Material for effectively inhibiting non-laser-induced crystallization of perovskite in laser direct writing and preparation method and application thereof

Abstract

The invention provides a material for effectively inhibiting non-laser-induced crystallization of perovskite in laser direct writing as well as a preparation method and application of the material. The material comprises ion-substituted perovskite and a polymer containing an ester group, the chemical composition of the ion-substituted perovskite is Cs (PbzW1-z) (ClxBryI1-x-y) 3, W is a transition metal ion and comprises at least one of Mn < 2 + >, Ni < 2 + >, Cu < 2 + >, Zn < 2 + >, Co < 2 + >, Cr < 3 + > and Fe < 3 + >, 0.8 < = z < = 1, 0 < = x < = 1, 0 < = y < = 1, and x + y < = 1. The material provided by the invention can effectively inhibit perovskite non-laser induced crystallization in laser direct writing, and improves the performance and stability of a laser direct writing perovskite device. The invention also provides a preparation method and application of the material.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing luminescent composite materials, and in particular relates to a material that effectively inhibits non-laser-induced crystallization of perovskite during laser direct writing, and a preparation method and application thereof. Background Art

[0002] With the advancement of science and technology, laser direct writing technology has been widely used in the field of micro-nano manufacturing. Perovskite materials have great application potential in the fields of solar cells, light-emitting diodes, photodetectors and lasers due to their excellent optoelectronic properties. Laser direct writing perovskite patterning is a method of directional crystallization by directly irradiating a laser beam into a transparent medium material such as glass or film containing perovskite. Since perovskite easily forms the γ phase at room temperature, non-laser induced crystallization (spontaneous crystallization) is prone to occur in the non-laser irradiated area of the perovskite film, which seriously limits its further development. Therefore, the development of a material and preparation method that effectively inhibits the non-laser induced crystallization of perovskite is of great significance for improving the performance of perovskite laser direct writing devices.

[0003] In related technologies, methods for inhibiting non-laser-induced crystallization of perovskites mainly include adding inhibitors, optimizing laser parameters, and improving substrate materials. However, these methods have certain limitations in practical applications. For example, specific inhibitors are used to stabilize the phase of perovskites, but adding inhibitors may introduce impurities, affecting the purity and performance of the perovskite material; optimizing laser parameters (such as laser power, scanning speed, and beam size) requires precise control and high technical requirements for operators; and improving substrate materials may increase costs and reduce the cost-effectiveness of devices.

[0004] Therefore, it is necessary to develop a new material that can effectively inhibit the non-laser induced crystallization of perovskite during laser direct writing, so as to improve the performance and stability of laser direct writing perovskite devices. Summary of the Invention

[0005] The present invention aims to address at least one of the aforementioned technical problems in the prior art. To this end, the present invention provides a material that effectively inhibits non-laser-induced crystallization of perovskites during laser direct writing. This material can effectively inhibit non-laser-induced crystallization of perovskites during laser direct writing, thereby improving the performance and stability of laser direct writing perovskite devices.

[0006] The invention also provides a preparation method of the material.

[0007] The present invention also provides a patterned film containing the material.

[0008] The present invention also provides applications of the patterned film in Micro-LED display, information encryption, anti-counterfeiting and optical data storage.

[0009] The first aspect of the present invention provides a material for effectively inhibiting non-laser-induced crystallization of perovskite in laser direct writing, wherein the material comprises an ion-substituted perovskite and a polymer containing an ester group, wherein the chemical composition of the ion-substituted perovskite is: Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3, wherein W is a transition metal ion, including Mn 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Co 2+ Cr 3 + and Fe 3+ At least one of the following, 0.8≤z≤1, 0≤x≤1, 0≤y≤1, x+y≤1.

[0010] The material of the present invention that effectively inhibits non-laser-induced crystallization of perovskite during laser direct writing has at least the following beneficial effects:

[0011] The present invention effectively inhibits the non-laser induced crystallization of perovskite in laser direct writing. By introducing transition metal ions to increase the formation energy of perovskite, the coordination between perovskite ions is slowed down, thereby inhibiting the non-laser induced crystallization. 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Co 2+ Cr 3+ 、Fe 3+ etc., the ionic radius of these ions is smaller than that of Pb 2+ ionic radius) is doped, and transition metal ions with smaller ionic radius are used to replace CsPb (Cl x Br y I 1-x-y )3, (0≤x≤1, 0≤y≤1, x+y≤1) in Pb 2+ , can not only effectively regulate [PbX6] 4- The tolerance factor of the octahedron can also increase the crystal formation energy, preventing the perovskite from rapidly nucleating and growing at room temperature, thereby initially inhibiting its non-laser induced crystallization.

[0012] Using polymers containing ester groups, the -COO- (ester group) functional group blocks the coordination of perovskite cations and hinders the normal nucleation and growth process of perovskite, thereby inhibiting the occurrence of non-laser induced crystallization.+ and Pb 2+ The cations are coordinated by van der Waals force and have strong coordination ability, forming a stable precursor-polymer structure at room temperature, thereby enhancing the ion migration barrier and making the Cs in the perovskite precursor solution + and Pb 2+ The cations will not coordinate and crystallize quickly, hindering the normal nucleation and growth process of perovskite and inhibiting its non-laser induced crystallization.

[0013] The material of the present invention is a film made by fully mixing the perovskite precursor and the polymer material. By regulating the power and irradiation time of the continuous wave laser, a strong electric field gradient is formed in the irradiation area. Under the action of the strong electric field gradient, the special functional group and the Cs + (or Pb 2+ ) and destroy the van der Waals forces between the precursor and the polymer chain, destroying the interaction between the precursor and the polymer chain. In addition, the laser can cause the irradiated area of the film to collapse, thereby promoting ion migration and reducing the crystallization and growth temperature of the perovskite. At the same time, laser direct writing will promote the optical trapping effect, enhance the capture force of the precursor ions, increase the concentration of the precursor solution in the laser irradiated area, and cause the precursor ions to rearrange and realize the nucleation of the perovskite. Then, the accumulation of laser energy causes the temperature to rise and desolvation to achieve the growth of the perovskite, and finally achieve patterning.

[0014] The material of the present invention can be patterned by direct laser writing using a continuous wave laser, which allows the material to precipitate perovskite crystals in situ.

[0015] According to some embodiments of the present invention, the material is a luminescent material, and its colors include red, green, blue and orange-red.

[0016] The second aspect of the present invention provides a method for preparing the material of the first aspect of the present invention, comprising the steps of introducing transition metal ions and ester groups into a perovskite raw material.

[0017] A technical solution in the material preparation method of the present invention has at least the following beneficial effects:

[0018] The preparation method of the present invention does not require expensive equipment and complicated process control, has undemanding reaction conditions, has readily available raw materials, has low production costs, and is easy to industrialize.

[0019] According to some embodiments of the present invention, a method for preparing a material that effectively inhibits non-laser induced crystallization of perovskite during laser direct writing comprises the following steps:

[0020] S1: dissolving the perovskite raw material and the halide containing transition metal ions in solvent A to obtain solution B;

[0021] S2: adding the polymer material containing an ester group into solvent C and dissolving it to obtain solution D;

[0022] S3: adding the solution B to the solution D to obtain solution E;

[0023] S4: Spin-coating the solution E on a substrate, and drying to obtain the material that effectively inhibits non-laser induced crystallization of perovskite during laser direct writing.

[0024] According to some embodiments of the present invention, the perovskite raw material includes at least one of CsCl, CsBr, CsI, PbCl2, PbBr2 and PbI2.

[0025] According to some embodiments of the present invention, the halide containing transition metal ions includes at least one of MnCl2, MnBr2, MnI2, ZnCl2, ZnBr2 and ZnI2.

[0026] According to some embodiments of the present invention, in step S1, the mass proportion of the halide containing transition metal ions in solution B is ≤20%.

[0027] According to some embodiments of the present invention, the polymer material containing an ester group includes polyvinyl acetate (PVAC) and polymethyl methacrylate (PMMA).

[0028] According to some embodiments of the present invention, the solvent A comprises N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).

[0029] According to some embodiments of the present invention, the solvent C comprises N,N-dimethylformamide or dimethyl sulfoxide.

[0030] According to some embodiments of the present invention, in step S2, the polymer material containing an ester group is added to solvent C for dissolution, and the mass volume ratio of the polymer material containing an ester group to solvent C is 1:5 to 15 mL.

[0031] According to some embodiments of the present invention, the method further comprises filtering the solution B before adding the solution B to the solution D.

[0032] According to some embodiments of the present invention, the solution B is filtered, and the filter material is a tetrafluoroethylene (PTFE) filter head.

[0033] In step S4, for the material emitting red light, the drying temperature is 50°C.

[0034] In step S4, for the green light emitting material, the drying temperature is 200°C.

[0035] When the material's anions are primarily composed of I ions, the material emits red light. Since this red-light material is relatively less susceptible to non-laser-induced crystallization, the drying temperature can be relatively low, 50°C.

[0036] When the material's anions are primarily Br ions, the material emits green light. Since this green light material is relatively prone to non-laser-induced crystallization, the drying temperature is higher, requiring 200°C.

[0037] The third aspect of the present invention provides a patterned film, which is prepared by laser direct writing from the material of the first aspect of the present invention.

[0038] One of the technical solutions of the present invention regarding the patterned thin film has at least the following beneficial effects:

[0039] The patterned film of the present invention is a film with high luminous efficiency. High luminous efficiency specifically refers to a luminous efficiency greater than 50%.

[0040] The present invention significantly suppresses non-laser-induced crystallization by doping transition metal ions into CsPb(Cl / Br / I)3 perovskite and combining it with ester-containing polymers (such as PVAC and PMMA), making the perovskite precursor stable at room temperature. Through laser direct writing technology, the thermal effect and electric field gradient of the laser are used only in the irradiated area to destroy the polymer-ion coordination, inducing selective crystallization of the perovskite, thereby achieving patterned films with high resolution and high luminous efficiency. This method is simple and low-cost, and can be used to prepare red / green light-emitting films on flexible substrates at low temperatures (50–200°C). It has broad application prospects in fields such as micro-displays, optical storage, and flexible electronics.

[0041] Laser direct writing can be accomplished using a laser direct writing platform. The laser can be a 405nm single-mode continuous wave laser with a power range of 0-30mW. The laser direct writing platform has a 50x objective lens and a high-precision motorized translation stage.

[0042] A fourth aspect of the present invention provides applications of patterned films in Micro-LED display, information encryption, anti-counterfeiting, and optical data storage.

[0043] In Micro-LED displays, laser direct writing enables ultra-high-resolution (micrometer-level) pixel arrays, meeting the demands of next-generation display technology. Transition metal doping optimizes luminous efficiency, achieves high color purity, and enables precise control of red and green light emission. Low-temperature processing is compatible with flexible substrates, making it suitable for foldable and wearable display devices.

[0044] In information encryption and anti-counterfeiting, laser direct writing can generate hidden micropatterns that only appear under specific excitation light, enhancing anti-counterfeiting security. Perovskite luminescence properties (such as wavelength and lifetime) can be engineered to provide multiple encryption dimensions, increasing the difficulty of cracking. The polymer matrix protects the pattern's stability, resists environmental aging, and extends the life of the security label.

[0045] In optical data storage, laser-induced perovskite phase changes enable high-density optical storage (e.g., binary or multi-state information encoding). Fluorescent / phosphorescent signals can be optically read, resulting in fast read / write speeds and suitable for high-capacity storage media. The material's stability supports long-term data preservation, surpassing traditional organic fluorescent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the pattern of the material in Example 1 after laser direct writing.

[0047] Figure 2 This is the pattern of the material of Example 2 after laser direct writing.

[0048] Figure 3 This is the X-ray diffractometer test result of the material in Example 1.

[0049] Figure 4 This is the X-ray diffractometer test result of the material in Example 2.

[0050] Figure 5 These are the emission spectra of the materials of Examples 1 and 2 obtained at an excitation wavelength of 405 nm.

[0051] Figure 6 This is the line width of the material in Example 2 at different powers.

[0052] Figure 7 This is the line width of the material of Example 2 at different speeds. DETAILED DESCRIPTION

[0053] The following will clearly and completely describe the concept and technical effects of the present invention in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0054] In the description of the present invention, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that the specific features, structures, materials, or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the exemplary expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0055] Unless otherwise specified, "room temperature" in the present invention means 25°C±5°C.

[0056] Unless otherwise specified, “about” in the present invention means that the allowable error is within ±2%.

[0057] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0058] Example 1

[0059] A material that effectively inhibits the non-laser-induced crystallization of perovskite in laser direct writing is prepared. The material includes ion-substituted perovskite Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3 and polymers containing ester groups, ion-substituted perovskite to CsPb 0.95 Mn 0.05 Br3, at this time z is 0.95, x is 0, y is 1, and the polymer containing ester group is PVAC.

[0060] The chemical composition of the material can be written as CsPb 0.95 Mn 0.05 Br3-PVAC, the material does not emit light at this time. After being written with a laser direct writing platform, when the luminescent material is excited with 405nm light, the luminescent material emits green light, such as Figure 1 As shown in the figure, it can be observed that no non-laser induced crystallization occurs in the area outside the laser direct writing. The specific preparation steps are:

[0061] (1) The perovskite raw materials CsBr, PbBr2 and the halide material containing transition metal ions MnBr2 were added into 5 mL of DMF in a ratio of 5% of the halide material containing transition metal ions and fully dissolved and mixed to obtain the precursor solution CsPb 0.95 Mn 0.05 Br3-DMF;

[0062] (2) 1 g of PVAC was added to 10 mL of DMF and thoroughly dissolved and mixed to obtain a colloidal solution of PVAC-DMF;

[0063] (3) The above precursor solution CsPb 0.95 Mn 0.05 Br3-DMF was filtered through a PTFE filter and added to the colloidal solution PVAC-DMF and mixed evenly to obtain a colloidal solution of CsPb 0.95 Mn 0.05 Br3-PVAC;

[0064] (4) The colloidal solution CsPb 0.95 Mn 0.05 Br3-PVAC was spin-coated on a glass substrate and then dried at 200°C to obtain CsPb 0.95 Mn 0.05 Br3-PVAC film, and finally irradiated with 405nm single-mode continuous wave laser with power of 10.45mW on a laser direct writing platform with a 50x objective lens, so that CsPb 0.95 Mn 0.05 Perovskite crystals CsPbBr3 are in situ precipitated in the Br3-PVAC film, thereby preparing a patterned film with high luminescence efficiency.

[0065] Example 2

[0066] A material that effectively inhibits the non-laser-induced crystallization of perovskite in laser direct writing is prepared. The material includes ion-substituted perovskite Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3 and polymers containing ester groups, ion-substituted perovskite to CsPb 0.95 Mn 0.05 I3, at this time z is 0.95, x is 0, y is 0, and the polymer containing ester groups is PVAC.

[0067] The chemical composition of the material can be written as CsPb 0.95 Mn 0.05 I3-PVAC, the material does not emit light at this time. After being written with a laser direct writing platform, when the luminescent material is excited with 405nm light, the luminescent material emits red light, such as Figure 2 As shown in the figure, it can be observed that no non-laser induced crystallization occurs in the area outside the laser direct writing. The specific preparation steps are:

[0068] (1) The perovskite raw materials CsI, PbI2 and the halide material containing transition metal ions MnI2 were added into 5 mL of DMF in a ratio of 5% of the halide material containing transition metal ions and fully dissolved and mixed to obtain the precursor solution CsPb 0.95 Mn 0.05 I3-DMF;

[0069] (2) 1 g of PVAC was added to 10 mL of DMF and thoroughly dissolved and mixed to obtain a colloidal solution of PVAC-DMF;

[0070] (3) The above precursor solution CsPb 0.95 Mn 0.05 I3-DMF was filtered through a PTFE filter and added to the colloidal solution PVAC-DMF and mixed evenly to obtain a colloidal solution of CsPb 0.95 Mn 0.05 I3-PVAC;

[0071] (4) The colloidal solution CsPb 0.95 Mn 0.05 I3-PVAC was spin-coated on a glass substrate and then dried at 50°C to obtain CsPb 0.95 Mn 0.05 I3-PVAC film, and finally irradiated with 405nm single-mode continuous wave laser with power of 10.45mW on a laser direct writing platform with objective lens of 50 times, so that CsPb 0.95 Mn 0.05 Perovskite crystals CsPbI3 were in situ precipitated in the I3-PVAC film, and then a high-luminescence-efficiency patterned film with a minimum line width of 1.47 μm was prepared, such as Figure 6 and Figure 7 shown.

[0072] Example 3

[0073] A material that effectively inhibits the non-laser-induced crystallization of perovskite in laser direct writing is prepared. The material includes ion-substituted perovskite Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3 and polymers containing ester groups, ion-substituted perovskite to CsPb 0.95 Mn 0.05 Cl3, at this time z is 0.95, x is 1, y is 0, and the polymer containing ester groups is PVAC.

[0074] The chemical composition of the material can be written as CsPb 0.95 Mn 0.05Cl3-PVAC, the material does not emit light at this time. After being written with a laser direct writing platform, the luminescent material emits blue light when excited by 405nm light. The specific preparation steps are:

[0075] (1) The perovskite raw materials CsCl, PbCl2 and the halide material containing transition metal ions MnCl2 were added into 5 mL of DMF in a ratio of 5% of the halide material containing transition metal ions and fully dissolved and mixed to obtain the precursor solution CsPb 0.95 Mn 0.05 Cl3-DMF;

[0076] (2) 1 g of PVAC was added to 10 mL of DMF and thoroughly dissolved and mixed to obtain a colloidal solution of PVAC-DMF;

[0077] (3) The above precursor solution CsPb 0.95 Mn 0.05 Cl3-DMF was filtered through a PTFE filter and added to the colloidal solution PVAC-DMF and mixed evenly to obtain a colloidal solution of CsPb 0.95 Mn 0.05 Cl3-PVAC;

[0078] (4) The colloidal solution CsPb 0.95 Mn 0.05 Cl3-PVAC was spin-coated on a glass substrate and then dried at 100°C to obtain CsPb 0.95 Mn 0.05 Cl3-PVAC film, and finally irradiated with 405nm single-mode continuous wave laser with power of 10.45mW on a laser direct writing platform with objective lens of 50 times, so that CsPb 0.95 Mn 0.05 Perovskite crystals CsPbCl3 are in situ precipitated in the Cl3-PVAC film, thereby preparing a patterned film with high luminous efficiency.

[0079] Example 4

[0080] A material that effectively inhibits the non-laser-induced crystallization of perovskite in laser direct writing is prepared. The material includes ion-substituted perovskite Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3 and polymers containing ester groups, ion-substituted perovskite to CsPb 0.95 Zn 0.05 I3, at this time z is 0.95, x is 0, y is 0, and the polymer containing ester groups is PVAC.

[0081] The chemical composition of the material can be written as CsPb 0.95 Zn 0.05 I3-PVAC, the material does not emit light at this time. After being written with a laser direct writing platform, the luminescent material emits red light when excited by 405nm light. The specific preparation steps are:

[0082] (1) The perovskite raw materials CsI, PbI2 and the halide material containing transition metal ions ZnI2 were added into 5 mL of DMF in a ratio of 5% of the halide material containing transition metal ions and fully dissolved and mixed to obtain the precursor solution CsPb 0.95 Zn 0.05 I3-DMF;

[0083] (2) 1 g of PVAC was added to 10 mL of DMF and thoroughly dissolved and mixed to obtain a colloidal solution of PVAC-DMF;

[0084] (3) The above precursor solution CsPb 0.95 Zn 0.05 I3-DMF was filtered through a PTFE filter and added to the colloidal solution PVAC-DMF and mixed evenly to obtain a colloidal solution of CsPb 0.95 Zn 0.05 I3-PVAC;

[0085] (4) The colloidal solution CsPb 0.95 Zn 0.05 I3-PVAC was spin-coated on a glass substrate and then dried at 50°C to obtain CsPb 0.95 Zn 0.05 I3-PVAC film, and finally irradiated with 405nm single-mode continuous wave laser with power of 10.45mW on a laser direct writing platform with objective lens of 50 times, so that CsPb 0.95 Zn 0.05 Perovskite crystals CsPbI3 were in situ precipitated in the I3-PVAC film, and a high-luminescence-efficiency patterned film with a minimum line width of 1.47 μm was prepared.

[0086] Example 5

[0087] A material that effectively inhibits the non-laser-induced crystallization of perovskite in laser direct writing is prepared. The material includes ion-substituted perovskite Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3 and polymers containing ester groups, ion-substituted perovskite to CsPb 0.95 Zn 0.05BrI2, at this time z is 0.95, x is 0, y is 1 / 3, and the polymer containing ester groups is PVAC.

[0088] The chemical composition of the material can be written as CsPb 0.95 Zn 0.05 BrI2-PVAC, the material does not emit light at this time. After being written with a laser direct writing platform, the luminescent material emits orange-red light when excited by 405nm light. The specific preparation steps are:

[0089] (1) The perovskite raw materials CsI, CsBr, PbI2, PbBr2 and the halide material containing transition metal ions ZnI2 were added into 5 mL of DMF in a ratio of 5% of the halide material containing transition metal ions and fully dissolved and mixed to obtain the precursor solution CsPb 0.95 Zn 0.05 BrI2-DMF;

[0090] (2) 1 g of PVAC was added to 10 mL of DMF and thoroughly dissolved and mixed to obtain a colloidal solution of PVAC-DMF;

[0091] (3) The above precursor solution CsPb 0.95 Zn 0.05 BrI2-DMF was filtered through a PTFE filter and added to the colloidal solution PVAC-DMF and mixed evenly to obtain a colloidal solution of CsPb 0.95 Zn 0.05 BrI2-PVAC;

[0092] (4) The colloidal solution CsPb 0.95 Zn 0.05 BrI2-PVAC was spin-coated on a glass substrate and then dried at 50°C to obtain CsPb 0.95 Zn 0.05 BrI2-PVAC film, and finally irradiated with 405nm single-mode continuous wave laser with power of 10.45mW on a laser direct writing platform with 50 times objective lens, so that CsPb 0.95 Zn 0.05 Perovskite crystals CsPbI3 were in situ precipitated in the BrI2-PVAC film, and a high-luminescence-efficiency patterned film with a minimum line width of 1.47 μm was prepared.

[0093] Comparative Example 1

[0094] The difference between this comparative example and Example 1 is that the halide-doped material without transition metal ions: CsPb(Cl x Br y I 1-x-y)3-PVAC, (0≤x≤1, 0≤y≤1, x+y≤1), since the material does not contain transition metal ions, the formation energy is high, and thus non-laser induced crystallization is likely to occur.

[0095] Comparative Example 2

[0096] The difference between this comparative example and Example 1 is that the material without adding PVAC: Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3, (W is a transition metal ion, 0.8≤z≤1, 0≤x≤1, 0≤y≤1, x+y≤1), since there is no blocking effect of the functional group ─COO─ in the PVAC polymer, it is easy to make the free Cs + and Pb 2+ The cations are coordinated to allow non-laser-induced crystallization to occur.

[0097] Comparative Example 3

[0098] The difference between this comparative example and Example 1 is that the polymer PVDF (polyvinylidene fluoride) is added instead of the PVAC material: Cs (Pb z W 1-z )(Cl x Br y I 1-x-y )3-PVDF, (W is a transition metal ion, 0.8≤z≤1, 0≤x≤1, 0≤y≤1, x+y≤1), because the C─F (carbon-fluorine bond) in PVDF cannot react well with the free Cs + and Pb 2+ The cations are coordinated and thus non-laser-induced crystallization is also easily possible.

[0099] Using the laser direct writing platform to perform laser direct writing in materials that effectively inhibit non-laser induced crystallization of perovskite can produce exquisite luminescent patterns, and non-laser induced crystallization can be well suppressed in the non-laser direct writing area, such as Figure 1 and Figure 2 shown.

[0100] from Figure 1 and Figure 2 The non-laser-written portion is black, demonstrating that the materials and methods of the present invention effectively inhibit non-laser-induced crystallization of perovskites. When the material contains Br, the image is green; when the material contains I, the image is red. The color changes with the halogen element.

[0101] Figures 3 to 7The results show that after laser direct writing, the luminescent material has good crystallinity and luminescence efficiency, proving that it is suitable for use in Micro-LED display, information encryption, anti-counterfeiting and optical data storage.

[0102] from Figure 3 It can be seen that no corresponding green light material crystals are produced before laser direct writing using the material of the present invention, indicating that the non-laser induced crystallization of perovskite can be effectively suppressed. The XRD of the green light sample synthesized after laser direct writing using the method of the present invention is similar to that of the standard card ICSD#97851, indicating that the green light material synthesized by the present invention has a high degree of crystallinity.

[0103] from Figure 4 It can be seen that no corresponding red light material crystals are produced before laser direct writing using the material of the present invention, indicating that the non-laser induced crystallization of perovskite can be effectively suppressed. The XRD of the red light sample synthesized after laser direct writing using the method of the present invention is similar to that of the standard card ICSD#27979, indicating that the red light material synthesized by the present invention has a high degree of crystallinity.

[0104] from Figure 5 It can be seen that the emission spectrum of the material synthesized by the method of the present invention is smooth and has a narrow half-peak width, indicating that the material of the present invention has a high luminous efficiency.

[0105] from Figure 6 It can be seen that different line widths can be achieved by patterning using the laser direct writing method of the present invention at the same scanning speed and different powers, indicating that the ideal pattern line width can be achieved by adjusting the power.

[0106] from Figure 7 It can be seen that different line widths can be achieved by patterning using the laser direct writing method of the present invention at different scanning speeds at the same power, indicating that the ideal pattern line width can be achieved by adjusting the scanning speed.

[0107] The present invention has been described in detail above with reference to the embodiments. However, the present invention is not limited to the above embodiments. Various changes can be made within the scope of knowledge possessed by ordinary technicians in the relevant technical field without departing from the spirit of the present invention.

Claims

1. A material that effectively inhibits non-laser-induced crystallization of perovskite during laser direct writing, characterized in that: The material includes ion-substituted perovskite and a polymer containing an ester group. The chemical composition of the ion-substituted perovskite is: Cs(Pb z W 1-z )(Cl x Br y I 1-x-y )3, wherein W is a transition metal ion, including Mn 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Co 2+ Cr 3+ and Fe 3+ At least one of the following, 0.8≤z≤1, 0≤x≤1, 0≤y≤1, x+y≤1.

2. The material according to claim 1, characterized in that The material is a luminescent material, and its colors include red, green, blue and orange-red.

3. A method for preparing the material according to claim 1 or 2, characterized in that: The method includes the steps of introducing transition metal ions and ester groups into a perovskite raw material.

4. The method according to claim 3, characterized in that The following steps are involved: S1: dissolving the perovskite raw material and the halide containing transition metal ions in solvent A to obtain solution B; S2: adding the polymer material containing an ester group into solvent C and dissolving it to obtain solution D; S3: adding the solution B to the solution D to obtain solution E; S4: Spin-coating the solution E on a substrate, and drying to obtain the material that effectively inhibits non-laser induced crystallization of perovskite during laser direct writing.

5. The method according to claim 4, characterized in that The perovskite raw material includes at least one of CsCl, CsBr, CsI, PbCl2, PbBr2 and PbI2.

6. The method according to claim 4, characterized in that The halide containing transition metal ions includes at least one of MnCl2, MnBr2, MnI2, ZnCl2, ZnBr2 and ZnI2.

7. The method according to claim 4, characterized in that The polymer material containing an ester group includes polyvinyl acetate and polymethyl methacrylate.

8. The method according to claim 4, characterized in that The solvent A includes N,N-dimethylformamide or dimethyl sulfoxide; the solvent C includes N,N-dimethylformamide or dimethyl sulfoxide.

9. A patterned film, characterized in that: The material according to claim 1 or 2 is prepared by laser direct writing.

10. Application of the patterned film according to claim 9 in Micro-LED display, information encryption, anti-counterfeiting and optical data storage.

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