Manganese-doped flexible lead halide perovskite material and room-temperature in-situ preparation method thereof

Abstract

The method comprises the following steps: dissolving lead chloride, manganese chloride, hydrochloric acid and polyether amine D400 in N, N-dimethylformamide to form a polar precursor solution, mixing the polar precursor solution with an oleic acid / n-octane weak polar solvent containing cesium acetate, stirring for 1 hour at 20-30 DEG C and 400 r / min, centrifuging for 3-5 minutes at 8000-10000 r / min, and drying to obtain the manganese-doped flexible lead halide perovskite material. And washing with n-hexane for three times. The material is composed of an amorphous perovskite network and embedded nanocrystals with the average diameter of 6.8 nanometers, and has polymer-like viscoelasticity and 3D printing capacity; the photoluminescence quantum yield exceeds 50%, and the Stokes shift is gt; the X-ray excitation light yield is about 8.07 * 10 < 4 > photons / megaelectron volts, and the imaging resolution is 9.0 line pairs / mm. The material is still excellent in performance after being subjected to 300% stretching, 5000 times of bending circulation, air storage for nearly two months and 5 minutes of self-healing, and is suitable for flexible electronic devices, wearable X-ray detection equipment and complex three-dimensional common imaging systems.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of flexible electronic materials, and particularly relates to a manganese-doped flexible lead halide perovskite material and a room-temperature in-situ preparation method thereof. BACKGROUND

[0002] Perovskite materials are widely studied and applied in the field of radiation detection and imaging due to their excellent photoluminescence performance and X-ray absorption capacity. Among them, lead halide perovskite materials have become an important direction for developing a new generation of X-ray scintillator materials due to their high X-ray absorption cross section and adjustable luminescence characteristics. Typical materials include CsPbCl3, CsPbBr3, MAPbBr3, BA2PbBr4, etc. They are mostly applied in imaging systems in the form of bulk single crystals or powder tablets.

[0003] However, there are still many significant problems in the application of existing perovskite scintillators. First, these materials generally have a small Stokes shift, which easily causes fluorescence self-absorption when emitting under X-ray excitation, resulting in a decrease in effective light output and affecting the imaging quality. Second, these materials are mostly rigid structures, lacking flexibility and extensibility, and are not suitable for flexible electronic imaging systems that conform to complex topographies or are wearable. In addition, existing flexible perovskite materials usually require complex preparation processes such as high-temperature annealing, ultraviolet light curing, or polar solvent assistance, which are difficult to meet the new manufacturing requirements of low energy consumption, stable and efficient rapid film formation, or 3D printing.

[0004] To solve the problem of self-absorption, some studies have attempted to introduce metal ion doping to adjust the luminescence path. For example, doping manganese ions (Mn 2+ ) can effectively improve the Stokes shift and enhance the luminescence efficiency by introducing 4 T1→ 6 A1 transition channels. However, single doping regulation is still difficult to fundamentally overcome the processing adaptability problem caused by the rigid structure of the material.

[0005] On the other hand, flexible modification strategies have also been proposed to improve the material formability, mainly including the compounding of perovskite nanocrystals with a polymer matrix. However, such composite systems often face the following technical difficulties: first, the interfacial bonding ability between perovskite and polymer is weak, resulting in poor overall mechanical stability; second, the polarity difference between the materials is large, which easily causes phase separation and reduces the optical performance; third, the preparation or processing process is sensitive to temperature, light or solvent conditions, limiting the material preparation efficiency and large-scale application possibility. In addition, most flexible perovskite materials lack self-repairing ability and are invalid once they are broken or fatigued during device use, reducing their service life in wearable imaging scenarios.

[0006] Therefore, how to maintain the excellent optical properties of perovskites while introducing polymer-like processability and flexible structures, and achieving low-cost, room-temperature, and rapid fabrication, has become a key technical challenge in the current research of flexible X-ray scintillation materials. To address these technical bottlenecks, there is an urgent need to develop a perovskite material system with high Stokes shift, high quantum yield, flexible processability, self-healing ability, and controllable room-temperature fabrication characteristics to meet the application requirements of complex imaging scenarios and novel flexible electronic devices. Summary of the Invention

[0007] To address the technical problems of existing perovskite materials, such as small Stokes shift, poor flexible processability, severe self-absorption, and demanding preparation conditions, this invention provides a manganese-doped flexible lead halide perovskite material and its room-temperature in-situ preparation method. Furthermore, it proposes application schemes for this material in flexible electronic devices and X-ray imaging. The following detailed description, using several specific embodiments, clarifies the structural design, component selection, preparation steps, and application forms achieved by this invention.

[0008] In one embodiment of the present invention, a manganese-doped flexible lead halide perovskite material is provided, which is composed of an amorphous perovskite network and crystalline perovskite nanoparticles embedded therein. The crystalline nanoparticles have an average particle size of 4-10 nanometers and are uniformly dispersed in the amorphous network. A protonated oligomeric diamine is introduced into the amorphous network as an A-site organic cation. The material exhibits polymer-like processability and plasticity at room temperature of 20-30°C and has the performance characteristics of a Stokes shift greater than 200 nanometers, a photoluminescence quantum yield greater than 50%, and high responsiveness to X-rays.

[0009] Furthermore, the oligomeric diamine is polyetheramine D400, with the molecular formula H2NCH(CH3)CH2[OCH2CH(CH3)]. 5.6 NH2, the polyetheramine D400 is introduced into the perovskite crystal structure as an A-site cation, so that the material can obtain polymer-like viscoelasticity and flexibility while maintaining the optical properties of perovskite.

[0010] Furthermore, the manganese element is introduced into the perovskite lattice as a B-site dopant, with a lead molar ratio of 1:0 to 1:3. This doping method not only modulates the luminescence efficiency of the material but also... 4 T1→ 6 The A1 transition channel significantly improves the Stokes shift and suppresses the fluorescence self-absorption effect in traditional materials.

[0011] Furthermore, cesium is introduced into the material. Cesium ions exist as A-site inorganic cations in the perovskite structure, and their molar ratio with polyetheramine D400 is 1:12 to 1:118. This is used to regulate the viscoelastic behavior and mechanical response characteristics of the material, enabling it to exhibit reversible switching between fluid and solid states under different stresses.

[0012] In one embodiment of the present invention, a method for in-situ preparation of the above-mentioned material at room temperature is provided, comprising the following steps: S1. Dissolve lead source, manganese source, halogen source and oligomeric diamine in a polar solvent to form a polar solvent phase; S2. Dissolve the cesium source in a weakly polar solvent to form a weakly polar solvent phase; S3. Under conditions of 20~30°C, the polar solvent phase and the weakly polar solvent phase are mixed and reacted under stirring conditions to form the composite material; S4. The obtained reaction product is centrifuged, washed and dried to obtain manganese-doped flexible lead halide perovskite material.

[0013] Preferably, the lead source is lead chloride (PbCl2), the manganese source is manganese chloride (MnCl2), the halogen source is hydrochloric acid (HCl), and the cesium source is cesium acetate (CsOAc) oleic acid solution; the polar solvent is N,N-dimethylformamide (DMF), and the weakly polar solvent is a mixture of oleic acid and n-octane in a volume ratio of 1:2.

[0014] Preferably, the reaction process is carried out at 20~30°C for 0.5~2 hours, the centrifugation conditions are 8000~10000 rpm for 3~5 minutes, and the washing step is to wash three times with n-hexane to obtain the target product with high purity.

[0015] In one embodiment of the present invention, the material can be processed by hand shaping, pressing or 3D printing to construct flexible electronic devices or flexible detection components, which are particularly suitable for large-area, complex morphology or conformal bonding scenarios.

[0016] In one embodiment of the present invention, the material is formed into a flexible film by cold pressing or 3D printing, which can be used for X-ray imaging. The film exhibits an imaging resolution of not less than 9.0 line pairs / mm under X-ray irradiation and can withstand tensile strain of more than 300%, and its imaging performance is not significantly dependent on strain.

[0017] Alternatively, after the aforementioned film breaks, it can self-heal by contacting it at room temperature for 5 to 10 minutes. After recovery, the imaging quality remains essentially unchanged, thereby significantly improving the reliability and durability of the flexible scintillator in long-term dynamic application environments.

[0018] Based on the above technical solution, the manganese-doped flexible lead halide perovskite material of the present invention, by introducing crystalline nanoparticles, protonated oligomeric diamine, and manganese ion doping into an amorphous perovskite network, constructs a composite material system that combines high optical performance with polymer-like flexibility, solving several core problems existing in the field of traditional perovskites in X-ray imaging, and has the following significant technical advantages: First, the material constructs a composite structure of "amorphous network + nanocrystal embedding," which can effectively alleviate energy migration losses caused by crystal inhomogeneity or interface defects, and improve the uniformity and stability of the material structure. The introduced nanocrystals are uniform in size, with an average particle size controlled at 4~10 nanometers, which is conducive to achieving an efficient excitation-emission process, thereby obtaining stable and bright orange-red emission under X-ray excitation.

[0019] Secondly, by introducing oligomeric diamines such as polyetheramine D400 into the A-site structure, perovskite materials are endowed with good viscoelasticity and room-temperature processability, allowing them to undergo arbitrary deformation at room temperature through processes such as cold pressing, hand shaping, or 3D printing. This polymer-like property enables the material to meet the structural adaptability requirements of flexible electronic devices and co-forming imaging systems, significantly expanding its application scenarios.

[0020] Third, by adjusting the manganese source content, the optical properties of the material can be designed in a controllable manner. The introduction of manganese ions not only provides... 4 T1→ 6 The A1 emission transition channel significantly improves the Stokes shift (>200 nm), effectively solving the problem of self-absorption in traditional perovskite scintillators under X-ray excitation. It also improves the photoluminescence quantum yield (>50%), significantly enhancing the material's energy conversion efficiency to X-rays.

[0021] Fourth, by adjusting the cesium source content, the viscoelastic properties of the material-like polymer can be continuously and programmably controlled, allowing it to reversibly switch between a "fluid state" and a "solid state," thus balancing flexible processability and molding stability. This characteristic enables the material of this invention to flexibly adapt to processing requirements such as 3D printing, large-area film formation, and complex morphology construction.

[0022] Fifth, the material of this invention has excellent mechanical elasticity and environmental stability. It can withstand tensile strain of more than 300%, maintain its luminescent performance after being repeatedly bent 5,000 times, and retain more than 99% of its initial photoluminescence performance after being stored in ambient air for 2 months, thus meeting the requirements for high reliability and long service life.

[0023] Sixth, the material has self-healing ability. When a structural fracture occurs, the structural continuity can be restored and the original imaging performance can be maintained by contacting it at room temperature for only 5 to 10 minutes. This significantly improves the actual service life and maintenance convenience of flexible scintillator materials in wearable devices and dynamic imaging systems.

[0024] Seventh, the material exhibits excellent linear response to X-rays, with the output intensity showing a highly linear relationship with the input dose within a dose rate range of 0.001–1.0 mGry / s (R0). 2 With a strength of >0.999, it can be used as a quantitative X-ray responsive material in medical, security, and industrial testing applications.

[0025] In summary, this invention achieves comprehensive optimization of materials in multiple dimensions such as performance, processability, and functional adaptability through unique structural design and doping control strategies. It proposes a novel material solution suitable for flexible X-ray imaging and wearable electronic systems, which has broad promotional value and industrial application potential. Attached Figure Description

[0026] Figure 1 The figures show the photoluminescence quantum yield test results of the manganese-doped flexible lead halide perovskite materials prepared in Examples 1-7, demonstrating the regulatory effect of manganese doping amount on the luminescence efficiency of the materials. Figure 2 The rheological test results of the materials prepared in Examples 8-11 and Example 1 show the relationship between angular frequency and storage modulus and loss modulus, which are used to evaluate the viscoelastic regulation behavior of the materials. Figure 3 The image shows a scanning electron microscope image of the material prepared in Example 1, demonstrating the uniformity and phase-separation-free structure of the material at the micrometer scale. Figure 4 Transmission electron microscope images of the manganese-doped flexible lead halide perovskite material prepared in Example 1. (a) shows the overall morphology of the material; (b) shows a magnified view of a portion of the nanoparticles in the material, with the inset showing their particle size distribution. The average diameter of the nanoparticles is approximately 6.8 nanometers. Figure 5 The UV-Vis absorption and photoluminescence spectra of the material prepared in Example 1 are shown to characterize the band-edge absorption and redshift emission characteristics caused by manganese ion doping. Figure 6 The rheological properties test diagrams of the material prepared in Example 1 are as follows: (a) is the strain-modulus scan result, and (b) is the flow behavior test result, reflecting the material's ability to transition from solid to liquid state and its shear thinning behavior characteristics. Figure 7 The alternating step strain test results of the material prepared in Example 1 show the response relationship between the storage modulus and loss modulus of the material under different strain states, demonstrating its rapid response and reshapeability. Figure 8 The geometric shape transformation process of the material prepared in Example 1 after manual rolling cycle processing is shown, demonstrating its good cyclic plasticity; Figure 9 The images show the material from Example 1 after it was pressed into a 15cm×15cm film at room temperature under natural light (left) and 365nm ultraviolet light (right), verifying its large-area processing capability and photoresponse performance. Figure 10 The images show two-dimensional and three-dimensional structures formed by 3D printing of the material in Example 1 under conditions of no high temperature, no polar solvent, and no UV curing, verifying its room temperature printing adaptability. Figure 11 The grayscale image of the radiation emission intensity of the thin film under X-ray irradiation was prepared for Example 1 to characterize the uniformity of the film emission and its high response to X-rays. Figure 12 The image shows the X-ray excitation emission intensity of the thin film of Example 1 after 5000 bending cycles, compared with... Figure 11 The comparison showed no significant attenuation, verifying its excellent mechanical stability.

[0027] Figure 13 The luminescence intensity response curves of the material in Example 1 are shown in the dose rate range of 0.001~1.0 mGry / s, with correlation coefficient R. 2 The value >0.999 demonstrates its excellent X-ray linear response characteristics; Figure 14 The photoluminescence quantum yield retention rate of the material in Example 1 after being stored in air for nearly two months was over 99%, demonstrating its excellent environmental stability. Figure 15 X-ray imaging images of the material from Example 1 after film formation were shown for use in samples such as capsule springs, fish-shaped pendants, and keys, demonstrating clear imaging edges and rich details. Figure 16 The image shows a comparison of the self-healing imaging effect of the thin film of Example 1 before and after fracture. The crack disappeared after 5 minutes of contact at room temperature, and the imaging performance remained basically unchanged. Figure 17 The X-ray imaging resolution test image of the material in Example 1 shows a resolution of 9.0 line pairs / mm, verifying its high imaging clarity. Figure 18 The relative light yield of the material in Example 1 at different X-ray dose rates is shown, with an average value of 80693 photons / Megaelectronvolts, demonstrating its excellent X-ray energy conversion capability. Figure 19 Photographs of the manganese-doped flexible lead halide perovskite scintillator film prepared in Example 1 being stretched with the aid of high-performance double-sided tape (VHB tape). (a) shows that the material has strong stretchability, and the image is clearly visible within the stretch recovery cycle (b), demonstrating its excellent stretch adaptability; Figure 20The images of the manganese-doped flexible lead halide perovskite scintillator film prepared in Example 1 under different morphologies are shown in the following images: (a) X-ray imaging results of the film in a planar state; (b) X-ray imaging results of the film when it is attached to the surface of a curved object. These images are used to compare and demonstrate the imaging capabilities of the film under planar and curved conditions, showing that the material has good imaging capabilities under curved and bonded conditions. Figure 21 for Figure 20 Photographs of the appearance of objects with different curvature angles under indoor light were used for analysis to correspond with X-ray imaging effects. Figure 22 The images show conformal X-ray imaging results of a hollow porous metal hemisphere at different angles on a manganese-doped flexible lead halide perovskite thin film prepared in Example 1. (a) and (b) show the image details obtained by the film at different viewing angles, demonstrating its imaging capability for complex curved surfaces. Figure 23 for Figure 22 The front view (a) and side view (b) of the hollow porous metal hemisphere shown under ambient light are used for comparison. Detailed Implementation

[0028] The following will provide a more detailed description of the manganese-doped flexible lead halide perovskite material, its room-temperature in-situ preparation method, and its applications, in conjunction with the accompanying drawings and specific examples, so that those skilled in the art can understand and implement the technical solution of the present invention.

[0029] It should be noted that the embodiments described are only used to illustrate the technical principles and specific implementation paths of the present invention, and do not constitute a limitation on the scope of protection of the present invention. Those skilled in the art to which this invention pertains may make equivalent substitutions or adjustments in material types, doping ratios, solvent systems, reaction conditions, and structural applications without departing from the spirit and essence of the present invention; these modifications should also fall within the scope of protection of the present invention.

[0030] Example 1: Standard preparation method of manganese-doped flexible lead halide perovskite material (lead:manganese = 1:1.5, cesium:polyetheramine D400 = 1:15) In this embodiment, a one-step room-temperature method for preparing manganese-doped flexible lead halide perovskite materials is provided. This method has advantages such as mild synthesis conditions, simple operation, and stable product structure. The obtained material possesses both excellent optical properties and flexible processing capabilities, making it a preferred approach for the flexible X-ray scintillator technology solution described in this invention.

[0031] In the specific implementation process, 8.34 mg (30.0 μmol) of lead chloride (PbCl2) and 5.67 mg (45.0 μmol) of manganese chloride (MnCl2) were first dissolved in 1.0 mL of N,N-dimethylformamide (DMF) as the base components of the polar precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially to provide the halogen source and the A-site organic cation. The resulting mixed solution was ultrasonically treated in an ultrasonic cleaner (40 kHz, 50 W) until it became clear and transparent, forming a homogeneous polar solvent phase.

[0032] Simultaneously, 123.0 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid, and 20.0 μL of this solution was added to a pre-prepared mixture of 5.0 mL of oleic acid and 10.0 mL of n-octane to construct a weakly polar solvent phase, which was then mixed under ultrasonic conditions. Subsequently, the polar solvent phase was rapidly injected into the weakly polar solvent phase under stirring, and the reaction was carried out at room temperature (20–30°C) with stirring at 400 rpm for 1 hour, during which a white precipitate gradually formed in the system.

[0033] After the reaction was completed, the supernatant was removed by high-speed centrifugation at 8000 rpm for 5 minutes. The resulting precipitate was washed three times with n-hexane to remove residual organic phase and unreacted components, and finally manganese-doped flexible lead halide perovskite material was obtained.

[0034] The obtained material exhibited good overall performance in structural characterization and performance testing. Scanning electron microscope images (see...) Figure 3 The study showed that the material has a uniform structure at the micrometer scale, and no obvious phase separation was observed. Transmission electron microscopy further revealed that the material is a composite structure of "amorphous perovskite network + embedded crystalline nanoparticles," with good nanoparticle dispersion, uniform particle size, and an average diameter of approximately 6.8 nanometers (see [link to study]). Figure 4 This indicates that the material in this embodiment has a stable interlocking configuration at the nanoscale.

[0035] Regarding optical performance, the results of ultraviolet-visible absorption spectroscopy and photoluminescence spectroscopy analysis are as follows: Figure 5 As shown, the material exhibits significant band-edge absorption at 384 nm, and under UV excitation at 365 nm, manganese ions appear at a wavelength of 608 nm. 4 T1→ 6 The A1 transition exhibits an orange-red emission peak with a Stokes shift of 224 nm, significantly higher than that of traditional lead halide perovskite materials, effectively suppressing the self-absorption effect during luminescence. Quantum yield test results are shown below. Figure 1 This indicates that under the condition of a manganese doping ratio of lead:manganese = 1:1.5, the photoluminescence quantum yield of the material reaches its peak, exceeding 50%.

[0036] Furthermore, rheological tests on the material of Example 1 further verified its flexible processing capability and viscoelastic properties (see...). Figure 2 and Figure 6 ). Figure 2 As shown, the storage modulus (G') of the material in Example 1 is higher than the loss modulus (G''), exhibiting typical solid-like behavior within the range of angular frequency variation. Figure 6 (a) shows that when the strain exceeds 1%, the storage modulus drops sharply and falls below the loss modulus, resulting in yielding behavior and demonstrating the reversible transformation capability from solid to liquid. Figure 6 (b) The flow scan results show obvious shear-thinning behavior, indicating that the material has good formability and external force response, such as Figure 7 The alternating step strain test results shown indicate that the material exhibits rapid response and reshapeability under different strain states, making it suitable for flexible processing technologies such as 3D printing.

[0037] In summary, Example 1 achieved the efficient preparation of manganese-doped flexible lead halide perovskite materials by constructing a polar-weakly polar solvent interface system at room temperature. The resulting material has a uniform structure, controllable particle size, high quantum yield, large Stokes shift, excellent viscoelastic properties, and room-temperature processability. It is particularly suitable for various applications such as flexible conformal X-ray imaging, conformal printed devices, self-supporting scintillators, and wearable radiation detection systems, verifying the effectiveness and feasibility of the technical solution proposed in this invention.

[0038] Example 2: Preparation of undoped flexible lead halide perovskite material (lead:manganese = 1:0, cesium:polyetheramine D400 = 1:15) In this embodiment, to compare and verify the effect of manganese ions in the flexible lead halide perovskite material of the present invention, the same raw material types and operating procedures as in Example 1 were used, except that the manganese source was removed, i.e., an undoped flexible lead halide perovskite material was prepared under the condition of lead:manganese = 1:0. The material obtained through this embodiment can be used to compare and analyze the effect of manganese doping on the optical properties of the material. In the specific operation, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) was first added to 1.0 mL of N,N-dimethylformamide (DMF) and stirred at room temperature to dissolve, yielding a clear and transparent precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the solution was ultrasonicated in a 40 kHz, 50 W ultrasonic cleaner until completely homogeneous, thus obtaining the polar solvent phase. The only difference between this example and Example 1 is that no manganese source was added to ensure that there are no manganese ion B-site doping components in the material system.

[0039] To maintain a consistent cesium ion content in the system, the cesium source was prepared as in Example 1: 123.0 mg of cesium acetate (CsOAc, 640.8 μmol) was pre-dissolved in 1.0 mL of oleic acid, and 20.0 μL of this solution was added to a weakly polar solvent system consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane (volume ratio 1:2). The solution was then fully dispersed under the same ultrasonic conditions to ensure the uniformity of the weakly polar phase.

[0040] Subsequently, the ultrasonically homogenized polar solvent phase was rapidly injected into the weakly polar solvent phase under magnetic stirring, with the stirring speed controlled at 400 rpm, and the reaction was carried out at room temperature (20~30°C) for 1 hour. As the reaction proceeded, a white precipitate gradually formed in the system, creating a flexible lead halide perovskite precursor material without manganese doping.

[0041] After the reaction was completed, the same purification process as in Example 1 was used, centrifuging at 8000 rpm for 5 minutes and discarding the supernatant; the resulting precipitate was then washed three times with n-hexane to remove excess organic matter and unreacted substances, and finally a flexible undoped manganese lead halide perovskite material was obtained.

[0042] A comparison with the materials of Example 1 shows that, because the undoped manganese system mainly exhibits weak intrinsic emission from the perovskite matrix under ultraviolet excitation, its Stokes shift is significantly smaller than that of the material prepared in Example 1, and its photoluminescence quantum yield is significantly lower than that of the manganese-doped sample (see Example 1). Figure 1 This indicates that the appropriate introduction of manganese ions is a crucial factor in enabling the material of this invention to achieve a large Stokes shift, high luminous efficiency, and effective suppression of self-absorption. Furthermore, the material retains the viscoelastic properties of a polymer.

[0043] This embodiment can serve as a control group in the system of the present invention to verify the core role of manganese ions in constructing high-performance flexible scintillators.

[0044] Example 3: Preparation of low-manganese-doped flexible lead halide perovskite material (lead:manganese = 1:0.5, cesium:polyetheramine D400 = 1:15) In this embodiment, to study the effect of low-doped manganese ions on the optical properties of flexible lead halide perovskite materials, the same solvent system, cation source and reaction conditions as in Example 1 were used, but the amount of manganese source added was adjusted to a molar ratio of lead ions to manganese ions of 1:0.5 to prepare low-manganese-doped flexible perovskite materials.

[0045] In the specific implementation process, firstly, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 1.89 mg of manganese chloride (MnCl2, 15.0 μmol) were weighed and added to 1.0 mL of N,N-dimethylformamide (DMF) solvent. The solution was stirred and dissolved at room temperature to obtain a clear and transparent metal precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially to this solution, and the solution was ultrasonically treated in a 40 kHz, 50 W ultrasonic cleaner until a homogeneous and transparent polar solvent phase was formed. During this stage, hydrochloric acid provides a halogen source to maintain system equilibrium, while polyetheramine D400, as an A-site organic cation, enters the perovskite precursor structure, laying the foundation for the subsequent formation of a flexible network in the material.

[0046] To maintain the cesium content consistent with Example 1, 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid to prepare an oleic acid solution containing the cesium source. 20.0 μL of this solution was added to a pre-mixed mixture of 5.0 mL of oleic acid and 10.0 mL of n-octane, and a homogeneous, weakly polar solvent system was generated through stirring and sonication. This weakly polar solvent phase, acting as an antisolvent, promotes the rapid nucleation and growth of perovskite nanocrystals during subsequent mixing.

[0047] During the preparation process, the ultrasonically homogenized polar solvent phase was rapidly injected into the weakly polar solvent phase under magnetic stirring, and the stirring rate was maintained at 400 rpm. The reaction was continued at room temperature (20~30°C) for 1 hour. As ion exchange and antisolvent effects gradually increased at the solvent interface, a white solid precipitate was formed in the system, indicating that the basic structure of the low-manganese-doped perovskite precursor was formed.

[0048] After the reaction was completed, the reaction system was centrifuged at 8000 rpm for 5 minutes. The supernatant was discarded, and the resulting precipitate was washed three times with n-hexane to remove residual organic solvents and substances that did not participate in the reaction. The material obtained after washing was in a flexible viscoelastic state and had a certain degree of plasticity, which is the low-manganese-doped flexible lead halide perovskite material of this embodiment.

[0049] The material exhibited photoluminescence behavior different from that of Example 1 in subsequent tests: due to the lower manganese doping content, the manganese ions in the material... 4 T1→ 6 The A1 characteristic emission peak is relatively weak, resulting in a low photoluminescence quantum yield, but it is still significantly higher than that of the undoped manganese sample (Example 2). Figure 1The trend confirms this phenomenon, namely, within the low manganese doping range, the photoluminescence quantum yield increases with increasing manganese content. Therefore, this embodiment is located at the low to mid-end of the quantum yield enhancement range. Furthermore, the material retains its polymer-like viscoelastic properties.

[0050] Through comprehensive structural characterization and optical performance analysis of the material, it can be seen that the material obtained in this embodiment can serve as an intermediate doping state for performance regulation, and the key regulatory role of manganese doping in the material system of this invention is verified.

[0051] Example 4: Preparation of moderately manganese-doped flexible lead halide perovskite material (lead:manganese = 1:1, cesium:polyetheramine D400 = 1:15) In this embodiment, a moderately manganese-doped flexible lead halide perovskite material was prepared by adjusting the amount of manganese source to be equimolar with that of lead source, resulting in a lead:manganese molar ratio of 1:1. This embodiment aims to further explore the luminescence performance of the material at a moderate doping level, providing experimental basis for optimizing the manganese doping ratio.

[0052] In the specific implementation process, firstly, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 3.78 mg of manganese chloride (MnCl2, 30.0 μmol) were weighed and added to 1.0 mL of N,N-dimethylformamide (DMF). The solution was stirred and dissolved at room temperature to obtain a clear and transparent precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the solution was ultrasonically treated in a 40 kHz, 50 W ultrasonic cleaner until the system was completely mixed and homogeneous, forming a stable and transparent polar solvent phase. Similar to Examples 1-3, polyetheramine D400 provides A-site organic cations to the system, enabling the material to construct an amorphous network framework during structure formation, thus endowing the material with flexibility and remodelability.

[0053] To maintain the comparability of cesium ion content in the materials, this embodiment uses the same cesium source preparation method as in Example 1: 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid as a cesium ion precursor solution. Subsequently, 20.0 μL of this solution was added to a weakly polar solvent system consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane mixed in a volume ratio of 1:2, and the mixture was gently stirred to obtain the weakly polar solvent phase.

[0054] During the preparation process, the polar solvent phase was rapidly injected into the weakly polar solvent system under magnetic stirring, and the stirring speed was maintained at 400 rpm to allow the solvent interface reaction to proceed rapidly. The reaction was continued with stirring at room temperature (20~30°C) for 1 hour. As ion exchange and antisolvent effects progressed, a white solid product gradually precipitated in the system, indicating that the main structure of the material had been formed.

[0055] After the reaction was complete, the mixture was centrifuged at 8000 rpm for 5 minutes in a high-speed centrifuge. The supernatant was discarded, and the precipitate was collected and washed three times with n-hexane to remove unreacted substances and allow for solvent residue. The final solid exhibited the typical viscoelastic morphology of flexible perovskite materials and could be lightly pressed into shape or further processed at room temperature.

[0056] In terms of performance evaluation, the behavior of the material in this embodiment falls between that of Example 3 (low manganese doping) and Example 1 (high luminous efficiency manganese doping range). Figure 1 The photoluminescence quantum yield trend shown indicates that the luminescence efficiency of the medium manganese doping ratio (1:1) sample is higher than that of the low manganese doped material, but slightly lower than that of the sample in Example 1 with a manganese doping ratio of 1:1.5. This suggests that as the manganese doping level increases, the luminescence efficiency of manganese ions increases. 4 T1→ 6 The A1 transition luminescence mechanism begins to significantly contribute to the photoluminescence intensity, but it remains in an upward trend of performance improvement until the doping range is exceeded. Furthermore, the material retains its polymer-like viscoelastic properties.

[0057] In summary, Example 4 successfully prepared a moderately manganese-doped flexible lead halide perovskite material with a lead:manganese ratio of 1:1. This material exhibits clear doping-controlled characteristics in its luminescence behavior, providing an experimental basis for the manganese doping control strategy proposed in this invention.

[0058] Example 5: Preparation of highly manganese-doped flexible lead halide perovskite materials (lead:manganese = 1:2, cesium:polyetheramine D400 = 1:15) Based on Examples 1-4, this embodiment further increases the doping ratio of manganese ions to twice that of lead (lead:manganese = 1:2) to explore the effect of manganese ions on the luminescence efficiency of flexible lead halide perovskite materials under high doping conditions.

[0059] In the preparation process, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 7.55 mg of manganese chloride (MnCl2, 60.0 μmol) were first weighed and dissolved together in 1.0 mL of N,N-dimethylformamide (DMF). This ratio of manganese source is significantly higher than the 1:1.5 ratio in Example 1, and is used to construct a material system under highly doped conditions. To ensure solution homogeneity, the above mixture was ultrasonically treated in a 40 kHz, 50 W ultrasonic cleaner until the metal salt was completely dissolved, obtaining a clear precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the mixture was ultrasonically mixed again to form a stable polar solvent phase.

[0060] Meanwhile, the cesium source was prepared in the same manner as in the previous embodiment: 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid as a stock solution, and 20.0 μL of the stock solution was added to a mixed solvent consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane (volume ratio 1:2) to obtain a uniform weakly polar solvent phase.

[0061] Subsequently, the polar solvent phase was rapidly poured into the weakly polar solvent system under magnetic stirring, with the stirring rate controlled at 400 rpm, and the reaction was carried out at room temperature (20~30°C) for 1 hour. During the reaction, a white precipitate gradually formed in the solution, indicating that in the high-manganese doped system, perovskite nanocrystals and amorphous networks jointly constructed the main structure of the material.

[0062] After the reaction was complete, the mixture was centrifuged at 8000 rpm for 5 minutes, the supernatant was discarded, and the precipitate was collected. The precipitate was washed three times with n-hexane to remove excess solvent residue and unreacted organic components, ultimately yielding a flexible manganese-doped lead halide perovskite material.

[0063] From the performance results, Figure 1 The photoluminescence quantum yield test showed that when the manganese doping ratio exceeded 1.5 (as in Example 1:2), the photoluminescence efficiency of the material began to decline. This indicates that excessive manganese doping may introduce manganese-manganese coupling interactions, providing a channel for non-radiative energy transfer, thereby reducing the photoluminescence quantum yield, but the material still retains the viscoelastic properties of a polymer.

[0064] In summary, Example 5 verified that under higher manganese doping conditions, although the material still possesses typical flexible perovskite characteristics, its luminescence performance tends to deteriorate. This further confirms that the manganese doping ratio needs to be controlled within a reasonable range, with a preferred manganese doping molar ratio of approximately 1:1.5 to obtain the best optical performance and structural stability.

[0065] Example 6: Preparation of high-manganese-doped flexible lead halide perovskite material (lead:manganese = 1:2.5, cesium:polyetheramine D400 = 1:15) This embodiment further increases the amount of manganese source based on the aforementioned manganese doping ratio, controlling the molar ratio of lead to manganese to be 1:2.5, in order to explore the trend of optical performance changes in materials under high manganese doping conditions. This experiment provides experimental evidence for clarifying the upper limit of manganese ion doping and avoiding performance degradation.

[0066] In the specific operation, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 9.45 mg of manganese chloride (MnCl2, 75.0 μmol) were weighed and added together to 1.0 mL of N,N-dimethylformamide (DMF). The mixture was stirred at room temperature until completely dissolved, forming a transparent and homogeneous metal ion precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially. The mixture was then sonicated in a 40 kHz, 50 W ultrasonic cleaner to form a stable polar solvent phase. Since the manganese doping level in this system has reached the high doping range, good homogeneity and complexation stability of the precursor solution are required to ensure the smooth progress of subsequent reactions.

[0067] Meanwhile, 123.0 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid. 20.0 μL of this solution was then injected into a weakly polar solvent consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane, and gently stirred to obtain the desired weakly polar solvent phase. This system was used to provide cesium cation and antisolvent conditions to induce the precipitation of nanocrystals.

[0068] The polar solvent phase was rapidly injected into the weakly polar solvent phase at room temperature (20-30°C), and the mixture was continuously stirred at 400 rpm for 1 hour. A white solid product gradually precipitated from the system. After the reaction was completed, the precipitate was immediately recovered by centrifugation at 8000 rpm for 5 minutes. The supernatant was discarded, and the mixture was washed three times with n-hexane to remove excess organic matter and impurities, finally obtaining the flexible perovskite material.

[0069] In terms of performance, the photoluminescence test results showed that the luminescence intensity was further reduced compared to the samples with a manganese doping ratio of 1:1.5 or 1:2. Figure 1 The data also confirms this trend: when the manganese doping level exceeds a certain range, the luminescence quantum yield of the material decreases significantly. This is mainly because the high doping level causes the manganese ions to be too close together, resulting in strong interactions and providing a non-radiative dissipation pathway for excited-state energy. In terms of rheological properties, the material still exhibits typical polymer-like viscoelasticity.

[0070] In summary, the high-manganese-doped flexible perovskite material obtained in Example 6 still possesses advantages in terms of structure and mechanical properties, but its optical properties are significantly lower than those of materials with a moderate manganese doping ratio. This indicates that the optimal range for manganese ion doping should be controlled around a lead:manganese ratio of approximately 1:1.5. This example provides an important experimental reference for understanding the performance degradation caused by excessively high manganese doping ratios.

[0071] Example 7: Preparation of flexible perovskite materials with ultra-high manganese doping (lead:manganese = 1:3, cesium:polyetheramine D400 = 1:15) In this embodiment, the proportion of manganese source is further increased, and the molar ratio of lead to manganese is controlled at 1:3, so as to construct a flexible lead halide perovskite material system under ultra-high manganese doping conditions and evaluate the effect of high manganese content on the luminescence performance of the material.

[0072] In the specific implementation process, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 11.34 mg of manganese chloride (MnCl2, 90.0 μmol) were weighed and added to 1.0 mL of N,N-dimethylformamide (DMF). The mixture was stirred at room temperature for pre-dissolution, and then further treated in a 40 kHz, 50 W ultrasonic cleaner to ensure complete dissolution of the metal salts and the formation of a clear, transparent, and homogeneous precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the mixture was continued to be sonicated until fully mixed to obtain the polar solvent phase.

[0073] Meanwhile, 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid, and 20.0 μL of the solution was slowly added to a weakly polar solvent phase consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane (volume ratio 1:2), and the mixture was gently stirred to form a stable and homogeneous reaction medium.

[0074] The polar solvent phase described above was rapidly injected into the weakly polar solvent system under magnetic stirring, and the stirring speed was maintained at 400 rpm. The reaction was carried out at room temperature (20~30°C) for 1 hour. As the reaction proceeded, a white precipitate gradually formed in the system, and the color change was obvious, indicating that high concentrations of manganese ions had been incorporated into the perovskite structure formation process and occupied some B sites.

[0075] Immediately after the reaction was completed, the product was recovered by centrifugation at 8000 rpm for 5 minutes. The supernatant was discarded, and the precipitate was washed three times with n-hexane to finally obtain the flexible perovskite material.

[0076] Luminescence test results ( Figure 1The results showed that its photoluminescence intensity was significantly lower than that of Examples 1 and 4-6, demonstrating an enhanced nonradiative recombination tendency. While the photoluminescence quantum yield was lower than the aforementioned samples, it remained at a high level, demonstrating its ability to produce high photoluminescence for scintillation applications. The material still exhibited typical polymer-like viscoelasticity.

[0077] This embodiment demonstrates that manganese ions may induce manganese-manganese interactions under excessive doping conditions, leading to harmful energy migration and a decline in the overall performance of the material, thus providing a boundary reference for setting the manganese doping ratio.

[0078] Summary of Examples 1-7: The effect of manganese doping ratio on the performance of flexible perovskite materials and the definition of the optimal range. To systematically investigate the effect of manganese ion doping ratio on the properties of flexible lead halide perovskite materials, this invention conducted continuous control experiments on a series of lead:manganese molar ratios ranging from 1:0 to 1:3 through Examples 1 to 7. The above examples employed standardized room-temperature reaction routes, keeping other variables constant and only varying the manganese ion doping level to accurately assess the comprehensive impact of doping concentration on material structure formation, optical response, and viscoelastic behavior.

[0079] Experimental results show that manganese doping has a significant regulatory effect on the photoluminescence performance of the material, exhibiting a nonlinear response trend: in the low-doping region (such as in Examples 3 and 4), the luminescence efficiency increases significantly with the increase of manganese doping amount; in the medium-high doping region (such as in Examples 1 and 5), the luminescence performance of the material reaches the peak or remains at a high level; while at higher doping levels (Examples 6 and 7), the quantum yield gradually decreases and the photoluminescence intensity drops, indicating that excessive manganese ions may cause an increase in nonradiative recombination.

[0080] Comprehensive evaluation revealed that the preferred lead:manganese doping molar ratio is 1:1.5±0.5, within which the material exhibits the following characteristics: Photoluminescence quantum yield > 50%; Stokes shift > 200 nm, suppressing self-absorption effect; The nanoparticles have a uniform particle size (approximately 6.8 nanometers) and good dispersibility. It exhibits stable rheological behavior and combines processability with viscoelasticity. The material can be processed into flexible imaging elements by hand forming, molding, or 3D printing.

[0081] Therefore, the above systematic embodiments verify the core regulatory role of the manganese doping ratio in the flexible X-ray scintillation material technology of the present invention, and constitute the key experimental basis for the implementation strategy of the present invention.

[0082] Example 8: Preparation of manganese-doped flexible lead halide perovskite material under low cesium ratio conditions (lead:manganese = 1:1.5, cesium:polyetheramine D400 = 1:118) This embodiment aims to investigate the regulatory effect of cesium source content on the rheological behavior and microstructure stability of flexible perovskite materials. While maintaining a consistent lead to manganese ratio (lead:manganese = 1:1.5), the amount of cesium source was significantly reduced, with cesium:polyetheramine D400 = 1:118, to explore the changes in the material formation mechanism and viscoelastic response characteristics under low cesium conditions.

[0083] In the specific operation, firstly, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 5.67 mg of manganese chloride (MnCl2, 45.0 μmol) were weighed and added to 1.0 mL of N,N-dimethylformamide (DMF) and stirred to dissolve. The solution was then ultrasonically treated in a 40 kHz, 50 W ultrasonic cleaner to ensure the formation of a clear and transparent metal salt precursor solution. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the mixture was ultrasonically mixed again to form a homogeneous and transparent polar solvent phase.

[0084] To construct a low-concentration cesium environment, 123.00 mg of cesium acetate (CsOAc) was pre-dissolved in 1.0 mL of oleic acid as a stock solution. Only 2.5 μL of this stock solution was taken and added to a weakly polar solvent system consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane (volume ratio 1:2). The mixture was gently stirred until homogeneous, resulting in a weakly polar solvent phase with a significantly reduced cesium content. This controlled ratio resulted in a cesium ion concentration of only 1.6 μmol in the system, simulating the structural role of A-site metal ions under extreme doping conditions.

[0085] Subsequently, the polar solvent phase was rapidly poured into the weakly polar solvent system, and the stirring rate was maintained at 400 rpm. The reaction was carried out at room temperature (20~30°C) for 1 hour. Compared with the system with normal cesium content (such as Example 1), the precipitation rate in this system was significantly faster during the reaction, and the solid product showed a strong aggregation trend. This indicates that the nucleation process of the material is limited under low cesium content, and the system tends to form a fluid-like structure with strong fluidity.

[0086] After the reaction was completed, the precipitate was recovered by centrifugation at 8000 rpm for 3 minutes, the supernatant was discarded, and the mixture was washed three times with n-hexane to finally obtain a flexible perovskite material with a certain degree of viscoelasticity.

[0087] In subsequent performance tests (see...) Figure 2In this embodiment, the storage modulus (G') remains lower than the loss modulus (G'') throughout the entire strain range, indicating that it exhibits significant fluid behavior at room temperature. This shift in rheological behavior can be attributed to the weakening of the inorganic framework support due to the decrease in cesium ion concentration, allowing the polyetheramine-dominated network structure to take over, thus presenting a dynamic network resembling a soft matter fluid state. Compared to Example 1, this material is more suitable for flexible electronic device applications requiring higher degrees of freedom in molding.

[0088] In summary, Example 8 demonstrates the reversible transition behavior of flexible perovskite materials from a solid-like state to a fluid state under extremely low cesium ratio conditions, providing experimental evidence for the "morphology control of polymer-like perovskite materials" strategy proposed in this invention, and expanding the adaptability of materials in different forming processes.

[0089] Example 9: Preparation of manganese-doped flexible lead halide perovskite material with moderate cesium content (lead:manganese = 1:1.5, cesium:polyetheramine D400 = 1:59) This embodiment controls the amount of cesium source to achieve a cesium:polyetheramine D400 molar ratio of 1:59, which falls between low and standard cesium doping levels. The aim is to investigate the regulatory effect of moderate cesium content on the viscoelastic response performance of flexible perovskite materials and further clarify the dominant role of A-site cations in the morphological behavior of polymer-like materials.

[0090] In the specific preparation process, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 5.67 mg of manganese chloride (MnCl2, 45.0 μmol) were weighed and dissolved together in 1.0 mL of N,N-dimethylformamide (DMF). A clear solution was formed under stirring at room temperature. Then, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially. The solution was ultrasonically treated in an ultrasonic cleaner at 40 kHz and 50 W to ensure that the precursors were fully mixed and formed a uniform and stable polar solvent phase.

[0091] The cesium source was prepared using conventional methods. 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was dissolved in 1.0 mL of oleic acid as a stock solution. In this embodiment, 5.0 μL of the stock solution was added to a mixture of 15.0 mL of oleic acid and n-octane (volume ratio 1:2) to form a weakly polar solvent phase with a cesium concentration of 3.3 μmol, so that the molar ratio of cesium to polyetheramine D400 in the entire reaction system was controlled at 1:59.

[0092] Subsequently, the polar solvent phase was rapidly injected into a weakly polar solvent at room temperature (20–30°C), and the reaction was maintained at a stirring speed of 400 rpm for 1 hour. As the reaction proceeded, a milky precipitate gradually appeared in the system, indicating that the particles initially precipitated and interacted in the solvent network to form a flexible structure of a certain strength. After the reaction was completed, the mixture was immediately centrifuged at 8000 rpm for 3 minutes, the supernatant was discarded, and the precipitate was washed three times with n-hexane to finally obtain a white, viscoelastic flexible perovskite material.

[0093] from Figure 2 The rheological test results show that the storage modulus (G') of the material in this embodiment is consistently lower than the loss modulus (G'') throughout the entire strain range, indicating that it exhibits obvious fluid behavior at room temperature. However, compared to Example 8, G' and G'' are closer. This behavior verifies that the morphology of the material gradually transitions from fluid to solid-like under moderate cesium content, achieving a good balance between material structural support and deformation response.

[0094] Combining the aforementioned low cesium conditions (Example 8) and standard cesium ratio (Example 1), this example further fills in the intermediate segment control parameters, clarifying that the introduction of cesium ions not only regulates structural stability, but also plays a key role in the configuration and flow properties of polymer-like viscoelastic networks, and is the core of the control of the "flowability-plasticity" transition of flexible perovskite materials.

[0095] Example 10: Preparation of manganese-doped flexible lead halide perovskite material with high cesium content (lead:manganese = 1:1.5, cesium:polyetheramine D400 = 1:29) This embodiment maintains a lead to manganese molar ratio of 1:1.5 while moderately increasing the proportion of cesium ions at the A site, so that the molar ratio of cesium to polyetheramine D400 reaches 1:29. The aim is to explore the performance of flexible perovskite materials in terms of viscoelastic response under conditions of higher cesium content.

[0096] In the specific experimental procedure, 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 5.67 mg of manganese chloride (MnCl2, 45.0 μmol) were weighed and added to 1.0 mL of N,N-dimethylformamide (DMF), and pre-dissolved by stirring at room temperature. Subsequently, 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) were added sequentially, and the mixture was thoroughly ultrasonicated in a 40 kHz, 50 W ultrasonic cleaner to ensure that the precursors were fully complexed and uniformly dispersed, forming a clear and transparent polar solvent phase.

[0097] For the cesium source preparation, 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) was completely dissolved in 1.0 mL of oleic acid to serve as a cesium stock solution. In this embodiment, 10.0 μL of the cesium source oleic acid solution (corresponding to a molar amount of approximately 6.6 μmol) was added dropwise to a weakly polar solvent mixture consisting of 5.0 mL of oleic acid and 10.0 mL of n-octane at a volume ratio of 1:2. After gentle stirring, a homogeneous weakly polar solvent phase was formed, maintaining the molar ratio of cesium to polyetheramine D400 in the system at 1:29.

[0098] During the reaction phase, the polar solvent phase was rapidly injected into the weakly polar solvent phase, and the reaction was carried out at room temperature (20-30°C) for 1 hour with a stirring rate of 400 rpm. During this process, a white precipitate gradually formed. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 3 minutes, the supernatant was discarded, and the precipitate was washed three times with n-hexane to finally obtain the flexible perovskite material.

[0099] Figure 2 Rheological analysis further confirmed that the material in this embodiment underwent a further transformation. The storage modulus (G') was lower than the loss modulus (G'') throughout the strain range, indicating that it exhibits significant fluid behavior at room temperature. However, compared to Example 9, G' is closer to G''. Furthermore, compared to fluid-state materials under low cesium conditions (such as Example 8), this embodiment achieves a better balance between structural stability and processing adaptability, providing a good material basis for realizing flexible electronic devices with controllable structures.

[0100] Example 11: Preparation of ultra-high cesium-doped manganese-doped flexible lead halide perovskite material (lead:manganese = 1:1.5, cesium:polyetheramine D400 = 1:12) This embodiment aims to explore the boundary effects of cesium ions on the macroscopic viscoelastic behavior of materials under high doping conditions, with particular focus on the regulatory limits of the transition from polymer-like fluidity to solid-state-like plasticity. To this end, the molar ratio of lead to polyetheramine D400 was further increased to 1:12, which represents the upper limit of the doping range set in this invention.

[0101] The specific operating steps are basically the same as those in the previous embodiments: First, weigh 8.34 mg of lead chloride (PbCl2, 30.0 μmol) and 5.67 mg of manganese chloride (MnCl2, 45.0 μmol) and add them to 1.0 mL of N,N-dimethylformamide (DMF). Stir and dissolve the solution thoroughly at room temperature. Then, add 14.8 μL of hydrochloric acid (HCl, 177.6 μmol) and 80.0 μL of polyetheramine D400 (194.0 μmol) in sequence, and ultrasonically mix them in an ultrasonic cleaner at 40 kHz and 50 W to form a stable polar solvent phase.

[0102] The cesium source was prepared by dissolving 123.00 mg of cesium acetate (CsOAc, 640.8 μmol) in 1.0 mL of oleic acid to form a cesium stock solution. In this embodiment, 25.0 μL of the stock solution (containing approximately 16.0 μmol of cesium ions) was added to a mixed solvent of 15.0 mL of oleic acid and n-octane (volume ratio 1:2) to prepare a high-concentration weakly polar solvent phase.

[0103] The polar solvent phase was rapidly injected into the aforementioned weakly polar solvent, and the reaction was carried out at room temperature (20~30°C) with stirring at 400 rpm for 1 hour. With a significant increase in cesium concentration, the crystal nucleation rate in the system accelerated, the precipitation rate decreased significantly, and the precipitate was viscous and not easy to flow.

[0104] After the reaction was completed, the precipitate was immediately collected by centrifugation at 10,000 rpm for 5 minutes. The supernatant was discarded, and the precipitate was washed three times with n-hexane to finally obtain a perovskite material with a dense appearance and reduced flexibility.

[0105] Through rheological testing (see...) Figure 2 As can be seen, the material exhibits a solid-like state under static conditions, with its storage modulus (G') significantly higher than its loss modulus (G''), indicating a clear elastic-dominated behavior. Compared to Examples 1 and 10, this sample has a larger modulus, indicating a further improvement in its structural integration.

[0106] In summary, Example 11 demonstrates that at an ultra-high doping level of cesium:polyetheramine D400 = 1:12, the material exhibits a trend towards a quasi-solid-state morphology, with reduced viscoelasticity and increased rigidity, making it more suitable for the film formation requirements of static device construction and high-resolution imaging structures. It also establishes the upper limit of cesium doping's influence on material morphology control, providing experimental boundary support for the construction of a switchable elastic-solid-state platform in this invention, and is one of the preferred mixing ratios in this invention.

[0107] Summary of Examples 8-11 and Example 1: Systematic evaluation of the effect of cesium doping ratio on structural morphology and application process window Through Examples 8-11 and Example 1, this invention systematically investigated the effect of adjusting the cesium ion doping ratio on the structural morphology and viscoelastic properties of the obtained flexible lead halide perovskite material under the condition of keeping the manganese doping ratio constant (lead:manganese = 1:1.5), and clarified the phase transition behavior, processing adaptability and potential application process window of the material under different cesium loads.

[0108] Experimental results show that cesium ions mainly play a role in spatial stability and framework support in the system, and their doping concentration has a decisive influence on the transition of the material from a fluid-like state to a solid-like state. In the low cesium ratio range (such as in Example 8, cesium:polyetheramine D400 = 1:119), the material exhibits significant fluid properties, with a storage modulus much lower than the loss modulus. The system has strong injectability and self-leveling ability, making it suitable for high-degree-of-freedom forming processes such as 3D printing. However, the material's structural integrity and elastic recovery ability are relatively weak, and it is prone to microstructural damage due to deformation under external forces.

[0109] At moderate cesium doping ratios (e.g., in Examples 9-10, cesium:polyetheramine D400 = 1:59, 1:29), the storage modulus of the material remained lower than its loss modulus throughout the entire strain range, indicating that it exhibited significant fluid behavior at room temperature. However, compared to Example 8, the storage modulus was closer to the loss modulus. This behavior verifies that the morphology of the material with moderate cesium content gradually transitions from fluid to solid-like, exhibits weak structure retention, is easily affected by external factors, and is suitable for soft-mold molding processes.

[0110] At high cesium doping levels (such as in Example 1, cesium:polyetheramine D400 = 1:15), the material enters a quasi-solid-state platform, with storage modulus exceeding loss modulus. Its rheological behavior is predominantly elastic, and its viscoelastic morphology tends to stabilize. The material exhibits good structural resilience and stress buffering capacity, making it suitable for lamination, 3D printing, and other processing methods. It is particularly suitable for various applications such as flexible X-ray imaging, conformal printed devices, self-supporting scintillators, and wearable radiation detection systems.

[0111] At extremely high cesium ratios (such as in Example 11, cesium:polyetheramine D400 = 1:12), the material transforms into a high-strength, low-flowability state, and its processing flexibility is reduced due to the excessively large modulus.

[0112] Variations in the cesium ion feed amount can easily control the polymer-like viscoelastic properties of the material. Too low or too high cesium content may cause unstable network structure, excessive fluidity, or excessive rigidity, affecting the material's durability and processability.

[0113] In summary, this invention achieves continuous and adjustable material morphology from injectable state to stretchable state to supportable state through systematic control of the cesium doping ratio. It constructs a material application window covering various processes such as flexible molding, thin film processing, and shape customization, providing unified technical support for subsequent implementation of different X-ray response platforms (such as wearable detection, stretchable imaging, and printable devices) based on the same material system, demonstrating extremely high practical value and expansion potential.

[0114] To further illustrate the technical advantages of the manganese-doped flexible lead halide perovskite material provided by this invention in terms of structural design, performance, and application scenarios, the inventors conducted systematic tests on multiple dimensions, including the material's rheological behavior, X-ray response performance, environmental stability, and configuration adaptability, based on typical embodiments. Detailed results can be found in [link to relevant documentation]. Figures 6 to 23 .

[0115] First, in terms of rheological behavior and molding capability assessment ( Figures 6~10 The material of this invention exhibits typical polymer-like viscoelastic properties. For example... Figure 6 As shown, the material exhibits solid-state characteristics with a higher storage modulus than loss modulus within a small strain range. However, under high strain conditions, the storage modulus decreases and falls below the loss modulus, indicating that the material can undergo a transition from a solid to a liquid state. Figure 6 (b) exhibits obvious shear-thinning characteristics. Figure 7 This further verified the material's rapid mechanical response and reversible behavior. Under alternating small and large strains, the modulus value could stably switch, demonstrating good self-healing and reshaping properties. Based on this characteristic, Figure 8 This demonstrates the material's ability to undergo multiple shape reconstructions under manual manipulation, proving its cyclic plasticity. Figure 9 , Figure 10 This demonstrates that the material can achieve large-area thin film pressing and 3D printing at room temperature without high-temperature melting or UV-assisted curing, verifying its excellent low-energy processing adaptability.

[0116] In terms of X-ray response performance evaluation ( Figures 11~18 The material of this invention can not only produce uniform high-intensity luminescence under X-ray excitation ( Figure 11 Moreover, it maintains good radiative luminescence intensity even after undergoing 5000 bending-recovery cycles. Figure 12 It exhibits excellent mechanical stability. Figure 13 The results show that, within the dose rate range of 0.001–1.0 mGry / s, the luminescence intensity of the material exhibits an excellent linear relationship with the dose (R0). 2 >0.999), suitable for precise measurement scenarios. Figure 14 This indicates that after being stored in an air environment for nearly two months, the photoluminescence quantum yield of the material remains at over 99%, demonstrating excellent environmental stability. Figures 15 to 17 The material's performance in actual X-ray imaging was demonstrated, producing images with clear boundaries and a resolution of up to 9.0 line pairs / mm, and it was able to restore its imaging function even after self-healing from fracture. Figure 16 ). Figure 18 The relative light yield of the material can reach 80693 photons / megaelectron volts, exhibiting high X-ray energy conversion efficiency, making it suitable for high-sensitivity scintillation applications.

[0117] In terms of environmental adaptability and durability assessment ( Figure 14 , Figure 16 This material can maintain its optical performance for a long time under natural conditions, and also has the ability to self-heal at room temperature. It can automatically repair the light-emitting channel after minor damage, thereby effectively extending the device life and improving the system reliability.

[0118] In terms of configuration and co-formation imaging adaptability ( Figures 19~23 This material maintains good structure and imaging quality even under strain ranges up to 300%. Figure 19 ), suitable for wearable X-ray systems in dynamic stretching environments. Figure 20 , Figure 21 It demonstrates the material's ability to laminate and image on curved target surfaces, producing clear, complete images with accurate details. Figure 22 , Figure 23 Further extending to complex three-dimensional curved surface configurations, conformal scintillators were constructed using 3D printing, enabling full-angle imaging of hollow porous metal structures and solving the problems of image distortion and uneven brightness that traditional scintillators easily produce on complex geometric surfaces.

[0119] In summary, through the analysis of... Figures 6 to 23 The combined analysis fully demonstrates the significant performance advantages of the manganese-doped flexible lead halide perovskite material proposed in this invention in key dimensions such as flow processing, mechanical tunability, optical response, high stability and three-dimensional configuration capability, providing solid material support and process foundation for its application in multiple fields such as flexible X-ray imaging, wearable radiation monitoring, and 3D printing medical flaw detection.

[0120] In summary, this invention, through the rational design of manganese and cesium doping ratios and polyetheramine template construction strategies, constructs a flexible perovskite material that combines high luminescence performance, mechanical flexibility, and configuration adaptability. It solves key problems in existing technologies such as high material rigidity, difficult molding, poor stability, and low luminescence efficiency, and has extremely high promotional value and application prospects.

[0121] It should be understood that although the specific embodiments described above detail the principles and practices of the present invention, those skilled in the art can make equivalent adjustments or substitutions to the formulation, reaction method, specific concentration, stirring speed, centrifugation conditions, and washing steps without departing from the concept of the present invention. These technical tweaks and extensions should be considered within the scope of protection of the present invention. Therefore, all technical modifications, equivalent substitutions, and combinations that fall within the spirit and substance of the present invention should be covered within the scope defined by the patent claims of the present invention.

Claims

1. A manganese-doped flexible lead halide perovskite material, characterized in that, It consists of an amorphous perovskite network and embedded crystalline perovskite nanoparticles, wherein the average particle size of the crystalline nanoparticles is 4-10 nanometers and they are uniformly dispersed in the amorphous network. The amorphous network incorporates protonated oligomeric diamines as organic cations at the A-site. The material exhibits polymer-like processability and plasticity, and has the performance characteristics of Stokes shift greater than 200 nanometers, photoluminescence quantum yield greater than 50%, and high responsiveness to X-rays.

2. The material according to claim 1, characterized in that, The oligomeric diamine is polyetheramine D400, with the molecular formula H2NCH(CH3)CH2[OCH2CH(CH3)]. 5.6 NH2, the protonated polyetheramine D400 is introduced into the perovskite crystal structure as an A-site cation.

3. The material according to claim 1, characterized in that, The manganese element is introduced into the perovskite lattice in the form of B-site doping, and the molar ratio of lead to manganese is 1:0 to 1:3, which is used to control the optical properties of the material.

4. The material according to claim 1, characterized in that, The material contains cesium, with cesium ions existing as A-site inorganic cations in the perovskite structure. The molar ratio of cesium ions to polyetheramine D400 is 1:12 to 1:118, which is used to regulate the polymer-like viscoelastic properties of the material.

5. A method for in-situ preparation of manganese-doped flexible lead halide perovskite material at room temperature according to any one of claims 1 to 4, characterized in that, Includes the following steps: S1. Dissolve lead source, manganese source, halogen source and oligomeric diamine in a polar solvent to form a polar solvent phase; S2. Dissolve the cesium source in a weakly polar solvent to form a weakly polar solvent phase; S3. At 20~30°C, the polar solvent phase and the weakly polar solvent phase are mixed and reacted under stirring conditions to generate the composite material. S4. The reaction products are centrifuged, washed and dried to obtain the target material.

6. The method according to claim 5, characterized in that, The lead source is lead chloride (PbCl2), the manganese source is manganese chloride (MnCl2), the halogen source is hydrochloric acid (HCl), and the cesium source is cesium acetate (CsOAc) oleic acid solution. The polar solvent is N,N-dimethylformamide (DMF), and the weakly polar solvent is a mixture of oleic acid and n-octane in a volume ratio of 1:

2.

7. The method according to claim 5, characterized in that, The reaction time is 0.5 to 2 hours, the centrifugation speed is 8000 to 10000 rpm, and the duration is 3 to 5 minutes; The washing process uses hexane as the detergent and is repeated three times.

8. The application of the material according to any one of claims 1 to 4 in flexible electronic devices, characterized in that, The material can be processed into flexible structures that adapt to different shaped surfaces through manual shaping, compression molding, or 3D printing, and can be used in the manufacture of wearable imaging devices, flexible detection components, or conformal sensors.

9. The application of the material according to any one of claims 1 to 4 as a flexible X-ray imaging scintillator material, characterized in that, The material, through cold pressing or 3D printing, forms a flexible film that has an imaging resolution of not less than 9.0 line pairs / mm under X-ray irradiation; The film can withstand tensile deformation of more than 300%, and its imaging performance is not significantly dependent on strain.

10. The application according to claim 9, characterized in that, After structural fracture, the film can self-heal by contacting it at room temperature for 5-10 minutes, and its X-ray imaging effect remains basically unchanged after recovery.

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