METHOD FOR THE SOLVENT-FREE DEPOSITION OF PEROVSKITE

Abstract

A method for solventless perovskite deposition. The method comprises loading a lead target and one or more samples adhered to a substrate support into a deposition chamber, pumping to a high vacuum pressure, and filling the deposition chamber with the vapor of a salt precursor to form a perovskite material.

Description

This application relates in general to compositions for use in photovoltaic and optoelectronic devices, and more particularly to methods for solventless perovskite deposition. BACKGROUND OF THE INVENTION The use of photovoltaic (PV) energy to generate electricity from solar energy or radiation can provide many benefits, including, for example, a source of energy, low or zero emissions, power production independent of the electrical grid, durable physical structures (without moving parts), stable and reliable systems, modular construction, relatively quick installation, safe manufacturing and use, and good public opinion and acceptance of use. Perovskite materials can be incorporated into one or more aspects of a photovoltaic device. This greater tolerance reduces production costs. However, traditional solvent-based methods for manufacturing perovskite cells can produce uneven layer thickness. This limits the ability to effectively coat large surfaces and create efficient multi-stack films. The features and advantages of this disclosure will be readily apparent to those skilled in the art. Although those skilled in the art may make numerous changes, such changes are within the spirit of the invention. BRIEF DESCRIPTION OF THE INVENTION According to one embodiment, a solventless perovskite deposition method comprises loading a lead target and a substrate into a deposition chamber. The method further comprises reducing the pressure in the deposition chamber to less than or equal to 5 x 10⁻⁶ Torr. The method further comprises vaporizing the lead target. In addition, the method comprises filling the deposition chamber with the vapors of a salt precursor. Finally, the method comprises depositing a perovskite material onto the substrate. In another embodiment, a solventless method for perovskite deposition comprises loading a lead powder sample into a crucible. The method further comprises placing an upside-down substrate onto the powder in the crucible. The method further comprises reducing the pressure in the deposition chamber to 200 mTorr. The method further comprises sublimating the lead powder sample. Finally, the method comprises performing a first deposition onto the substrate. In an additional embodiment, a solventless perovskite deposition method comprises loading a lead salt precursor into a crucible. The method further comprises loading a substrate onto a sample holder. The method further comprises reducing the pressure in the deposition chamber to at least 10.3 Torr. The method further comprises applying a current to ionize the lead salt precursor. The method further comprises filling the deposition chamber with the vapors of a second salt precursor. Finally, the method comprises depositing a perovskite material onto the substrate. In another embodiment, a solventless perovskite deposition method comprises loading a lead salt precursor into a crucible. The method further comprises loading a substrate onto a sample holder. The method further comprises reducing the pressure in the deposition chamber to between 5 Torr and 760 Torr. The method further comprises vaporizing the lead salt precursor. The method further comprises performing metal-organic framework epitaxy on the vapor. The method further comprises filling the deposition chamber with the vapors of a second salt precursor. Finally, the method comprises depositing a perovskite material onto the substrate under an inert gas. BRIEF DESCRIPTION OF THE DRAWINGS FIGURE 1 is a flow diagram of an example solventless perovskite deposition method. DETAILED DESCRIPTION OF THE INVENTION The methods described in this disclosure for depositing perovskite on a substrate can be used to fabricate one or more aspects of a perovskite. Other potential applications include, but are not limited to, batteries, field-effect transistors (FETs), light-emitting diodes (LEDs), nonlinear optical devices, memristors, capacitors, rectifiers, and / or rectifying antennas. A perovskite material may have the general formula CMX3, where: C comprises one or more cations (e.g., an amine, ammonium, phosphonium, a Group 1 metal, a Group 2 metal, and / or other cations or cationic-type compounds); M comprises one or more metals (e.g., Be, Mg, Ca, Sr, Ba, Fe, Cd, Co, Ni, Cu, Ag, Au, Hg, Sn, Ge, Ga, Pb, In, Ti, Sb, B1, Ti, Zn, Cd, Hg, and Zr); and X comprises one or more anions. In particular forms, C may comprise formamidinium or methylammonium.Although many of the methods described below are illustrated using lead perovskite, these methods can be used to achieve other perovskites by substituting the desired metal (M) or metal halide (MXn). In some embodiments, this disclosure provides methods for depositing perovskite based on physical vapor deposition. In additional embodiments, this disclosure provides methods for depositing perovskite based on chemical vapor deposition. Several embodiments of the physical and chemical vapor deposition methods are described in detail below. MA / C / ZUZZ / UUO l Zó In each of the modes described below, the resulting perovskite film pattern can be achieved by placing a fitted shadow mask directly onto the substrate before loading the substrate into the vacuum chamber. Physical methods of vapor deposition Generally, physical vapor deposition involves vaporizing the deposition material, transporting the vapor to the target substrate, the reaction between the metal atoms and a reactive gas during the transport stage, and the deposition onto the substrate. This disclosure includes several physical vapor deposition methods. Specifically, methods for sputtering, reactive sputtering, electron beam deposition, cathode arc deposition, pulsed laser deposition, molecular beam epitaxy, enclosed space sublimation, thermal evaporation and co-evaporation with annealing, vapor-assisted solution processing, ion-assisted deposition, and activated reactive evaporation are described. Cathodic sputtering In certain embodiments, a solventless perovskite deposition method comprises loading a PbL (lead(II) iodide) target into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure is pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems are under a static vacuum of 10⁻⁸ Torr. The method further comprises loading samples adhered to a substrate support into a charge-blocking chamber. The method further comprises pumping the charge-blocking chamber to a high vacuum (10⁻³ to 10⁻⁵ Torr) and transferring a sample holder to the sputtering chamber. In some embodiments, the high vacuum may be less than 1 × 10⁻⁵ Torr.The method further comprises applying an inert gas, such as argon (Ar), to the PbL target to induce a sputtering effect, filling the sputtering chamber with formamidinium iodide (FAI) and / or methyl ammonium iodide (MAI) vapor, and depositing a perovskite material. The chamber can be filled using a mass flow controller (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a solventless perovskite deposition method comprises loading a lead (Pb) target into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure should be pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems should be under a static vacuum of 10⁻⁸ Torr. The method further comprises loading samples adhered to a substrate support into a charge-blocking chamber. The method continues with pumping the charge-blocking chamber to a high vacuum pressure (10⁻³ to 10⁻⁵ Torr) and transferring a sample holder. MA / t / ZUZZ / UUÓ l ¿ó to the charge-locking chamber. The method further comprises applying an inert gas, such as Ar, to the Pb target to induce a sputtering effect, filling the chamber with Hl (hydrogen iodide) and one or both of FAI or MAI vapor, and depositing a perovskite material. The chamber can be filled using an MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MAI or FAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a solventless method for the deposition of perovskite material comprises loading a Pb target (either Pb with Hl or Pbl2) into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure should be pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems should be under a static vacuum of 10⁸ Torr. The method further comprises loading a sample adhered to a substrate support into a charge-blocking chamber and pumping the charge-blocking chamber to a high vacuum pressure (10³ to 10⁵ Torr) before transferring a sample support into the chamber. The method continues by applying an inert gas, such as Ar, to the Pbl2 target to induce a sputtering effect, filling the chamber with Hl, and depositing a perovskite material. The chamber filling can be performed using a multi-stage carbon filter (MSC) at a rate of between 2 and 100 sccm.In some formulations, Hl can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. The method concludes by removing the Pbl2 film from the chamber and transferring it to a different instrument, such as a thermal evaporator, for FAI and / or MAI deposition. Reactive sputtering In other embodiments, a method for solventless perovskite deposition comprises loading a Pbl2 target into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure should be pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems should be under a static vacuum of 10⁻⁸ Torr. The method further comprises loading samples adhered to a substrate support into the sputtering chamber. The method further comprises pumping a charge-blocking chamber to a high vacuum pressure (10⁻³ to 10⁻⁵ Torr) and transferring a sample holder into the charge-blocking chamber. The method further comprises applying a reactive gas, such as oxygen or nitrogen, to the Pbl2 target to induce a sputtering effect, filling the chamber with FAI and / or MAI vapor, and depositing a perovskite material. The chamber can be filled using an MFC at a rate of between 2 and 100 sccm.In some modalities, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method assumes that the. MA / t / ZUZZ / UUÓ l ¿or the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a solventless method for deposition of perovskite material comprises loading a Pb (lead) target into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure should be pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems should be under a static vacuum of 10⁻⁸ Torr. The method further comprises loading samples adhered to a substrate support into a charge-blocking chamber. The method continues with pumping the charge-blocking chamber to a high vacuum pressure (10⁻³ to 10⁻⁵ Torr) and transferring a sample holder into the charge-blocking chamber. The method further comprises applying a reactive gas, such as oxygen or nitrogen, to the Pb target to induce a sputtering effect, filling the chamber with HL (hydrogen iodide) and one or both of FAI or MAI vapor, and depositing a perovskite material.The chamber can be filled using an MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MAI or FAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a solventless method for deposing perovskite material comprises loading a Pb target into a sputtering chamber and pumping it to a high-to-ultra-high vacuum pressure. For example, the pressure should be pumped to less than or equal to 10⁻⁶ Torr. Preferably, the systems should be under a static vacuum of 10⁻⁸ Torr. The method further comprises loading a sample adhered to a substrate support into a charge-blocking chamber and pumping the charge-blocking chamber to a high vacuum pressure (10⁻³ to 10⁻⁵ Torr) before transferring a sample support into the chamber. The method continues by applying a reactive gas, such as oxygen or nitrogen, to the Pb target to induce a sputtering effect, filling the chamber with H₂I, and depositing a perovskite material. The chamber can be filled using a multi-stage carbon filter (MSC) at a rate of between 2 and 100 sccm. In some modalities, Hl can be introduced at a rate of between 5 and 30 sccm.The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. The method concludes by removing the Pblz film from the chamber and transferring it to a different instrument, such as a thermal evaporator, for FAI and / or MAL deposition. Physical deposition of electron beam vapor or electron beam deposition Figure 1 illustrates a method 100 for the solventless deposition of perovskite material. Step 102 comprises loading a Pbk target into a deposition chamber. MA / t / ZUZZ / UUÓ l ¿ó Step 104 involves loading samples adhered to the substrate support into the deposition chamber. Method 100 continues in step 106 with pumping to a high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr). In step 108, an electron beam is applied to the Pbh target. Method 100 then proceeds to step 110 where the deposition chamber is filled with FAI and / or MAI vapor. The chamber can be filled using an MFC at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. Finally, the example method concludes in step 112 by depositing a perovskite material. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a solventless method for the deposition of perovskite material comprises loading a lead (Pb) target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping up to a high vacuum pressure (less than or equal to 5 x 10⁶ Torr) and applying an electron beam to the Pb target. The method continues by filling the chamber with hydrochloric acid (Hl) and formamidine vapor and / or methylamine (MA) and depositing a perovskite material. The chamber can be filled using a multi-fuel (MFC) system at a rate of between 2 and 100 sccm. In some embodiments, the Hl and the formamidine vapor and / or MA can be introduced at a rate of between 5 and 30 sccm. The method contemplates that the first 20 nm of perovskite should be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a solventless method for deposing perovskite material comprises loading a lead (Pb) target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping up to a high vacuum pressure (less than or equal to 5 x 10⁶ Torr) and applying an electron beam to the lead (Pb) target. The method continues by filling the chamber with hydrogen vapor (H₂) and depositing a perovskite material. The chamber can be filled using a multi-fuel (MFC) system at a rate of between 2 and 100 sccm. In some embodiments, the hydrogen vapor can be introduced at a rate of between 5 and 30 sccm. The method concludes by removing the Pbls film from the chamber and transferring the film to a different instrument, such as a thermal evaporator, for FAI and / or MAL deposition. The method contemplates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Physical depositions of cathode arc vapor In certain embodiments, a solventless method for deposition of perovskite material comprises loading a Pb target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping to an ultra-high vacuum pressure (10⁻⁸ to 10⁻¹² Torr) and applying a cathodic arc to the Pb target. The method continues by filling the chamber with H₂O vapor and depositing a perovskite material. The chamber can be filled using a multi-fuel converter (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the H₂O can be introduced at a rate of between 5 and 30 sccm. The method concludes by removing the Pb₂ film from the chamber and transferring the film to a different instrument, such as a thermal evaporator, for the deposition of FAI and / or MAI. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Pulsed laser deposition In certain embodiments, a solventless method for the deposition of perovskite material comprises loading a PbI₂ target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping to a high vacuum pressure (10⁻⁶ to 10⁻⁸ Torr) and applying a pulsed laser to the PbI₂ target. The method continues by filling the chamber with FAI and / or MAI vapor and depositing a perovskite material. The chamber can be filled using a multi-function torch (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method contemplates that the first 20 nm of perovskite should be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a solventless method for deposing perovskite material comprises loading a Pb target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping to a high vacuum pressure (10⁻⁶ to 10⁻⁸ Torr) and applying a pulsed laser to the Pb target. The method continues by filling the chamber with Hl and one or both of MAI or FAI vapor and depositing a perovskite material. The chamber can be filled using a MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MAI or FAI can be introduced at a rate of between 5 and 30 sccm. The method contemplates that the first 20 nm of perovskite should be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a solventless method for deposing perovskite material comprises loading a Pb target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping to a high vacuum pressure (10⁻⁶ to 10⁻⁸ Torr) and applying a pulsed laser to the Pb target. The method continues by filling the chamber with Hl vapor and depositing a perovskite material. The chamber can be filled using a multi-function carbon (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the Hl can be introduced at a rate of between 5 and 30 sccm. The method concludes by removing the Pbl₂ film from the chamber and transferring the film to an instrument. MA / t / ZUZZ / UUÓ l ¿or different, such as a thermal evaporator, for the deposition of FAI and / or MAI. The method contemplates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Molecular beam epitaxy In certain embodiments, a solventless method for deposition of perovskite material comprises loading a Pb target into a deposition chamber and loading samples adhered to a substrate support into the deposition chamber. The method further comprises pumping to an ultra-high vacuum pressure (10⁻⁸ to 10⁻¹² Torr) and applying a molecular beam to the Pb target. The method continues by filling the chamber with H₂O vapor and depositing a perovskite material. The chamber can be filled using a molecular flight converter (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the H₂O can be introduced at a rate of between 5 and 30 sccm. The method concludes by removing the Pb₂ film from the chamber and transferring the film to a different instrument, such as a thermal evaporator, for the deposition of FAI and / or MAI. The method stipulates that the first 20 nm of perovskite must be deposited at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Sublimation of enclosed spaces In certain embodiments, a method for solventless perovskite material deposition comprises loading a Pbl2 powder sample into a crucible and placing the substrate on top of the sample, upside down. The method further comprises pumping the Pbl2 powder sample to a low vacuum pressure (-200 mTorr) and sublimating it. The method continues by filling a chamber with FAI and / or MAI vapor and depositing the perovskite material. The chamber can be filled using a multi-fuel converter (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of deposition should be carried out at a rate of approximately 0.5 Å / second to ensure that the material adheres to the substrate. In other embodiments, a method for solventless perovskite material deposition comprises loading a Pb powder sample into a crucible and covering the crucible with the Pb powder sample upside down. The method further comprises pumping under low vacuum pressure (~200 mTorr), sublimating the Pb sample, and making a first deposition. The method continues by filling a chamber with Hl and one or both of formylimidamide (FA) or methylamine (MA) vapor and making a second deposition. The chamber can be filled using a MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MA or FA can be introduced at a rate of between 5 and 30 sccm. The method contemplates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another modality, a method for the deposition of perovskite material without MA / C / ZUZZ / UUO l Solvent Zó comprises loading a sample of Pbb powder into a crucible and covering the crucible with the Pbl2 powder sample upside down. The method further comprises pumping to a low vacuum pressure (~200 mTorr), sublimating the Pbl2 powder sample, and making a first deposition. The method further comprises replacing the Pbl2 powder sample with MAI and / or FAI powder samples and placing the MAI and / or FAI powder samples upside down onto the crucible. The method concludes by pumping to a pressure of 200 mTorr, sublimating the MAI and / or powder samples, and making a second deposition. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In a further embodiment, a solventless method for perovskite deposition comprises growing a single-crystal perovskite with the ABX3 structure using any method known to the skilled trades. The method further comprises loading a single crystal into a crucible and loading the substrate upside down onto the substrate holder. Depending on the crystal size, it may be necessary to crush the perovskite crystal into more uniform pieces using a mortar and pestle. The method further comprises pumping under low vacuum pressure (~200 mTorr), sublimating the crystal, and performing a first deposition. Thermal evaporation and co-evaporation with annealing In certain embodiments, a method for solventless perovskite material deposition comprises loading a Pbl2 powder sample into a crucible and loading substrates onto a sample holder. The method further comprises pumping under high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr) and evaporating the Pbl2 powder sample by applying a voltage between two metal posts. The method continues by filling a chamber with FAI and / or MAI vapor and making depositions. The chamber can be filled using a microfilter at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of depositions should be made at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a method for solventless perovskite material deposition comprises loading a Pbl2 powder sample into a first crucible and loading MAI and / or FAI samples into a second crucible. The method further comprises loading substrates into a sample holder and pumping to a high vacuum pressure (less than or equal to 5 x 10⁶ Torr). The method continues by evaporating the Pbl2 and MAI and / or FAI samples by applying a voltage between two metal posts and simultaneously depositing Pbl2 and MAI and / or FAI. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a method for solventless deposition of perovskite material comprises loading a sample of Pb into a crucible, loading substrates onto a holder MA / C / ZUZZ / UUO l Zó samples are pumped under high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr). The method further comprises evaporating the Pb sample by applying a voltage between two metal posts. The method continues by filling the chamber with Hl and one or both of FAI or MAI vapor and making depositions. The chamber can be filled using an MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MAI or FAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of depositions should be made at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In additional embodiments, a solventless method for deposition of perovskite material comprises loading a Pbl2 powder sample into a crucible, loading substrates onto a sample holder, and pumping under high vacuum pressure (less than or equal to 5 x 10⁶ Torr). The method further comprises evaporating the Pbl2 powder sample by applying a voltage between two metal posts and making a first deposition. The method continues by replacing the Pbl2 powder sample with an MAI and / or FAI powder sample and pumping under high vacuum pressure (less than or equal to 5 x 10⁶ Torr). The method concludes by evaporating the MAI and / or FAI powder sample by applying a voltage between two metal posts and making a second deposition. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In still other embodiments, a solventless perovskite deposition method comprises growing a single-crystal perovskite with the ABX3 structure by any method. The method further comprises loading the single crystal or crystals into a crucible. In some cases, it may be necessary to crush the crystals in a mortar to obtain smaller, more uniform pieces. The method further comprises loading samples onto a substrate support. The method further comprises pumping the deposition chamber to a high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr). The method concludes by applying a voltage to two metal posts connected to the precursor crucible to evaporate the crystal or crystals and deposition them onto the sample. Vapor-assisted solution processing or hybrid physical chemical deposition In certain embodiments, a method for solventless perovskite material deposition comprises depositing a PbI2 layer onto a film using any of the methods described above. The PbI2 film can be shaped using a fitted shadow mask. The method further comprises placing the film with the PbI2 layer facing upwards in a reduced-pressure chamber (between 200 mTorr and 10⁻⁶Torr) and introducing hydrogen iodide (HI) vapor. The method concludes with a vapor flow of methylamine (MA) and / or formylimidamide (FA), which may exist as its formamidine tautomer in the gas phase, into the reduced-pressure chamber. The MA and / or FA vapor can be introduced using MA / C / ZUZZ / UUO l ¿or an MFC at a rate of between 2 and 100 sccm. In some modalities, it can be introduced at a rate of between 5 and 30 sccm. In certain embodiments, a method for solventless perovskite material deposition comprises depositing a layer of HPbh onto a film using any of the methods described above. The method further comprises placing the film with the HPbh layer facing upwards in a reduced-pressure chamber. The method concludes with the flow of methylamine (CH3NH2) and / or formylimidamide (NH2CHNH) vapor into the reduced-pressure chamber. Alternatively, the methylamine (CH3NH2) and / or formylimidamide (NH2CHNH) vapor is added first to Pbl2, and then followed by Hl. Thermal spraying (spray coating) In certain embodiments, a solventless method for deposing perovskite material comprises spraying a Pbl2 sample, heated to 20–80 °C, onto a film at atmospheric pressure and placing the film with the Pbl2 layer facing upwards in a reduced-pressure chamber (between 200 mTorr and 106 Torr). The method concludes with the influx of MA and / or FA vapor into the reduced-pressure chamber. The MA and / or FA vapor can be introduced using a MFC at a rate of between 2 and 100 sccm. In some embodiments, it can be introduced at a rate of between 5 and 30 sccm. Ionic plating or ion-assisted deposition In one embodiment, a solventless method for deposition of perovskite material comprises loading a Pb target into a deposition chamber, loading samples adhered to a substrate support into the deposition chamber, and pumping the chamber at 10⁻⁵ Torr or less. In some embodiments, the chamber is pumped at 10⁻⁸ Torr. The method further comprises evaporating the Pb target by bombarding the source material with particles. Particle bombardment vaporization can be achieved using evaporation, sputtering, arc vaporization, or chemical means. This form of vaporization requires the addition of an inert gas (e.g., Ar) or a reagent (e.g., O₂ or N₂). The method further comprises filling the chamber with H₂O vapor and making depositions. The chamber can be filled using a multi-stage carbon filter (MSC) at a rate of 2 to 100 sccm. In some embodiments, the H₂O can be introduced at a rate of 5 to 30 sccm.The method concludes by removing the Pbl2 film from the chamber and transferring the film to a different instrument, such as a thermal evaporator, for the deposition of FAI and / or MAL. The method stipulates that the first 20 nm of depositions should be carried out at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Activated reactive evaporation In certain embodiments, a method for solventless perovskite material deposition comprises loading a Pbk target into a deposition chamber, loading samples The method involves depositing the target material onto a substrate support in the deposition chamber and pumping it under high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr). The method further comprises evaporating the Pbb target in the presence of a reactive gas and a plasma. The method continues by filling the chamber with FAI and / or MAI vapor and making depositions. The chamber can be filled using a microfiltration unit (MFC) at a rate of between 2 and 100 sccm. In some embodiments, the FAI and / or MAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of depositions should be made at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a method for solventless perovskite material deposition comprises loading a Pb target into a deposition chamber, loading samples adhered to a substrate support into the deposition chamber, and pumping under high vacuum pressure (less than or equal to 5 x 10⁶ Torr). The method further comprises evaporating the Pb target in the presence of a reactive gas and a plasma. The method continues by filling the chamber with Hl and one or both of MAI or FAI vapor and making depositions. The chamber can be filled using a MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both MAI or FAI can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a method for solventless perovskite material deposition comprises loading a Pb target into a deposition chamber, loading samples adhered to a substrate support into the deposition chamber, and pumping under high vacuum pressure (less than or equal to 5 x 10⁻⁶ Torr). The method further comprises evaporating the Pb target in the presence of a reactive gas and a plasma. The method continues by filling the chamber with Hl vapor and making depositions. The chamber can be filled using a MFC at a rate of between 2 and 100 sccm. In some embodiments, the Hl can be introduced at a rate of between 5 and 30 sccm. The method concludes by removing the Pbl₂ film from the deposition chamber and transferring the film to a different instrument, such as a thermal evaporator, for FAI and / or MAL deposition. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. Chemical vapor deposition Generally, chemical vapor deposition involves the vaporization of a precursor, the delivery of the vapor to the target substrate, the chemical reaction between the precursor vapors and the surface to be coated, and the deposition onto the substrate. Several precursors can be used with each of the chemical vapor deposition methods described below. Potential lead precursors generally include lead alkoxides, lead alkylamides, MA / t / ZUZZ / UU or l ¿or lead alkyl sulfides, lead alkyl selenides, plumbanes, and plumbilenes. In some embodiments, the lead precursor may be bis(1-dimethylamine-2-methyl-2-propanolate)lead(II) (Pb(DMAMP)2); bis(2,2,6,6-tetramethyl-3,5-heptanedionate)lead(II) (Pb(THD)2); lead(II) hexafluoroacetylacetonate; plumbocene (PbCp2); tetraethyl lead(IV); bis[bis(trimethylsilyl)amido]lead(II); or rac-N2,N3-di-tert-butane-2,3-diamido(II)lead. Possible iodine precursors generally include metal iodides and alkylammonium iodide salts. In some formulations, the iodine precursor may be trimethylsil(II) iodide (TMSI); iodine (I2); hydrogen iodide (HI); hydriodic acid; tin(IV) iodide; or methylammonium iodide. Possible formamidinium iodide precursors generally include formamidinium salts, formamidinium precursor reagents (formates, imide esters, triazines), ammonium salts, and cyanide salts.In some forms, the formamidinium precursor may be formamidinium iodide (FAI); formamidinium acetate; triethoxyl orthoformate; ethylmethanimidinium iodide; 1,3,5-triazine; ammonia (NH3); ammonium iodide (NH4I); ammonium hydroxide (NH4OH); or hydrogen cyanide (HCN). This disclosure includes several physical vapor deposition methods. Specifically, it describes methods for atomic layer deposition, plasma-enhanced chemical vapor deposition, metal-organic vapor-phase epitaxy, hydride vapor-phase epitaxy, thin-film vapor-liquid-solid conversion, and liquid-phase epitaxy. Atomic layer deposition In certain embodiments, a method for solventless perovskite material deposition comprises loading a Pbl2 precursor into a deposition chamber and loading a sample of FAI into the deposition chamber. The method further comprises pumping under low vacuum pressure (100–500 mTorr), pulsing a first Pbl2 precursor for at least 0.015 seconds, waiting 10–30 seconds to allow time for a reaction to occur on the substrate, pulsing a second Pbl2 precursor for at least 0.015 seconds, waiting 10–30 seconds to allow time for a reaction to occur on the substrate, and then repeating the cycle until the desired material thickness is achieved. The depositions are carried out under carrier gas, typically N2. In certain embodiments, the method requires depositing PbS into a deposition chamber and producing Pbl2 before loading the Pbl2 precursor into the deposition chamber. For example, after loading a sample of FAI into the deposition chamber and pumping the vacuum to a low pressure, lead(II) acetate is introduced into the chamber, making a first deposition. After waiting 30 seconds, trimethylsilyl iodide is introduced into the chamber, making a second deposition. The second deposition reacts with the first deposition to form a P112 layer. The example method further comprises waiting another 30 seconds before restarting the cycle by introducing lead(II) acetate into the MA / t / ZUZZ / UUÓ l ¿or be carried out at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a method for solvent-free perovskite material deposition comprises loading a Pb precursor into a crucible, loading substrates onto a sample holder, pumping the chamber to a moderate pressure (between 5 Torr and 760 Torr), and applying heat or an electron flow. The electrons from the Pb precursor create Pb vapor. The method further comprises applying a metal-organic framework (MOF) vapor-phase epitaxy process to the Pb vapor. The method continues by filling a chamber with hydrochloric acid (Hl) and one or both of metal-organic framework (MAI) or fluorine-infused alumina (FAI), and making depositions under an inert carrier gas such as argon (Ar). The chamber can be filled using a metal-organic framework (MOF) at a rate of between 2 and 100 sccm. In some embodiments, the Hl and one or both of the MAI or FAI vapor can be introduced at a rate of between 5 and 30 sccm. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In yet another embodiment, a solventless method for deposing perovskite material comprises loading a Pb precursor into a crucible, loading substrates onto a sample holder, and pumping the chamber at a moderate pressure (between 5 Torr and 760 Torr). The method further comprises applying heat or an electron beam to the Pb precursor to create Pb vapor. The method further comprises applying a metal-organic framework (MOF) vapor-phase epitaxy process to the Pb vapor under an inert carrier gas such as argon (Ar). The method continues by transferring the film to an instrument, such as a thermal evaporator, and depositing FAI and / or MAI. The method stipulates that the first 20 nm of depositions should be performed at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In each of the modes described above for metal-organic vapor-phase epitaxy, the Pb precursor can be plumbocene or plumbilene. Any of the other Pb precursors detailed in this description are also suitable. Hydride vapor-phase epitaxy In certain embodiments, a method for the solvent-free deposition of perovskite material comprises loading a Pb precursor into a crucible, loading substrates onto a sample holder, pumping the chamber to a moderate pressure (between 5 Torr and 760 Torr), and applying heat or an electron flow. The electrons from the Pb precursor create Pb vapor. The method further comprises applying HCl (hydrochloric acid). The method continues by filling a chamber with HL and one or both of MAI or FAI vapor and making depositions. The chamber can be filled using a MFC at a rate of between 2 and 100 sccm. In some embodiments, the HL and one or both of MAI or FAI vapor can be introduced at a rate of between 5 and 30 sccm. Carrier gases are used in some embodiments to facilitate deposition. Suitable carrier gases include NH3, H2 and chlorides. The method stipulates that the first 20 nm of depositions must be carried out at a rate of approximately 0.5 Å / second to ensure that the material adheres to a substrate. In other embodiments, a method for the solvent-free deposition of perovskite material comprises loading a Pb precursor into a crucible, loading substrates onto a sample holder, pumping the chamber to a moderate pressure (between 5 Torr and 760 Torr), and applying heat or an electron flow. The electrons from the Pb precursor create Pb vapor. The method further comprises the application of HCl. The method continues by filling a chamber with Hl vapor and making deposits in a film. The chamber can be filled using a multi-stage fuel cell (MSFC) at a rate of between 2 and 100 sccm. In some embodiments, the Hl can be introduced at a rate of between 5 and 30 sccm. Carrier gases are used in some embodiments to facilitate deposition. Suitable carrier gases include NH3, H2, and chlorides. The method concludes by transferring the film to an instrument, such as a thermal evaporator, and depositing FAI and / or MAL. Vapor-liquid-solid thin film conversion In certain embodiments, a solventless perovskite deposition method comprises applying at least one heat or electron flow to a metal, C (where C is, for example, group I or II cations as listed in the preferred embodiments), M (for example, Pb, Sn, etc., as described in the preferred embodiments), or a mixture of metals C and M to evaporate the metals onto a substrate. The method further comprises the direct application of the liquid metal C or M, or alloys or compounds thereof (for example, lead(II) acetate trihydrate). The method continues by heating the substrate and stabilizing the temperature above the melting point of the metal or metal mixture. The method further comprises the use of substrate surface treatments and inert porous capping layers to prevent dehumidification of the liquid metal(s) from the substrate.The method continues with the application of HX, X2, and / or CX vapor to the chamber to produce a thin film of the CMX3 compound. In particular embodiments, H1, I2, and / or Cs1 vapor is applied to the chamber containing a liquid metal film of Pb, Cs, or Cs and Pb to form a thin film of CsPbl3. In certain embodiments, the method further comprises the use of other compounds to stabilize the CX vapor at high temperatures, including the decay products of C if C is an organic cation that might otherwise be unstable at the temperature required to melt the C, M, or CM metal alloy. Alternative precursor compounds, such as lead(II) acetate trihydrate, may be used. Liquid-phase epitaxy Any of the thin-film vapor-liquid-solid conversion methods described above can be performed on a crystalline substrate with the goal of epitaxial growth. In some methods, the substrate can be single-crystal perovskite substrates or other network-paired compounds. While several modalities have been provided in this disclosure, it should be understood that the systems and methods described could be implemented in many other specific ways without departing from the spirit or scope of this disclosure. The examples provided are illustrative and not restrictive, and the intent is not limited to the details given herein. For example, the various elements or components may be combined or integrated into another system, or certain features may be omitted or not implemented. Furthermore, the techniques, systems, subsystems, and methods described and illustrated in the various forms as discrete or separate may be combined or integrated with other systems, modules, techniques, or methods without departing from the scope of this disclosure. Other elements shown or discussed as coupled or directly coupled or communicating with each other may be indirectly coupled or communicate through some intermediate interface, device, or component, whether electrically, mechanically, or otherwise. A person skilled in the art may verify other examples of changes, substitutions, and alterations, and these could be made without departing from the spirit and scope described herein. To assist the Patent Office and readers of any patent issued on this application in interpreting the appended claims hereto, applicants should be aware that they do not intend for any of the appended claims to invoke 35 USC § 112(f) as it exists on the filing date hereof, unless the words “means to” or “step to” are explicitly used in the particular claim.

Claims

1. A method for solventless perovskite deposition characterized in that it comprises: loading a lead target and a substrate into a deposition chamber; reducing the pressure in the deposition chamber to less than or equal to 5x10-6 Torr; vaporizing the lead target; filling the deposition chamber with the vapors of a salt precursor; and depositing a perovskite material onto the substrate.

2. The method according to claim 1, characterized in that: vaporization is produced by applying an electron beam to the lead target; the lead target comprises lead(II) iodide; the salt precursor comprises a salt selected from the group consisting of formamidinium iodide, methylammonium iodide and combinations thereof.

3. The method according to claim 1, characterized in that: vaporization is produced by applying an electron beam to the lead target; the salt precursor comprises a salt selected from the group consisting of formamidine, methylamine and combinations thereof; and the method further comprises filling the deposition chamber with hydrogen iodide vapor.

4. The method according to claim 1, characterized in that the first 20 nm of depositions are performed at a rate of 0.5 Å / second.

5. The method according to claim 1, characterized in that: vaporization is produced by applying an electron beam to the lead target; the salt precursor comprises hydrogen iodide; and the method further comprises: transferring the perovskite material to a thermal evaporator; and depositing a second salt precursor selected from the group consisting of formamidinium iodide, methyl ammonium iodide, and combinations thereof.

6. The method according to claim 1, characterized in that: vaporization occurs by applying a cathodic arc to the lead target; the pressure in the chamber is reduced to the range of 10-8 to 10-12 Torr; the salt precursor comprises hydrogen iodide; and the method further comprises: transferring the perovskite material to a thermal evaporator; and depositing a second salt precursor selected from the group consisting of formamidinium iodide, methyl ammonium iodide, and combinations thereof.

7. The method according to claim 1, characterized in that: vaporization is produced by applying a pulsed laser to the lead target; the pressure in the chamber is reduced to the range of 10-8 to 10-12 Torr; the salt precursor comprises a salt selected from the group consisting of formamidinium iodide, methylammonium iodide and combinations thereof.

8. The method according to claim 1, characterized in that the filling occurs at a rate in the range of 2-100 sccm.

9. A method for solventless perovskite deposition, characterized in that it comprises: loading a sample of lead powder into a crucible; placing a substrate upside down on the powder in the crucible; reducing the pressure in the deposition chamber to 200 mTorr; sublimating the lead powder sample; and making a first deposition on the substrate.

10. The method according to claim 9, characterized in that: the lead powder sample comprises lead(II) iodide; the method further comprises filling the deposition chamber with the vapors of a salt precursor before making the first deposit, the salt precursor comprising a salt selected from the group consisting of formamidinium iodide, methyl ammonium iodide and combinations thereof; and wherein the first deposition is a perovskite material.

11. The method according to claim 10, characterized in that the first 20 nm of depositions are performed at a rate of 0.5 Å / second.

12. The method according to claim 9, characterized in that it further comprises: after making the first deposition, filling the deposition chamber with hydrogen iodide vapor and one or both of formamidine or methylamine; making a second deposition on the substrate, the second deposition being a perovskite material.

13. The method according to claim 9, characterized in that: the lead powder sample comprises lead(II) iodide; and the method further comprises: replacing the excess lead powder sample in the crucible with a salt precursor powder, the salt precursor comprising a salt selected from the group consisting of formamidinium iodide, methyl ammonium iodide and combinations thereof; sublimating the salt precursor; making a second deposition on the substrate, the second deposition being a perovskite material.

14. The method according to claim 13, characterized in that the first 20 nm of depositions are carried out at a rate of 0.5 Å / second.

15. The method according to claim 10, characterized in that the filling occurs at a rate in the range of 2-100 sccm.

16. The method according to claim 9, characterized in that the lead powder sample is a single-crystal perovskite with ABX3 structure.

17. A method for solventless perovskite deposition, characterized in that it comprises: loading a lead salt precursor into a crucible; loading a substrate into a sample holder; reducing the pressure in the deposition chamber to at least 10'3 Torr; applying a current to ionize the lead salt precursor; filling the deposition chamber with the vapors of a second salt precursor; and depositing a perovskite material onto the substrate.

18. The method according to claim 17, characterized in that: the lead salt precursor comprises lead(II) iodide; the second salt precursor comprises hydrogen iodide; and the method further comprises filling the deposition chamber with the vapors of a salt selected from the group consisting of formamidinium iodide, methyl ammonium iodide, and combinations thereof.

19. The method according to claim 17, characterized in that: the lead salt precursor is ionized in the presence of a reactive gas; the second salt precursor comprises a salt precursor selected from the group consisting of formamidinium iodide, methylammonium iodide and combinations thereof.

20. The method according to claim 19, characterized in that the reactive gas is selected from the group consisting of water, oxygen, nitrous oxide, ammonia, and nitrogen.

21. The method according to claim 17, characterized in that the lead salt precursor comprises a salt selected from the group consisting of MA / t / ZUZZ / UUÓ l ¿ó 22 lead alkoxides, lead alkylamides, lead alkylsulfides, lead alkylselenides, plumbanes and plumbilenes.

22. The method according to claim 17, characterized in that the first 20 nm of depositions are performed at a rate of 0.5 Å / second.

23. The method according to claim 17, characterized in that the lead salt precursor comprises a salt selected from the group consisting of bis(1 dimethylamino-2-methyl-2-propanolate)lead(II) (Pb(DMAMP)2); bis(2,2,6,6-tetramethyl-3,5-heptanedionate)lead(II) (Pb(THD)2); lead(II) hexafluoroacetylacetonate; plumbocene (PbCp2); tetraethyl lead(IV); bis[bis(trimethylsilyl)amido]lead(II); and lead rac-N2,N3-di-tert-butane-2,3-diamido(II).

24. A method for solventless perovskite deposition, characterized in that it comprises: loading a lead salt precursor into a crucible; loading a substrate into a sample holder; reducing the pressure in the deposition chamber to between 5 Torr and 760; vaporizing the lead salt precursor; performing metal-organic vapor-phase epitaxy on the vapor; filling the deposition chamber with the vapors of a second salt precursor; and depositing, under an inert gas, a perovskite material onto the substrate.

25. The method according to claim 24, characterized in that the second salt precursor comprises a salt selected from the group consisting of formamidinium iodide, methyl ammonium iodide and combinations thereof.

26. The method according to claim 24, characterized in that: the second salt precursor comprises hydrogen iodide; and the method further comprises filling the deposition chamber with hydrogen iodide vapor.

27. The method according to claim 24, characterized in that the vaporization is produced by applying heat or an electron flow to the lead salt precursor.

28. The method according to claim 24, characterized in that the lead salt precursor comprises a salt selected from the group consisting of lead alkoxides, lead alkylamides, lead alkylsulfides, lead alkylselenides, plumbanes and plumbilenes.

29. The method according to claim 24, characterized in that the lead salt precursor comprises a salt selected from the group consisting of bis(1 dimethylamino-2-methyl-2-propanolate)lead(II) (Pb(DMAMP)2); bis(2,2,6,6-tetramethyl-3,5-heptanedionate)lead(II) (Pb(THD)2); lead(II) hexafluoroacetylacetonate; plumbocene (PbCp2); tetraethyl lead(IV); bis[bis(trimethylsyl)amido]lead(II); and lead rac-N2,N3-di-tert-butane-2,3-diamido(II).

30. The method according to claim 24, characterized in that the first 5 20 nm of depositions are performed at a rate of 0.5 Å / second.