CN115651019A - Self-recoverable elastic force luminous organic-inorganic hybrid metal halide crystal and synthetic method and application thereof - Google Patents
Self-recoverable elastic force luminous organic-inorganic hybrid metal halide crystal and synthetic method and application thereof Download PDFInfo
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Abstract
The invention relates to an organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force luminescence, a synthetic method and application thereof. 1) Weighing methyl triphenyl phosphine bromide in a container filled with absolute ethyl alcohol to prepare a solution with the concentration of 0.2-0.8mol/L, and fully shaking to dissolve the solution to obtain a clear solution; 2) Weighing manganese bromide, adding the solution obtained in the step 1), adding hydrobromic acid, and ultrasonically stirring at room temperature to dissolve the hydrobromic acid to obtain a clear solution; 3) Standing the clear solution obtained in the step 2) at room temperature to volatilize the solvent, and obtaining a verdure blocky crystal, namely an organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force to cause luminescence. The invention effectively avoids the defects of a pure organic system and an inorganic doped system, has good luminous performance, extremely high mechanoluminescence intensity, self-recovery and reproducible mechanoluminescence characteristics, and meets the requirements of high brightness, repeatability, reproducibility and the like of the novel mechanoluminescence material.
Description
Technical Field
The invention belongs to the technical field of functional hybrid materials, and relates to an organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force luminescence, a synthesis method and application thereof.
Background
In 1605, francis bacon discovered the mechanoluminescence for the first time when sugar crystals were scraped with a knife. The mechanoluminescence is a luminescence phenomenon generated by materials under the action of external mechanical force (such as compression, stretching, scraping, tearing or grinding). Under the action of mechanical force, the material generates strain, and positive and negative charge centers in the piezoelectric material are separated to generate a built-in electric field, so that electronic transition between related energy levels of luminous center ions is induced, and finally, mechanoluminescence is generated. Since mechanical energy is ubiquitous in nature, mechanoluminescence materials can provide a sustainable solution to problems in the fields of biology, optoelectronics, and energy and environmental science. Furthermore, force-induced luminescence remote transmission of light can be realized through non-contact forces of ultrasonic waves and magnetic fields, which enables non-invasive diagnosis and treatment.
In general, there are two main forms of mechanoluminescence, destructive and non-destructive. Destructive force luminescence, which is a response to crystal breakage; non-destructive mechanoluminescence includes triboelectric, tribochemical reaction or frictional heat, tribo-mechanoluminescence caused by plastic deformation and elastic deformation, plastic mechanoluminescence and elastic mechanoluminescence.
According to the statistics of 2014, the mechanoluminescence phenomenon exists in nearly 50% of inorganic salts and organic molecules. However, these photoluminescence are mostly plastic or destructive, irreversible, the photoluminescence intensity is extremely low, the luminescence process is not repeatable, and thus there is no practical application. In recent years, there has been a great interest in the development of electroluminescent materials, which can improve the luminescent properties such as brightness, reproducibility, and spectral tunability. Researchers have discovered several materials that produce mechanoluminescence by elastic deformation. Of these, inorganic doping systems are more common, such as ZnS system, srAl 2 O 4 System and the like [1] By doping various transition metal ions and lanthanide ions, adjustable elastic force luminescence is realized. However, the doping system needs to add rare earth elements, which results in high cost and difficult realization of industrial production. Most of the elastic force luminescent materials formed by the system depend on the supplementary restoring force of external ultraviolet energy to emit light, and the in-situ self-restoring force luminescent cannot be realized.
The mechanoluminescence material is mainly composed of a pure organic system and an inorganic doped system. The mechanoluminescence intensity and quantum yield of a pure organic system are generally extremely low, and the optical performance is poor; while the inorganic doping system needs to be doped with rare earth elements, and the synthesis cost is too high [2、3] 。
Reference documents:
1Chandra,B.P.,Chandra,V.K.&Jha,P.Models for intrinsic and extrinsic fracto-mechanoluminescence of solids.Journal of Luminescence135,139-153,doi:https://doi.org/10.1016/j.jlumin.2012.10.009(2013).
2Chen,B.,Zhang,X.&Wang,F.Expanding the Toolbox of Inorganic Mechanoluminescence Materials.Accounts of Materials Research2,364-373,doi:10.1021/accountsmr.1c00041(2021).
3Xie,Y.&Li,Z.Triboluminescence:Recalling Interest and New Aspects.Chem4,943-971,doi:https://doi.org/10.1016/j.chempr.2018.01.001(2018).
disclosure of Invention
The present invention is aimed at providing a solution to the above-mentioned problems, and provides a self-recoverable elastic force-induced luminescent organic-inorganic hybrid metal halide crystal and its synthesis method. The invention effectively avoids the defects of a pure organic system and an inorganic doped system, selects an organic-inorganic hybrid system, uses methyl triphenyl phosphonium bromide as a raw material to prepare the noncentrosymmetric organic-inorganic hybrid metal halide crystal with mechanoluminescence, has low synthesis cost, environmental protection, good luminescent performance of the material, extremely high mechanoluminescence intensity, self-recovery and reproducible mechanoluminescence characteristics, and meets the requirements of novel mechanoluminescence materials on high brightness, repeatability, reproducibility, environmental protection and the like.
The invention utilizes methyl triphenyl phosphonium bromide ligand as raw material to synthesize self-recoverable organic-inorganic hybrid metal halide crystal with elastic force luminescence property. The reaction does not need to be carried out at high temperature and high pressure, and the requirement on experimental equipment is low. The crystal is grown by a solvent volatilization method, and the method is green and environment-friendly and is simple to operate.
The technical scheme of the invention is as follows:
a self-recoverable, elastic force-luminescent organic-inorganic hybrid metal halide crystal, which is a hybrid metal halide crystal of non-centrosymmetric zero-dimensional (0D) structure, named methyltriphenylphosphine manganese bromide, of the formula [ C 19 H 18 P] 2 Br 4 Mn; the space group is P2 1 The unit cell parameters are:
α＝90°，β＝104.9970(10)°，γ＝90°。
the crystal structure is shown in fig. 2, and the crystal structure data are shown in table 1.
The invention discloses a synthesis method of an organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force to cause luminescence, which is characterized in that methyl triphenyl phosphonium bromide is used as a raw material and is prepared by a room-temperature solvent volatilization method, and the synthesis method specifically comprises the following steps:
1) Weighing methyl triphenyl phosphonium bromide in a container containing absolute ethyl alcohol to prepare a solution with the concentration of 0.2-0.8mol/L, and fully shaking to dissolve the solution to obtain a clear solution;
2) Weighing manganese bromide, adding the manganese bromide into the solution obtained in the step 1), adding hydrobromic acid, and ultrasonically stirring at room temperature to dissolve the hydrobromic acid to obtain a clear solution;
3) And standing the clear solution obtained in the step 2) at room temperature to volatilize the solvent to obtain emerald green blocky crystals, namely the organic-inorganic hybrid metal halide crystals capable of self-recovering and causing the elasticity to emit light.
The methyl triphenyl phosphonium bromide in the step 1) has the following structure;
the amount of the protonated hydrobromic acid added in step 2) is 1.5mL.
And 3) in the standing solvent volatilization process in the synthesis process, sealing the container filled with the solution by using a sealing film, and uniformly pricking a plurality of small holes on the sealing film by using a needle cylinder.
If a 25mL beaker is sealed by a sealing film, a 1mL syringe is used to uniformly prick 15-20 small holes on the sealing film.
The raw material formula preferably selects methyl triphenyl phosphonium bromide with the mass of 0.7144g, manganese bromide with the mass of 0.2148g, absolute ethyl alcohol with the mass of 5mL and hydrobromic acid with the mass of 1.5mL.
Step 3) the humidity of the crystal growth environment is not higher than 30% by volume Rh; the temperature is not higher than 25 ℃.
Preferably, the bulk crystal obtained in step 3) is placed in an oven at 50 ℃ and dried for 6h.
The crystal obtained by the method is bright emerald green block crystal with regular shape, and the size is 5-10mm.
The organic-inorganic hybrid metal halide crystal of the present invention, which can self-restore the elastic photoluminescence, has excellent thermal stability, and the decomposition temperature thereof is 360 ℃ as can be obtained from the thermogravimetric curve of fig. 3.
The self-restorable elastic force luminescent organic-inorganic hybrid metal halide crystal of the invention has super-strong green emission under the excitation of ultraviolet light, and the quantum yield under the excitation of the ultraviolet light of 363nm is 92.53 percent, as shown in figure 4 (a).
The self-restorable elastic force luminescent organic-inorganic hybrid metal halide crystal of the present invention has self-restorable elastic force luminescent properties, and has strong green emission when stimulated by external force, as shown in fig. 4 (b).
The elastic force luminous performance of the self-recoverable elastic force luminous organic-inorganic hybrid metal halide crystal has the characteristic of self-recovering. After hundreds of external stimuli, the mechanoluminescence is attenuated, and the fatigue resistance is excellent, as shown in fig. 7. After standing for 2-10 minutes in the dark, the mechanoluminescence properties of the compound were recovered as shown in FIG. 8.
The elastic force luminous performance of the self-recoverable elastic force luminous organic-inorganic hybrid metal halide crystal has the reproducible characteristic. After being stimulated by destructive external force, the crystal structure is destroyed, the crystal structure is cooled after being subjected to heat treatment at 180 ℃, and a sample obtained by recrystallization has the same strong green light emission as the initial state of the crystal and can be circulated for many times, as shown in figure 9.
The non-centrosymmetric organic-inorganic hybrid metal halide crystal shows strong elastic force luminescence property, and the force luminescence property of the crystal can be recovered and regenerated, so that the crystal can be applied to the fields of photoelectric devices, microcrack exploration, wind power monitoring, electronic signatures, anti-counterfeiting, sensing and the like.
As shown in FIG. 10 (a), which shows the promising application prospect of the crystal in the wind power monitoring and sensing field, a small-sized (3-5 mm) single crystal is placed in a glass bottle, and nitrogen (N) with 0.5MPa of pressure is blown in by a gas blow gun 2 ). The elastic force luminescence is excited when gas is blown through the crystal, and also shows fragmentation force luminescence when the crystal is blown up by the gas flow and hits the bottle wall. Furthermore, these samples exhibited extremely sensitive mechanoluminescence properties even in polycrystalline thin films. Fig. 10 (b) shows the promising application prospect of the crystal in the fields of electronic signatures, sensing, microcrack exploration and photoelectric devices, and when a polycrystalline thin film obtained by melt cooling is scribed or stamped by a pen, bright green light can be emitted. The single crystal can generate a mechanoluminescence signal when being squeezed, pressed, bent by fingers and bent by wrists, as shown in fig. 10 (c), which shows that the crystal is expected to be applied to the application prospect of the sensing field. When finger bending and wrist bending force photoluminescence tests are carried out, for convenience of operation and prevention of crystal fracture, the single crystal is sealed by using photosensitive glue.
The invention relates to a performance characterization device of an elastic force luminous organic-inorganic hybrid metal halide crystal capable of self-recovering, which is used for characterizing the force luminous performance of the crystal by applying a falling ball method. A large number of experiments verify that the material of the falling ball, the quality of the falling ball and the height of the falling ball which can excite the elastic force to emit light when the crystal structure is not damaged are determined. The experiment finally used a wood ball of diameter 18mm, mass 1.8-2.2g, dropped 25cm above the crystal. An acrylic box with good light transmission and high mechanical strength is selected as an operation table for the experiment. In order to ensure that the mechanoluminescence of the crystal is elastic mechanoluminescence (nondestructive mechanoluminescence), a transparent nano adhesive tape is selected to wrap the crystal in an experiment, so that the crystal cannot be broken in the implementation process of a ball dropping method. The crystal wrapped by the transparent nano adhesive tape is placed on an acrylic box, a wooden ball selected for experiments is released from a 25cm glass tube opening, the crystal generates elastic force to emit light after being stimulated by force, a photomultiplier photosensitive probe placed below the crystal receives signals, the signals are transmitted to an oscilloscope through the photomultiplier, the optical signals are converted into electric signals, and the electric signals are displayed on the oscilloscope, and the specific device is shown in figure 11.
Compared with the prior art, the method adopts a solvent volatilization method, has simple operation process, low cost, pure target product and little environmental pollution, and is suitable for popularization and application. The synthesized organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force luminescence has high thermal stability, and shows strong photoluminescence and force luminescence, and the force luminescence has the characteristics of self-recovering and reproducibility.
Drawings
FIG. 1 is an XRD pattern of a synthesized self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 2 is a structural diagram of a synthesized self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 3 is a thermogram of a synthesized self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 4 is a phosphorescence and photoluminescence spectrum of a self-recoverable elastic mechanoluminescence-organic-inorganic hybrid metal halide crystal synthesized in accordance with the present invention;
FIG. 5 is a graph of the phosphorescence lifetime of a synthesized self-recoverable, elastic force-luminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 6 is a graph of the process of mechanoluminescence of a synthesized self-recoverable elastic mechanoluminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 7 is a plot of the mechanoluminescence fatigue for a self-recoverable elastic mechanoluminescent organic-inorganic hybrid metal halide crystal synthesized in accordance with the present invention;
FIG. 8 is a graph of the self-recovery of the mechanoluminescence of a synthesized self-recoverable elastomeric mechanoluminescent organic-inorganic hybrid metal halide crystal of the present invention;
FIG. 9 is a thermally processed reproducible plot of a synthesized self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal of the present invention.
FIG. 10 is a graph showing the performance of the synthesized self-recoverable elasto-luminescent hybrid organic-inorganic metal halide crystals of the present invention.
FIG. 11 is a diagram of a self-made mechanoluminescence test device for a self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal synthesized in accordance with the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail by the following embodiments, and the described embodiments are only for the purpose of facilitating better understanding of the present invention and are not to be considered as specific limitations of the present invention. The methods mentioned in the following examples are, unless otherwise specified, considered to be conventional in the art.
Example 1
Preparation of self-recoverable elastic force luminescent organic-inorganic hybrid metal halide crystals:
1) Weighing 2mmol (0.7144 g) of methyl triphenyl phosphine bromide in a 25mL beaker, taking 5mL of absolute ethyl alcohol by using a liquid transfer gun, and adding the absolute ethyl alcohol into the beaker to completely dissolve the absolute ethyl alcohol;
2) Adding 1mmol (0.2148 g) of manganese bromide, adding 1.5mL of hydrobromic acid by using a 1mL of liquid-transferring gun in two times, wherein the molar ratio of methyl triphenyl phosphonium bromide to manganese bromide is 2, and ultrasonically stirring at room temperature to dissolve the mixture;
3) After the solution in the beaker is clear and transparent, sealing the opening of the beaker by using a sealing film, and uniformly pricking 15-20 small holes on the sealing film by using a 1mL needle cylinder; standing at room temperature for volatilizing the solvent to obtain emerald green bulk crystals after 3-4 days, wherein the humidity of crystal growth environment is not higher than 30%;
4) Taking out the crystal from the mother solution by using a spoon, sucking the mother solution on the surface of the crystal by using filter paper, and drying in a drying oven at 50 ℃ for 6 hours to obtain a target product, namely the organic-inorganic hybrid metal halide crystal which can self-recover and cause the luminescence by elastic force.
Example 2
The self-restorable elasto-luminescent hybrid metal halide crystal prepared in example 1 was characterized by XRD powder diffraction with a maximum voltage of 40KV. The instrument switch is turned on, and then MiniFlex guide software is turned on for aging. And placing the ground powder sample on a clean silicon wafer, paving and compacting the ground powder sample, pressing a 'Door Lock' button, opening a bin Door after two sounds are sounded, placing the silicon wafer with the sample, and pressing the 'Door Lock' button after the bin Door is closed. Setting test conditions, wherein the sweeping speed is 2deg/min, and the 2 theta is 3-50 degrees. The data obtained were refined with topas. The results are shown in fig. 1, where Obs = true, calc = calculated, diff = difference between true and calculated. As is apparent from fig. 1, the XRD pattern of the crystal is almost identical to the result of fitting the theoretically calculated value, indicating that the obtained crystal is high in purity. The structure of the self-recoverable elastic force-luminescent organic-inorganic hybrid metal halide crystal of example 1 is shown in fig. 2, and the crystal structure data is shown in table 1.
TABLE 1.C 38 H 36 Br 4 MnP 2 P2 of 1 Phase crystal structure data and test parameters
a) R 1 ＝∑||F o |-|F c ||/∑|F o |； b) wR 2 ＝{∑[w(F o 2 -F c 2 ) 2 ]/∑[w(F o 2 ) 2 ]} 1/2
Example 3
The heat stability of the self-restorable elastoluminescent organic-inorganic hybrid metal halide crystals prepared above was tested using a thermogravimetric analyzer. The scanning is carried out in the air atmosphere, the scanning range is 24.98-800.00 ℃, and the scanning speed is 10 ℃/min. The result of weighing 6.15mg of the sample is shown in FIG. 3, from which it is apparent that the organic-inorganic hybrid metal halide crystal has excellent thermal stability and a decomposition temperature of 360 ℃.
Example 4
The crystals were subjected to a spectrum test using Horiba LabRAM HR Evolution spectrometer (Horiba jobyvon s.a.s., france) with an excitation wavelength of 325nm and emitted 520nm green light with high intensity, and the spectrum is shown in fig. 4 (a). The crystal was subjected to a spectrum test of forced luminescence using a marine spectrometer, crushed with a glass slide, and detected by a spectrometer with a strong emission of 519nm green light, the spectrum being shown in fig. 4 (b). The organic-inorganic hybrid metal halide crystal which can self-restore elastic force to give luminescence and is prepared by the method of testing the phosphorescence lifetime and the quantum yield by using an Edinburgh FLS980 spectrometer, wherein the excitation wavelength is 363nm, the phosphorescence lifetime is 315.64 mu m, and the quantum yield is 92.53 percent, as shown in figure 5.
Example 5
The instantaneous change of the process of the mechanoluminescence is explored by using a marine optical spectrometer, 200 groups of spectral data are captured in 1 minute by setting instrument parameters to obtain the spectral change of the process of the mechanoluminescence, and the change of crystal luminescence in the process of the mechanoluminescence is captured by using the continuous shooting function of a camera, as shown in fig. 6.
Example 6
The crystal is subjected to the fatigue test characterization of the mechanoluminescence by using the falling ball method, and the mechanoluminescence of the crystal is attenuated only after continuous hundreds of times of force stimulation, so that the mechanoluminescence of the crystal has good fatigue resistance, and the result is shown in figure 7. The crystal is characterized by a self-recovery experiment after fatigue of mechanoluminescence by using a falling ball method, after hundreds of continuous times of force stimulation, the mechanoluminescence of the crystal is attenuated, after standing for 2 minutes in a dark place, the crystal is subjected to force stimulation by using the falling ball method again to obtain a mechanoluminescence optical signal after the crystal self-recovery, and the result is shown in figure 8, and the experiment of the part is repeated for 6 times, which shows that the crystal obtained by the invention has self-recovery mechanoluminescence performance.
Example 7
The crystal is subjected to fragmental force action by utilizing a falling sphere method to enable the crystal to emit light, the crystal structure is damaged after the crystal is stimulated by destructive external force, the crystal is cooled after heat treatment at 180 ℃, and a sample obtained by recrystallization still has strong mechanoluminescence signals, the part of experiments are repeated for four times, so that the crystal obtained by the invention has reproducible mechanoluminescence characteristics after heat treatment, and the experimental result is shown in figure 9.
Example 8
Placing small-sized (3-5 mm) single crystal into a glass bottle, and blowing nitrogen (N) with pressure of 0.5MPa with an air blow gun 2 ). The elastic force luminescence is excited when gas is blown through the crystal, and also shows fragmentation force luminescence when the crystal is blown up by the gas flow and hits the bottle wall. Furthermore, these samples exhibited extremely sensitive mechanoluminescence properties even in polycrystalline thin films. When a polycrystalline thin film obtained by melt cooling is stamped with steel strokes, a bright green light can be emitted. Single crystals also produce mechanoluminescence signals when squeezed, pressed, bent by fingers, and bent by wrists. When the finger bending and wrist bending force photoluminescence test is carried out, in order to facilitate the operation and prevent the crystal from breaking, the photosensitive glue is adopted to seal the single crystal. As can be seen from figure 10, the material has excellent practical application prospect and is expected to be used in the fields of wind power monitoring, micro-crack monitoring, photoelectric display, sensing and the like.
Example 9
The mechanoluminescence test device according to the ball drop method is shown in FIG. 11. A wood ball with a diameter of 18mm and a mass of 2g was chosen for the experiment and dropped 25cm above the crystal. An acrylic box with good light transmission and high mechanical strength is selected as an operation table. In order to ensure that the mechanoluminescence of the crystal is elastic mechanoluminescence (nondestructive mechanoluminescence), a transparent nano adhesive tape is selected to wrap the crystal in an experiment, so that the crystal cannot be broken in the implementation process of a ball dropping method. The crystal wrapped by the transparent nano adhesive tape is placed on an acrylic box, a wood ball selected for experiments is released from a 25cm glass tube opening, the crystal generates elastic force to emit light after being stimulated by force, a photomultiplier photosensitive probe placed below the crystal receives signals, the signals are transmitted to an oscilloscope through a photomultiplier, the optical signals are converted into electric signals to be displayed on the oscilloscope, and test results show that the crystal has strong luminous performance (figure 6), and fatigue resistance, restorability and reproducibility tests show that the crystal also has excellent fatigue resistance (figure 7), self-restorability (figure 8) and reproducibility (figure 9) and elastic force to emit light.
The applicant states that the present invention further illustrates the preparation method, performance, application scenario and apparatus of the self-recoverable organic-inorganic hybrid metal halide crystal with elastic force photoluminescence by using the above examples, but not limited to the specific process steps, and other persons skilled in the art will be able to make any improvement of the present invention by adding or replacing the above means within the protection scope of the present invention.
Claims (10)
1. A self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystal, wherein the organic-inorganic hybrid metal halide crystal is a non-centrosymmetric zero-dimensional hybrid metal halide crystal, namely methyltriphenylphosphine manganese bromide, of the formula [ C 19 H 18 P] 2 Br 4 Mn; the space group is P2 1 The unit cell parameters are:
α =90 °, β =104.9970 (10) °, γ =90 °; differential scanning calorimetry tests show that the crystal has no phase change in the temperature range of-20 ℃ to 250 ℃.
2. A method of synthesizing self-recoverable, elastic force-luminescent organic-inorganic hybrid metal halide crystals according to claim 1, comprising the steps of:
1) Weighing methyl triphenyl phosphonium bromide in a container containing absolute ethyl alcohol to prepare a solution with the concentration of 0.2-0.8mol/L, and fully shaking to dissolve the solution to obtain a clear solution;
2) Weighing manganese bromide, adding the manganese bromide into the solution obtained in the step 1), adding hydrobromic acid, and ultrasonically stirring at room temperature to dissolve the hydrobromic acid to obtain a clear solution;
3) And standing the clear solution obtained in the step 2 at room temperature to volatilize the solvent to obtain a emerald green blocky crystal, namely the organic-inorganic hybrid metal halide crystal capable of self-recovering elastic force to cause luminescence.
3. The method for synthesizing self-recoverable, elasto-luminescent hybrid metal halide crystals as claimed in claim 2, wherein hydrobromic acid is added in an amount of 1.5mL in step 2).
4. The method for synthesizing a self-recoverable, elastic, luminescent organic-inorganic hybrid metal halide crystal according to claim 2, wherein the container containing the solution is sealed with a sealing film and a plurality of small holes are uniformly formed in the sealing film by a syringe during the evaporation of the solvent by standing in the synthesis process of step 3).
5. The method for synthesizing self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystals as claimed in claim 4, wherein a 25mL beaker is sealed with a sealing film, and 15-20 small holes are uniformly punched in the sealing film using a 1mL syringe.
6. The method for synthesizing self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystals as claimed in claim 2, wherein the mass of methyltriphenylphosphine bromide is 0.7144g, the mass of manganese bromide is 0.2148g, the volume of absolute ethanol is 5mL, and the volume of hydrobromic acid is 1.5mL.
7. A method of synthesizing self-recoverable, elastic force-luminescent organic-inorganic hybrid metal halide crystals as claimed in claim 2, wherein the humidity of the crystal growth environment in step 3) is not more than 30% rh; the temperature is not higher than 25 ℃.
8. A method for synthesizing self-recoverable, elastic force-photoluminescent organic-inorganic hybrid metal halide crystals as defined in claim 2 wherein the bulk crystals obtained in step 3) are dried in an oven at 50 ℃ for 6 hours.
9. A method of synthesizing self-recoverable elasto-luminescent organic-inorganic hybrid metal halide crystals as claimed in claim 2, wherein the crystals obtained are bright emerald green regularly shaped bulk crystals of size 5-10mm.
10. Use of a self-recoverable, elastic force-luminescent organic-inorganic hybrid metal halide crystal according to claim 1, characterized in that the organic-inorganic hybrid metal halide crystal exhibits strong elastic force-luminescent properties and the force-luminescent properties of the crystal are self-recoverable, reproducible and useful in the fields of opto-electronics, micro-crack exploration, wind monitoring, electronic signatures, anti-counterfeiting and sensing.
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| CN114656364A (en) * | 2022-03-09 | 2022-06-24 | 北京科技大学 | Mn-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof |
| CN115043881A (en) * | 2022-07-04 | 2022-09-13 | 中国科学院兰州化学物理研究所 | Metal ion complex fluorescent probe, preparation thereof and application thereof in detection of chloroform gas molecules |
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| CN114656364A (en) * | 2022-03-09 | 2022-06-24 | 北京科技大学 | Mn-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof |
| CN115043881A (en) * | 2022-07-04 | 2022-09-13 | 中国科学院兰州化学物理研究所 | Metal ion complex fluorescent probe, preparation thereof and application thereof in detection of chloroform gas molecules |
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