Method for realizing perovskite thin film patterning through dry etching by using reactive ion etching technology

Abstract

The invention discloses a method for realizing perovskite thin film patterning through dry etching by using a reactive ion etching technology. The method comprises the following steps: 1) cleaning a substrate / base; 2) depositing a perovskite thin film; and 3) performing reactive ion beam etching on the perovskite thin film. According to the invention, the perovskite is etched by using a reactive ion beam process for the first time, and a new process strategy is provided for a perovskite array patterning scheme; moreover, the dry etching perovskite process avoids the condition that the perovskite is corroded by a solvent, is not restricted by the types of the perovskite, and is suitable for all types of perovskite thin film materials. Compared with the prior art that a template method is used for manufacturing the perovskite patterning process, the method is simpler, the reactive ion beam etching equipment is simple in structure, low in cost and compatible with all MEMS scale manufacturing factories, and the manufacturing cost is reduced to a great extent; the method is suitable for any base or substrate material, and the compatibility of manufacturing various functional materials is widened.

Description

Technical Field

[0001] The invention belongs to the technical field of perovskite film patterning preparation, and in particular relates to a method for realizing perovskite film patterning by dry etching using reactive ion etching technology. Background Art

[0002] Perovskite materials have the advantages of suitable band gap, high carrier mobility, high absorption coefficient, low exciton binding energy, and long carrier lifetime. Perovskite-based quantum dots, nanowires and other structural materials have also become a new generation of optoelectronic functional materials and have achieved rapid development in the fields of light-emitting diodes, solar cells, resistive memristors, etc. Therefore, they have received widespread attention in the fields of communications, displays, photovoltaics, etc.

[0003] Graphicsing of thin films of functional materials is one of the important steps in the development of micro-nanoelectronic devices, and is usually achieved with the help of micro-electromechanical systems (MEMS) processing technology. The solution to achieve thin film graphics is usually to cover the surface of the film or substrate with photoresist, and then use laser direct writing, ultraviolet exposure or electron beam exposure to pattern the photoresist. Through the development step, the film surface exposes the film area to be removed, or the substrate surface exposes the area where the film is to be deposited to show the pattern, and then further uses the stripping, etching or deposition process. For etching and deposition, the photoresist still needs to be further removed. Another graphic scheme is to use a mask to cover the surface of the functional material film and directly perform dry etching. Dry etching includes chemical-based reactive ion beam etching (RIE) and physical sputtering-based ion beam etching (IBE), as well as a physical and chemical etching technology (RIBE) that combines both.

[0004] For perovskite film, it is very sensitive to photoresist and developer, and is easily corroded by solvents in these liquid chemicals. Therefore, the design of the perovskite film patterning process must avoid direct contact with liquid chemicals such as photoresist and developer. Therefore, the perovskite film patterning technology is still a challenge. One solution is to directly use the mask to fit the surface of the perovskite film, perform dry etching, and directly remove the uncovered perovskite film area outside the mask to form a pattern. However, there have been no reports of similar solutions so far. The reasons for its technical difficulty are roughly the following two points: 1. The dry etching process ultimately requires the reaction product to become gaseous, and then exclude the reaction chamber, and the presence of Pb and Cs heavy metal elements in the perovskite film makes it difficult to form gaseous products; 2. There is no corresponding template that can be used to form a perovskite array dot pattern.

[0005] For dry etching in current MEMS process technology, reactive ion beam (RIE) is the most mainstream, with fast etching rate, higher etching selectivity than IBE, and controllable parameters. It is commonly used for etching Si-based film layers in MEMS processes, such as Si, SiO2, SiNx, and SiC, and the main components of the film are Si, O, C, and N. The elemental composition of perovskite material films is Pb, halogen elements (Cl, Br, I), C, O, and H, including the heavy metal element Pb, which increases the difficulty of RIE etching and is very different from the existing Si-based thin film etching technology. Therefore, there is no report on the reactive ion beam etching solution for perovskite films.

[0006] As for the research and development of perovskite film patterning technology, there have been a few reports since 2015. For example, the most popular solution is the hydrophilic-hydrophobic template method to make perovskite array patterns, that is, using octadecyltrichlorosilane (OTS) to hydrophobically treat the SiO2 / Si substrate, and control the perovskite precursor to infiltrate and grow in the hydrophobically treated pattern area, thereby achieving perovskite patterning. Light-emitting diodes have been developed using a similar solution. In this hydrophilic-hydrophobic template method technology, Al2O3 is added to assist in forming large-scale perovskite array points.

[0007] The hydrophilic-hydrophobic template method for patterning perovskite thin films is to first form hydrophobic and hydrophilic areas on the substrate, and then use a one-step spin coating deposition scheme or a two-step spin coating deposition scheme, both of which spin-coat the perovskite precursor liquid so that the precursor liquid only covers the wettable hydrophilic area, and then after heating, the perovskite film is crystallized only in the wetted area to form a pattern. Disadvantages: 1. There are many types of perovskites, and the materials used for specified functional devices (light-emitting diodes, memristors, light sensors, etc.) need to select perovskites with specific optoelectronic effects as active materials. However, in the perovskite family, the hydrophilic-hydrophobic template method is not suitable for most thin film preparation; 2. When the resolution level of the perovskite array point pattern is in the range of tens of nanometers to several microns, the perovskite array points are not easy to control within the pattern, because the hydrophilic-hydrophobic template method is to limit the pattern to which the perovskite precursor liquid adheres, and then the perovskite continues to grow on the pattern. Usually, the perovskite grain size is tens to hundreds of microns, which can easily exceed the edge of the pattern, resulting in the edge and size of the perovskite film pattern not being completely consistent with the pattern; 3. There are certain requirements for the substrate material. In order to realize the photolithography process of the hydrophilic-hydrophobic layer, the substrate is generally required to be covered with a special coating material (ITO, FTO, ZnO, TiO2), and then the hydrophilic-hydrophobic template method is used. This template method process requires the coating of a hydrophilic film and a photoresist, and the use of photolithography technology, which leads to very high overall process complexity and technical requirements, which is not conducive to the large-scale development of MEMS electronic devices. Summary of the invention

[0008] The purpose of the present invention is to provide a method for realizing the patterning of perovskite film by dry etching using reactive ion etching technology. The invention realizes the patterning of perovskite film by using the dry etching technology of reactive ion beam etching, avoids contact with any solvent, and prevents the perovskite film from being damaged by non-polar solvents; because the reactive ion beam etching of the present invention is carried out in a high vacuum environment, the perovskite film is avoided from being in contact with water molecules in the air for a long time during the patterning process, resulting in the problem of performance attenuation or failure of the perovskite film; the technical solution of the present invention has low requirements on process equipment and is easy to be compatible in MEMS process.

[0009] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0010] A method for patterning a perovskite film by dry etching using reactive ion etching technology, comprising the following steps: 1) cleaning a substrate / base; 2) depositing a perovskite film; 3) reactive ion beam etching of the perovskite film; wherein the method of reactive ion beam etching in step 3) is:

[0011] a. First, cover the surface of the perovskite film with a hollow hard mask plate with a corresponding pattern, and use a sticky resin glue or a spring pressure piece to fix the mask plate and the perovskite film substrate; in this step, if it is necessary to calibrate the position of the mask plate in the perovskite film etching pattern, it is necessary to use the substrate transfer platform to complete the alignment operation, and contact the designed pattern hollow mask plate on the surface of the perovskite film according to the alignment mark. First, coarsely align the substrate with an accuracy error of <50μm, and then finely align the substrate with an alignment error of <5μm. After the mask plate is aligned, use a sticky resin glue or a spring pressure piece to fix the mask plate and the perovskite film substrate. Among them, the sticky resin glue can buffer the micro-motion between the mask plate and the perovskite film substrate; the squeezing force of the spring pressure piece on the mask plate and the substrate can prevent the two from being misaligned. The specific use depends on the accuracy of the etching layout. If the etching pattern accuracy is high, both methods must be used. If the etching pattern accuracy is low, only the spring pressure piece can be used. Both can prevent the mask from moving between the perovskite film substrate and improve the accuracy of the perovskite film etching pattern;

[0012] b. Place the perovskite film substrate covered with a mask plate into the reactive ion beam reactive etching chamber. The reactive etching process parameters are as follows: the process gas is a combined mixed atmosphere of CF4+CHF3, the CF4 flow rate is set to 30sccm, the CHF3 flow rate is set to 10sccm, the electrode power is 80W, the gas pressure is 3Pa, the time is 5-10s, and under the action of the electrode high-energy high-frequency magnetic field, the mixed process gas is excited to produce free matrix F - and H + , the perovskite film without mask shielding contacts the free substrate and undergoes corrosion reaction, generating gas, which is then discharged from the reaction chamber, as shown in the following reaction formula:

[0013] CF4→CF x + +CF y -

[0014] CF4+e-→CF X +CF y +F - +e -

[0015] CF x + +e-→CF x

[0016] CHF3→CF x +H + +e -

[0017] CHF3+e - →CHF2+F -

[0018] The perovskite film without mask plate contacts the free matrix and undergoes corrosion reaction, generating gas, which is then discharged from the reaction chamber; the reaction formula is as follows:

[0019] i. CH3NH3PbI3 as an example, the reaction equation is as follows:

[0020] CH3NH3 + H + → CH x (gas) + NH x (gas)

[0021] Pb 2+ + F - → PbF2 (g)

[0022] I - + H+→ HI (g)

[0023] ii. Taking CH3NH3PbBr3 as an example, the reaction equation is as follows:

[0024] CH3NH3 + H + → CH x (gas) + NH x (gas)

[0025] Pb 2+ + F - → PbF2 (g)

[0026] Br - + H+→ HBr (g)

[0027] iii. Taking CsPbI3 as an example, the reaction equation is as follows:

[0028] Cs + + F - → CsF (g)

[0029] Pb 2+ + F - → PbF2 (g)

[0030] I - + H+→ HI (g)

[0031] iv. Taking [CH3NH3]SnI3 as an example, the reaction equation is as follows:

[0032] CH3NH3 + H + → CH x (gas) + NH x (gas)

[0033] Sn + + F - → SnF (g)

[0034] I - + H+→ HI (g)

[0035] c. After the reactive ion beam etching is completed, the perovskite film substrate and the mask plate are removed. If a second etching is required, the above steps a and b are repeated.

[0036] As a further preferred embodiment of the present invention, in step a., the material of the hard mask plate is selected from one of stainless steel, silicon dioxide, silicon nitride and silicon wafer.

[0037] As a further preferred embodiment of the present invention, in step 1), the material of the substrate / base is selected from one of Si-based wafer, sapphire (Al2O3), ITO, glass, polyethylene, polyethylene terephthalate (PET) and polyimide (PI).

[0038] As a further preferred embodiment of the present invention, in step 1), the cleaning is first carried out by washing with deionized water for one or two times and blowing dry, washing with acetone and blowing dry, washing with alcohol and blowing dry, and then O2 / Ar plasma degumming is used to remove surface organic impurities; ultrasonic cleaning is used for each cleaning to ensure more thorough cleaning.

[0039] As a further preferred embodiment of the present invention, in step 2), the perovskite film is ABX3, wherein A can be NH4 + 、[(CH3)NH4] +、[(CH2)3NH2] + 、[NH2(CH)NH2] + 、[(CH3)2NH2] + 、[(C2H5)NH3] + 、[C(NH2)3] + 、[(CH3)4N] + One or more organic groups, or Cs + , Rb + , K + One or more metal ions; B is Pb 2+ Sn 2+ One or more heavy metal ions such as chlorine or iodine; X is one or more halogen elements: Cl, Br, I.

[0040] As a further preferred embodiment of the present invention, in step 2), the deposited perovskite film is prepared by a one-step method or a two-step method; the one-step method is to form a perovskite film by nucleating and growing a precursor solution containing all compounds of the perovskite; the two-step method is to mix two precursor solution solvents respectively, gradually deposit various precursor liquids, initially spin-coat one precursor solution, and deposit the other by immersion or spin coating, and then perform heating and annealing treatment to evaporate the solvent and the perovskite crystallize into a film.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] 1) The dry etching perovskite process of the present invention avoids the situation where perovskite is corroded by solvents and is not restricted by the type of perovskite, and is applicable to all types of perovskite thin film materials;

[0043] 2) The present invention proposes for the first time to use a reactive ion beam process to etch perovskite, and proposes a new process strategy for perovskite array patterning;

[0044] 3) Compared with the previously proposed template method for making perovskite patterning, the process is simpler. Secondly, the reactive ion beam etching equipment has a simple structure, is cheap, and is compatible with all MEMS scale manufacturing plants, which greatly reduces the manufacturing cost;

[0045] 4) The solution proposed by the present invention is applicable to any substrate or substrate material, such as glass or PET with ITO, FTO, ZnO, TiO2 substrates, and plastic substrates; it broadens the compatibility of manufacturing various functional materials;

[0046] 5) The perovskite substrate etched by the proposed solution of the present invention can produce array points with a resolution ranging from hundreds of microns to tens of nanometers, depending on the resolution of the mask. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] In order to more clearly illustrate the technical solution of the present invention, 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 those skilled in the art, other drawings can be obtained based on these drawings without paying creative work.

[0048] Figure 1 This is an optical microscope photo of a stainless steel mask;

[0049] Figure 2 It is a perovskite film through-hole array etched using a through-hole mask. DETAILED DESCRIPTION

[0050] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention is described in detail below, but the following embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by those skilled in the art without making creative work belong to the scope of protection of the present invention.

[0051] There are many types of perovskite film materials, each with different photoelectric properties. In the dry etching method of the present invention, no requirements are made on the type or element of the perovskite film. The perovskite used is ABX3, where A can be NH4 + 、[(CH3)NH4] + 、[(CH2)3NH2] + 、[NH2(CH)NH2] + 、[(CH3)2NH2] + 、[(C2H5)NH3] + 、[C(NH2)3] + 、[(CH3)4N] + Single or multiple organic groups, or Cs + , Rb + , K + One or more metal ions; wherein B is Pb 2+ Sn 2+ X is one or more of the halogen elements: Cl, Br, I. The present invention provides that the perovskite film can be prepared by a one-step method or a two-step method.

[0052] Among them, the one-step method is the nucleation and growth of the perovskite film in the precursor solution containing all the compounds of the perovskite. Taking the preparation of CH3NH3PbI3 as an example, the first step is to prepare the precursor solution: a certain amount of CH3NH3I and PbI2 are mixed in a molar ratio of 1:1 in one or more solvents of N, N-dimethylformamide (DMF), γ-butyrolactone (GBL) and or dimethyl sulfoxide (DMSO), and the total molar concentration can be 1-100 mol / mL; the second step can be a spin coating process, the substrate or substrate is adsorbed on the spin coater or the coating machine, the precursor solution is covered on the surface of the substrate or substrate, and the pre-running speed is 300-500rpm for 3-10 seconds, and then the speed is 2000-3000rpm for 30-60s; the third step is to place the substrate or substrate with the perovskite precursor solution on a heating plate at 100-180 degrees Celsius for annealing, so that the solvent evaporates and crystallizes to form a perovskite film.

[0053] For example, when preparing [(CH2)3NH2]PbI3 thin film, the precursor solution is a mixed salt solution of [(CH2)3NH2]I and PbI2 with a certain concentration and amount according to the proportion and molar mass. For example, when preparing [CH3NH3]PbBr3 thin film, a mixed salt solution of [CH3NH3]Br and PbBr2 with a certain concentration and amount according to the proportion and molar mass is prepared, and the solvent is the same as above. For example, when preparing [CH3NH3]SnI3 thin film, a mixed salt solution of [(CH2)3NH2]I and SnI2 with a certain concentration and amount according to the proportion and molar mass is prepared. Other solutions similar to [(CH2)3NH2]PbBr 3-a-b I a Cl b The perovskite with mixed element components at the A, B or X positions can be prepared by analogy as above, and the corresponding salt mixed solution can be prepared. The solvent used to prepare the precursor solution can be one or two mixed solvents of DMF, GBL and or DMSO. The second step of coating the substrate or substrate with the perovskite precursor solution and the third step of perovskite crystallization film formation are the same as above.

[0054] The two-step method for preparing perovskite thin films is to mix two precursor liquid solvents separately, gradually deposit various precursor liquids, spin-coat one precursor liquid for the first time, and deposit the other by immersion or spin coating, and then heat annealing to evaporate the solvent and perovskite crystallize into a film. Taking the two-step method for preparing CH3NH3PbI3 as an example, the specific method is as follows: the first step is to prepare precursor solutions respectively, dissolve a certain amount of CH3NH3I salt in isopropanol IPA to form a solution with a concentration of 1 to 100 mol / mL, and dissolve PbI2 in DMF solvent to form a 1 to 100 mol / mL solution; the second step is step-by-step deposition, and the PbI2 film layer can be deposited on the substrate or base by a spin coating process, which can be pre-run at a speed of 300 to 500 rpm for 3 to 10 seconds, and then run at a speed of 2000 to 3000 rpm for 30 to 60 seconds, and then deposit CH3NH3I salt by an immersion process or a spin coating process, wherein the immersion process is to place the substrate or substrate in a salt solution for several seconds, and the spin coating process can adopt the deposition scheme of the former; the third step is to place the substrate or substrate on a heating plate at 100 to 180 degrees Celsius for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0055] For example, when preparing [(CH2)3NH2]PbI3 thin film, the precursor solution is respectively configured with two salt solutions of [(CH2)3NH2]I and PbI2 according to certain dosage and concentration; when preparing [CH3NH3]PbBr3 thin film, the precursor solution is respectively configured with two salt solutions of [CH3NH3]Br and PbBr2 according to certain dosage and concentration; when preparing [CH3NH3]SnI3 thin film, the precursor solution is respectively configured with two salt solutions of [(CH2)3NH2]I and SnI2 according to certain dosage and concentration; other similar [(CH2)3NH2]PbBr 3-a-b I a Cl b The perovskite with mixed element components at the A, B or X positions can be prepared by analogy as above, and the corresponding two salt solutions can be prepared. The solvents used to prepare the precursor solution can be one or two mixed solvents of IPA, DMF, GBL and DMSO. The second step of coating the substrate or substrate with the perovskite precursor solution and the third step of crystallizing the perovskite film are the same as above.

[0056] The reactive ion beam etching scheme of the present invention is applicable to both conventional perovskite films and perovskite films with modified element positions (A / B / X). The morphology of the perovskite film can be a crystal particle covering layer, a linear shape, or a mesh shape. In short, the dry etching scheme for the perovskite film does not impose any restrictions on the type, element, morphology, and structure of the perovskite.

[0057] Example 1

[0058] The present invention provides a method for realizing the patterning of perovskite thin film by dry etching using reactive ion etching technology, and provides a method for dry etching of [(CH2)3NH2]PbBrI2 perovskite thin film pores. The specific preparation method of the array comprises the following steps:

[0059] 1) Using a glass substrate with an ITO coating as a perovskite film substrate; sequentially using deionized water ultrasonic cleaning once or twice and blowing dry, acetone ultrasonic cleaning and blowing dry, alcohol ultrasonic cleaning and blowing dry, and then O2 / Ar plasma degumming to remove surface organic impurities;

[0060] 2) Deposition of [(CH2)3NH2]PbBrI2 perovskite film using a two-step method:

[0061] The first step is to prepare the precursor solution: a certain amount of [(CH2)3NH2]Br and [(CH2)3NH2]I are mixed in a DMSO solvent at a molar ratio of 1:1, and the total molar concentration can be 1 mol / mL; in addition, a certain amount of PbI2 is dissolved in a DMF solvent to form a 1 mol / mL solution; the second step is to deposit the PbI2 film on the ITO substrate in steps by using a spin coating process, pre-running at a speed of 400rpm for 3 to 10 seconds, and then running at a speed of 3000rpm for 50s, and then immersing the substrate coated with the PbI2 film in the mixed salt of [(CH2)3NH2]Br and [(CH2)3NH2]I for 15s, then taking it out and blowing it dry; the third step is to place the substrate or substrate on a heating plate at 120°C for annealing to evaporate the solvent and crystallize it to form a perovskite film;

[0062] 3) Reactive ion beam etching of perovskite films:

[0063] a. Use 50um thick stainless steel to make a through hole Array mask (such as Figure 1 Optical microscope photo of a stainless steel mask plate); use a substrate transfer platform to complete the alignment operation, and contact the hollow through-hole pattern mask plate with the surface of the perovskite film; first, coarse adjustment is performed to align the substrate, and the accuracy error is <50μm, and then fine adjustment is performed to align the substrate, and the alignment error is <5μm; after the mask plate is aligned, a spring pressure piece is used to fix the mask plate and the perovskite film substrate;

[0064] b. Place the perovskite thin film substrate covered with a mask plate into the reactive ion beam reactive etching chamber. The reactive etching process parameters are: the process gas is a combined mixed atmosphere of CF4+CHF3, the CF4 flow rate is set to 30sccm, the CHF3 flow rate is set to 10sccm, the electrode power is 80W, the gas pressure is 3Pa, the time is 5-10s, and under the action of the high-energy high-frequency magnetic field of the electrode, the mixed process gas is excited to produce free matrix F -and H + , the perovskite film without mask shielding contacts the free substrate and undergoes corrosion reaction, generating gas, which is then discharged from the reaction chamber, as shown in the following reaction formula:

[0065] CF4→CF x + +CF y -

[0066] CF4+e-→CF X +CF y +F - +e -

[0067] CF x + +e-→CF x

[0068] CHF3→CF x +H + +e -

[0069] CHF3+e - →CHF2+F -

[0070] The perovskite film without mask shielding contacts the free matrix and undergoes corrosion reaction, generating gas which is then discharged from the reaction chamber as shown in the following reaction formula:

[0071] Taking [(CH2)3NH2]PbBrI2 as an example, the reaction equation is as follows:

[0072] (CH2)3NH2 + + H + → CH x (gas) + NH x (gas)

[0073] Pb 2+ + F - → PbF2 (g)

[0074] Br - + H+→ HBr (g)

[0075] I - + H+→ HI (g)

[0076] c. After the reactive ion beam etching is completed, take out the perovskite film substrate and mask plate, such as Figure 2 After etching, a perovskite film hole array is formed according to the mask pattern, thereby realizing the patterning of the perovskite film.

[0077] Example 2

[0078] The present embodiment provides a method for patterning a perovskite film by dry etching using reactive ion etching technology, which is the same as that of Embodiment 1, except that [(CH2)3NH2]PbBrI2 is replaced by CH3NH3PbBr3.

[0079] Taking CH3NH3PbBr3 as an example, the reaction equation is as follows:

[0080] CH3NH3 + + H + → CH x (gas) + NH x (gas)

[0081] Pb 2+ + F - → PbF2 (g)

[0082] Br - +H+→HBr(g).

[0083] Example 3

[0084] The present embodiment provides a method for patterning a perovskite film by dry etching using reactive ion etching technology, which is the same as that of Embodiment 1, except that [(CH2)3NH2]PbBrI2 is replaced by CsPbI3.

[0085] Taking CsPbI3 as an example, the reaction equation is as follows:

[0086] Cs + + F - → CsF (g)

[0087] Pb 2+ + F - → PbF2 (g)

[0088] I - +H+→HI(g).

[0089] Example 4

[0090] The present embodiment provides a method for patterning a perovskite film by dry etching using reactive ion etching technology, which is the same as that of Embodiment 1, except that [(CH2)3NH2]PbBrI2 is replaced by [CH3NH3]SnI3.

[0091] Taking [CH3NH3]SnI3 as an example, the reaction equation is as follows:

[0092] (CH2)3NH2 + + H +→ CH x (gas) + NH x (gas)

[0093] Sn + + F - → SnF (g)

[0094] I - +H+→HI(g).

[0095] In other embodiments, in step 1), the material of the substrate is selected from one of Si-based wafer, sapphire (Al2O3), ITO, polyethylene, polyethylene terephthalate (PET) and polyimide (PI), all of which can achieve the effect of the present invention.

[0096] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for patterning a perovskite film by dry etching using reactive ion etching technology, characterized in that: The following steps are involved: 1) Substrate / base cleaning; 2) Deposition of perovskite film; 3) Reactive ion beam etching of perovskite film; Wherein, the method of reactive ion beam etching in step 3) is: a. First, a hollow hard mask plate with a corresponding pattern is covered on the surface of the perovskite film, and a sticky resin glue or a spring press is used to fix the mask plate and the perovskite film substrate; b. Place the perovskite film substrate covered with a mask plate into the reactive etching chamber of the reactive ion beam. The reactive etching process parameters are as follows: the process gas is a combined mixed atmosphere of CF4+CHF3, the CF4 flow rate is set to 30sccm, the CHF3 flow rate is set to 10sccm, the electrode power is 80W, the gas pressure is 3Pa, the time is 5-10s, and under the action of the high-energy high-frequency magnetic field of the electrode, the mixed process gas is excited to produce free matrix F - and H + , the perovskite film without mask shielding contacts the free matrix and undergoes corrosion reaction, generating gas which is then discharged from the reaction chamber; c. After the reactive ion beam etching is completed, the perovskite film substrate and the mask plate can be removed.

2. The method for realizing perovskite film patterning by dry etching using reactive ion etching technology according to claim 1, characterized in that: In step a., the material of the hard mask plate is selected from one of stainless steel, silicon dioxide, silicon nitride and silicon wafer.

3. The method for realizing perovskite film patterning by dry etching using reactive ion etching technology according to claim 1, characterized in that: In step 1), the material of the substrate / base is selected from one of Si-based wafer, sapphire (Al2O3), ITO, glass, polyethylene, polyethylene terephthalate (PET) and polyimide (PI).

4. The method for realizing perovskite film patterning by dry etching using reactive ion etching technology according to claim 1, characterized in that: In step 1), the cleaning is first carried out by washing with deionized water for one or two times and blowing dry, washing with acetone and blowing dry, washing with alcohol and blowing dry, and then removing organic impurities on the surface by O2 / Ar plasma degumming; ultrasonic cleaning is used for each cleaning to ensure more thorough cleaning.

5. The method for realizing perovskite film patterning by dry etching using reactive ion etching technology according to claim 1, characterized in that: In step 2), the perovskite film is ABX3, wherein A can be NH4 + 、[(CH3)NH4] + 、[(CH2)3NH2] + 、[NH2(CH)NH2] + 、[(CH3)2NH2] + 、[(C2H5)NH3] + 、[C(NH2)3] + 、[(CH3)4N] + One or more organic groups, or Cs + , Rb + , K + One or more metal ions; B is Pb 2+ Sn 2+ One or more heavy metal ions such as chlorine or iodine; X is one or more halogen elements: Cl, Br, I.

6. The method for realizing perovskite film patterning by dry etching using reactive ion etching technology according to claim 1, characterized in that: The deposited perovskite film is prepared by a one-step method or a two-step method; the one-step method is to form a perovskite film by nucleating and growing a precursor solution containing all compounds of the perovskite; the two-step method is to mix two precursor solution solvents respectively, gradually deposit various precursor liquids, initially spin-coat one precursor solution, and deposit the other by immersion or spin-coating, and then perform heating and annealing treatment to evaporate the solvent and perovskite crystallize into a film.

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