MODIFIED PEROVSKITES AND PEROVSKITE LIKES AND USES THEREOF

Abstract

Present invention concerns optical processing of materials comprising complex phase behaviour, such as perovskites for stabilizing the optically active phase of thin films of materials with complex phase behaviour, such as perovskites.

Claims

1-81. (canceled)

82. A method of manufacturing an optically active perovskite phase material that is stable at ambient environment, the method comprising subjecting an area of a metal halide perovskite material to an irradiation treatment.

83. The method of claim 82, wherein the irradiation treatment comprises irradiating the area of the metal halide perovskite material locoregionally and in a grid pattern.

84. The method of the claim 82, wherein the irradiation treatment creates a pattern as micron scale square blocks.

85. The method of claim 82, wherein the irradiation treatment comprises grafting a grid pattern of barrels or cups in the area of the metal halide perovskite material.

86. The method of claim 85, wherein the barrels or cups have a cubic, tubular, cylindrical, discoidal, spherical, tabular, ellipsoidal, irregular, or squared shape.

87. The method of claim 82, wherein the irradiation treatment is a masked illumination.

88. The method of claim 82, wherein the irradiation treatment is a masked illumination of the material through a mask pattern by which certain locoregions on the material are illuminated and other regions are not illuminated.

89. An optically active perovskite phase material that is stable at ambient condition, the optically active perovskite phase material comprising a metal halide perovskite material with a grid pattern of material alterations in the metal halide perovskite material.

90. The optically active perovskite phase material of claim 89, wherein the material alterations separate metal halide perovskite material units.

91. The optically active perovskite phase material of claim 89, wherein the grid pattern of material alterations in the metal halide perovskite material are barrels or cups.

92. The optically active perovskite phase material of claim 89, wherein the pattern of material alterations in metal halide perovskite material have a tubular, cylindrical, discoidal, spherical, tabular, ellipsoidal, irregular, or squared shape.

93. The optically active perovskite phase material of claim 89, wherein the metal halide perovskite material is selected from: (a) compounds AMX.sub.3, (b) mixed compounds A.sub.mA.sub.nA.sub.(1mn)MX.sub.xX.sub.yX.sub.(3xy), (c) mixed compounds M.sub.mM.sub.nM.sub.(1mn)AX.sub.xX.sub.yX.sub.(3xy), and (d) compounds according to (a), (b), or (c) that are doped with manganese, tin, magnesium, potassium, sodium, rubidium, or silver, where: A, A, and A are independently chosen monovalent cations; M, M, and M are independently chosen divalent metal ions; X, X, and X are independently selected from the group consisting of fluoride (F.sup.), chloride (Cl.sup.), bromide (Br.sup.), iodide (I.sup.) and astatide (At.sup.); m and n are independently from 0 to 1; m+n=1; x and y are independently from 0 to 3; and x+y=3.

94. The optically active perovskite phase material of claim 93, wherein: A, A, and A are independently chosen from methylammonium (MA), formamidinium (FA.sup.+), and cesium (Cs.sup.+); and M, M, and M are Pb.sup.2+.

95. The optically active perovskite phase material of claim 89, wherein the metal halide perovskite material comprises a compound CsPbX.sub.3, where each X is F, Cl, Br, or I.

96. The optically active perovskite phase material of claim 89, wherein the metal halide perovskite material comprises a compound FAPbX.sub.3, where FA is formamidium and each X is Cl, Br, or I.

97. The optically active perovskite phase material of claim 89, wherein the material alterations on the metal halide perovskite material are applied at temperatures more than 50 C. below the phase transition temperature of the metal halide perovskite material.

98. The optically active perovskite phase material of claim 89, wherein the material alterations are chemical alterations or physical alterations.

Description

DETAILED DESCRIPTION

Detailed Description of Embodiments of the Invention

[0042] The following detailed description of the invention refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. Also, the following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims and equivalents thereof.

[0043] The following detailed description of the invention refers to the accompanying drawings. The same reference numbers in different drawings identify the same or similar elements. Also, the following detailed description does not limit the invention. Instead, the scope of the invention is defined by the appended claims and equivalents thereof.

[0044] Several documents are cited throughout the text of this specification. Each of the documents herein (including any manufacturer's specifications, instructions etc.) are hereby incorporated by reference; however, there is no admission that any document cited is indeed prior art of the present invention.

[0045] The present invention will be described with respect to particular embodiments and with reference to certain drawings but the invention is not limited thereto but only by the claims. The drawings described are only schematic and are non-limiting. In the drawings, the size of some of the elements may be exaggerated and not drawn to scale for illustrative purposes. The dimensions and the relative dimensions do not correspond to actual reductions to practice of the invention.

[0046] Furthermore, the terms first, second, third and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.

[0047] Moreover, the terms top, bottom, over, under and the like in the description and the claims are used for descriptive purposes and not necessarily for describing relative positions. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other orientations than described or illustrated herein.

[0048] It is to be noticed that the term comprising, used in the claims, should not be interpreted as being restricted to the means listed thereafter; it does not exclude other elements or steps. It is thus to be interpreted as specifying the presence of the stated features, integers, steps or components as referred to, but does not preclude the presence or addition of one or more other features, integers, steps or components, or groups thereof. Thus, the scope of the expression a device comprising means A and B should not be limited to the devices consisting only of components A and B. It means that with respect to the present invention, the only relevant components of the device are A and B.

[0049] Reference throughout this specification to one embodiment or an embodiment means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases in one embodiment or in an embodiment in various places throughout this specification are not necessarily all referring to the same embodiment but may. Furthermore, the particular features, structures or characteristics may be combined in any suitable manner, as would be apparent to one of ordinary skill in the art from this disclosure, in one or more embodiments.

[0050] Similarly, it should be appreciated that in the description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding the understanding of one or more of the various inventive aspects. This method of disclosure, however, is not to be interpreted as reflecting an intention that the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

[0051] Furthermore, while some embodiments described herein include some but not other features included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention, and form different embodiments, as would be understood by those in the art. For example, in the following claims, any of the claimed embodiments can be used in any combination.

[0052] In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the invention may be practiced without these specific details. In other instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.

[0053] Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.

[0054] It is intended that the specification and examples be considered as exemplary only.

[0055] Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are part of the description and are a further description and are in addition to the preferred embodiments of the present invention.

[0056] Each of the claims set out a particular embodiment of the invention.

[0057] The following terms are provided solely to aid in the understanding of the invention.

Definitions

[0058] Particular and preferred aspects of the invention are set out in the accompanying independent and dependent claims. Features from the dependent claims may be combined with features of the independent claims and with features of other dependent claims as appropriate and not merely as explicitly set out in the claims.

[0059] Ambient stable is stable at ambient condition and/or in an ambient environment.

[0060] Present invention concerns a novel all-optical technique to stabilize the black phase of a halide perovskites AMX3, whereby M is a metal ion such as Pb.sup.2+ and A is a cation such as methylammonium (MA+), formamidinium (FA+), cesium (Cs+), . . . and X is of the group consisting of fluoride (F.sup.), chloride (Cl.sup.), bromide (Br.sup.), iodide (I.sup.) and astatide (At.sup.) at temperatures below its phase transition temperature, for instance to stabilize the black phase of CsPbX (X=F, Cl, Br, I, At) or for instance to stabilize the black phase of FAPbX3 (X=F, Cl, Br, I, At). This stabilization can be carried out far below the phase transition temperature of the material, more than 50 C. thereunder, even more preferably more than 100 C. thereunder and yet more preferably more than 200 C. thereunder.

[0061] A particular embodiment concerns the all-optical technique to stabilize the black phase of a cesium lead iodide (CsPbX.sub.3) at temperatures far below its phase transition temperature of 320 Celsius degree, for instance more than 50 C. thereunder, even more preferably more than 100 C. thereunder and yet more preferably more than 200 C. thereunder.

[0062] The method is fast, low cost and can be easily applied onto large-scale processing.

[0063] By this method of stabilization of present invention pattern grid structures is created by a laser beam onto an AMX3 material, whereby M is a metal ion such as Pb.sup.2+ and A is a cation such as methylammonium (MA+), formamidinium (FA+), cesium (Cs+), . . . and X is of the group consisting of fluoride (F.sup.), chloride (Cl.sup.), bromide (Br.sup.), iodide (I.sup.) and astatide (At.sup.).

[0064] This method was particular found to be suitable to create such pattern grid structures onto cesium lead iodide combination for instance in CsPbI.sub.3 whereby we could achieve such pattern grid structures of locoregional physical and chemical changes where a light beam regardless of wavelength illuminated.

[0065] As shown in FIG. 1, the optically treated area or locoregional physicochemical modifications formed boundaries which acts to locally stabilize the phase of the material, greatly suppress the nucleation rate and slow down phase transition processes in the enclosed material region.

[0066] A thin film material that is optically processes by present invention and converted into its black phase, via thermal annealing, forms a stable black phase even after cooling to room temperature and this can last for weeks. This is in contrast to untreated thin film materials, which will only last in the order of 10s to minutes to several hours. Moreover, this method is reversible by optical or thermal treatments.

[0067] This technique enables stabilization of black phase inorganic perovskites for optoelectronic devices, including photovoltaics, light emitting, photo-detection, X-ray detection, Gamma-ray detection, imaging sensors, chemical sensors, etc.

Example

[0068] The optical processing is performed using an optical beam, regardless of the wavelength, coherence, illumination area and polarization, to create connected patterns onto the perovskite thin film, atop a substrate like glass or ITO.

[0069] The optical patterning can be created by either a focused optical beam, structured illumination or by masked wide-file illumination. In an example, as shown in FIG. 1, a laser beam (458 nm wavelength) and a CsPbI.sub.3 film prepared by the conventional film deposition method are used for demonstration.

[0070] The CsPbI3 solution was prepared by dissolving anhydrous CsI and PbI2 into anhydrous DMF. The typical concentration of CsPbI3 solution is 0.1-0.4 M. The CsPbI3 film was prepared by spincoating in a nitrogen glove box. Chlorobenzene was used as the antisolvent.

[0071] In a typical film deposition protocol, CsPbI3 solution filtered by a 0.45 um PTFE filter was dropped onto a clean glass slide, followed by spincoating at 1500 rpm for 30 s and 3000 rpm for 60 seconds. 30 seconds before the spincoating stopped, 100 uL of the antisolvent was injected quickly at the center of the film. The film was then transferred onto a hotplate for annealing at 160 C. for 60 seconds.

[0072] The optical beam (458 nm) in these examples is focused onto the perovskite film surface by an optical objective (10, 0.4 NA). A motorized XYZ stage is used for precise sample positioning and for scanning the focused beam across the surface, forming the pattern. The power of the optical focal spot (20 mW) is controlled via a laser current supply module and a set of neutral-density filters and is monitored using a calibrated power meter (ThorLabs photodiode S130VC). Optical processing is then achieved by moving the substrate under the focused optical illumination using the XYZ stage. The optical patterning is defined by a series of XYZ coordinates controlled by a computer, permitting designs of different patterns. In the example, the perovskite thin film is patterned with square blocks ranging from 1010 m.sup.2 to 220220 m.sup.2 in dimension (FIG. 2). The substrate is then submitted to thermal treatments above the thermal phase transition (>320 Celsius degrees for CsPbI.sub.3) to trigger the yellow-to-black phase transition. After rapid cooling back to room temperature (within a few minutes), the black phase of the materials remains within the patterned area. As shown in the transmission image in FIG. 2 (recorded 36 hours after thermal treatment and stored under ambient), the dark areas (highly light absorbing) represent the stabilized black phase perovskite, with the lighter portion of the image representing the part of the thin film which has returned to the yellow phase. The stabilizing effect is clearly present for all grid sizes presented in FIG. 2, a higher frequency of black phase stabilization appears to occur for smaller grid sizes.

[0073] For the 4040 m2 grid size used for the stability test shown in FIG. 3, the sample exposed to ambient conditions and is found to be far more stable than the control film which was not subjected to the optical patterning before the thermal treatment. A further increase in the black phase stabilization can be achieved by protecting the film from the ambient moisture (dry sample in FIG. 3).

[0074] In FIGS. 4a and b, the 4040 m2 grid is patterned over a 22 cm2 area of a CsPbI.sub.3 thin film. After 24 hours, the patterned area is found stable under ambient conditions and highly light absorbing and luminescent.

[0075] In FIG. 5, perovskite thin films prepared on indium tin oxide/glass substrates are found to also experience the same stabilizing influence of the optical patterning treatment.

[0076] Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.

DRAWING DESCRIPTION

Brief Description of the Drawings

[0077] The present invention will become more fully understood from the detailed description given herein below and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:

[0078] FIG. 1 Schematic diagram showing the optical processing, whereby focused light-induced patterns are introduced onto the thin film surface prior to thermal annealing. In FIG. 1a the following elements are displayed 1=beam expander, 2 is the ND filter, 3=the beam splitter, 4 is the bandpass filter, 5=the tunable Ar+ laser, 6 is the current controller, 7=the video camera, 8 is the objective, 9=the tuning prism, 10 is sample mounted on a XYZ translation stage, 11 is the computer with the processor and acquisition software and 13=a mirror.

[0079] FIG. 2 Optical transmission images of optically treated 1414 boxes of varying square size patterns (1010 m2, 2020 m2, 4040 m2, 6060 m2, 8080 m2, 100100 m2, 120120 m2, 160160 m2, 220220 m2) recorded 24 hours after thermal annealing. The smaller patterns at the lower row are magnified 2 with respect to the patterns in the upper row.

[0080] FIG. 3 Survival of 4040 m2 square optically treated grid areas over time under both ambient and dry atmospheres, compared to the untreated film under ambient conditions (dashed line). The symbol .box-tangle-solidup. means ambient and the symbol .circle-solid. means dry.

[0081] FIG. 4 (a) optical image of an optically treated perovskite film on a glass substrate, area consisting of 4040 m2 grids covering a 22 cm.sup.2 area. The dark central region was optically treated. (b) Dark field image of this film from using .sub.exc=488 nm, where there the absorbed light is the black phase perovskite stabilized by the optical treatment. (c) The glowing emission of the black phase perovskite across the corresponding film in (b) recorded at 488 nm excitation and detecting the emission around 700 nm as indicated in (d), (d) Emission spectra corresponding to an emission of the room-temperature black phase CsPbI.sub.3 material (producing the image in (c)), stabilized through the laser optical treatment. The detection window used to record (c) is indicated.

[0082] FIG. 5 Optical transmission images of optically treated 1414 boxes of 4040 m2 recorded 24 hours after thermal annealing. The perovskite film was deposited on the ITO layer of an ITO/glass slide.