dip coating.

[0048] The design of the nozzle for spraying the solution, as well as the mode of spraying, have a direct impact on the amount of substance falling on the substrate per unit of time and the size of the droplets, which affects the uniformity of the coating of the substrate with the solution. The optimal parameters can be chosen experimentally. The geometry of the mutual arrangement of the nozzle and the substrate also affects the quality of the coating and can be chosen experimentally. A distance of 10 cm was tested, and the angle of inclination of the nozzle was 0-15 between the direction of spraying and the normal to the substrate.

[0049] Implementation of the method was tested in the following modes: the flow rate of the solution 0.5 ml/sec; cyclic solution supply for 2 seconds with 10 seconds pauses. Pauses may be necessary to maintain the required temperature of the substrate, to ensure complete and rapid drying of the droplets and to avoid undesirable spreading of the solution over the surface.

[0050] The total time of spraying the solution, sprayed with pauses or without pauses, was selected separately for each composition. For MAPbI.sub.3, to obtain single-phase films, the range of total deposition times was used from 14 to 18 seconds (72 s, 92 s). When going beyond the boundaries of the optimal range, films with impurities were formed, which was caused by a substantial surplus or lack of reagents in the solution. Nitrogen and argon were used as carrier gas for spraying. It is also possible to use air and other gases, as well as the use of gases containing special modifying additives.