CN114934310B - RbCu 2 Br 3 Synthesis and use of single crystals - Google Patents
RbCu 2 Br 3 Synthesis and use of single crystals Download PDFInfo
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Abstract
The invention relates to the technical field of crystal chemistry, in particular to RbCu 2 Br 3 The synthesis and application of single crystals comprises the following steps: s1, mixing and dissolving RbBr and CuBr in a molar ratio of 1:2 into HBr acid and deionized water with a volume ratio of 1-3:1; the concentration of RbBr formed is 0.5-2 mmol/mL; s2, adding hypophosphorous acid into the mixed solution in the step S1, and preserving heat for 1-3 hours at the temperature of 95-105 ℃; s3, cooling the mixed solution obtained in the step S2 to room temperature at a cooling rate of 0.5-3 ℃/h, and crystallizing; s4, drying the crystal formed in the step S3 to obtain the crystal. The invention changes photoluminescence from blue light to orange light along with temperature decrease, and the detector has stable performance under the long-time large-dose irradiation and high electric field intensity work. Thus, rbCu 2 Br 3 The material is used as a scintillator field, a photoelectric detector field and an X-ray detection field.
Description
Technical Field
The invention relates to the technical field of crystal chemistry, in particular to RbCu 2 Br 3 Synthesis and use of single crystals.
Technical Field
In recent years, metal halide perovskite (ABX 3 And (A) the following steps: small treatments, B: metal treatments, x=cl, br, I) due to their outstanding optoelectronic properties, such as high absorption efficiency over a broad spectral range, high defect tolerance, tunable light-emitting band gap and high PLQY, low cost and simple synthesis method. Make it be equipped in the fields of photoelectric detector, light-emitting diode and ionization radiation detectionAttention is paid. Of these, lead-containing organic and inorganic halides are distinguished, e.g. CsPbX 3 、MAPbX 3 、PEAPbX 3 、FAPbX 3 (MA＝CH 3 NH 3 + ， PEA＝C 6 H 5 CH 2 CH 2 NH 3 + ，FA＝NH 2 CH＝NH 2 + ) Has become one of the most promising classes of photovoltaic materials. However, environmental problems associated with lead toxicity are not appreciated in commercial applications. Therefore, sn is used as 2+ 、Bi 3+ 、 Sb 3+ 、Ge 2+ Researches on substitution of B cations have been endlessly carried out. However, divalent Sn 2+ Oxidation to Sn 4+ Is a spontaneous process that results in crystal autodoping and thus degrading device performance. Perovskite materials containing Bi and Sb are limited in the ultraviolet or deep ultraviolet region in the photodetection band due to the excessively narrow band gap. Thus, there is a need to seek environmentally friendly, resource-rich and inexpensive metal halide perovskite materials to remedy the above disadvantages.
Copper-based halide perovskite derivative A l Cu m X n (a=rb and Cs; x=cl, br, and I) in the near three years of brand new angle of head. Due to the abundant Cu valence and the characteristics of the perovskite material, namely the multi-dimension and multi-morphology, the perovskite material has a changeable crystal structure and abundant chemical and physical properties. For example, hosono et al report a zero-dimensional electronic structure Cs that is air stable, visible blue light emitting and high PLQY (90%) 3 Cu 2 I 5 Single crystal, lin et al successfully prepared a yellow light emitting one-dimensional electronic structure CsCu 2 I 3 And (3) single crystals. Niu et al propose Rb for one-dimensional electronic structure with near-unity photoluminescence quantum yield (98.6%) 2 CuBr 3 And (3) single crystals. Thereafter, research on various structural forms such as single crystals/nanocrystals/nanowires/nanoplatelets, films, etc. of these materials and applications in various fields has been rapidly progressed. Computational studies according to the first principles of Yin et al with respect to copper-based halides have shown that there are a large number of potential phase-stable materials that have not been reported.
Disclosure of Invention
The present invention aims to overcome the problems in the prior art and provide RbCu 2 Br 3 The synthesis and application of single crystals.
The aim of the invention is realized by the following technical scheme:
RbCu 2 Br 3 The method for synthesizing the monocrystal comprises the following steps:
s1, mixing and dissolving RbBr and CuBr in a molar ratio of 1:2 into HBr acid and deionized water with a volume ratio of 1-3:1; the concentration of RbBr formed is 0.5-2 mmol/mL;
s2, adding hypophosphorous acid into the mixed solution in the step S1, and preserving heat for 1-3 hours at the temperature of 95-105 ℃;
s3, cooling the mixed solution obtained in the step S2 to room temperature at a cooling rate of 0.5-3 ℃/h, and crystallizing;
s4, drying the crystal formed in the step S3 to obtain the crystal.
Preferably, in the step S1, the volume ratio of HBr acid to deionized water is 2:1; the concentration of RbBr formed was 1mmol/mL.
Preferably, in the step S2, the temperature is maintained at 100 ℃ for 2 hours.
Preferably, in the step S3, the temperature is reduced to room temperature at a temperature reduction rate of 1 ℃/h.
The RbCu 2 Br 3 RbCu prepared by single crystal synthesis method 2 Br 3 A single crystal.
The RbCu 2 Br 3 The single crystal is an orthorhombic crystal, wherein, the point group:space group: the Cmcm of the material is equal to the total length of the material,α＝β＝γ＝90°,/>
the RbCu 2 Br 3 Single crystal the single crystal is an orthorhombic crystal when at 145K temperature, wherein the group of points:space group: pnma, ->α＝β＝γ＝90°,
Preferably, the single crystal changes phase along with temperature change, and the phase change temperature point is 145K; the monocrystal photoluminescence, with temperature decrease, is transferred from blue light to orange light
The RbCu 2 Br 3 The single crystal is applied to the preparation of photoelectric detectors, light emitting diodes and ionization radiation detection.
The RbCu 2 Br 3 The single crystal is applied to preparing scintillator materials and X-ray detectors.
Compared with the prior art, the invention has the following technical effects:
RbCu of the invention 2 Br 3 Synthesis and application of monocrystal, rbCu with large-size, high-quality and non-rigid one-dimensional electronic structure 2 Br 3 The material is obtained from RbBr and CuBr directly by a liquid phase method. In the temperature-variable photoluminescence study, rbCu 2 Br 3 The single crystal macroscopically exhibits a transition from blue light emission to orange light. And below 145K, both under laser and X-ray radiation, exhibit radiative recombination of excitons (free excitons and self-trapping excitons). This particular optical property is due to the fact that the crystal shows a phase change (transition of the space group from Cmcm to Pnma) with a decrease in temperature, caused by a local symmetry break. In addition, the strong X-ray absorption coefficient makes it also perform well in direct X-ray detection. The working pair RbCu 2 Br 3 The basic physical properties of single crystals are systematically researched, and a good foundation is laid for the potential application research of copper-based halides.
Drawings
FIG. 1 is RbCu 2 Br 3 Single crystal and photoluminescence experimental phenomenon displayAnd (5) physical property characterization. (a) RbCu 2 Br 3 Single crystal size photomicrographs, inset is a plot of a number of samples. (b) RbCu 2 Br 3 Crystal ultraviolet-visible absorption spectrum. (c) PLE and excitation light at 390nm were PL spectra at 292nm band for the sample at room temperature. (d) RbCu under 292nm pulse laser test 2 Br 3 Time resolved PL decay spectra of the crystals. (e) And (f) luminescent material object diagrams of the samples at 8K and 295K, respectively. (g) And (h) photoluminescence spectra of the sample at 8K and 295K, excitation light at 266nm. (i) RbCu 2 Br 3 A single crystal rocking curve tested at the crystal (440) plane;
FIG. 2 is RbCu 2 Br 3 A crystal structure before and after single crystal phase transformation. (a) Is RbCu 2 Br 3 Polyhedral grid (polyhedral) structure perspective view at room temperature of single crystal, purple and green semitransparent grids respectively correspond to [ RbBr ] 8 ]Ten-sided body and [ CuBr 4 ]Tetrahedra. The purple rectangular frame is the coordination relation between Rb atoms and Cu atoms and Br atoms, and the bond length. (b) single crystal XRD diffraction patterns at room temperature and at low temperature. Below the spectrum is the unit cell structure of the crystalline Pnma and Cmcm phases. (c) For the corresponding RbCu 2 Br 3 Perspective structure, coordination relation and bond length of single crystal low temperature Pnma phase crystal;
FIG. 3 is RbCu 2 Br 3 Single crystal temperature dependent luminescence mechanism studies. (a) RbCu 2 Br 3 Single crystal temperature dependent PL spectrum pseudocolor map. (b) STE (STE) (B) And STE (STE) (O) And (5) a graph of the integral intensity of the luminescence peak and the laser power. (c) The upper graph is Cmcm phase RbCu 2 Br 3 Luminescence mechanism at Room Temperature (RT) of single crystal. FC is in a free carrier state, FE is in a free exciton state, STE (B) Is the self-trapping exciton state of blue light, and TQ is thermal quenching. (c) Changes in luminescence mechanism caused by generation of a Pnma phase in the middle, STE (O) The self-trapping exciton state is orange light, and the ISC is an intersystem crossing conversion channel. (c) The lower part is STE in the range of 95-295K of the luminescence mechanisms (d) and (e) when Pnma phase occupies the main component after the temperature continuously decreases (B) Extraction and fitting of luminous intensity and half-width experimental data points. (f) Phase transition process occurring with temperature decrease of crystal, cmcm phase and PChange in Rb-Br coordination in nma phase;
FIG. 4 is RbCu 2 Br 3 Single crystal X-ray irradiance characterization. (a) RbCu 2 Br 3 RL pseudocolor map of single crystal as a function of temperature. (b) RbCu at 8K 2 Br 3 Single crystal RL spectrum, inset 145K RL spectrum. (c) STE (STE) (O) And (3) a relation graph of the integral intensity of the luminescence peak along with the change of temperature, wherein the curve is a fitting curve of formula (1). (d) STE at 8K (O) And FE (UV) The luminous intensity varies with the X-ray dose. (e) And (f) is RbCu 2 Br 3 An X-ray radiation luminescence mechanism of single crystal along with temperature change;
FIG. 5 is RbCu 2 Br 3 The crystal is applied to the research of X-ray direct detection. (a) RbCu 2 Br 3 Crystals and commonly known scintillators absorb coefficients and photon energy spectra. (b) RbCu prepared by the work 2 Br 3 Single crystal vertical device (Au/RbCu) 2 Br 3 The illustration is a physical diagram. (c) I-V curve of the device under X-ray on/off. (d) device I-V curves at different X-ray doses. (e) The devices under different X-ray doses and electric fields photo-generate current responses. (f) device sensitivity under different applied electric fields. (g) 9.74 mu Gy air I-T curves at different applied fields at/s radiation dose. h) And i) device switching time obtained by extracting the rising edge and the falling edge of the single ray response;
FIG. 6 is RbCu 2 Br 3 Single crystal XRD diffractograms of the crystals (upper), powder X-ray diffractograms (middle), bulk XRD patterns (lower);
FIG. 7 is RbCu 2 Br 3 HREM (a) and SAED (b) characterization plots of crystals;
FIG. 8 is RbCu 2 Br 3 A nuclear energy spectrum amplified in a small energy range of single crystal XPS full spectrum (a), cu element (b), rb (c) and Br (d);
FIG. 9 is RbCu 2 Br 3 And (3) calculating an energy band structure (a) and a state density diagram (b) according to the first principle of the crystal. A contour plot of the real space charge distribution of the crystal conduction band bottom (c) and the valence band top (d);
FIG. 10 is RbCu 2 Br 3 (Single Crystal)Phase change structure (Pnma) theory. (a) And (b) energy band and state density diagrams obtained by DFT calculation respectively;
FIG. 11 is RbCu 2 Br 3 A single crystal phase transition versus temperature diagram; wherein (a) RbCu 2 Br 3 STE within the single crystal full temperature range (8-295K) (B) And STE (STE) (O) And extracting the data of the integral intensity of the luminescence peak along with the temperature change. STE with temperature change (B) (b) And STE (STE) (O) (c) Two photoluminescence intensity fits, wherein the middle point of the figure is an experimental data point, and the solid line and the dotted line are fitting curves of formulas (1) and (3) respectively;
FIG. 12 is RbCu 2 Br 3 The single crystal vertical device is related to the photoconductivity along with bias under the excitation of X rays, points are experimental data points, and a curve is a fitting curve of a Hecht equation;
FIG. 13 is 20V mm -1 RbCu collected under electric field 2 Br 3 I-T curves of the detector at different X-ray doses are calculated and their corresponding SNR is calculated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail with reference to specific examples and comparative examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Except for the special description, the equipment used in the embodiment is conventional experimental equipment, and the materials and reagents used are all obtained in the market unless the special description is made, and the experimental method without the special description is also conventional experimental method.
Example 1
Materials: rubidium bromide (99.8%) was purchased from Alfa Aesar. Cuprous bromide (99.99%), hydrobromic acid (48 wt.%) were purchased from microphone (Macklin), and hypophosphorous acid (50 wt.%) was purchased from aladin. All chemicals were not further purified.
And (3) crystal synthesis: 0.992g of RbBr (6 mmol) and 1.721g CuBr (12 mmol) were dissolved in 4mL HBr acid and 2mL deionized water, and a further 120. Mu.L of 50wt.% hypophosphorous acid was added to prevent Cu + Is a metal oxide semiconductor device. The precursor was dissolved at 100℃for 2 hours. Then the mixture is placed in a muffle furnace and cooled to room temperature from 1 ℃ per hour, and the bulk single crystal is crystallized at the bottom of the bottle. The crystals were dried under vacuum at 60 ℃.
Experimental example
Single crystal XRD was characterized using Rigaku XtalAB PRO MM007 DW. X-ray diffraction was obtained from malvern panaceae PANalytical Empyrean3 DY02394 ID209080 spectrometer testing. The single crystal rocking curve is provided by the Wavetest D8 Discover instrument. SEM and EDS are characterized by the AURIGA focused ion beam etching system. The HREM image of the sample was taken by JEOL JEM 2100F transmission electron microscopy. XPS was obtained from Thermo Scientific K-alpha+ instrument tests. The absorption spectrum was measured by a Shimadzu UV-3600-Plus ultraviolet-visible-near infrared spectrophotometer. PL, PLE and TRPL were each characterized by an Ediburgh FLS1000 transient fluorescence spectrometer. The variable temperature PL and RL excitation sources are a 266nm laser and a Moxtek TUB 00140-W06X-ray source respectively, the temperature control (8-295K) is controlled by a Montana C2 CRYOSTATION low-temperature optical thermostat, and the spectra are collected by a marine spectrometer (QE 65 Pro). The X-ray detector photocurrent characterization was obtained from 4200A-SCS source list (Keithley) and Clarius software testing.
And (3) calculating: the first principle calculation is carried out in VASP software by adopting a density functional theory, perdew Burke Ernzerhof (PBE) is pseudo potential, and the fixed cutoff energy is 500eV. Total error of 10 -6 eV, ion relaxation motion limitation toAnd adopting a 3 multiplied by 6 k point grid sample at Gamma points and respectively carrying out structural optimization and self-consistent calculation. The charge density calculations for VBM and CBM were performed on bands 104 and 105 in the band calculation, with the K-point extending to 8X 8.
RbCu of example 1 2 Br 3 The single crystal sample is in a colorless transparent rod shape, and a single crystal with the size of 20mm can be grown by 6mmol of solute, as shown in the optical photograph of FIG. 1 a. Studies were conducted from the luminescence characteristics of the materials. FIG. 1b is an ultraviolet-visible light absorption spectrum of the crystal, 330nmThere is a distinct exciton absorption peak from side to side. Excitons, direct band edge energy states, band tails all contribute to the photoelectric properties of the absorption edge, and the absorption cut-off edge of the single crystal is about 350 nm. The PLE and PL spectra at room temperature showed two peaks in excitation efficiency at about 270nm and 290nm (FIG. 1 c). RbCu under 292nm wave band deuterium lamp excitation 2 Br 3 The crystal showed a broad spectrum of blue light emission at 390 nm. The luminescence peak has a stokes shift of 40nm, which is consistent with the ubiquitous self-trapping exciton radiative recombination of copper-based halide perovskite. The time resolved PL decay spectrum of blue luminescence at room temperature (shown in figure 1 d) of the sample was tested using a 292nm pulsed laser, and the decay lifetime of 56.57 mus was obtained by single exponential fitting, such long decay time indicating that luminescence at this point was not free exciton radiative recombination. However, the PL spectrum of this material shows, with temperature change, a luminescence phenomenon which is not exactly the same as that at room temperature. RbCu was measured using 266nm laser at low temperature (8K) and room temperature (295K), respectively 2 Br 3 The single crystal luminescence spectrum was tested as shown in fig. 1e, f. The sample macroscopically showed a glaring orange luminescence at low temperature, and the PL spectrum showed a plurality of luminescence peaks (FIG. 1 g), rbCu at room temperature 2 Br 3 The crystal emits blue light and the PL spectrum is shown in figure 1 h.
For RbCu 2 Br 3 Is developed. RbCu by single crystal X-ray diffraction (SCXRD) 2 Br 3 The sample was subjected to structural analysis, and the material was of orthorhombic (dot group:space group: the Cmcm of the material is equal to the total length of the material,α＝β＝γ＝90°,/>) The schematic crystal structure is shown in fig. 2 a. Rb atoms are coordinated with 8 Br atoms to form an 11-face body, and the Rb-Br bond length is within +.>Cu atoms are coordinated with 4 Br atoms to form tetrahedra, and the bond length of Cu-Br is in the range +.>Rb and Cu atoms are along [001 ]]The directions are arranged in a one-dimensional banded structure, tetrahedrons and 11-face bodies are stacked to form an octagonal hollow channel, and specific crystal structure information is shown in tables 1-4.
TABLE 1 RbCu 2 Br 3 Crystal data and structure refinement of (a).
TABLE 2 RbCu 2 Br 3 Fractional atomic coordinates (x 10) 4 ) And equivalent isotropic displacement parameterU (eq) Is defined as orthogonalization U ij One third of the tensor trajectory.
TABLE 3 RbCu 2 Br 3 Selected bond length of (2)And angle [ deg ]]。
Symmetric transformations for generating equivalent atoms:
#1-x,1-y,1-z；2#-x,1-y,2-z；3#+x,+y,3/2-z；4#-x,1-y,-1/2+z；7#-x,+y,3/2-z；8#1/2-x,3/2-y,1-z；9#1/2-x,3/2-y,2-z；10#-1/2+x,3/2-y,1/2+z；11#-1/2+x,3/2-y,-1/2+z；13#+x,1-y,1/2+z
TABLE 4 RbCu 2 Br 3 Anisotropic displacement parameter of (2)The anisotropic displacement factor index is in the form of: -2pi 2 [h 2 a 2 *U11 +...+2hk a*b*U12]。
In XRD contrast pattern 6, rbCu 2 Br 3 The powder XRD is consistent with a single crystal XRD standard diffraction pattern, which shows that the obtained sample is pure and free of impurities. The XRD spectrum of the bulk sample shows sharp three diffraction peaks, namely (220), (330) and (440) crystal planes respectively. And single crystal rocking curve test was performed on the (440) plane (FIG. 1 i) to obtain the orientation with a lower half-width of 0.0305 °, indicating RbCu 2 Br 3 The single crystal has higher crystallization quality. Analysis by Scanning Electron Microscopy (SEM) and energy spectroscopy (EDS) revealed that the Rb, cu, br elements were uniformly distributed in the sample (fig. S2). Under the characterization of high resolution electron microscope image (HREM) and Selected Area Electron Diffraction (SAED) (FIGS. 7a,7 b), crystal planes with spacing of 0.19nm and 0.21nm were clearly observed, and corresponding to diffraction spots, were identified as along [ 0.1 ]]The crystal is down (440) and (430) planes. X-ray photoelectron spectroscopy (XPS) is one of the main means for obtaining atomic valence state information, and the existence of Rb, cu and Br elements is confirmed in the XPS full spectrum of FIG. S4a, spin-orbit coupling splitting occurs in the amplified spectrum of a small-range energy region, and the combination energy difference between the two components is an important basis for researching elements. Fitting Cu nuclear energy spectrum (core-level spectrum)Binding energy is 932.68eV (Cu 2 p) 3/2 ) And 952.48eV (Cu 2 p) 1/2 ) 2p dipole of (2), wherein the separation energy is 19.8eV, with Cu + Anastomosis (fig. 8 b). Rb (108.46 eV 3 d) 5/2 )、Br(66.78eV 3d 5/2 ) Is a nuclear energy spectrum of (2).
RbCu was calculated by Density Functional Theory (DFT) 2 Br 3 The band structure and the density of states (shown in FIGS. 9a,9 b). RbCu 2 Br 3 At Γ is a direct bandgap material with a bandgap of 1.647eV. DOS and PDOS indicate that RbCu 2 Br 3 The Conduction Band Minimum (CBM) of (C) is mainly composed of Cu-4s, br-4s and Br-4p orbitals, and the Valence Band Maximum (VBM) is mainly composed of Cu-3d and Br-4p orbitals. Rb ions do not contribute to the electronic structure of CBM and VBM. The three-dimensional partial charge density (fig. 9c,9 d) (The partial charge density) clearly shows the iso-surface plot of the real space charge distribution at the bottom of the conduction band and the top of the valence band, with electrons mostly localized in the Cu-Br tetrahedra, and electrons at the bottom of the valence band more localized, consistent with small band dispersion at the valence band in the band structure. And the transport of carriers appears to be predicted to be a dominant transport property along the c-direction due to the inherent one-dimensional properties of electrons.
For RbCu at low temperature 2 Br 3 The crystal structure was studied, and we surprisingly found that RbCu was found by single crystal XRD diffraction test at 100K 2 Br 3 The crystals undergo a phase change at low temperatures. Compared with room temperature, the single crystal XRD diffraction pattern of the structure has new peaks at 25.42 degrees, 30.4 degrees, 30.84 degrees, 31.8 degrees, 45.36 degrees and the like (shown in figure 2 b) except for partial peak position movement. The structure is the orthorhombic system (point group:space group: pnma, ->α＝β＝γ＝90°,/>) Its related crystal structure information and schematic diagramAs shown in tables 5-8 and fig. 2 c. By comparison with fig. 2, after the transition from Cmcm to Pnma structure is clearly found from the atomic club model of crystal unit cell, the lattice structure is twisted and the symmetry is reduced. The coordination number of Br atoms around Rb atoms and the bond angles of Rb-Br and Cu-Br are changed. And DFT theoretical calculation of the structure shows that the atomic orbit which mainly contributes to the system state density in the crystal after phase transition is unchanged, the weak reduction of the band gap of the crystal is 1.63eV, and the structure is shown in figures 10a and 10 b.
TABLE 5 RbCu 2 Br 3 Crystal data and structure refinement at 100K.
TABLE 6 RbCu 2 Br 3 Fractional atomic coordinates at 100K (x 10 4 ) And equivalent isotropic displacement parameterU (eq) Is defined as orthogonalization U ij One third of the tensor trajectory.
TABLE 7 RbCu 2 Br 3 Selected bond length at 100KAnd angle [ deg ]]。
Symmetric transformations for generating equivalent atoms:
#2x+1/2,y-1,-z+1/2 #3x+1/2,y,-z+1/2 #4-x+3/2,-y,z-1/2 #5x,y-1,z#6-x+1,-y+1,-z
#7-x+1,-y,-z #8x,-y+1/2,z #9-x+1,y-1/2,-z+1 #10-x+1,-y+1,-z+1 #11x,-y+3/2,z
#12x-1/2,y,-z+1/2 #13x-1/2,y+1,-z+1/2 #14x,y+1,z #15-x+3/2,-y,z+1/2
TABLE 8 RbCu 2 Br 3 Anisotropic displacement parameter at 100KThe anisotropic displacement factor index is in the form of: -2pi 2 [h 2 a 2 *U11+...+2hk a*b*U12]。
This phase change process for temperature influence is further explored. FIG. 3a shows RbCu in the full temperature range (8-295K) 2 Br 3 Crystal PL pseudo-color plot. The spectrogram intuitively shows the appearance of a new luminescence peak at 600nm at low temperature, and the intensity of the luminescence peak is not singly increased or decreased. The luminescence intensity at two places in the process is extracted to obtain the relation between the integral intensity and 1/T (figure 11 a), 600nm (abbreviated STE (O) ) The orange spectrum undergoes a process of increasing and then decreasing to vanishing in the range of 8-145K, 390nm (abbreviated STE (B) ) The luminescence peak is STE (O) The maximum value is reached when the luminescence peak disappears, which indicates that a certain conversion relationship exists between the two luminescence sources. Meanwhile, positive correlation of PL integrated intensity and laser power indicates (fig. 3 b), STE (B) And STE (STE) (O) Both emission peaks are derived from self-trapping exciton radiative recombination (STE), non-permanent defect recombination luminescence.
Therefore, we comb the whole temperature-changing luminescence process. RbCu 2 Br 3 The crystal is helpful to generate strong photo-acoustic coupling effect due to the binding of the one-dimensional electron structure to electrons and the soft lattice structure, and forms self-trapped excitons. Free excitons pumped to the excited state at room temperature are more prone to transfer to the lower energy self-trapping state, STE (B) Luminescence is dominant, and a luminescence mechanism diagram is shown in fig. 3c (top). STE when only 95-295K temperature change is considered (B) The activation energy Ea at the luminescence peak can be obtained from the following formula:
wherein I is 0 And I (T) are the PL integral intensities at temperatures of 0K and T, respectively. A is a constant, k B Is the boltzmann constant (Boltzmann constant). Fitting the STE B The emission peak exciton binding energy ea= 218.89meV, as shown in fig. 3 d. This value is much greater than other two-dimensional, three-dimensional perovskite materials, and therefore the blue luminescence of the material is less affected by thermal quenching and is observable at room temperature.
Since STE emission is mainly dependent on electron-phonon coupling, the variation in exciton emission linewidth is derived from fluctuation in exciton binding caused by atomic vibration. Thus, the dependence of the half-height width on temperature can be given by:
fitting, STE (B) Yellow-kunming factor (S) and phonon frequency of luminescence peak19.28 and 28.01meV, respectively, as shown in FIG. 3e, a relatively large yellow insect factor (e.g., csPbBr 3 The nano-sheets are 3.223) shows that the material has soft lattice property and is easier to form self-trapping excitons. Notably, at lower temperatures, rbCu 2 Br 3 The crystal is STE (B) And STE (STE) (O) The place is reversedThe luminous intensity tends to decrease with decreasing temperature. The descent phase may introduce a negative activation (-Ea) energy treatment:
as shown in fig. 11b,11c, the dashed line is the fitting result of formula (3), -Ea (b) = -1.198meV, -Ea (o) = -1.937 meV. Thus, at low temperatures, excited photoelectrons may be thermally excited to self-trapping exciton states at lower activation energies, which thermal activation process may lead to new radiative recombination events.
From the occurrence of phase transition of the material at low temperature we can easily explain STE at low temperature (o) The occurrence of luminescence peaks is accompanied by STE (B) And a decrease in luminous intensity. With decreasing temperature, due to RbCu 2 Br 3 The crystal has a non-rigid and porous structure, the crystal body is actively and easily contracted, br atoms at the edge of the hollow channel are extruded into the frame, the space between the atoms or ions is shortened or a new linking bond is formed, 9 Br atom coordination is formed around Rb atoms, the crystal structure is twisted, and the crystal field in the material is changed. The superposition of such local deviations results in a break in the symmetry of the crystal structure (symmetry breaking), forming a lower energy lattice structure (Pnma), the phase transition of the crystal being shown in fig. 3 f. Thus at about 145K, the crystals emit a sparkling orange light accompanied by STE (B) The luminous intensity decreases. Meanwhile, due to the opening of the intersystem cross conversion channel, STE (O) The luminous intensity at this point rises briefly (fig. 3c (middle)). With further decrease in temperature, rbCu 2 Br 3 The crystal is converted into Pnma phase, and ultraviolet luminescence in the luminescence spectrum may be generated by decreasing symmetry of the crystal and increasing transition probability of excitons. Meanwhile, since lattice activity is relatively small at low temperature, carrier transport is slow, aggregation is liable to occur, and energy cleavage is caused, and thus a plurality of luminescence peaks appear in PL spectrum at low temperature (shown in fig. 1g and 3c (bottom)). And the luminous intensity is weakened everywhere due to the mutual competition of excitons among a plurality of luminous peaks.
Relative to lightIn the case of luminescence, under X-ray excitation, the energy of the radiation is deposited and converted inside the material and the scintillation process is not completely uniform. As shown in fig. 4a, the temperature-dependent luminescence spectrum (RL) pseudocolor plot shows two luminescence peaks at low temperature, corresponding to the free exciton luminescence (FE UV 340 nm) and self-trapping exciton luminescence (STE (O) ). And with increasing temperature STE (O) Exhibits a trend of change consistent with photoluminescence. The RL spectra at 8K and 145K temperature points are shown in fig. 4 b. Since free exciton radiation is quenched too rapidly with increasing temperature, STE alone (O) The emission peak exciton binding energy ea=165.29 meV, as obtained by fitting the formula (1), was close to the positive activation energy fitting result in photoluminescence (ea= 171.32 meV). Furthermore, at 8K temperature point, FE UV And STE (STE) (O) The luminescence intensity at both sites was positively correlated with the X-ray dose rate (fig. 4 d), and therefore, it was once again confirmed that the luminescence peaks at both sites originated from exciton radiative recombination. Fig. 4e, f are diagrams of possible luminescence mechanisms under X-ray excitation, and due to ionization process occurring inside the material under X-ray bombardment, a large amount of high-energy carriers are generated, and the high-energy carriers are inelastically scattered in the scintillator, so that multiplication of low-energy carriers is realized. Subsequently, due to the thermal relaxation process, part of the carriers are captured by the non-radiative channels, thus STE in the Cmcm structure (B) The luminescence peak of (c) is not detected in the radiation detection, possibly due to some shielding effect or the opening of a non-radiative recombination channel. As the temperature reaches below about 145K, rbCu 2 Br 3 The crystal undergoes phase transition (Cmcm to Pnma) caused by local symmetry break, and self-trapped state with lower energy captures exciton, STE (O) Enhanced luminescence peak compared to FE UV Possibly due to severe effects of thermal quenching, are only observable at very low temperatures.
To further explore RbCu 2 Br 3 Application in the field of crystal X-ray detection. From the photon cross-section database, rbCu is plotted 2 Br 3 Crystals and commonly known scintillators absorb coefficients versus photon energy spectrum (shown in fig. 5 a). Its absorption coefficient is comparable to that of scintillators with better performance at presentAnd (5) simulating. In particular, the absorption coefficient in the range of 13-33keV is much higher than that of CsI in the field of medical digital radiography (18-30 keV). Thus, a single crystal X-ray direct detector (Au/RbCu) was prepared using the vertical structure shown in fig. 5b 2 Br 3 Ga/Sn), and the physical diagram of the device is shown in the inset. The I-V curves of the detector at different X-ray radiation doses and in the dark state are shown in fig. 5c, d. The device had a dark current of hundred picoseconds at-20V at 974. Mu. Gy air /(s*cm 2 ) The current response under X-ray radiation is about 4 times the dark current. The product of the carrier mobility μ and the charge carrier lifetime τ is a measure of the charge collection capability of the X-ray detector, with a larger μτ indicating a stronger collection capability. We fit the photoconductivity using the modified Hecht equation as follows:
wherein is I 0 V, L, s are the saturated photocurrent, applied voltage, device thickness and surface recombination velocity, respectively. As shown in FIG. 12, the result of the μτ fit is 6.586 ×10 -5 cm 2 V -1 . Comparable to other single crystal perovskites, e.g. MAPbI 3 (4*10 -4 cm 2 V -1 )， 41 Cs 3 Bi 2 I 9 (7.97*10 -4 cm 2 V -1 )。
The sensitivity (S) of the X-ray detector reflects the detector' S ability to recognize changes in the X-ray dose by generating a current response (fig. 5 e) under different electric fields and doses, viaWherein the photo-generated current I ph ＝I light -I dark D is the X-ray irradiation dose rate and a is the device effective irradiation area) to obtain the device sensitivity by calculation, as shown in fig. 5 f. 20V mm -1 Under the intensity of an electric field, the sensitivity of the device reaches 29.3 mu C Gy air -1 cm -2 . And 10 (V) 4 V mm -1 Stationary alpha-Se device at operating field strengthSensitivity (20 μC Gy) air -1 cm -2 ) Equivalent. Furthermore, the signal obtained is only identifiable according to the International Union of Pure and Applied Chemistry (IUPAC) specification when the signal-to-noise ratio (SNR) is at least greater than 3. FIG. 13 shows 20V mm at different radiation doses -1 I-T curve of applied electric field, defined by snr=i signal /I noise (wherein I signal Representing the signal current, I is the average photocurrent minus the average dark current noise Representing noise current, standard deviation of photocurrent), 20V mm -1 Under bias, rbCu 2 Br 3 The detection limit of the detector is 1.41 mu Gy air About/s, compared with the conventional medical diagnosis, 5.5 mu Gy air The criterion of/s is much lower. 42 The stability of the device is another important index of the X-ray detector, and the stability of the device is 9.74 mu Gy in FIG. 5g air I-T curves at different applied electric fields at/s radiation dose, the device exhibits repeatable photoelectric properties in periodic radiation response. The rising and falling edges of the individual ray responses are extracted (fig. 5h, i), where the rise (fall) time is defined as the time it takes for the photocurrent to rise (fall) to a maximum of 90% (10%). As the bias voltage increases, the switching time remains within a range as the bias voltage changes. Indicating that the applied electric field has less influence on the carrier transport inside the device. By the above continuous radiation and high electric field intensity (974. Mu. Gy air s -1 cm -2 ，20V mm -1 ) The device exhibits extremely high operational stability due to the properties of the material itself, such as all-inorganic, high crystallinity, etc.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1.RbCu 2 Br 3 A method for synthesizing a single crystal, characterized byComprising the following steps:
s1, mixing and dissolving RbBr and CuBr in a molar ratio of 1:2 into HBr acid and deionized water with a volume ratio of 1-3:1; the concentration of RbBr formed is 0.5-2 mmol/mL;
s2, adding hypophosphorous acid into the mixed solution in the step S1, and preserving heat for 1-3 hours at the temperature of 95-105 ℃;
s3, cooling the mixed solution obtained in the step S2 to room temperature at a cooling rate of 0.5-3 ℃/h, and crystallizing;
s4, drying the crystal formed in the step S3 to obtain the crystal.
2. The RbCu of claim 1 2 Br 3 The method for synthesizing the single crystal is characterized in that in the step S1, the volume ratio of HBr acid to deionized water is 2:1; the concentration of RbBr formed was 1mmol/mL.
3. The RbCu of claim 1 2 Br 3 A method for synthesizing a single crystal, characterized in that in the step S2, the temperature is kept at 100℃for 2 hours.
4. The RbCu of claim 1 2 Br 3 The method for synthesizing single crystals is characterized in that in the step S3, the temperature is lowered to the room temperature at a cooling rate of 1 ℃/h.
5. The RbCu of any of claims 1 to 4 2 Br 3 RbCu prepared by single crystal synthesis method 2 Br 3 And (3) single crystals.
6. The RbCu of claim 5 2 Br 3 A single crystal, characterized in that the single crystal is an orthorhombic crystal, wherein the group of points:space group: cm, ->α＝β＝γ＝90°,/>
7. The RbCu of claim 5 2 Br 3 A single crystal, characterized in that the single crystal is an orthorhombic crystal when at 145K temperature, wherein the group of points:space group: pnma, ->α＝β＝γ＝90°,/>
8. The RbCu of claim 5 2 Br 3 The single crystal is characterized in that the single crystal changes phase along with temperature change, and the phase change temperature point is 145K; the single crystal photoluminescence, which is shifted from blue to orange light, occurs as the temperature decreases.
9. The RbCu of any of claims 5 to 8 2 Br 3 The single crystal is applied to the preparation of photoelectric detectors, light emitting diodes and ionization radiation detection.
10. The RbCu of any of claims 5 to 8 2 Br 3 The application of single crystal in preparing scintillator material and X-ray detector.
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