A perovskite double-layer heterojunction and its preparation method and application

Abstract

The invention discloses a perovskite double-layer heterojunction and a preparation method and application thereof, comprising: a perovskite film and a perovskite substrate; dissolving a first perovskite in a solvent to prepare a perovskite solution; preparing a second perovskite into a perovskite substrate by a vapor deposition method or a vapor assisted deposition method; depositing the perovskite solution on the second perovskite substrate by a solution method to form a perovskite film, and then preparing a perovskite double-layer heterojunction; the perovskite film is prepared from a first perovskite having a van der Waals bond as a main chemical composition and containing at least 1.2 times the van der Waals bond as compared with the second perovskite; the perovskite substrate is prepared from a second perovskite having an ionic bond and / or a covalent bond as a main chemical composition; the perovskite double-layer heterojunction is used to prepare solar cells, photodetectors, light-emitting diodes, light-emitting triodes, etc., and the double-layer heterojunction mentioned in the invention improves the performance of optoelectronic devices and reduces the preparation cost of the perovskite double-layer heterojunction.

Description

Technical Field

[0001] The present invention relates to the technical field of photovoltaic devices, and in particular to a perovskite double-layer heterojunction and a preparation method and application thereof. Background Art

[0002] As an emerging semiconductor material, perovskite has the advantages of high absorption coefficient, low defect density, long carrier diffusion distance, high fluorescence quantum yield, and low exciton binding energy in the visible light band. It is an ideal material for preparing optoelectronic devices such as solar cells, light-emitting diodes, and photodetectors, and has attracted widespread attention from researchers. In recent years, organic-inorganic hybrid perovskite solar cells have received widespread attention due to their excellent optoelectronic performance. The photoelectric conversion efficiency of optoelectronic devices prepared using perovskite materials has increased from 3.8% reported in 2009 to the current highest of 25.2%. In the field of light-emitting diodes, the external quantum efficiency of red and green LED devices based on perovskite materials has also exceeded 20%, and the device performance of perovskite blue LEDs is also constantly improving; wide-spectrum, infrared, ultraviolet and other detection devices based on perovskite materials have also attracted the attention of many researchers. In the process of perovskite development, the design and preparation of heterojunctions can improve carrier transport, increase the optical absorption range, and enhance the stability of devices through energy level matching. Therefore, the preparation of perovskite heterojunctions is a hot topic and an important research direction in this field.

[0003] The most common perovskite heterojunctions are perovskite-silicon heterojunction, perovskite-organic material heterojunction, and perovskite-perovskite heterojunction. Perovskite-perovskite heterojunction is mainly prepared by evaporation. Compared with the evaporation method, the solution method does not require high-energy consumption equipment and the process flow is simpler. However, since the upper and lower films of the perovskite-perovskite heterojunction are both perovskite material systems, the use of conventional perovskite materials, solvents or solution methods for preparation will directly destroy and dissolve the lower layer of perovskite, and no heterojunction can be obtained.

[0004] Therefore, there is an urgent need for a perovskite double-layer heterojunction and a preparation method thereof, which can select suitable solvents and perovskite materials, will not destroy the dissolved lower layer of perovskite after the solution method window time, and can prepare double-layer heterojunctions of different perovskite material types and thicknesses by the solution method, thereby reducing the preparation cost of the perovskite double-layer heterojunction. Summary of the invention

[0005] In order to solve the above problems, the present application provides a perovskite double-layer heterojunction, characterized in that it includes:

[0006] A perovskite film on an upper layer and a perovskite substrate on a lower layer;

[0007] The perovskite film is prepared from the first perovskite;

[0008] The perovskite substrate is prepared from a second perovskite;

[0009] The ratio of the van der Waals bonds of the first perovskite to the metal element cations of Pb, Sn or a mixture of Pb and Sn in the perovskite is at least 1.2 times that of the second perovskite.

[0010] Preferably, the second perovskite may not include van der Waals bonds.

[0011] Preferably, the first perovskite is a two-dimensional perovskite material having a Ruddlesden–Popper structure, or a two-dimensional perovskite material having a cation-adjustable structure in a space-separated layer, or a mixture of the two in a certain ratio.

[0012] Preferably, the second perovskite is a three-dimensional perovskite material, or a two-dimensional perovskite material having a Dion-Jacobson structure, or a mixture of the two in a certain ratio;

[0013] The second perovskite also includes two-dimensional perovskite materials mixed with a small amount of Ruddlesden–Popper structure, or two-dimensional perovskite materials with Ruddlesden–Popper structure, or two-dimensional perovskite materials with adjustable structure of space-separated layer cations.

[0014] The present invention also discloses a method for preparing a double-layer perovskite heterojunction, which is characterized in that the method for preparing a double-layer perovskite heterojunction comprises the following steps:

[0015] dissolving the first perovskite using a solvent to prepare a perovskite solution, wherein the concentration of the perovskite solution is positively correlated with the thickness of the perovskite film;

[0016] The second perovskite is prepared into a perovskite substrate by vapor deposition or vapor-assisted deposition;

[0017] The perovskite solution is deposited on a second perovskite substrate by a solution method to form a perovskite film, and then a perovskite double-layer heterojunction is prepared, wherein the solubility of the second perovskite in the solvent is less than the solubility of the first perovskite.

[0018] Preferably, in the process of preparing the perovskite solution, the solvent is any one of acetonitrile, propylene carbonate, ethylene carbonate, tetramethyl sulfone, acetone, propionitrile, pyridine, or a mixture of several solvents.

[0019] Preferably, in the process of preparing the perovskite substrate, the method for preparing the perovskite substrate further comprises: any one of an anti-solvent method, a one-step solution method, a two-step solution method, epitaxial growth, and a sol-gel method.

[0020] Preferably, in the process of depositing the perovskite solution on the second perovskite substrate by a solution method, the solution method includes any one or more of spraying, spin coating, blade coating, and dynamic spin coating.

[0021] Preferably, in the process of preparing the perovskite double-layer heterojunction, the thickness of the perovskite film is not less than 1 nm.

[0022] The present invention also discloses an application of a perovskite double-layer heterojunction, and uses the perovskite double-layer heterojunction to prepare a photoelectric device;

[0023] The optoelectronic device is any one of a solar cell, a photodetector, a light emitting diode, and a light emitting triode.

[0024] The present invention discloses the following technical effects:

[0025] The present invention selects suitable solvents and perovskite materials, takes into account the difference in solubility of solvents for different perovskite materials, and can achieve successful deposition of the upper perovskite on the lower perovskite without completely dissolving the lower perovskite during the solution method residence window time, which is beneficial to improving the stability and photoelectric performance of perovskite solar cells. The double-layer heterojunctions of different perovskite material types and thicknesses are prepared by the solution method, which improves the flexibility of preparing the perovskite heterojunction, thereby reducing the preparation cost of the double-layer heterojunction of the perovskite. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0027] Figure 1 is a schematic diagram of the perovskite double-layer heterojunction structure of the present invention;

[0028] Figure 2 It is a schematic flow chart of a method for preparing a double-layer perovskite heterojunction according to an embodiment of the present invention. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. The components of the embodiments of the present application generally described and shown in the drawings here can be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the application claimed for protection, but merely represents the selected embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application.

[0030] like Figure 1-2 As shown, the present invention provides a perovskite double-layer heterojunction, characterized in that it includes:

[0031] A perovskite film on an upper layer and a perovskite substrate on a lower layer;

[0032] The perovskite film is prepared from the first perovskite;

[0033] The perovskite substrate is prepared from a second perovskite;

[0034] The ratio of van der Waals bonds of the first perovskite to metal cations of Pb, Sn, or a mixture of Pb and Sn in the perovskite is at least 1.2 times the ratio of van der Waals bonds of the second perovskite to metal cations of Pb, Sn, or a mixture of Pb and Sn in the perovskite.

[0035] Further preferably, the second perovskite may not include van der Waals bonds.

[0036] Further preferably, the first perovskite is a two-dimensional perovskite material having a Ruddlesden–Popper structure, or a two-dimensional perovskite material having a cation-adjustable structure in a space-separated layer, or a mixture of the two in a certain proportion.

[0037] Further preferably, the second perovskite is a three-dimensional perovskite material, or a two-dimensional perovskite material having a Dion-Jacobson structure, or a mixture of the two in a certain ratio;

[0038] The second perovskite also includes two-dimensional perovskite materials mixed with a small amount of Ruddlesden–Popper structure, or two-dimensional perovskite materials with Ruddlesden–Popper structure, or two-dimensional perovskite materials with adjustable structure of space-separated layer cations.

[0039] The present invention also discloses a method for preparing a double-layer perovskite heterojunction, which is characterized in that the method for preparing a double-layer perovskite heterojunction comprises the following steps:

[0040] dissolving the first perovskite using a solvent to prepare a perovskite solution, wherein the concentration of the perovskite solution is positively correlated with the thickness of the perovskite film;

[0041] The second perovskite is prepared into a perovskite substrate by vapor deposition or vapor-assisted deposition;

[0042] The perovskite solution is deposited on a second perovskite substrate by a solution method to form a perovskite film, and then a perovskite double-layer heterojunction is prepared, wherein the solubility of the second perovskite in the solvent is less than the solubility of the first perovskite.

[0043] Further preferably, in the process of preparing the perovskite solution, the solvent is any one of acetonitrile, propylene carbonate, ethylene carbonate, tetramethyl sulfone, acetone, propionitrile, pyridine, or a mixture of several solvents.

[0044] Further preferably, in the process of preparing the perovskite substrate, the method for preparing the perovskite substrate also includes: any one of an anti-solvent method, a one-step solution method, a two-step solution method, epitaxial growth, and a sol-gel method.

[0045] Further preferably, in the process of depositing the perovskite solution on the second perovskite substrate by a solution method, the solution method includes any one or more of spraying, spin coating, scraping, and dynamic spin coating.

[0046] Further preferably, in the process of preparing the perovskite double-layer heterojunction, the thickness of the perovskite film is not less than 1 nm.

[0047] The present invention also discloses an application of a perovskite double-layer heterojunction, and uses the perovskite double-layer heterojunction to prepare a photoelectric device;

[0048] The optoelectronic device is any one of a solar cell, a photodetector, a light emitting diode, and a light emitting triode.

[0049] Based on the principle that strong chemical bonds such as ionic bonds and chemical bonds are at least 1 to 2 orders of magnitude stronger than weak chemical bonds such as van der Waals bonds, the present invention designs two perovskites containing different van der Waals bond ratios, and refers to the polarity, dipole moment, dielectric constant, surface tension, donor number, boiling point, volatility and other parameters of the solvent, and selects a solvent that has different solubility for the two perovskites and can dissolve the lower layer of perovskite without completely destroying it after the solution method window time. The solvent is used as the solvent for the upper perovskite, and then the perovskite double-layer heterojunction is prepared by solution methods such as spin coating, spraying, scraping, and dynamic spin coating.

[0050] Figure 1A schematic diagram of a double-layer heterojunction structure of a perovskite according to an embodiment of the present invention is shown. The upper layer is a perovskite film, and the lower layer is a perovskite substrate. In order to prepare a double-layer heterojunction of a perovskite using a solution method, considering the difference in solubility of the two perovskite materials in the solvent, a perovskite material with van der Waals bonds as one of the main chemical connections is first selected as the first perovskite. The intermolecular interaction force of the perovskite material with van der Waals bonds as the main one is generally easier to destroy, and the solvent has a higher solubility in it. In some embodiments of the present invention, the first perovskite can be a two-dimensional RP (Ruddlesden–Popper) type perovskite, which has ultra-high humidity stability, and the chemical formula is generally (C)2(A) n-1 X n Y 3n+1 , where C is a spatial cation that can participate in the formation of RP structure perovskite, such as butylamine ion BA + (CH3(CH2)3NH3 + ), phenylethylamine ion PEA + (C6H5CH3CH2NH3 + ), etc., A is including but not limited to CH3NH3 + 、CH(NH2)2 + , Cs, etc., X includes but is not limited to metal elements such as Pb and Sn, and Y includes but is not limited to elements such as I, Cl, and Br. The first perovskite can also be an ACI alternating cation structure, and its chemical formula is DA n X n Y 3n+1 , where D is a spatial cation that can participate in the formation of ACI structure perovskite, such as guanamine ion GA + (C(NH2)3 + ), etc., A, X, and Y are as described above. In some embodiments of the present invention, the first perovskite may also be a perovskite in which an ACI structure and an RP structure are mixed in a certain proportion, and the change of different n values ​​(number of inorganic layers) and the change of perovskite materials with van der Waals bonds may be adjusted according to actual needs.

[0051] The second perovskite mainly contains ionic bonds and covalent bonds, and may also contain van der Waals bonds, but the proportion of van der Waals bonds contained is much smaller than the proportion of van der Waals bonds contained in the first perovskite. The second perovskite with ionic bonds and covalent bonds as the main chemical composition can be selected as the substrate. Strong chemical bonds such as ionic bonds, covalent bonds, and metal bonds are not easily destroyed, and the solvent has low solubility for them. According to one embodiment of the present invention, the second perovskite includes but is not limited to the three-dimensional perovskite AXY3 in the usual sense, A, X, and Y are as described above, and perovskite materials such as two-dimensional perovskite materials with DJ structures, and Dion-Jacobson (DJ) type two-dimensional layered perovskite materials. Compared with RP-type two-dimensional perovskites, DJ-type two-dimensional perovskites have no interlayer van der Waals interactions, and their organic cations are connected to the inorganic perovskite layer by hydrogen bonds at both ends of the molecule, so they have better structural stability. Its chemical formula is EA n-1 X n Y 3n+1 , where E is a steric cation that can participate in the formation of DJ structure perovskite, such as 3-(aminomethyl)piperidine (3AMP) + ions and 4-(aminomethyl)piperidinium (4AMP) + ions, etc., A, X, and Y are as described above. In some embodiments of the present invention, the second perovskite may also be a perovskite in which an AXY3 three-dimensional perovskite and a DJ structure are mixed in a certain proportion. The changes in different n values ​​(number of inorganic layers) and the changes in perovskite materials with van der Waals bonds may be adjusted according to actual needs.

[0052] The perovskite structure in the present invention is based on an octahedral structural framework composed of metal elements such as Pb, Sn and halides, and van der Waals bonds act on the octahedral structural framework. Therefore, when the molar amount of the framework is consistent, that is, when the molar amounts of the metal elements of Pb, Sn or their Pb, Sn mixture are equal, the number of van der Waals bonds in the first perovskite and the second perovskite are compared, and the number of van der Waals bonds in the upper perovskite film is greater than 1.2 times the van der Waals bond content of the lower perovskite substrate.

[0053] Figure 2 FIG. 2 is a schematic flow chart of a method 200 for preparing a double-layer heterojunction of a perovskite according to an embodiment of the present invention. Figure 2As shown, the method 200 begins at step S201, using a predetermined solvent to dissolve the first perovskite to prepare a perovskite solution, wherein the solubility of the solvent for the first perovskite is greater than the solubility of the solvent for the second perovskite. A similar solvent such as acetonitrile, acetone, propionitrile, pyridine, propylene carbonate, ethylene carbonate, tetramethyl sulfone, etc. can be selected, and the solubility of the first perovskite is significantly higher than the solubility of the second perovskite. In one embodiment of the present invention, an RP-type perovskite (BA)2(MA)2Pb3I10 having a van der Waals bond can be selected as the first perovskite, wherein BA + is butylamine ion (CH3(CH2)3NH3 + ), chemical formula is X, MA is methylamine ion CH3NH3 + The concentration of the first perovskite can be adjusted according to the specific film thickness requirements by using acetonitrile solvent. The dissolution can be carried out by ultrasonic oscillation or magnetic stirring for more than 1 hour to obtain (BA)2(MA)2Pb3I 10 The concentration of the perovskite solution is positively correlated with the thickness of the perovskite film to be prepared, and the concentration of the perovskite solution can be adjusted according to actual needs.

[0054] Then, step S202 is performed to prepare a perovskite substrate. The perovskite substrate is generally in the form of a thin film or a single crystal in a solid form. The perovskite substrate can be prepared by any method such as vapor deposition, vapor-assisted deposition, anti-solvent method, one-step solution method, two-step solution method, epitaxial growth, sol-gel method, etc., and the present invention is not limited to this. In one embodiment of the present invention, MAPbI3 can be selected as the second perovskite. MAPbI3 is a classic three-dimensional structure perovskite, which does not contain van der Waals bonds, so acetonitrile has very limited solubility in it and can react with (BA)2(MA)2Pb3I 10 The solubility of perovskite in acetonitrile forms a significant difference. In this embodiment, MAPbI3 film is used as the perovskite substrate. The perovskite substrate can be prepared by spin coating precipitation. First, use DMF dimethyl sulfoxide and DMSO dimethylformamide to prepare a 1Mol concentration of MAPbI3 solution. Add 461mg of PbI2 and 159mg of MAI to 1ml of DMF and DMSO in a ratio of 4:1. Stir the solution at room temperature for 30 minutes, take 80 microliters of the solution and drop it on a 4cm 2The glass substrate needs to be cleaned in advance. The substrate can be cleaned with detergent water, acetone, anhydrous ethanol and deionized water for 15 minutes, then dried and treated with ultraviolet ozone for 15 minutes before use. Spin coating is performed at a speed of 4000 rpm for 30 seconds. At the beginning of the 5th second, 500 microliters of ether are used to rinse the film during spin coating. After the spin coating is completed, anneal it on a hot stage at 100°C for 10 minutes. The MAPbI3 film obtained after returning to room temperature is the perovskite substrate.

[0055] Finally, step S203 is performed, and the perovskite solution is used to deposit the first perovskite on the perovskite substrate by a solution method, and a perovskite film is formed on the perovskite substrate to obtain a perovskite double-layer heterojunction. The solution method includes any one or more methods of spraying, spin coating, scraping, and dynamic spin coating. The perovskite substrate will not be completely dissolved or destroyed during the residence time on the second perovskite in the solution method process. In one embodiment of the present invention, the perovskite substrate can be placed on a spin coater, and a speed of 4000 revolutions per minute is used for spin coating for 30 seconds. At the 10th second of the start of spin coating, 50 microliters of perovskite solution is dripped, and after the spin coating is completed, annealing and drying are performed on a hot stage at 100°C for 5 minutes to obtain a perovskite double-layer heterojunction. In the formed heterojunction, the first perovskite and the second perovskite have a certain thickness, and the thickness of the perovskite film should be not less than 1nm, which is different from the perovskite-perovskite composite film obtained by the surface modification and surface passivation process for surface treatment.

[0056] The present invention also provides a photoelectric device, which at least includes a perovskite double-layer heterojunction prepared by the method described above, and can be any photoelectric device such as a solar cell, a photodetector, a light-emitting diode, a light-emitting triode, etc.

[0057] According to the scheme of the present invention, by selecting appropriate solvents and perovskite materials, considering the difference in solubility of solvents for different perovskite materials, the lower layer of perovskite can be dissolved without destroying it during the window time of the solution method, and the upper layer of perovskite can be successfully deposited on the lower layer of perovskite, which is beneficial to improving the stability of perovskite solar cells. The double-layer heterojunctions of different perovskite material types and thicknesses are prepared by the solution method, which improves the flexibility of preparing perovskite heterojunctions, thereby reducing the preparation cost of perovskite double-layer heterojunctions.

[0058] The present invention has been described in detail above. The above description is only a preferred embodiment of the present invention, and it cannot limit the scope of implementation of the present invention. That is, all equivalent changes and modifications made according to the scope of this application should still be within the scope of the present invention. As used herein, unless otherwise specified, the use of ordinal numbers "first", "second", "third", etc. to describe common objects only refers to different instances of similar objects, and is not intended to imply that the objects described in this way must have a given order in time, space, sorting, or in any other way.

[0059] Although the present invention has been described according to a limited number of embodiments, it will be apparent to those skilled in the art, with the benefit of the above description, that other embodiments may be envisioned within the scope of the invention thus described. In addition, it should be noted that the language used in this specification is selected primarily for readability and teaching purposes, rather than for explaining or defining the subject matter of the present invention. Therefore, many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the appended claims. The disclosure of the present invention is illustrative, not restrictive, with respect to the scope of the present invention, which is defined by the appended claims.

Claims

1. A perovskite double-layer heterojunction, characterized in that: include: A perovskite film on an upper layer and a perovskite substrate on a lower layer; The perovskite film is prepared from a first perovskite; The perovskite substrate is prepared from a second perovskite; When the molar amounts of Pb, Sn or a mixture of Pb and Sn are equal, the van der Waals bond of the first perovskite is at least 1.2 times that of the second perovskite; The first perovskite is a two-dimensional perovskite material having a Ruddlesden–Popper structure, or a two-dimensional perovskite material having a cation-adjustable structure in a space-separated layer, or a mixture of the two in a certain ratio; The method for preparing the perovskite double-layer heterojunction comprises the following steps: Dissolving the first perovskite using a solvent to prepare a perovskite solution, wherein the concentration of the perovskite solution is positively correlated with the thickness of the perovskite film; The second perovskite is prepared into the perovskite substrate by vapor deposition or vapor-assisted deposition; Depositing the perovskite solution on a second perovskite substrate by a solution method to form the perovskite film, and then preparing the perovskite double-layer heterojunction, wherein the solubility of the second perovskite in the solvent is less than the solubility of the first perovskite; In the process of preparing the perovskite solution, the solvent is any one of propylene carbonate, ethylene carbonate, tetramethyl sulfone, acetone, and pyridine, or a mixture of several solvents; In the process of depositing the perovskite solution on the second perovskite substrate by a solution method, the solution method includes one or more of spray coating, spin coating and blade coating.

2. A perovskite double-layer heterojunction according to claim 1, characterized in that: The second perovskite does not include the van der Waals bonds.

3. The perovskite double-layer heterojunction according to claim 1, characterized in that: The second perovskite is a three-dimensional perovskite material, or a two-dimensional perovskite material having a Dion-Jacobson structure, or a mixture of the two in a certain proportion; The second perovskite also includes a two-dimensional perovskite material mixed with a small amount of Ruddlesden-Popper structure, or a two-dimensional perovskite material with a Ruddlesden-Popper structure, or a two-dimensional perovskite material with a space-separated layer cation adjustable structure.

4. A method for preparing a perovskite double-layer heterojunction, characterized in that: A method for preparing a perovskite double-layer heterojunction as claimed in any one of claims 1 to 3, comprising the following steps: Dissolving the first perovskite using a solvent to prepare a perovskite solution, wherein the concentration of the perovskite solution is positively correlated with the thickness of the perovskite film; The second perovskite is prepared into the perovskite substrate by vapor deposition or vapor-assisted deposition; Depositing the perovskite solution on a second perovskite substrate by a solution method to form the perovskite film, and then preparing the perovskite double-layer heterojunction, wherein the solubility of the second perovskite in the solvent is less than the solubility of the first perovskite; In the process of preparing the perovskite solution, the solvent is any one of propylene carbonate, ethylene carbonate, tetramethyl sulfone, acetone, and pyridine, or a mixture of several solvents; In the process of depositing the perovskite solution on the second perovskite substrate by a solution method, the solution method includes one or more of spray coating, spin coating and blade coating.

5. The method for preparing a double-layer perovskite heterojunction according to claim 4, characterized in that: In the process of preparing the perovskite substrate, the method for preparing the perovskite substrate also includes: any one of an anti-solvent method, a one-step solution method, a two-step solution method, epitaxial growth, and a sol-gel method.

6. The method for preparing a double-layer perovskite heterojunction according to claim 4, characterized in that: In the process of preparing the perovskite double-layer heterojunction, the thickness of the perovskite film is not less than 1 nm.

7. An application of a perovskite double-layer heterojunction, characterized in that: Using the perovskite double-layer heterojunction prepared by the method as described in any one of claims 4 to 6 to prepare an optoelectronic device; The photoelectric device is any one of a solar cell, a photodetector, a light emitting diode, and a light emitting triode.

Images