Method for manufacturing halide perovskite array pattern by inductively coupled plasma etching technology

Abstract

The invention discloses a method for manufacturing a halide perovskite array pattern by an inductively coupled plasma etching technology. The method comprises the following steps: 1) preparing a halide perovskite thin film; and 2) performing ion etching on the array pattern: covering a mask plate on the halide perovskite thin film, enabling a pattern formed by the mask plate to correspond to the halide perovskite array pattern, performing etching by using an inductive coupling plasma etching technology, and taking down the mask plate to form the halide perovskite thin film array pattern. According to the method, a stainless steel mask plate is used as an etching mask tool for perovskite array patterning (hundreds of microns and above), and free electrons, fluorine-based ions and chlorine-based ions excited by an inductive coupling plasma technology are used for etching halide perovskite thin film materials outside the mask plate twice, so that perovskite thin film patterning is realized; the method is simple, does not contact with any solvent, effectively prevents the perovskite thin film from being corroded by a non-polar solvent, is not restricted by perovskite types, and is suitable for all types of perovskite thin film materials.

Description

Technical Field

[0001] The invention belongs to the technical field of perovskite array patterning, and in particular relates to a method for manufacturing halide perovskite array patterns by using an inductively coupled plasma etching technology. Background Art

[0002] Halide perovskite (hereinafter referred to as "perovskite") materials have the advantages of suitable band gap, high carrier mobility, high absorption coefficient, low exciton binding energy, long carrier lifetime, etc. Among them, quantum dots, nanowires and other structural materials based on perovskites 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 also received extensive attention in the fields of communications, displays, photovoltaics, etc. The efficient, precise and large-scale construction of perovskite microstructure arrays on the substrate is an important prerequisite for the device application of perovskite materials.

[0003] At present, in the manufacture of MEMS devices, the array patterning production scheme is completed by using photolithography technology. For example, photolithography technology is first used to perform hydrophilic-hydrophobic patterning on a special substrate, such as a polyethylene terephthalate flexible substrate or a silicon-based substrate with silicon dioxide. The perovskite precursor solution can be only infiltrated in the hydrophilic area. After degradation and the formation of perovskite crystals, a perovskite patterned pattern is obtained. In the above-mentioned photolithography technology, the steps of coating, developing, and degumming require the use of a large amount of solution containing polar solvents, and polar solvents will corrode perovskites, so photolithography technology cannot be used to produce perovskite thin film array patterning.

[0004] In recent years, all the perovskite patterning schemes developed are hydrophilic-hydrophobic template methods, that is, after the substrate on which the perovskite is deposited is patterned, the perovskite is deposited and grown in the hydrophilic area to finally obtain a pattern. This scheme has many disadvantages, such as: 1. The types of perovskites are limited: There are many types of perovskites, and they are used for designated functional devices, such as light-emitting diodes, memristors, light sensors and other materials. Perovskites with specific photoelectric effects need to be selected as active materials, but in the perovskite family, there are films that are not suitable for the hydrophilic-hydrophobic template method. 2. There are irregularities at the edges of the pattern: When the resolution level of the perovskite array point pattern is 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 is attached, 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 problem that the edge and size of the perovskite film pattern cannot be completely consistent with the pattern. 3. High technical requirements: There are certain requirements for the substrate material. In order to realize the photolithography process of the hydrophilic-hydrophobic layer, the substrate generally needs to be covered with special coating materials (ITO, FTO, ZnO, TiO2). 4. Complex process: The hydrophilic-hydrophobic template method process requires the coating of a hydrophilic film and photoresist, and the use of photolithography technology, which leads to a complex overall process and very high technical requirements, which is not conducive to the large-scale development and manufacturing of MEMS electronic devices. Summary of the invention

[0005] The present invention aims to provide a method for producing halide perovskite array patterns by using inductively coupled plasma etching technology.

[0006] Based on the above purpose, the present invention adopts the following technical solutions: A method for fabricating a halide perovskite array pattern using an inductively coupled plasma etching technique comprises the following steps: 1) Preparation of halide perovskite thin films; 2) Ion etching array pattern: A mask is covered on the halide perovskite film in step 1), and the pattern formed by the mask corresponds to the halide perovskite array pattern. After etching using inductively coupled plasma etching technology, the mask is removed to form a halide perovskite film array pattern.

[0007] In step 2), the mask plate includes a first mask plate and a second mask plate, and a pattern formed by the combination of the first mask plate and the second mask plate corresponds to the halide perovskite array pattern.

[0008] In step 2), the first mask plate and the second mask plate are both made of stainless steel thin plates.

[0009] In step 2), the first mask plate is made into a hollow grid-shaped horizontal stripe mask plate, and the second mask plate is made into a hollow grid-shaped vertical stripe mask plate. The pattern of the overlapping area formed by the combination of the first mask plate and the second mask plate corresponds to the halide perovskite array pattern.

[0010] In step 2), the ion etching adopts an inductively coupled plasma etching system, and the etching method includes the following steps: a. First, cover the halide perovskite film with the first mask plate, fix it in place, and place it in the fast sampling chamber of the inductively coupled plasma etching system. -2 Pa), after the halide perovskite film and the first mask are transferred to the etching chamber, the vacuum degree is adjusted to 1.0e -7 -1.0 e -9 Pa; b. Etching the perovskite film: introducing gas, with the upper electrode power at 300-800 W, the lower electrode power at 20-100 W, the process pressure at 1-10 mTorr, etching for 1-20 min, taking out the halide perovskite film and the first mask, and removing the first mask; c. Cover the halide perovskite film with a second mask plate, fix it in place, and place it in the fast sampling chamber of the inductively coupled plasma etching system. Referring to steps a and b, etch the perovskite film, take out the halide perovskite film and the second mask plate, and then remove the second mask plate.

[0011] In steps b and c, when etching the perovskite film, the gas at least includes a chlorine-based atmosphere.

[0012] In steps b and c, the chlorine-based atmosphere is one or a combination of Cl2 and BCl3.

[0013] In steps b and c, the gas further comprises an atmosphere of one or a combination of CHF3 and Ar.

[0014] In steps b and c, the chlorine-based atmosphere gas flow rate is 10-40 sccm, the CHF3 gas flow rate is 1-5 sccm, the Ar gas flow rate is 1-20 sccm, and other process parameter values ​​of the system are: sample stage temperature is 20-30°C, and back helium pressure is 5-15 Torr.

[0015] In step 1), the halide perovskite film is prepared by a one-step spin coating method or a two-step spin coating method.

[0016] The perovskite array pattern takes an n (column) × m (row) array as an example, the length and width of the dot matrix are a and b respectively, and the row and column resolutions are c and d, where the size range of a, b, c, d is >100 μm. The thickness of the first mask and the second mask is 5 μm-100 μm.

[0017] How to make the mask: 1. The first mask plate is made into a hollow grid-shaped horizontal stripe mask plate, such as Figure 1 As shown, the length and width of the transverse stripes are n*d and b respectively, the longitudinal spacing between the transverse stripes and the adjacent stripes (the spacing between the center lines of two adjacent transverse stripes) is c, there are m stripes in total, and the stainless steel sheet is completed by laser cutting and engraving technology, which can ensure that the size accuracy of the grating stripes is >50μm.

[0018] 2. The second mask plate is made into a hollow grid-shaped vertical stripe mask plate, such as Figure 2 As shown, the length and width of the vertical stripes are m*c and a respectively, the lateral spacing between the vertical stripes and the adjacent stripes (the spacing between the center lines of two adjacent longitudinal stripes) is d, and there are n stripes in total. The hollow plate is made using laser cutting and engraving technology to ensure that the stripe size accuracy is >50 μm.

[0019] In addition, if n = m, a = b, c = d, the first mask can be rotated 90° along the XY plane to become the second mask. Therefore, the second mask can be replaced by the first mask without repeated production. When etching the perovskite film, the first mask is rotated 90° along the XY plane and used as the second mask.

[0020] There are many types of perovskite film materials, each with different photoelectric properties. In the dry etching method of the present invention, there is no restriction on the type, element, morphology and structure of the perovskite film. It is applicable to traditional perovskite films and also to perovskite films with modified element positions (A / B / X). The morphology of the perovskite film can be a crystal particle covering layer, a line or a mesh.

[0021] Perovskite thin film materials can be made of ABX3 type materials, 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; B is Pb 2+ Sn 2+ One or more heavy metal ions such as chlorine; X is a halide ion, Cl - Br - ,I - One or more of .

[0022] The method for preparing a perovskite film comprises the following steps: 1. Substrate / base cleaning; 2. Perovskite film deposition: one-step spin coating or two-step spin coating.

[0023] In step 1, the cleaning method is: first use a detergent prepared with deionized water (deionized water and detergent powder are conventionally prepared, and there is no special requirement for the ratio) to clean (ultrasonic cleaning method can be used) one or two times, rinse with deionized water and blow dry; then clean with acetone (ultrasonic cleaning method can be used), blow dry; then clean with alcohol (ultrasonic cleaning method can be used), blow dry; O2 or Ar plasma can be used to remove organic impurities on the surface of the substrate / base; the material of the substrate can be Si-based wafer, sapphire (Al2O3), ITO, glass, polyethylene, polyethylene terephthalate (PET) or polyimide (PI) and other materials.

[0024] The one-step spin coating method is to nucleate and grow the perovskite film in the precursor solution containing all the compounds of the perovskite. The specific method is as follows: 1) Prepare the perovskite precursor solution: mix the ABX3 compound with the solvent to prepare the precursor solution; 2) Spin coating: adsorb the cleaned substrate or substrate on a spin coater or a spin coater, cover the surface of the substrate or substrate with the perovskite precursor solution, pre-run at a speed of 300-500 rpm for 3-10 s, and then run at a speed of 2000-3000 rpm for 30-60 s; 3) Place the substrate or substrate with the spin-coated perovskite precursor solution on a hot plate at 100-180° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0025] Preparation of CH3NH3PbI3 thin film: 1) preparing perovskite precursor solution: mixing a certain amount of CH3NH3I and PbI2 in a molar ratio of 1:1 in an organic solvent, wherein the total molar concentration of CH3NH3I and PbI2 is 1-100 mol / L; 2) Spin coating process can be used: adsorb the substrate or substrate on the spin coater or coater, cover the surface of the substrate or substrate with the perovskite precursor solution, pre-run at a speed of 300-500 rpm for 3-10 s, and then run at a speed of 2000-3000 rpm for 30-60 s; 3) Place the substrate or substrate on which the perovskite precursor solution is spin-coated on a heating plate at 100-180° for annealing to evaporate the solvent and crystallize to form a perovskite film. The organic solvent is one or a mixed solvent of two or more of N,N-dimethylformamide (DMF), gamma-butyrolactone (GBL), and dimethyl sulfoxide (DMSO).

[0026] The difference from the preparation of CH3NH3PbI3 film is that in the preparation of [(CH2)3NH2]PbI3 film, the perovskite precursor solution is prepared by preparing a mixed salt solution of [(CH2)3NH2]I and PbI2 of a certain concentration according to the proportion and molar mass, the molar ratio of [(CH2)3NH2]I and PbI2 is 1:1, and the total molar concentration of [(CH2)3NH2]I and PbI2 is 1-50 mol / L.

[0027] To prepare [CH3NH3]PbBr3 thin film, a mixed salt solution of [CH3NH3]Br and PbBr2 of a certain concentration is prepared according to the proportion and molar mass, the molar ratio of [CH3NH3]Br and PbBr2 is 1:1, and the total molar concentration is 1-100 mol / L.

[0028] To prepare [CH3NH3]SnI3 thin film, a mixed salt solution of [(CH2)3NH2]I and SnI2 of a certain concentration is prepared according to the proportion and molar mass, the molar ratio of [(CH2)3NH2]I and SnI2 is 1:1, and the total molar concentration is 1-50 mol / L.

[0029] Other 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 according to the above and so on, and the corresponding salt mixed solution can be prepared. The solvents used to prepare the precursor solution can be one or more mixed solvents of DMF, GBL and DMSO.

[0030] The two-step spin coating method is suitable for the case where the perovskite film material is two or more compounds. The specific method is to mix two or more compounds separately to form precursor solvents respectively, and then gradually deposit each precursor solution, and then perform heating annealing treatment to evaporate the solvent and crystallize to form a perovskite film.

[0031] The CH3NH3PbI3 film was prepared by a two-step method, and the specific method is as follows: 1) preparing the perovskite precursor solution separately, dissolving a certain amount of CH3NH3I salt in isopropyl alcohol (IPA) to prepare a solution with a concentration of 1-100 mol / L, and dissolving PbI2 in DMF solvent to prepare a solution with a concentration of 1-100 mol / L; 2) Step-by-step deposition, the PbI2 film layer can be deposited on the substrate or base by spin coating process, pre-running at a speed of 300-500 rpm for 3-10 s, then running at a speed of 2000-3000 rpm for 30-60 s, and then depositing CH3NH3I salt by immersion or spin coating, wherein the immersion method is to place the substrate or base in the salt solution for a few seconds, and the spin coating method is the same as the above method; 3) Place the substrate or substrate on a hot plate at 100-180° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0032] To prepare [(CH2)3NH2]PbI3 thin film, the perovskite precursor solution is prepared with [(CH2)3NH2]I and PbI2 salt solutions according to certain dosage and concentration. To prepare [CH3NH3]PbBr3 thin film, the perovskite precursor solution is prepared with [CH3NH3]Br and PbBr2 salt solutions according to certain dosage and concentration. To prepare [CH3NH3]SnI3 thin film, the precursor solution is prepared with [(CH2)3NH2]I and SnI2 salt solutions 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 more mixed solvents of IPA, DMF, GBL and DMSO. Steps 2) and 3) refer to the above two-step method for preparing CH3NH3PbI3 thin film.

[0033] Compared with the prior art, the present invention has the following beneficial effects: 1) The present invention uses a stainless steel mask plate as an etching mask tool for perovskite array patterning (hundred micrometers and above), and uses free electrons excited by inductively coupled plasma technology, fluorine-based and chlorine-based ions to etch the halide perovskite thin film material outside the mask plate twice. According to the element composition and film thickness of the halide perovskite material, suitable inductively coupled plasma etching process parameters such as atmosphere combination, atmosphere flow, plasma source radio frequency excitation power, lower electrode power, etching time and other process technical parameters are designed to achieve perovskite film patterning without contacting any solvent, effectively preventing the perovskite film from being corroded by non-polar solvents, and is not restricted by the type of perovskite, and is applicable to all types of perovskite thin film materials; 2) Reactive ion beam etching is carried out in a high vacuum environment, which prevents the perovskite film from being in contact with water molecules in the air for a long time during the patterning process, which would cause the perovskite film to decay or fail. This provides a new process direction for the perovskite array patterning scheme; 3) Compared with the existing template method for making perovskite patterning process, the technical solution of the present invention is simpler, and the plasma etching equipment is simple in structure, compatible with all MEMS scale manufacturing plants, reducing the manufacturing cost; 4) The present invention is applicable to any substrate or substrate material, such as glass with ITO, FTO, ZnO, TiO2 substrate or plastic substrate such as PET, thus broadening the compatibility of manufacturing various functional materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] 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.

[0035] Figure 1 is a schematic structural diagram of a first mask plate; Figure 2 is a schematic structural diagram of a second mask plate; Figure 3 is the XRD diffraction curve diagram of the film of Example 1 of the present invention; Figure 4 This is a partial diagram of the halide perovskite array pattern of Example 1 of the present invention. DETAILED DESCRIPTION

[0036] 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.

[0037] Example 1 The following is to etch 230 nm thick (Cs x (CH3NH2) y (CH3NH3) 1-x-y )Pb(I 1-z Br z )3 film as an example: The perovskite array pattern takes an array of n=20 (columns) × m=20 (rows) as an example, the dot matrix is ​​a square with a side length of a = b = 500μm, and the row and column resolutions are c = d = 500μm. The thickness of the stainless steel plates used for the first mask plate and the second mask plate is 100μm.

[0038] A method for manufacturing a mask plate, wherein the first mask plate and the second mask plate are both made of stainless steel thin plates: 1. The first mask plate is made into a hollow grid-shaped horizontal stripe mask plate, such as Figure 1 As shown, the length and width of the transverse stripes are n*d and b respectively, the longitudinal spacing between the transverse stripes and the adjacent stripes is c, and there are m stripes in total. The stainless steel sheet is completed by laser cutting and engraving technology, which can ensure that the size accuracy of the grating stripes is >50 μm.

[0039] 2. The second mask plate is made into a hollow grid-shaped vertical stripe mask plate, such as Figure 2 As shown, the length and width of the vertical stripes are m*c and a respectively, the lateral spacing between the vertical stripes and the adjacent stripes is d, and there are n stripes in total. The hollow plate is made using laser cutting and engraving technology to ensure that the stripe size accuracy is >50 μm, and the pattern of the overlapping area formed by the combination of the first mask plate and the second mask plate corresponds to the halide perovskite array pattern.

[0040] In the first embodiment, n=m, a=b, c=d, and the first mask plate becomes the second mask plate after being rotated 90° along the XY plane. Therefore, the second mask plate can be replaced by the first mask plate.

[0041] A method for fabricating a halide perovskite array pattern using an inductively coupled plasma etching technique comprises the following steps: 1) One-step preparation of halide perovskite (Cs x (CH3NH2) y (CH3NH3) 1-x-y )Pb(I 1-z Br z )3 Film: a. Substrate cleaning: First, use a detergent prepared with deionized water (prepared with deionized water and detergent powder at a mass ratio of 20:1) to ultrasonically clean twice, rinse with deionized water and blow dry; then use acetone to ultrasonically clean once, blow dry; then use alcohol to ultrasonically clean once, blow dry; use O2 plasma to remove organic impurities on the surface of the ITO substrate; b. Perovskite film deposition: (1) Preparation of perovskite precursor solution: a certain amount of CH3NH2I, CH3NH3Br, PbI2 and PbBr2 were mixed in a mixture of DMF and DMSO (DMF and DMSO were in equal volumes), CsI was dissolved in the DMF solution, and the molar concentration of each substance was prepared to be 1 mol / L. Then the above five solvent substances were mixed in equal proportions; (2) Spin coating: The substrate is adsorbed on the spin coater, the perovskite precursor solution is covered on the substrate surface, and the spin coater is pre-run at a speed of 300 rpm for 5 s, and then run at a speed of 6000 rpm for 30 s; (3) Place the substrate with the spin-coated perovskite precursor solution on a hot plate at 100° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0042] 2) Ion etching array pattern: including the following steps: a. First, cover the halide perovskite film with the first mask plate and fix it in position (with the help of an optical microscope or a substrate transfer platform, calibrate the position of the mask plate on the perovskite film etching pattern to complete the alignment operation. After the mask plate is aligned, use resin glue or spring pressure plate to fix the mask plate and the perovskite film substrate. Among them, the sticky resin glue can buffer the micro-movement between the mask plate and the perovskite film substrate; the spring pressure plate can provide elastic buffering. Both can prevent the movement between the mask plate and the perovskite film substrate and improve the accuracy of the perovskite film etching pattern. With the help of thermal conductive silicone oil, the film to be etched is adhered to the equipment tray, and polyimide high-temperature tape is attached around the film to ensure the stability of the etching rate), and then placed in the fast sampling chamber of the inductively coupled plasma etching system (from Oxford Instruments, UK, ICP) in a vacuum environment (the vacuum degree is 1.0e during the transfer process -2 Pa), transfer the halide perovskite film and the first mask plate to the etching chamber, and adjust the vacuum degree to 1.0e -7 Pa; b. Etching perovskite film: the sample stage temperature is set to 30°C, the back helium pressure is 10 Torr, the upper electrode power is 800 W, the lower electrode power is 50 W, the Cl2 gas flow rate is 12 sccm, the CHF3 gas flow rate is 2 sccm, the Ar gas flow rate is 9 sccm, the process pressure is 4 mTorr, and the etching time is 8 min. The halide perovskite film and the first mask are taken out, and the first mask is removed. Under the action of the high-energy and high-frequency magnetic field of the electrode, the Ar in the combined atmosphere acts as a balance gas and is also excited to an excited state, which helps to stimulate the perovskite film to react with the corrosive ion gas. Cl2 and CHF3 can excite the production of free matrix Cl and F - and H + , the reaction formula is as follows: Ar→Ar + + e - Cl2+e - →Cl + Cl - Cl2+e - →Cl+Cl + e - Cl2+e - →Cl + +Cl - + e - CHF3 → CF x + H + + e - CHF3+ e - →CHF2+ F - Among them, free matrix electrons, H + , F - and Cl - The perovskite film without mask shielding contacts the free matrix to undergo chemical reaction, generating gas which is discharged from the reaction chamber. The reaction formula of CH3NH3PbI3 film is as follows: CH3NH3 + + e - → CH3NH3(gas) CH3NH2 + + H + +2e - → CH3NH3(gas) CH3NH3+H + → CH x (gas) + NH x (gas) Pb 2+ + F - → PbF2(gas) Pb 2+ + Cl - → PbCl2(gas) Cs + + F - → CsF (gas) Cs + + Cl - → CsCl (gas) I - + H + → HI (gas) c. Cover the halide perovskite film with a second mask, fix it in place (the same method as above), place it in the fast sample chamber of the inductively coupled plasma etching system, repeat the steps of transferring it to the etching chamber and etching the perovskite film (the process parameters are the same as above, etching for 6 min (2 min less than the first etching), take out the halide perovskite film and the second mask, remove the second mask, and the obtained 500 nm thick (Cs x (CH3NH2) y(CH3NH3) 1-x-y )Pb(I 1-z Br z )3 Thin film square perovskite array dot pattern with a side length of 500μm.

[0043] Figure 3 is the XRD diffraction curve of the film. Figure 3 It can be seen that the film only has diffraction peaks at 14.16°, 19.8°, 24.4°, 28.1°, 31.55°, 34.67°, 40.17° and 42.7°. The combination of these peaks is consistent with the crystal phase of the perovskite XRD rays, and there are no diffraction peaks of PbI2, PbBr2, FAI or MABr, which confirms that the thin film perovskite is a pure phase and high crystalline quality film.

[0044] Figure 4 To use the stainless steel as a mask, an array pattern with a side length of 500 μm was etched.

[0045] Example 2 The perovskite array pattern takes an n (column) × m (row) array as an example, the length and width of the dot matrix are a and b respectively, and the row and column resolutions are c and d, where the size range of a, b, c, d is >100 μm. The thickness of the first mask and the second mask is 50 μm.

[0046] The method for manufacturing the mask plate is similar to that of Example 1, wherein the first mask plate and the second mask plate are both made of stainless steel thin plates: A method for fabricating a halide perovskite array pattern using an inductively coupled plasma etching technique comprises the following steps: 1) Preparation of halide perovskite film (select [CH3NH3]PbBr3 film, one-step method): a. Substrate cleaning: first use a detergent prepared with deionized water (prepared with deionized water and detergent powder at a mass ratio of 20:1) to ultrasonically clean twice, rinse with deionized water and blow dry; then use acetone to ultrasonically clean once, blow dry; then use alcohol to ultrasonically clean once, blow dry; use O2 or Ar plasma to remove organic impurities on the surface of the ITO substrate; b. Perovskite film deposition: (1) Preparation of perovskite precursor solution: Mix a certain amount of [CH3NH3]Br and PbBr2 in DMF at a molar ratio of 1:1, with a total molar concentration of 1 mol / L; (2) Spin coating: The substrate is adsorbed on the spin coater, the perovskite precursor solution is covered on the substrate surface, and the spin coater is pre-run at 400 rpm for 3 s, and then run at 2500 rpm for 40 s; (3) Place the substrate or wafer with the spin-coated perovskite precursor solution on a hot plate at 150° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0047] 2) Ion etching array pattern: including the following steps: a. First, a first mask is covered on the halide perovskite film and fixed in position (refer to Example 1 for the method), and then placed in the fast sample injection chamber of an inductively coupled plasma etching system (from Oxford Instruments, UK, ICP) under a vacuum environment (the vacuum degree during the transfer process is 1.0e -2 Pa), after the halide perovskite film and the first mask are transferred to the etching chamber, the vacuum degree is adjusted to 1.0e -9 Pa; b. Etching perovskite film: The sample stage temperature was set to 30°C, the back helium pressure was 10 Torr, the upper electrode power was 800 W, the lower electrode power was 50 W, the Cl2 gas flow rate was 12 sccm, the CHF3 gas flow rate was 2 sccm, the Ar gas flow rate was 9 sccm, the process pressure was 4 mTorr, the etching time was 8 min, the halide perovskite film and the first mask were taken out, and the first mask was removed; under the action of the high-energy and high-frequency magnetic field of the electrode, the Ar in the combined atmosphere was used as a balance gas and was also excited to an excited state, which was helpful to stimulate the perovskite film to react with the corrosive ion gas. Cl2 and CHF3 can be excited to produce free matrix Cl and F - and H + , the reaction formula is as follows: Ar→Ar + + e - Cl2+e - →Cl + Cl - Cl2+e - →Cl+Cl + e - Cl2+e - →Cl + +Cl - + e - CHF3 → CF x + H + + e - CHF3+ e - →CHF2+ F - Among them, free matrix electrons, F - and Cl - The perovskite film without mask shielding contacts the free matrix to undergo chemical reaction, generating gas which is discharged from the reaction chamber. The reaction equation during etching is as follows: CH3NH3 + + e- → CH3NH3(gas) CH3NH3+H + → CH x (gas) + NH x (gas) Pb 2+ + F - → PbF2(gas) Pb 2+ + Cl - → PbCl2(gas) I - + H + → HI (gas) c. Cover the halide perovskite film with a second mask plate, fix it in place (same as above), place it in the fast injection chamber of the inductively coupled plasma etching system, repeat the steps of transferring it to the etching chamber and etching the perovskite film (same process parameters as above), take out the halide perovskite film and the second mask plate, and remove the second mask plate.

[0048] Example 3 The perovskite array pattern takes an n (column) × m (row) array as an example, the length and width of the dot matrix are a and b respectively, and the row and column resolutions are c and d, where the size range of a, b, c, d is >100 μm. The thickness of the first mask and the second mask is 100 μm.

[0049] The method for manufacturing the mask plate is as described in Example 1.

[0050] A method for fabricating a halide perovskite array pattern using an inductively coupled plasma etching technique comprises the following steps: 1) Preparation of halide perovskite film (select CsPbI3 film, one-step method): a. Substrate cleaning: first use a detergent prepared with deionized water (prepared with deionized water and detergent powder at a mass ratio of 20:1) to ultrasonically clean twice, rinse with deionized water and blow dry; then use acetone to ultrasonically clean once, blow dry; then use alcohol to ultrasonically clean once, blow dry; use O2 or Ar plasma to remove organic impurities on the surface of the ITO substrate; b. Perovskite film deposition: (1) Preparation of perovskite precursor solution: Mix a certain amount of CsI and PbI2 in DMF at a molar ratio of 1:1, with a total molar concentration of 10 mol / L; (2) Spin coating: The substrate is adsorbed on the spin coater, the perovskite precursor solution is covered on the substrate surface, and the spin coater is pre-run at a speed of 500 rpm for 10 s, and then run at a speed of 3000 rpm for 60 s; (3) The substrate or wafer with the spin-coated perovskite precursor solution is placed on a hot plate at 180° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0051] 2) Ion etching array pattern: including the following steps: a. First, a first mask is covered on the halide perovskite film and fixed in position (refer to Example 1 for the method), and then placed in the fast sample injection chamber of an inductively coupled plasma etching system (from Oxford Instruments, UK, ICP) under a vacuum environment (the vacuum degree during the transfer process is 1.0e -2 Pa), after the halide perovskite film and the first mask are transferred to the etching chamber, the vacuum degree is adjusted to 1.0e -7 Pa; b. Etching perovskite film: The sample stage temperature was set to 30 °C, the back helium pressure was 10 Torr, the upper electrode power was 300 W, the lower electrode power was 20 W, the BCl3 gas flow rate was 15 sccm, the CHF3 gas flow rate was 5 sccm, the Ar gas flow rate was 1 sccm, the process pressure was 3 mTorr, and the etching was performed for 8 min. The halide perovskite film and the first mask were taken out, and the first mask was removed. Under the action of the high-energy and high-frequency magnetic field of the electrode, the Ar in the combined atmosphere was used as a balance gas and was also excited to an excited state, which was helpful to stimulate the perovskite film to react with the corrosive ion gas. Cl2 and CHF3 can be excited to produce free matrix Cl and F - and H + , the reaction formula is as follows: Ar→Ar + + e - Cl2+e - →Cl + Cl - Cl2+e - →Cl+Cl + e - Cl2+e - →Cl + +Cl - + e - BCl3+e - →BCl2+ Cl - BCl2+e - →BCl+Cl + e - CHF3 → CF x + H + + e - CHF3+ e -→CHF2+ F - Among them, free matrix electrons, F - and Cl - The perovskite film without mask shielding contacts the free matrix to undergo chemical reaction, generating gas which is discharged from the reaction chamber. The reaction equation during etching is as follows: Cs + + F - → CsF (g) Cs + + Cl - → CsCl (gas) Pb 2+ + F - → PbF2(gas) Pb 2+ + Cl - → PbCl2(gas) I - + H + → HI (gas) c. Cover the halide perovskite film with a second mask plate, fix it in place (same as above), place it in the fast injection chamber of the inductively coupled plasma etching system, repeat the steps of transferring it to the etching chamber and etching the perovskite film (same process parameters as above), take out the halide perovskite film and the second mask plate, and remove the second mask plate.

[0052] Example 4 The perovskite array pattern takes an n (column) × m (row) array as an example, the length and width of the dot matrix are a and b respectively, and the row and column resolutions are c and d, where the size range of a, b, c, d is >100 μm. The thickness of the first mask and the second mask is 80 μm.

[0053] The method for manufacturing the mask plate is as described in Example 1.

[0054] A method for fabricating a halide perovskite array pattern using an inductively coupled plasma etching technique comprises the following steps: 1) Preparation of halide perovskite film (select [CH3NH3]SnI3 film): a. Substrate cleaning: first use a detergent prepared with deionized water (prepared with deionized water and detergent powder at a mass ratio of 20:1) to ultrasonically clean twice, rinse with deionized water and blow dry; then use acetone to ultrasonically clean once, blow dry; then use alcohol to ultrasonically clean once, blow dry; use O2 or Ar plasma to remove organic impurities on the surface of the ITO substrate; b. Perovskite film deposition: (1) Preparation of perovskite precursor solution: a certain amount of [(CH2)3NH2]I and SnI2 were mixed in GBL at a molar ratio of 1:1, with a total molar concentration of 1 mol / L; (2) Spin coating: The substrate is adsorbed on the spin coater, the perovskite precursor solution is covered on the substrate surface, and the spin coater is pre-run at a speed of 500 rpm for 10 s, and then run at a speed of 3000 rpm for 60 s; (3) The substrate or wafer with the spin-coated perovskite precursor solution is placed on a hot plate at 180° for annealing to evaporate the solvent and crystallize to form a perovskite film.

[0055] 2) Ion etching array pattern: including the following steps: a. First, a first mask is covered on the halide perovskite film and fixed in position (refer to Example 1 for the method), and then placed in the fast sample injection chamber of an inductively coupled plasma etching system (from Oxford Instruments, UK, ICP) under a vacuum environment (the vacuum degree during the transfer process is 1.0e -2 Pa), after the halide perovskite film and the first mask are transferred to the etching chamber, the vacuum degree is adjusted to 1.0e -7 Pa; b. Etching perovskite film: The sample stage temperature was set to 30 °C, the back helium pressure was 10 Torr, the upper electrode power was 800 W, the lower electrode power was 50 W, the Cl2 gas flow rate was 85 sccm, the CHF3 gas flow rate was 5 sccm, the Ar gas flow rate was 2 sccm, the process pressure was 4 mTorr, and the etching was performed for 10 minutes. The halide perovskite film and the first mask were taken out, and the first mask was removed. Under the action of the high-energy and high-frequency magnetic field of the electrode, the Ar in the combined atmosphere was used as a balance gas and was also excited to an excited state, which was helpful to stimulate the perovskite film to react with the corrosive ion gas. Cl2 and CHF3 can be excited to produce free matrix Cl and F - and H + , the reaction formula is as follows: Ar→Ar + + e - Cl2+e - →Cl + Cl - Cl2+e - →Cl+Cl + e - Cl2+e - →Cl + +Cl - + e - CHF3 → CF x + H+ + e - CHF3+ e - →CHF2+ F - Among them, free matrix electrons, F - and Cl - The perovskite film without mask shielding contacts the free matrix to undergo chemical reaction, generating gas which is discharged from the reaction chamber. The reaction equation during etching of [CH3NH3]SnI3 film is as follows: CH3NH3 + + e - → CH3NH3(gas) CH3NH3+H + → CH x (gas) + NH x (gas) Sn 2+ + F - → SnF2(gas) Sn 2+ + Cl - → SnCl2(gas) I - + H + → HI (gas) c. Cover the halide perovskite film with a second mask plate, fix it in place (same as above), place it in the fast injection chamber of the inductively coupled plasma etching system, repeat the steps of transferring it to the etching chamber and etching the perovskite film (same process parameters as above), take out the halide perovskite film and the second mask plate, and remove the second mask plate.

Claims

1. A method for fabricating halide perovskite array patterns using inductively coupled plasma etching technology, characterized in that: The following steps are involved: 1) Preparation of halide perovskite thin films; 2) Ion etching array pattern: A mask is covered on the halide perovskite film in step 1), and the pattern formed by the mask corresponds to the halide perovskite array pattern. After etching using inductively coupled plasma etching technology, the mask is removed to form a halide perovskite film array pattern.

2. The method for fabricating halide perovskite array patterns using inductively coupled plasma etching technology as claimed in claim 1, characterized in that: In step 2), the mask plate includes a first mask plate and a second mask plate, and a pattern formed by the combination of the first mask plate and the second mask plate corresponds to the halide perovskite array pattern.

3. The method for producing halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 2, characterized in that: In step 2), the first mask plate and the second mask plate are both made of stainless steel thin plates.

4. The method for producing halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 3, characterized in that: In step 2), the first mask plate is made into a hollow grid-shaped horizontal stripe mask plate, and the second mask plate is made into a hollow grid-shaped vertical stripe mask plate. The pattern of the overlapping area formed by the combination of the first mask plate and the second mask plate corresponds to the halide perovskite array pattern.

5. The method for producing halide perovskite array patterns by inductively coupled plasma etching technology according to claim 4, wherein in step 2), the ion etching adopts an inductively coupled plasma etching system, and the etching method comprises the following steps: a. First, a first mask plate is covered on the halide perovskite film, and after being fixed in position, it is placed in the fast sample injection chamber of the inductively coupled plasma etching system, and the halide perovskite film and the first mask plate are transferred to the etching chamber under a vacuum environment; b. Etching the perovskite film: introducing gas, etching for 1-20 min at an upper electrode power of 300-800 W, a lower electrode power of 20-100 W, and a process pressure of 1-10 mTorr, taking out the halide perovskite film and the first mask, and removing the first mask; c. Cover the halide perovskite film with a second mask plate, fix it in place, and place it in the fast sampling chamber of the inductively coupled plasma etching system. Referring to steps a and b, etch the perovskite film, take out the halide perovskite film and the second mask plate, and then remove the second mask plate.

6. The method for fabricating halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 5, characterized in that: In steps b and c, when etching the perovskite film, the gas at least includes a chlorine-based atmosphere.

7. The method for fabricating halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 6, characterized in that: In steps b and c, the chlorine-based atmosphere is one or a combination of Cl2 and BCl3.

8. The method for fabricating halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 7, characterized in that: In steps b and c, the gas further comprises an atmosphere of one or a combination of CHF3 and Ar.

9. The method for fabricating halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 8, characterized in that: In steps b and c, the chlorine-based atmosphere gas flow rate is 10-40 sccm, the CHF3 gas flow rate is 1-5 sccm, the Ar gas flow rate is 1-20 sccm, and other process parameter values ​​of the system are: sample stage temperature is 20-30 ° C, and the back helium pressure is 5-15 Torr.

10. The method for fabricating halide perovskite array patterns by inductively coupled plasma etching technology as claimed in claim 9, characterized in that: In step 1), the halide perovskite film is prepared by a one-step spin coating method or a two-step spin coating method.

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