Method for producing perovskite on a substrate, method for patterning perovskite, and perovskite pattern device

Abstract

A method for forming a perovskite on a substrate, a method for patterning a perovskite, and a perovskite pattern device are disclosed. The method for forming a perovskite on a substrate may include: a first step of vaporizing i (A(Xa)j) or k (B(Xa)l) on a substrate; and a second step in which, if i (A(Xa)j) is vaporized in the first step, i (A(Xa)j) is exposed to a reaction solution containing k (B(Xb)l) and reacted to form an AiBk(Xa)ij(Xb)kl perovskite, and if k (B(Xa)l) is vaporized in the first step, k (B(Xa)l) is exposed to a reaction solution containing i (A(Xa)j) and reacted to form an AiBk(Xb)ij(Xa)kl perovskite.

Description

Technology Field

[0001] The present invention relates to a method for forming a perovskite on a substrate, a perovskite patterning method, and a perovskite patterned device. Background Technology

[0002] Halide perovskites have the advantages of excellent optoelectronic properties such as long carrier diffusion distance, high absorption coefficient, and tunable band gap, as well as low cost and low-temperature processing, so they have recently been gaining attention in semiconductor fields such as photosensors, LEDs, lasers, memristors, and photosynapses, as well as solar cells.

[0003] Halide perovskites (hereinafter referred to as perovskites) are materials having an ABX3 structure, in which the A site consists of monovalent cations such as methylammonium (MA), formamidinium (FA), cesium (Cs), rubidium (Rb), and potassium (K); the B site consists of divalent cations such as lead (Pb), tin (Sn), and germanium (Ge); and the X site consists of monovalent anions such as iodine (I), bromine (Br), and chlorine (Cl). Generally, the band gap can be controlled from ~1.5 eV to ~3 eV by appropriately combining the X site ions with I, Br, and Cl, and it is known that the band gap increases almost linearly as the radius of the halide ion decreases (Fig. 1).

[0004] On the other hand, unlike energy devices such as solar cells, pixel patterning technology is required for high integration to realize practical semiconductor devices. In particular, for the realization of devices such as photosensors, LEDs, or optical synapses, it is essential to develop a technology that patterns pixels capable of individually absorbing and emitting the three elements of visible light—red, green, and blue—on a single substrate. Therefore, it is necessary to develop a technology capable of patterning perovskite pixels with different bandgaps (i.e., having various X-site compositions) on a single substrate.

[0005] Until now, liquid-phase processes such as spin coating and tape casting or vapor-phase processes such as thermal evaporation have been mainly used to form perovskite thin films, but it is difficult to pattern perovskite pixels with different band gaps on a single substrate using the thin film deposition technologies developed so far.

[0006] First, if only the liquid phase process is used, A i B k X (ij+kl) After first coating with the composition (i, j, k, l are integers, j is the oxidation number of the A ion, l is the oxidation number of the B ion), A' again at a specific location i B' k X' (ij+kl) The composition needs to be coated, and at this time, the solvent of the coating solution is A i B k X (ij+kl) Since the thin film of the composition is dissolved, it is difficult to coat perovskite thin films with various band gaps onto a single substrate. Although this problem can be solved by using technologies such as inkjet printing, there are still limitations such as difficulty in fine pattern control and formation of high-quality thin films, and low adhesion.

[0007] On the other hand, when using only vapor deposition, a shadow mask allows for the sequential deposition of perovskite compositions with different X-site compositions in desired regions. However, perovskites of specific compositions must contain Cl ions in a certain proportion or higher in addition to I and Br ions, and BCl is used as a Cl source. l The material exhibits high acidity in the gaseous state, posing a problem of corroding or contaminating the interior of the vapor deposition chamber. Specifically, it is known that gases from Cl-based sources react with metals inside the chamber to cause deformation, or that when the chamber is opened from the outside, they react with moisture in the air to form HCl, which then adsorbs onto the metals inside the chamber to induce corrosion.

[0008] To solve these problems, the present invention provides a method for forming one or more perovskite pixels having a composition containing Cl on a substrate by sequentially using vapor deposition and a solution process (Fig. 2).

[0009] The above halide perovskites are ABX3, A2BX4, A2BX6, A2BB'X6, A' i B j X (ij+kl) It includes a structure of (i, j, k, l are integers, j is the oxidation number of the A ion, l is the oxidation number of the B ion). The above A may be a monovalent cation, the above A' may be a cation, the above B may be a metallic material, and the above X may be a halogen element, and the above organic-inorganic hybrid perovskite is zero-dimensional (A2BX6, A3B2X 9, A4BX6), 2-dimensional (A2BX4, A3B2X9) or 3-dimensional (ABX 3, It can have an A2BB'X6) structure. The problem to be solved

[0010] One objective of the present invention is to provide a new synthesis process capable of forming a perovskite material on a substrate.

[0011] Another objective of the present invention is to provide a method for patterning one or more perovskite materials by applying the above-described perovskite formation method.

[0012] Another objective of the present invention is to provide a high-resolution perovskite patterned element manufactured by the patterning method described above. means of solving the problem

[0013] In one aspect, the present invention relates to i(A(X) on a substrate. a ) j A first step of vapor deposition of ); and the i(A(X a ) j ) is k(B(X b ) l After exposing to a reaction solution containing ) and reacting, A i B k (X a ) ij (X b ) kl A method for forming a perovskite on a substrate is provided, comprising a second step of forming a perovskite.

[0014] In another aspect, the present invention relates to k(B(X) on a substrate. a ) l A first step of vapor deposition of ); and the k(B(X a ) l ) is i(A(X b ) j After exposing to a reaction solution containing ) and reacting, A i B k (X b ) ij (X a ) kl A method for forming a perovskite on a substrate is provided, comprising a second step of forming a perovskite.

[0015] In terms of aspect, the present invention is on a substrate B(X a A first step of vapor deposition of )2; and the B(X a )2 is A(X bA method for forming a perovskite on a substrate is provided, comprising a second step of reacting after exposure to a reaction solution containing );

[0016] In another aspect, the present invention is on a substrate A(X a A first step of vapor deposition of ); and the above A(X a ) is B(X b A method for forming a perovskite on a substrate is provided, comprising a second step of reacting after exposure to a reaction solution containing )2.

[0017] In another aspect, the present invention on a substrate i(AX) a A first step of vapor deposition of ); and the above i(AX a ) is k(B(X b ) n After exposing to a reaction solution containing ) and reacting, A i B k (X a ) i (X b ) kn A method for forming a perovskite on a substrate is provided, comprising a second step of forming a perovskite.

[0018] In another aspect, the present invention relates to k(B(X) on a substrate. a ) n A first step of vapor deposition of ); and the k(B(X a ) n ) to i(AX b After exposing to a reaction solution containing ) and reacting, A i B k (X a ) kn (X b ) i A method for forming a perovskite on a substrate is provided, comprising a second step of forming a perovskite.

[0019] In one embodiment, the vapor-deposited material does not contain Cl, and the reaction solution may contain Cl.

[0020] In one embodiment, A and B are cationic elements, i, j, k, l, and n are positive integers, j is the oxidation number of the A ion, l and n are the oxidation numbers of the B ion, and X a and X b are each independently mixtures of halogen elements, and X a is not containing Cl, and X b It may contain Cl.

[0021] By depositing a Cl-free material through the steps described above and then introducing Cl into the perovskite, corrosion or contamination caused by the acidity of the Cl-containing material can be prevented.

[0022] In one embodiment, the X a It may be a phase of I, Br, or a mixture of I and Br.

[0023] As described above, by varying the composition of each vapor deposition material, it is possible to ultimately form patterns of various compositions containing Cl.

[0024] In one embodiment, B may include Pb.

[0025] As described above, a perovskite structure can be realized by including Pb.

[0026] In another aspect, the present invention is provided on a substrate k(B(X e ) l Form the first pixel pattern with ), and k(B(X f ) l Form a second pixel pattern with ), and k(B(X g ) l A pattern formation step for forming a third pixel pattern using ), wherein the order of formation of the first pixel, second pixel, and third pixel is independent of their names; and

[0027] The above first pixel pattern, second pixel pattern and third pixel pattern are i(A(X h ) jA perovskite patterning method is provided, comprising a pattern reaction step of reacting after exposure to a reaction solution containing ).

[0028] In one embodiment, A and B are cationic elements, i, j, k, and l are positive integers, j is the oxidation number of the A ion, l is the oxidation number of the B ion, and X e , X f and X g For each independently selected p and q, I p Br q With the chemical formula of, X h For each independently selected r, s, and t, I r Br s Cl t It has the chemical formula, where p and q are 0 or positive real numbers and their sum is 1, and r, s and t are 0 or positive real numbers and their sum is 1.

[0029] In one embodiment, A and B may be mixed-phase cationic elements.

[0030] As the composition of the reactants is determined as described above, a material that does not contain Cl is deposited and then converted into a material containing Cl, thereby minimizing corrosion and contamination caused by the acidity of the material containing Cl, and thus enabling the formation of a high-resolution pattern.

[0031] In one embodiment, the X e For p:q is It is approximately 9:1 to 10:0, and X f For , p:q is approximately 7:3 to 6:4, and X g For p:q, it can be approximately 1:9 to 0:10.

[0032] By determining as above, the pattern produced by the patterning method according to the embodiment of the present invention may have different compositions for each pixel.

[0033] In one embodiment, B may include Pb.

[0034] As described above, by including Pb in B, the patterning material according to the embodiment of the present invention can realize a perovskite structure.

[0035] In one embodiment, the X h Regarding s:t, it can be from approximately 0:10 to 5:5.

[0036] In one embodiment, the X h For r:s:t, it can be approximately 1:2:7.

[0037] The above vapor deposition can be performed by one or more methods selected from the group including sputtering, thermal vapor deposition, E-beam deposition, and chemical vapor deposition.

[0038] By selecting the composition as described above, a Cl-free perovskite material pattern can be converted into a patterning material capable of sensing and emitting light within a desired range of wavelengths.

[0039] In one embodiment, the concentration of the reaction solution may be about 0.1 to 0.4 M.

[0040] By selecting the reaction solution concentration as described above, a Cl-free perovskite material pattern can be converted into a patterning material capable of sensing and emitting light within a desired range of wavelengths.

[0041] By the above pattern reaction step, each of the first pixel pattern, the second pixel pattern, and the third pixel pattern can sense and emit light within a desired light wavelength range, particularly red, green, and blue light, respectively.

[0042] In one embodiment, the first pixel pattern can sense and emit red-colored light and / or the second pixel pattern can sense and emit green-colored light and / or the third pixel pattern can sense and emit blue-colored light.

[0043] In one embodiment, the first pixel pattern can sense and emit light with a wavelength of about 640 to 730 nm, and / or the second pixel pattern can sense and emit light with a wavelength of about 530 to 640 nm, and / or the third pixel pattern can sense and emit light with a wavelength of about 440 to 530 nm.

[0044] In one embodiment, the first pixel pattern may include a composition having a band gap of ~1.77 eV (~700 nm), the second pixel pattern may include a composition having a band gap of ~2.07 eV (~600 nm), and the third pixel pattern may include a composition having a band gap of ~2.48 eV (~500 nm).

[0045] In one embodiment, the substrate may be a substrate having a transparent electrode formed on a glass substrate.

[0046] In one embodiment, the first pixel pattern, the second pixel pattern, and the third pixel pattern can be formed on the transparent electrode.

[0047] In one embodiment, the transparent electrode may include ITO.

[0048] In one embodiment, the pattern reaction step can be performed by heat treatment and photo-annealing while a reaction solution film is formed on the substrate such that the first pixel pattern, the second pixel pattern, and the third pixel pattern are exposed to the reaction solution.

[0049] In one embodiment, the method of forming the reaction solution film may include spin coating, dip coating, or drop casting.

[0050] In one embodiment, the heat treatment may be carried out at about 80 to 150 ℃ for about 20 to 40 minutes.

[0051] In one embodiment, the residue removal step is such that the perovskite is not decomposed and A(X h ) jUsing a solvent that dissolves only the remaining A(X h ) j It can be removed.

[0052] In one embodiment, the solvent may include isopropanol.

[0053] In another aspect, the present invention provides a high-resolution perovskite pattern device manufactured by the high-resolution perovskite patterning method.

[0054] In one embodiment, the linewidth of each pixel included in the first pixel pattern, the second pixel pattern, and the third pixel pattern is determined according to the linewidth of the shadow mask used during vapor deposition. (As of now, a linewidth of up to 3 μm is possible.)

[0055] In this way, each of the above pixel patterns has a small size, thereby enabling the realization of a high-resolution perovskite pattern. Effects of the invention

[0056] The method for forming a perovskite on a substrate according to an embodiment of the present invention presents a new synthesis process capable of forming a perovskite material.

[0057] The high-resolution perovskite patterning method according to an embodiment of the present invention can pattern one or more perovskite materials at high resolution.

[0058] A high-resolution perovskite pattern element according to an embodiment of the present invention is manufactured by the patterning method and can achieve high resolution without corrosion or contamination of the equipment, even with a small pixel size. Brief explanation of the drawing

[0059] Figure 1 shows the band gap map of the MAPbX3 composition, a graph of band gap change according to lattice constant, and a graph of lattice constant change according to X site average ionic radius. FIG. 2 illustrates a high-resolution perovskite patterning method according to an embodiment of the present invention, a fabrication process of an optoelectronic device having perovskite pixels, and optical microscope images of actual fabricated samples at each step. Figure 3 shows a schematic diagram of patterned ITO, an actual photograph, and an optical microscope photograph. Figure 4 shows Pb(X) deposited via vapor deposition. a )2. Schematic diagrams, actual photographs, and optical microscope photographs are shown. Figure 5 shows MA(Br through a liquid phase process 0.3 Cl 0.7 A schematic diagram, actual photograph, and optical microscope photograph of a sample with a deposited layer are shown. Figure 6 shows a schematic diagram of patterned pixels after heat treatment, as well as actual photos and optical microscope photos. Figure 7 shows the residual MA (Br 0.3 Cl 0.7 A schematic diagram, actual photograph, and optical microscope photograph of the pixels removed using isopropanol are shown. Figure 8 shows a schematic diagram, actual photograph, and optical microscope photograph of a sample with an upper electrode deposited via vapor deposition. FIG. 9 shows a scanning electron microscope image and an XRD graph of a high-resolution perovskite pattern according to an embodiment of the present invention. FIG. 10 illustrates a device structure diagram that can be implemented according to an embodiment of the present invention. Specific details for implementing the invention

[0060] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. Since the present invention is susceptible to various modifications and may take various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed forms, and it should be understood that it includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the present invention. Similar reference numerals have been used for similar components in the description of each drawing. In the attached drawings, the dimensions of the structures are shown enlarged compared to the actual dimensions for the clarity of the present invention.

[0061] The terms used in this application are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “comprising” or “having” are intended to specify the presence of the features, numbers, steps, actions, components, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, or combinations thereof. In the context of this specification, terms such as “about” may mean about ± 1%, about ± 2%, about ± 3%, about ± 4%, about ± 5%, about ± 6%, about ± 7%, about ± 8%, about ± 9%, or about ± 10% of the figures described in the specification.

[0062] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0063] A method for forming a perovskite on a substrate according to an embodiment of the present invention is to i(A(X) on a substrate a ) j ) or k(B(X a ) l A first step of vapor deposition of ); and in the first step, i(A(X a ) j In the case where ) is vapor-deposited, the above i(A(X a ) j ) is k(B(X b ) l After exposing to a reaction solution containing ) and reacting, A i B k (X a ) ij (X b ) kl A perovskite is formed, and in the first step, k(B(X a ) l In the case where ) is vapor-deposited, the above k(B(X a ) l ) is i(A(X b ) j After exposing to a reaction solution containing ) and reacting, A i B k (X b ) ij (X a ) klIt may include a second step of forming a perovskite. In one embodiment, A and B are cationic elements, i, j, k, l are positive integers, j is the oxidation number of an A ion, l is the oxidation number of a B ion, and X a and X b are each independently mixtures of halogen elements, and X a is not containing Cl, and X b It may contain Cl. By depositing a Cl-free material through the above steps and then introducing Cl into the perovskite, corrosion or contamination caused by the acidity of the Cl-containing material can be prevented.

[0064] The first step described above is a step of vapor-depositing a precursor material on a substrate. In the context of this specification, “precursor material” may refer to a material prior to the synthesis of a target material. Accordingly, the material deposited in the first step may be a material that can serve as a reactant for the synthesis of the target perovskite through a subsequent process. In the first step, a precursor material is deposited rather than the perovskite itself, and the reason the precursor material does not contain Cl is that a material containing Cl may be acidic and thus could corrode and / or contaminate other materials or the substrate during the vapor deposition process. The present invention is based on the invention that a perovskite material containing Cl can be formed on a substrate in a desired form without corrosion and / or contamination by avoiding corrosion and / or contamination through the vapor deposition of a Cl-free material and then introducing Cl into a solution process.

[0065] Therefore, if the precursor material deposited in the first step does not contain Cl, in particular, includes a halogen material that is not Cl, one objective of the present invention can be achieved, so the X a is not particularly limited. In one embodiment, the X aIt may be a phase of I, Br, or a mixture of I and Br. By varying the composition of each vapor deposition material as described above, it is possible to form patterns of various compositions, including Cl, in the end.

[0066] In addition, as long as it is converted into a perovskite by a subsequent process, the type of the remaining material of the precursor, such as B, is not particularly limited. In one embodiment, B may include Pb. By including Pb as described above, a perovskite structure can be realized.

[0067] The vapor deposition of the first step above can be performed by one or more methods selected from the group including sputtering, thermal vapor deposition, E-beam deposition, and chemical vapor deposition.

[0068] The second step described above is a step of carrying out a reaction to convert at least a portion of the aforementioned Cl-free precursor into a Cl-containing substance by a solution process. Accordingly, in one embodiment, the solution may contain Cl.

[0069] The solution process used in the second step above may include spin coating or dip coating, or drop casting.

[0070] Meanwhile, the perovskite patterning method according to an embodiment of the present invention is k(B(X) on a substrate e ) l Form the first pixel pattern with ), and k(B(X f ) l Form a second pixel pattern with ), and k(B(X g ) l A pattern formation step of forming a third pixel pattern as ), wherein the order of formation of the first pixel, second pixel, and third pixel is independent of their names; and the first pixel pattern, second pixel pattern and third pixel pattern as i(A(X h ) jIt may include a pattern reaction step of reacting after exposure to a reaction solution containing ). In one embodiment, the perovskite patterning method according to an embodiment of the present invention comprises the remaining A(X h ) j It may further include a residue removal step of removing using a solvent. In one embodiment, A and B are cationic elements, and X e , X f and X g For each independently selected p and q, I p Br q With the chemical formula of, X h For each independently selected r, s, and t, I r Br s Cl t It has the chemical formula, where p and q are 0 or positive real numbers and their sum is 1, and r, s, and t are 0 or positive real numbers and their sum is 1. By determining the composition of the reactants as described above, a material that does not contain Cl is deposited and then converted into a material that contains Cl, thereby minimizing corrosion and contamination caused by the acidity of the material containing Cl, and thus enabling the formation of a high-resolution pattern.

[0071] Since the high-resolution perovskite patterning method according to the embodiment of the present invention can utilize the perovskite formation method on a substrate described above, it can be applied identically or similarly to the same or similar configurations or terms in the description above.

[0072] The above pattern formation step is a step of forming a pattern using a precursor material. The precursor material has the same or similar meaning as described above, and in the patterning method of this aspect, there may be one or more types of precursor materials. Furthermore, the above pattern formation step may be similar or identical to the first step of the perovskite formation method described above, and thus a pattern of the precursor material may be formed by vapor deposition.

[0073] The composition of the above precursor material may vary depending on the composition of the final target perovskite. In one embodiment, the X e For , p:q is approximately 9:1 to 10:0, and the above X f For , p:q is approximately 7:3 to 6:4, and the above X g Regarding p:q, it can be approximately 1:9 to 0:10. By determining as above, the pattern produced by the patterning method according to the embodiment of the present invention may have different compositions for each pixel.

[0074] The pattern reaction step described above is a step of synthesizing a perovskite material by reacting a precursor material. The pattern reaction step may be similar to or identical to the second step of the perovskite formation method described above, and thus the precursor material may be converted into a perovskite material by a solution process.

[0075] In one embodiment, B may include Pb. By having B include Pb as described above, the patterning material according to an embodiment of the present invention can realize a perovskite structure.

[0076] In one embodiment, the X h Regarding s:t, it can be from approximately 0:10 to 5:5.

[0077] In one embodiment, the X h For r:(s+t), r:(s+t) can be approximately 0:10 to 1:9.

[0078] By selecting the composition as described above, a Cl-free perovskite material pattern can be converted into a patterning material capable of sensing a desired optical wavelength range.

[0079] In one embodiment, the concentration of the reaction solution may be about 0.1 to 0.4 M. By selecting such a reaction solution concentration, a perovskite material pattern that does not contain Cl can be converted into a patterning material capable of sensing and emitting light within a desired range of light wavelengths.

[0080] Each of the above first pixel pattern, the above second pixel pattern, and the above third pixel pattern can sense and emit light within a desired light wavelength range, in particular, red, green, and blue series light, respectively.

[0081] In one embodiment, the first pixel pattern can sense and emit red-colored light and / or the second pixel pattern can sense and emit green-colored light and / or the third pixel pattern can sense and emit blue-colored light.

[0082] In one embodiment, the first pixel pattern can sense light of a wavelength of about 640 to 730 nm and / or the second pixel pattern can sense light of a wavelength of about 530 to 620 nm and / or the third pixel pattern can sense and emit light of a wavelength of about 440 to 530 nm.

[0083] In one embodiment, by the pattern reaction step, the first pixel pattern may include a composition having a band gap of ~1.77 eV (~700 nm), the second pixel pattern may include a composition having a band gap of ~2.07 eV (~600 nm), and the third pixel pattern may include a composition having a band gap of ~2.48 eV (~500 nm).

[0084] In one embodiment, by the pattern response step, the first pixel pattern is AB(I 0.6+α Br 0.4-2α Cl α Includes )3, and the second pixel pattern is AB(I 0.08+β Br 0.92-3β Cl 2β Includes )3, and the third pixel pattern is AB(Br 0.8±γ Cl 0.2±γIt may include )3. Here, α is a real number less than 0.2, β is a real number less than 0.3, and γ is a real number less than 0.2.

[0085] In one embodiment, the substrate may be a substrate having an ITO electrode formed on a glass substrate. In addition, in one embodiment, the first pixel pattern, the second pixel pattern, and the third pixel pattern may be formed on the ITO electrode. Accordingly, the first pixel pattern, the second pixel pattern, and the third pixel pattern may be electrically connected to an external device, etc.

[0086] In one embodiment, the pattern reaction step may be carried out by heat treatment and photo-annealing while a reaction solution film is formed on the substrate so that the first pixel pattern, the second pixel pattern, and the third pixel pattern are exposed to the reaction solution. In one embodiment, the heat treatment may be carried out at about 80 to 150°C for about 20 to 40 minutes. Perovskite may be realized in the first pixel pattern, the second pixel pattern, and the third pixel pattern by the heat treatment.

[0087] In one embodiment, the residue removal step is such that the perovskite is not decomposed and A(X h ) j Using a solvent that dissolves only the remaining A(X h ) j It can be removed. In one embodiment, the solvent may include isopropanol.

[0088] Meanwhile, a high-resolution perovskite pattern element according to an embodiment of the present invention can be manufactured using the high-resolution perovskite patterning method. In one embodiment, the area of ​​each pixel included in the first pixel pattern, the second pixel pattern, and the third pixel pattern is about 0.1 to 0.5 mm. 2It is possible. In this way, each of the above pixel patterns has a small size, thereby enabling the realization of a high-resolution perovskite pattern.

[0089] Embodiments of the present invention are described below. However, the embodiments described below are merely partial embodiments of the present invention, and the scope of the present invention is not limited to the following embodiments.

[0090] Examples

[0091] FIG. 2 illustrates a high-resolution perovskite patterning method according to an embodiment of the present invention, a fabrication process of an optoelectronic device having perovskite pixels, and optical microscope images of actual fabricated samples at each step.

[0092] First, prepare a substrate on which an ITO electrode is formed on glass (Fig. 3). NiO on the ITO electrode x A layer is formed. Each BX2 pixel having various I-Br ion ratios is vapor-deposited on the ITO electrode of the substrate using a shadow mask (Fig. 4), and then an AX material containing Cl ions is coated on the front surface of these pixels using a solution process (Fig. 5), and finally, a chemical reaction between BX2 and AX is induced (Fig. 6). Thus, an RGB pattern is formed (Fig. 7).

[0093] Specifically, the first step process is to pattern the B(I-Br)2 material, and the B(I-Br)2 material can be deposited by sputtering with different sputter powers on BI2 and BBr2 sources, thermally evaporating with different thicknesses of BI2 and BBr2 thin films, or using co-evaporation, and the B(I-Br)2 material can be patterned using a masking method using a shadow mask or a dry-etching method using photolithography.

[0094] Next, the second step process involves coating an AX solution containing ACl and then implementing an ABX3 composition through a chemical reaction. The AX solution coating can be performed using spin coating, dip coating, drop casting, etc., and the chemical reaction can be induced by heat treatment, optical annealing, etc.

[0095] SnO2, C as electron transport layers 60 PCBM, etc., can be used, and these thin film layers can be deposited using spin coating, dip coating, thermal evaporation, single-atom deposition, etc. Au, Cu, Ag, etc., can be used as the top electrode, and physical vapor deposition methods such as thermal evaporation or sputtering can be used. Therefore, perovskite pixels with various compositions can be realized on a single substrate. At this time, R, G, and B can be absorbed by pixels having band gaps of ~1.77 eV (~700 nm), ~2.07 eV (~600 nm), and ~2.48 eV (~500 nm), respectively, and can be emitted by pixels having band gaps of ~1.87 eV (~660 nm), ~2.25 eV (~550 nm), and ~2.75 eV (450 nm), respectively, so it is possible to implement devices such as photosensors, LEDs, or photosynapses (Fig. 10). In order to fabricate the above devices, it is important to control the composition and thickness of the BX2 pixels and the composition and concentration of the AX solution, as it is necessary to realize the composition of the final ABX3 pixels having the desired band gap.

[0096] A device was fabricated in which a perovskite layer is positioned between a front electrode (ITO) and a back electrode (Ag) vertically arranged in a cross-bar configuration (Fig. 8). In this case, a hole transport layer or an electron transport layer may be inserted between the perovskite and each electrode. The front and back electrodes were each fabricated as bar-type arrays (width 0.5 mm, spacing 2 mm). When viewed from above the substrate, the areas where the two electrodes overlap each other constitute the active layer, which acts as an individual pixel, and the area of ​​each active layer is 0.25 mm². 2 am.

[0097] ITO electrodes patterned as a bar-type array were fabricated by photoetching an ITO thin film deposited over the entire upper surface of the glass (Fig. 3). Subsequently, the patterned ITO substrate was ultrasonically cleaned using a glass cleaner, acetone, distilled water, and ethanol, dried using N2 gas, and then UV-ozone treated.

[0098] MAPbX3 pixels with three different compositions were formed in the active region. Each composition was designed to realize perovskite devices with wavelengths corresponding to R (approx. 700 nm), G (approx. 600 nm), and B (approx. 500 nm). Since the bandgap of MAPbX3 is nearly inversely proportional to the size of the X-site ion, the X-site composition was designed using the experimentally determined ion radius-bandgap relationship. As the bandgaps corresponding to red, green, and blue light are ~1.77 eV (600–700 nm), ~2.07 eV (500–600 nm), and ~2.48 eV (400–500 nm), respectively, the respective X-site composition ratios are I 0.6+x Br 0.4-2x Cl x , I 0.08+y Br 0.92-3y Cl 2y , Br 0.6 Cl 0.4 am.

[0099] Meanwhile, FIG. 1 illustrates the bandgap map of the MAPbX3 composition, a graph of bandgap change according to the lattice constant, and a graph of lattice constant change according to the average ionic radius of the X site. Referring to FIG. 1, since the X composition having a specific bandgap has an infinite number of cases due to the combination of I, Br, and Cl ions, it is not limited to the composition presented in this embodiment.

[0100] Referring to FIG. 1 and FIG. 2 together, in order to form pixels composed of the three compositions above on a substrate, the following process is performed.

[0101] In the first step, using a shadow mask created to match the array of active regions, PbI2 is applied to R-corresponding pixels and Pb(I2) is applied to G-corresponding pixels. 0.6 Br 0.4 )2, and PbBr2 in B corresponding pixels, each 700 x 700 μm 2 Thermal deposition was performed in the shape of squares of the specified size. Considering the target composition of the final ABX3 pixels, PbI 2100 nm was deposited on the R-corresponding pixels, PbI 260 nm and PbBr 240 nm on the G-corresponding pixels, and PbBr 2100 nm on the B-corresponding pixels. (Fig. 4)

[0102] In the second step, the substrate MA (Br on which the above PbX2 is deposited) 0.3 Cl 0.7 After adding 200 μl of the mixed solution (MABr 0.101 g / ml, MACl 0.142 g / ml in isopropanol), spin-coating was performed at 2000 rpm for 30 seconds (Fig. 5). Subsequently, MA(Br 0.3 Cl 0.7 A sample coated with ) was heat-treated at 100 degrees for 30 minutes to form MAPbX3 pixels through a chemical reaction (Fig. 6).

[0103] MA coated between pixels (Br 0.3 Cl 0.7 Since ) does not participate in the reaction, this residual MA(Br 0.3 Cl0.7 To remove ), the substrate was rinsed with isopropanol and then dried with N2 gas. Figure 7 shows the sample after drying with N2 gas. MA(Br 0.3 Cl 0.7 Since ) is an insulator, device characteristics can be verified even if the device is fabricated without removing it, but MA(Br 0.3 Cl 0.7 Since ) has the characteristic of vaporizing easily even at low temperatures, damage to the upper electrode may occur if it is not removed.

[0104] The compositions of the final MAPbX3 pixels analyzed by XRD are summarized in Table 1. The band gaps converted to each composition are also shown in Table 1. While the composition corresponding to B can be determined as a two-component system, the compositions corresponding to R and G are three-component systems; therefore, since the composition cannot be determined unless the ratio of one element is specified, they are expressed as a relationship.

[0105] Target PbX2 composition PbX2 thickness MAX composition Lattice constant band gap MAPbX3 composition R PbI2 100 nm MA(Br 0.3 Cl 0.7 ) 6.15 1.73 eV MAPb(I 0.6+x Br 0.4-2x Cl x )3 G Pb(I 0.6 Br 0.4 )2 100 nm MA(Br 0.3 Cl 0.7 ) 6.08 1.91 eV MAPb(I 0.08+y Br 0.92-3y Cl 2y )3 B PbBr2 100 nm MA(Br 0.3 Cl 0.7 ) 5.87 2.41 eV MAPb(Br 0.7 Cl 0.3 )3

[0106] Finally, an Ag back electrode was thermally deposited to a thickness of 100 nm. The band gap can be controlled depending on the AX solution applied dropwise, and an example is shown in the table below.

[0107]

[0108] Figure 3 is a diagram illustrating ITO etched into a bar type using a photolithography process.

[0109] Figure 4 shows Pb(X) deposited by vapor deposition on patterned ITO. a This is a schematic diagram and photograph of )2 deposited.

[0110] Figure 5 shows Pb(X a This is a diagram of a process for exposing a reaction solution to a sample on which )2 has been deposited.

[0111] Figure 6 is a process schematic diagram and image of the synthesized perovskite pattern and residue after the pattern reaction step.

[0112] Figure 7 is a schematic diagram and image showing the state in which only the perovskite pattern remains after removing the residue.

[0113] Figure 8 is a schematic diagram and image of a device fabricated by depositing a metal electrode on a perovskite pattern.

[0114] Figure 9 is a diagram showing the SEM image and XRD pattern of the pattern. It can be confirmed that the pattern is clearly well formed and that the perovskite was well synthesized.

[0115] Figure 10 is a schematic diagram showing the structure of optoelectronic devices that can be realized with patterned perovskite.

[0116] Although the present invention has been described above with reference to preferred embodiments, those skilled in the art will understand that various modifications and changes can be made to the invention without departing from the spirit and scope of the invention as set forth in the following claims.

Claims

Claim 1 delete Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 BI on the substrate l and / or BBr l Two or more types of k(B(X) through vapor deposition using as a deposition source e ) l A pattern formation step for forming a pixel pattern having a composition of ); and each pixel pattern i(A(X f ) j It includes a pattern reaction step of reacting after exposure to a reaction solution containing ), and two or more types of A having different anion compositions i B k (X e ) ij (X f ) kl A perovskite patterning method characterized by patterning a perovskite pattern on a single substrate: wherein A and B are cationic materials, i, j, k, l are positive integers, j is the oxidation number of an A ion, l is the oxidation number of a B ion, and X e is I p Br q It has the chemical formula, p+q=1, and the above X f is I r Br s Cl t It has the chemical formula r+s+t=1, and p, q, r, s, t are 0 or positive real numbers. Claim 9 A perovskite patterning method according to claim 8, wherein A is any one selected from the group consisting of methylammonium (MA), formamidinium (FA), cesium (Cs), rubidium (Rb), and potassium (K). Claim 10 A perovskite patterning method according to claim 8, wherein the pixel pattern comprises a first pixel pattern, a second pixel pattern and a third pixel pattern. Claim 11 A perovskite patterning method according to claim 10, wherein for the first pixel pattern, p:q is from 10:0 to 9:1, for the second pixel pattern, p:q is from 6:4 to 7:3, and for the third pixel pattern, p:q is from 1:9 to 0:

10. Claim 12 A perovskite patterning method according to claim 8, wherein B is any one selected from the group consisting of lead (Pb), tin (Sn), and germanium (Ge). Claim 13 In paragraph 8, the above X f A perovskite patterning method characterized by the atomic percentages (r:s:t) of 1:2:

7. Claim 14 A perovskite patterning method according to claim 8, wherein the vapor deposition is performed by one or more methods selected from the group comprising sputtering, thermal vapor deposition, E-beam deposition, and chemical vapor deposition. Claim 15 A perovskite patterning method according to claim 8, wherein the reaction solution is exposed by coating by spin coating, dip coating, or drop casting. Claim 16 A perovskite patterning method according to claim 8, wherein the pixel pattern is patterned using a masking method using a shadow mask or a dry-etching method using photolithography. Claim 17 A perovskite patterning method according to claim 10, wherein, by the pattern reaction step, the first pixel pattern senses and emits red-series light, the second pixel pattern senses and emits green-series light, and the third pixel pattern senses and emits blue-series light. Claim 18 A high-resolution perovskite patterning method according to claim 17, wherein the first pixel pattern senses and emits light of a wavelength of 640 to 730 nm, the second pixel pattern senses and emits light of a wavelength of 530 to 640 nm, and the third pixel pattern senses and emits light of a wavelength of 440 to 530 nm. Claim 19 In Clause 10, the above-mentioned first pixel pattern is AB(I 0.6+α Br 0.4-2α Cl α Includes )3, and the second pixel pattern is AB(I 0.08+β Br 0.92-3β Cl 2β Includes )3, and the third pixel pattern is AB(Br 0.8±γ Cl 0.2±γ A perovskite patterning method comprising )3:where α is a real number less than 0.2, β is a real number less than 0.3, and γ is a real number less than 0.

2. Claim 20 A perovskite patterning method according to claim 8, wherein the substrate is a substrate having a transparent electrode formed on a glass substrate, and each pixel pattern is formed on the transparent electrode. Claim 21 A high-resolution perovskite patterning method according to claim 20, wherein the substrate is a substrate having an ITO electrode formed on a glass substrate, and each pixel pattern is formed on the ITO electrode. Claim 22 A perovskite patterning method according to claim 8, wherein the pattern reaction step is performed by heat treatment or photo-annealing while a reaction solution film is formed on the substrate so that each pixel pattern is exposed to the reaction solution. Claim 23 In claim 8, the perovskite patterning method further comprises a residue removal step of removing residues of the reaction solution using a solvent, wherein the solvent removes only the residues of the reaction solution without decomposing the pixel pattern. Claim 24 A perovskite patterning method according to claim 23, wherein the solvent comprises isopropanol.

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