CN114292286B - Chiral organic-inorganic hybrid copper (I) halide crystal and preparation method and application thereof - Google Patents
Chiral organic-inorganic hybrid copper (I) halide crystal and preparation method and application thereof Download PDFInfo
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- -1 copper (I) halide Chemical class 0.000 title claims abstract description 59
- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 21
- 238000004891 communication Methods 0.000 claims description 5
- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
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- 150000004820 halides Chemical class 0.000 abstract description 7
- 238000009396 hybridization Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910001507 metal halide Inorganic materials 0.000 description 12
- 150000005309 metal halides Chemical class 0.000 description 12
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000002983 circular dichroism Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
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- RQEUFEKYXDPUSK-ZETCQYMHSA-N (1S)-1-phenylethanamine Chemical compound C[C@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-ZETCQYMHSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001142 circular dichroism spectrum Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000411 transmission spectrum Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 238000012984 biological imaging Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The application discloses a chiral organic-inorganic hybrid copper (I) halide crystal, a preparation method and application thereof, and relates to the field of optical materials. The chiral copper (I) halide prepared by taking copper (I) as a central metal of the material has a larger second-order nonlinear optical coefficient than copper (II) halide with d-d transition, and has a wider light transmission window and better light stability and heat stability in ultraviolet, visible light and infrared regions; the synthesis method comprises the steps of mixing halogen acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, and cooling and crystallizing to obtain corresponding chiral copper (I) halide colorless transparent crystals. The preparation method and the process steps are simple, the large-scale production of the chiral hybridization copper (I) halide crystal and the application of the chiral hybridization copper (I) halide crystal in the field of second-order nonlinear optics can be realized, and a new thought is provided for the design and development of second-order nonlinear optical materials.
Description
Technical Field
The application relates to the field of organic-inorganic hybrid copper (I) halides, in particular to a preparation method of novel chiral organic-inorganic hybrid copper (I) halide crystals and application thereof in the aspect of second-order nonlinear optics-Second Harmonic Generation (SHG).
Background
Organic-inorganic hybrid metal halides are widely used in solar cells, light emitting diodes, lasers, photodetectors, catalysis, etc. due to their high carrier mobility, excellent charge transport properties, low trap density, and low cost solution processability. The rich chemical and structural diversity, large oscillating strength and tunable band gap of organic-inorganic hybrid metal halides also enable their application in the field of nonlinear optics (NLO). SHG is widely used as the most widely applied second-order nonlinear optical phenomenon in various aspects such as communication, military, industrial production and life. However, implementation of second order nonlinear optics requires materials with non-centrosymmetric structures, which is a challenge for organic-inorganic hybrid metal halides.
Chiral materials have intrinsic non-central symmetry and generally exhibit unique optical properties such as Circular Dichroism (CD) and Circular Polarized Luminescence (CPL). It is exciting that the organic-inorganic hybrid metal halides allow the incorporation of chiral amines, which provides the possibility for the non-centrosymmetric structure required to induce the second order NLO effect. Over the past few years, many researchers have developed a number of chiral organic-inorganic hybrid metal halide materials for use in SHG, such as chiral halides based on lead (II), tin (II), bismuth (III), cadmium (II), and the like, which have nonlinear optical coefficients that are mostly comparable to commercial potassium dihydrogen phosphate (KDP). The copper-based organic-inorganic hybrid metal halide can avoid the toxicity problem of lead/cadmium halide and the instability problem of tin halide. Recently Guo et al reported a chiral hybrid copper (II) halide (R-/S-MBA) 2 CuCl 4 [ (R/S-MBA) is (R) - (+) -1-phenethylamine or (S) - (-) -1-phenethylamine]A film. Such films proved to have SHG properties. However, (R-/S-MBA) 2 CuCl 4 Extending the absorption range in the visible region to 450nm, resulting in severe self-absorption, thereby negatively affecting the transparent window and Laser Damage Threshold (LDT), similar to many other organic-inorganic hybrid metal halides.
The existing chiral organic-inorganic hybrid copper (II) halide has the problems of poor stability, poor optical transparency, small nonlinear response, low laser damage threshold and the like, and directly influences the application of the material as nonlinear crystals. The novel metal copper (I) without d-d transition is used as the central metal, the hybridized metal halide is constructed, the problem of self-absorption of crystals in a visible region is skillfully solved, the obtained material has stronger SHG signal, higher laser damage threshold and wider transmission window than copper (II) halide with d-d transition, and a novel thought is provided for design and development of chiral metal halide as a second-order nonlinear optical material.
Disclosure of Invention
The application provides a preparation method and application of chiral organic-inorganic hybrid copper (I) halide, which are nonlinear optical materials with wider light transmission wave band, larger second-order nonlinear optical coefficient, easy preparation and better stability, for solving the problems. The method is characterized in that no obvious absorption exists at the position of more than 280nm, and relatively most of organic-inorganic hybridization metal halides have larger band gaps, so that the problem of self absorption of chiral organic-inorganic copper (II) halides and other most of organic-inorganic hybridization metal halides in the visible light region is solved, meanwhile, the spectrum application range of SHG properties is widened, the SHG has good permeability in the ultraviolet-visible-infrared region, and the laser damage threshold is also increased by a plurality of times compared with corresponding copper (II) halides. The (R/S-MBA) CuBr exemplified by the present application 2 The material has the following characteristics: an excellent SHG signal in the full visible region; extremely high polarization ratio (97%); a transparent window (290 nm-3220 nm) with ultra-wide deep ultraviolet-visible light region and infrared light region; a good laser damage threshold; excellent air stability and thermal stability.
The chiral hybrid copper (I) halide crystal is prepared by (R-MBA) CuBr 2 For example, the crystal is monoclinic, and the space group is P2 1 The main crystallographic parameters are The chiral organic-inorganic hybrid copper (I) halide crystal prepared by the application is applied to the field of second-order nonlinear optics.
The technical scheme adopted by the application is as follows:
the preparation process of chiral organic-inorganic hybridized copper (I) halide crystal includes mixing chiral organic amine and cuprous halide solution, adding hypophosphorous acid, heating to dissolve, cooling and crystallizing to obtain colorless transparent crystal of chiral copper (I) halide.
Furthermore, the chiral organic amine has rich structure, and can be selected from one or more of cyclic or chain chiral alicyclic amines, chiral aromatic amines and other group substituted amines. The chiral alicyclic amine comprises compounds of the following formulas IA1-IA12, the chiral aromatic amine comprises compounds of the following formulas IB1-IB6, the halogen substituted amine comprises compounds of the following formulas IC1-IC12, and the other group substituted amine comprises compounds of the following formulas ID1-ID 2:
in the scheme, the hydrohalic acid comprises one or more of hydroiodic acid, hydrobromic acid and hydrochloric acid, so that the chiral hybrid copper (I) halide energy band can be effectively regulated.
In the scheme, the copper halide is coated with one of cuprous chloride, cuprous bromide, cuprous iodide and cuprous oxide.
In the above scheme, the method for heating, dissolving, cooling and crystallizing comprises the following steps: mixing the halogen acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, cooling and crystallizing at room temperature, and crystallizing after a preset time to obtain the chiral hybrid copper (I) halide microcrystal.
The application has the following technical advantages and positive effects:
the preparation method of the chiral hybrid copper (I) halide crystal has simple process and easy control, can realize mass production of the chiral organic-inorganic hybrid copper (I) halide crystal, and can be applied to the aspect of SHG. The metal copper (I) in the center of the crystal is in a monovalent state, and d-d transition does not exist, so that the crystal has a wider light transmission window and better light stability and heat stability in ultraviolet, visible and infrared regions, shows a larger second-order nonlinear optical coefficient, and is expected to be applied to the fields of biological imaging, optical communication and military.
Drawings
The application is described in further detail below with reference to the attached drawings and detailed description:
FIG. 1 is a synthetic route diagram of an embodiment of the present application;
FIG. 2 is a schematic diagram of a heating dissolution-cooling crystallization method according to an embodiment of the present application;
FIG. 3 is a representation of a chiral organic-inorganic hybrid copper (I) halide micro-plate under a bright field microscope and a polarizing microscope according to an embodiment of the present application;
FIG. 4 is a scanning electron microscope and elemental analysis characterization map of a chiral organic-inorganic hybrid copper (I) halide micro-plate according to an embodiment of the present application;
FIG. 5 is a diagram of a crystal structure model of chiral organic-inorganic hybrid copper (I) halide single crystal X-ray diffraction analysis in accordance with an embodiment of the present application;
FIG. 6 is an ultraviolet visible absorption spectrum and a circular dichroism spectrum of a chiral organic-inorganic hybrid copper (I) halide microchip according to an embodiment of the present application;
FIG. 7 is a transmission spectrum of chiral organic-inorganic hybrid copper (I) halide micro-plates of an embodiment of the present application;
FIG. 8 is a SHG spectrum of a chiral organic-inorganic hybrid copper (I) halide microchip according to an embodiment of the present application;
FIG. 9 left is a graph of the same thickness of an organic-inorganic hybrid copper (I) halide (R-MBA) CuBr 2 Micrometer tablet (strongest), urea micrometer tablet (medium) and (R-MBA) 2 CuCl 4 SHG relative intensity versus spectrum for the microchip (weakest). The right graph is (R-MBA) CuBr 2 Micron sheet (upper) and (R-MBA) 2 CuCl 4 SHG intensity versus excitation power plot for the microchip (bottom).
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials and reagents used in the application are all commercially purchased and are directly used without treatment, and the instruments and equipment used adopt the schemes and parameters recommended by manufacturers.
In an embodiment, single crystal X-ray diffraction data is obtained from RigakuXtalAB PRO MM007 DW diffractometer using Cu K alpha radiationOr Mo K alpha radiation->And (5) collecting. The ultraviolet-visible absorption spectrum is collected by an ultraviolet-visible spectrophotometer (UV 2600). Infrared (IR) transmission spectra were obtained on a fourier transform infrared spectrometer (tenor 37). Linear Circular Dichroism (CD) spectra were collected using a JASCO J-810 CD spectrometer.
The method for preparing the chiral hybrid copper (I) halide microcrystal and examples of the chiral hybrid copper (I) halide microcrystal according to the present application are described below.
The synthetic route diagram 1 of this embodiment is shown.
In a separate beaker, (R) - (+) -1-phenethylamine or (S) - (-) -1-phenethylamine (121 mg,1.0 mmol) was reacted with HBr (40 wt.%,0.5mL,3.5 mmol) under ice bath conditions; cuBr powder (143.4 mg1 mmol) was dissolved in a solution having H 3 PO 2 (170. Mu.L, 1.9 mmol) of HBr in water (40 wt.%,1mL,7 mmol) to form a clear solution. The solutions in the two beakers were then mixed, heated to dissolve, and cooled to room temperature, during which time the colourless crystals started to crystallise. After about 2 days the crystal growth was considered complete.
Morphology characterization:
referring to fig. 3 and 4, fig. 3 shows the morphology of the chiral copper (I) halide microchip crystal represented by a common electron microscope and a polarizing microscope, and the size and shape of the chiral copper (I) halide microchip crystal are intuitively shown; the morphology of the chiral copper (I) halide microchip is characterized by a scanning electron microscope in fig. 4, and the chiral copper (I) halide microchip is shown as a long rectangular microchip with a diameter of about 20-60 μm, and the Cu, br and C elements are uniformly distributed as can be seen from element analysis. To further illustrate that the resulting micro-plate is a chiral hybrid copper (I) halide, the structure of the micro-plate was resolved by single crystal X-ray diffraction,
structural characterization:
referring to fig. 5, the crystal structure of chiral hybrid copper (I) halide microchip crystals was characterized by an X-ray single crystal diffractometer. The chiral micron tablet crystal is (R) - (+) -1-phenethylamine or (S) - (-) -1-phenethylamine which takes copper (I) as a center and takes bromine atoms as tetrahedrons with vertexes to form ordered chain distribution; the center of the tetrahedron is copper atom, the vertex of the tetrahedron is nitrogen atom, the tetrahedron forms a one-dimensional long chain through side sharing, and organic amine ligands around the chain interact with hydrogen bonds through coulomb action, wherein the lighter color is carbon atom, and the darker color is nitrogen atom. (R-MBA) CuBr 2 And (S-MBA) CuBr 2 The two nano-sheet structures are mirror symmetry and are chiral hybridization copper (I) halide materials. The obtained chiral hybrid copper (I) halide microchip material is of a non-centrosymmetric structure.
Optical properties:
referring to FIG. 6, wherein the upper portion is the UV-visible absorption spectrum of the chiral hybrid copper (I) halide microchip crystal and the lower portion is the circular dichroism spectrum of the chiral hybrid copper (I) halide microchip crystal, wherein the solid line corresponds to (R-MBA) CuBr 2 Is (S-MBA) CuBr 2 Is a line of (3). In the circular dichroism, (R-MBA) CuBr 2 And (S-MBA) CuBr 2 Strong circular dichroism signals appear at 221nm,263nm and 283nm, and the signals are opposite. Obviously, these circular dichromatic responses are defined by (R-MBA) CuBr 2 And (S-MBA) CuBr 2 The koton effect of the intrinsic exciton absorption band of chiral copper (I) halide microchip crystals results, which corresponds to the absorption peak at 283nm (4.38 eV) of the uv-visible absorption spectrum. This fully demonstrates that chiral hybrid copper (I) halide microchip crystals are chiral and also necessarily non-centrosymmetric. Therefore, the chiral hybrid copper (I) halide material has wide application prospect in the fields of nonlinear optics, ferroelectric piezoelectricity and the like.
FIG. 7 shows the transmission spectrum of chiral copper (I) halide, which can be seen to have a transmittance of approximately 90% at 280-3200nm, which effectively increases the laser damage threshold; and directly show the potential of the copper (I) halide for wide application in the ultraviolet-visible-infrared region.
Nonlinear optical properties:
the application utilizes an autonomously built femtosecond laser test system to characterize the frequency multiplication performance of a single crystal of a sample. A chiral hybridization metal halide monocrystal with proper size is selected and placed on a quartz substrate of a sample carrying table, a femtosecond pulse laser (Spectra-Physics Mai Tai,690-1040nm, <100fs,80MHz;Spectra Physics Mai Tai) is taken as a light source, fundamental frequency light passes through a polaroid, enters the sample, reflected SHG signals are collected after passing through an objective lens, and the incident angle and the reflected angle are both 45 degrees. Imaging on CCD, and coupling the spectrum signal to the spectrometer for measurement.
Referring to FIG. 8, a single (R-MBA) CuBr is shown at the same energy 2 Wavelength dependent SHG spectrum of the microchip. The SHG spectrum is prepared by exciting wavelength from 800-1040nm (100 fs,80 MHz) and 1200-1500nm<50fs,1000 hz) with a step change of 20nm, graph a shows the relative intensities of SHG signals of different wavelengths, it can be seen that the incident light is strongest at 940nm, which can be up to 323 times that of the reference Y-cut quartz. Panel b shows (R-MBA) CuBr under the same test conditions 2 The signal intensity of the microchip at each wavelength is a multiple of the reference Y-cut quartz signal. FIG. c is (R-MBA) CuBr 2 The spectrum of the SHG signal after normalization of the microchip shows that the SHG has better response in the whole visible light region (400-750 nm). And the incident laser is expected to have better SHG response signals (300-1600 nm) within the range of 600-3200nm, so that the common communication wave band can be covered.
Referring to FIG. 9, a left view depicts (R-MBA) CuBr of the same thickness 2 Micrometer tablet (strongest, urea micrometer tablet (medium) and (R-MBA) 2 CuCl 4 SHG spectrum of the microchip (weakest). Impressively, (R-MBA) CuBr under 940nm pumping 2 Is strong in SHG signalThe degree is 2 times that of urea and is cupric (II) halide (R-MBA) 2 CuCl 4 20 times of the microchip. The right graph shows (R-MBA) CuBr 2 Micron sheet (upper) and (R-MBA) 2 CuCl 4 The plot of SHG intensity versus excitation power for the microchip (down) with a linear slope of 2 indicates a quadratic relationship between signal intensity and power, further confirming that this is a second order nonlinear physical mechanism. Intensity decreases at incident powers above 105mW, indicating cupric (II) halide (R-MBA) 2 CuCl 4 The laser damage threshold of the microchip was 105mW. Notably, monovalent copper (I) halides (R-MBA) CuBr 2 The laser damage threshold of the microchip was determined to be 415mW, which is about the corresponding cupric (II) halide (R-MBA) 2 CuCl 4 4 times of the laser damage threshold, the laser threshold is obviously improved. Therefore, the chiral organic-inorganic hybrid copper (I) halide material has wide application prospect in the fields of nonlinear optics, cell imaging, information communication and the like.
While the application has been described in terms of the preferred embodiment, it is not intended to limit the scope of the claims, and any person skilled in the art can make many variations and modifications without departing from the spirit of the application, so that the scope of the application shall be defined by the claims.
Claims (3)
1. A chiral organic-inorganic hybrid copper (I) halide crystal characterized in that: the crystal is chiral hybridized copper (I) halide (R-MBA) CuBr based on (R) - (+) -1-phenethylamine (R-MBA) 2 The crystal is monoclinic, and the space group is P2 1 The main crystallographic parameters are α＝90°，β＝108.826(10)°，γ＝90°，Z＝4，/>The chemical formula of the crystal is C 8 H 12 Br 2 CuN。
2. Use of a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 1 in second order nonlinear optics-Second Harmonic Generation (SHG).
3. Use of the chiral organic-inorganic hybrid copper (I) halide crystal according to claim 1 in the fields of bioimaging, optical communications.
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| CN114957335B (en) * | 2022-06-24 | 2024-04-05 | 南开大学 | Method for preparing chiral metal halide from achiral precursor through chiral induction |
Citations (3)
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| CN112520781A (en) * | 2020-12-03 | 2021-03-19 | 吉林大学 | Copper-doped ternary metal halide and preparation method thereof |
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