CN110093156B - Near-infrared luminous bismuth-doped strontium chloropentaborate crystal and preparation method thereof - Google Patents
Near-infrared luminous bismuth-doped strontium chloropentaborate crystal and preparation method thereof Download PDFInfo
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- CN110093156B CN110093156B CN201910283069.2A CN201910283069A CN110093156B CN 110093156 B CN110093156 B CN 110093156B CN 201910283069 A CN201910283069 A CN 201910283069A CN 110093156 B CN110093156 B CN 110093156B
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Abstract
The invention discloses a near-infrared luminous bismuth-doped strontium chloropentaborate crystal and a preparation method thereofPreparation method of the general formula Sr2(1‑x)B5O92xBi is Cl, and x is more than or equal to 0.1% and less than or equal to 3.0%. Respectively weighing strontium-containing, boron-containing, chlorine-containing and bismuth-containing compounds as raw materials, uniformly grinding the raw materials, pre-burning the raw materials for 3 to 6 hours at 623 to 823K, cooling the raw materials to room temperature, and uniformly grinding the raw materials; and calcining at 1073-1173K for 4-6 hours, cooling to room temperature, reacting the obtained sample for 15 minutes to 10 hours in a reducing atmosphere of 1073-1173K, cooling to room temperature, and grinding to obtain the crystal. The crystal near-infrared fluorescence has the full width at half maximum of more than 200nm, is wider than the luminescence of rare earth ions, has longer fluorescence life, is expected to be used as a laser gain medium, and is applied to the fields of novel ultra-wide band wavelength tunable laser light sources or ultrashort pulse lasers and the like.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a near-infrared luminescent bismuth-doped strontium chloropentaborate crystal and a preparation method thereof.
Background
With the development of information technology and the increasing data transmission capacity of optical communication networks, it is necessary to use photons or photoelectrons as information transmission carriers instead of electrons. The successive development of rare earth ion doped optical fiber amplifier and optical fiber laser has greatly promoted the development of information technology, however, due to the narrow band forbidden transition feature of rare earth ion, the rare earth ion doped optical fiber amplifier can only realize optical amplification in a limited wave band range, and limits the improvement of data transmission capacity and speed. Therefore, it is necessary to expand the light emitting bandwidth, develop an ultra-wideband fiber amplifier and find a fiber laser with a new wavelength band, which not only promotes the development of optical communication technology, but also promotes the development of a series of related science and technology due to the appearance of novel laser light sources and devices.
Due to the limitation of a luminescence principle, at present, no material based on rare earth ion doping can generate ultra-wideband fluorescence covering a 1-1.5 micron spectral region, and the bismuth-doped near-infrared luminescent material has the characteristics of ultra-wideband near-infrared luminescence covering 1000-1700nm, wide absorption and emission cross section, long fluorescence life and the like, and is expected to become a laser source of an ultra-wideband optical fiber amplifier and a laser of a brand new generation. However, the bismuth-doped near-infrared luminescent materials are mainly concentrated in glass materials at present, and few bismuth-doped near-infrared luminescent crystal materials are reported at present, and crystal laser output of bismuth is not realized.
Disclosure of Invention
In order to overcome the defect of insufficient fluorescence bandwidth of the existing rare earth doped material, the invention aims to provide a bismuth-doped strontium chloropentaborate crystal which has the near-infrared ultra-wideband luminescence characteristic.
The invention also aims to provide a preparation method of the bismuth-doped strontium chloropentaborate crystal.
The purpose of the invention is realized by the following technical scheme:
a near-infrared luminous bismuth-doped strontium chloropentaborate crystal with the general expression of Sr2(1-x)B5O9Cl is 2xBi, wherein x is a mole fraction, and x is more than or equal to 0.1% and less than or equal to 3.0%.
The crystal structure of the near-infrared luminous bismuth-doped strontium chloropentaborate crystal belongs to an orthorhombic system.
A preparation method of a near-infrared luminescent bismuth-doped strontium chloropentaborate crystal comprises the following steps:
(1) the molar ratio of Sr to B to Cl to Bi to 2(1-x) to 5 to 9 to 1 to 2x, wherein x is a molar fraction and is more than or equal to 0.1% and less than or equal to 3.0%; respectively weighing a strontium-containing compound, a boron-containing compound, a chlorine-containing compound and a bismuth-containing compound as raw materials;
(2) grinding the raw materials weighed in the step (1) uniformly, then pre-burning for 3-6 hours at 623-823K, cooling to room temperature, grinding and uniformly mixing; and calcining for 4-6 hours at 1073-1173K, cooling to room temperature along with the furnace, and grinding to obtain an intermediate sample.
(3) And (3) reacting the intermediate sample prepared in the step (2) for 15 minutes to 10 hours in a reducing atmosphere of 1073 to 1173K, cooling to room temperature, and grinding to obtain the bismuth-doped strontium chloropentaborate crystal.
The strontium-containing compound in the step (1) is strontium oxide or strontium carbonate.
The boron-containing compound in the step (1) is boron oxide or boric acid.
The chlorine-containing compound in the step (1) is strontium chloride, ammonium chloride or strontium chloride containing crystal water.
The bismuth-containing compound in the step (1) is bismuth trioxide or bismuth nitrate.
And (3) the reducing atmosphere is carbon monoxide or a mixed gas of hydrogen and nitrogen and hydrogen generated by incomplete combustion of graphite powder.
The novel near-infrared luminescent bismuth-doped strontium chloropentaborate crystal prepared by the invention has the advantages of stable structure, simple synthesis method, ultraviolet and visible light broadband absorption, and capability of generating 850-1500nm broadband near-infrared luminescence, and the material provides possibility for developing novel laser light sources. And the half-height width of fluorescence is larger than 200nm, is wider than the luminescence of rare earth ions (usually dozens of nanometers), has longer fluorescence life, is expected to be used as a laser gain medium and applied to the fields of ultra-wide band wavelength tunable novel laser light sources or ultrashort pulse lasers and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the bismuth-doped strontium chloropentaborate crystal material takes Bi ions as active ions, can be effectively excited by ultraviolet and visible light, has a wider excitation band, and is convenient for selecting a proper pumping scheme.
(2) The bismuth-doped strontium chloropentaborate crystal can generate 800-1500nm broadband near-infrared luminescence under ultraviolet and visible light pumping;
(3) the bismuth-doped strontium chloropentaborate crystal has near-infrared fluorescence full width at half maximum of more than 200nm, is expected to be used as a laser gain medium and applied to the fields of novel ultra-wideband wavelength tunable laser sources or ultrashort pulse lasers and the like.
(4) The near-infrared luminous bismuth-doped strontium chloropentaborate crystal has a stable structure, and the synthesis method is simple and is convenient for large-scale production.
Drawings
FIG. 1 is a graph comparing the X-ray powder diffraction pattern and standard card pattern of samples of bismuth-doped strontium chloropentaborate crystals prepared in formulations (1) to (5) of example 1.
FIG. 2 shows fluorescence spectra of bismuth-doped strontium chloropentaborate crystal prepared in formulation (3) of example 1 under excitation of different wavelengths.
FIG. 3 shows the excitation spectra of bismuth-doped strontium chloropentaborate crystals prepared in formulation (3) of example 1, with corresponding emission wavelengths of 1010nm and 1280nm, respectively.
FIG. 4 is a fluorescence attenuation curve of bismuth-doped strontium chloropentaborate crystal prepared in the formulation (3) of example 1, wherein the excitation wavelength is 428nm, and the emission wavelength is 1280 nm.
FIG. 5 shows the fluorescence attenuation curve of bismuth-doped strontium chloropentaborate crystal prepared in formulation (3) of example 1, with an excitation wavelength of 322nm and an emission wavelength of 1010 nm.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto, and process parameters not specifically mentioned may be performed by referring to the conventional techniques.
Example 1
Selecting strontium carbonate, boric acid, strontium chloride hexahydrate and bismuth trioxide as initial compound raw materials, and respectively weighing 5 groups of the compound raw materials according to the stoichiometric ratio of each element, wherein the mixture ratio is as follows:
(1) b, O, Cl, Bi, 1.998, 5, 9, 1, 0.002, corresponding to x, 0.1 percent;
(2) b, O, Cl, Bi, 1.99:5:9:1:0.01, corresponding to x, 0.5%;
(3) b, O, Cl, 1.98:5:9:1:0.02, corresponding to 1.0% of x;
(4) b, O, Cl, Bi, 1.96, 5, 9, 1, 0.04, corresponding to x, 2.0%;
(5) b is O, Cl and Bi are 1.94:5:9:1:0.06, and x is 3.0 percent;
grinding and uniformly mixing the raw materials, and then loading the mixture into a corundum crucible; the corundum crucible is placed in a corundum boat and put into a high-temperature box type electric furnace. Strictly controlling the heating rate, presintering for 5 hours at 773K, cooling to room temperature, grinding and uniformly mixing; then calcining for 10 hours at 1173K, cooling to room temperature along with the furnace, grinding uniformly, reacting the obtained sample for 2.5 hours in 1173K reducing atmosphere (5% hydrogen/95% nitrogen), cooling to room temperature, and grinding to obtain the bismuth-doped strontium chloropentaborate crystal.
FIG. 1 is a graph comparing the X-ray powder diffraction pattern and standard card pattern of samples of bismuth-doped strontium chloropentaborate crystals prepared in formulations (1) to (5) of example 1. By Adam of GermanyMeasured by an X-ray powder diffractometer of model D8 ADVANCE from Bruker. The radiation source is Cu target Kalpha ray test voltage 40kV, test current 40mA, scanning step size 0.02 degree/step, scanning speed: 0.12 s/step. XRD spectrum analysis shows that the phase of the sample obtained at 1173K is Sr2B5O9The Cl phase belongs to an orthorhombic system, and other phases or impurities are not introduced in the doping of the bismuth.
FIG. 2 shows fluorescence spectra of bismuth-doped strontium chloropentaborate crystal prepared in formulation (3) of example 1 under excitation of different wavelengths. Measured using a steady state transient fluorescence spectrometer model FLS920 from Edinburgh, england. A450-watt xenon lamp is used as an excitation light source and is provided with a time correction single photon counting card (TCSPC), a thermoelectric cold red sensitive Photomultiplier (PMT), a TM300 excitation monochromator and a double TM300 emission monochromator. As can be seen from FIG. 2, the samples can generate near-infrared luminescence centered at 1010nm and 1280nm under different excitation lights.
FIG. 3 shows the excitation spectra of bismuth-doped strontium chloropentaborate crystals prepared in formulation (3) of example 1, with corresponding emission wavelengths of 1010nm and 1280nm, respectively. The test conditions were the same as in fig. 2. As shown in FIG. 3, the excitation spectrum covers the ultraviolet and visible spectral regions and has absorption peaks at 292, 322, 338, 369, 428, 460, 550 and 625 nm.
FIG. 4 is a fluorescence attenuation curve of bismuth-doped strontium chloropentaborate crystal prepared in the formulation (3) of example 1, which is measured by a steady-state and transient fluorescence spectrometer of Edinburgh FLS920 in England, the average power of a microsecond pulse xenon lamp is 60 watts, the repetition frequency is set to be 100Hz, a detector is a Japanese Hamamatsu refrigeration type R5509-72 photomultiplier (working voltage-1600V), the data acquisition integration time is 0.2 second, and the scanning step length is 1 nm. As shown in FIG. 4, the powder product obtained in this example has a fluorescence lifetime of 16.19 μ s under excitation at 428nm and an emission wavelength of 1280 nm. The symbol ∘ in the figure represents the experimental result of emission wavelength 1280nm and excitation wavelength 428nm, and the fluorescence lifetime was obtained by fitting a single exponential decay equation.
FIG. 5 shows the fluorescence attenuation curve of bismuth-doped strontium chloropentaborate crystal prepared in formulation (3) of example 1 under similar test conditions to those in FIG. 4, wherein the excitation wavelength is 322nm, the emission wavelength is 1010nm, and the fluorescence lifetime is 0.8 ms.
Example 2
Selecting strontium carbonate, diboron trioxide, strontium chloride hexahydrate and bismuth trioxide as starting compound raw materials, respectively weighing the compound raw materials according to the molar ratio of Sr, O, Cl, Bi of 1.98:5:9:1:0.02 and corresponding x of 1.0, grinding the mixture uniformly, then loading the mixture into a corundum crucible, placing the corundum crucible into a corundum boat, and placing the corundum crucible into a high-temperature box type electric furnace. Strictly controlling the heating rate, presintering for 5 hours at 773K, cooling to room temperature, grinding and uniformly mixing; then calcining for 10 hours at 1173K, cooling to room temperature along with the furnace, grinding uniformly, reacting the obtained sample for 2.5 hours in 1173K reducing atmosphere (carbon monoxide generated by incomplete combustion of graphite powder), cooling to room temperature, and grinding to obtain the bismuth-doped strontium chloropentaborate crystal. XRD pattern analysis shows that the compound is Sr2B5O9The Cl phase belongs to an orthorhombic system, and other phases or impurities are not introduced in the doping of the bismuth. The photoluminescence spectral properties of the phosphor were similar to those of example 1.
Example 3
Selecting strontium carbonate, boric acid, strontium chloride hexahydrate and dibismuth trioxide as starting compound raw materials, respectively weighing the compound raw materials according to the molar ratio of Sr to O to Cl to Bi to 1.98 to 5 to 9 to 1 to 0.02 and corresponding x to 1.0, grinding the mixture uniformly, filling the mixture into a corundum crucible, placing the corundum crucible into a corundum boat, and placing the corundum crucible into a high-temperature box type electric furnace. Strictly controlling the heating rate, presintering for 5 hours at 773K, cooling to room temperature, grinding and uniformly mixing; then calcining at 1123K for 10 hours, cooling to room temperature along with the furnace, grinding uniformly, reacting the obtained sample in 1123K reducing atmosphere (5% hydrogen/95% nitrogen) for 1.5 hours, cooling to room temperature, and grinding to obtain the bismuth-doped strontium chloropentaborate crystal. XRD pattern analysis shows that the compound is Sr2B5O9The Cl phase belongs to an orthorhombic system, and other phases or impurities are not introduced in the doping of the bismuth. The photoluminescence spectral properties of the phosphor were similar to those of example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The near-infrared luminescent bismuth-doped strontium chloropentaborate crystal is characterized in that the expression general formula is Sr2(1-x)B5O92xBi, wherein x is a mole fraction and is more than or equal to 0.1% and less than or equal to 3.0%;
the crystal generates near-infrared luminescence with the centers at 1010nm and 1280 nm; the crystal structure belongs to the orthorhombic system.
2. The preparation method of the near-infrared luminescent bismuth-doped strontium chloropentaborate crystal, which is characterized by comprising the following steps:
(1) the molar ratio of Sr to B to Cl to Bi to 2(1-x) to 5 to 9 to 1 to 2x, wherein x is a molar fraction and is more than or equal to 0.1% and less than or equal to 3.0%; respectively weighing a strontium-containing compound, a boron-containing compound, a chlorine-containing compound and a bismuth-containing compound as raw materials;
(2) grinding the raw materials weighed in the step (1) uniformly, then pre-burning for 3-6 hours at 623-823K, cooling to room temperature, grinding and uniformly mixing; calcining for 4-6 hours at 1073-1173K, cooling to room temperature along with the furnace, and grinding to obtain an intermediate product;
(3) and (3) reacting the intermediate product prepared in the step (2) for 15 minutes to 10 hours in a reducing atmosphere of 1073 to 1173K, cooling to room temperature, and grinding to obtain the near-infrared luminous bismuth-doped strontium chloropentaborate crystal.
3. The method for preparing the near-infrared luminescent bismuth-doped strontium chloropentaborate crystal according to claim 2, wherein the strontium-containing compound in the step (1) is strontium oxide or strontium carbonate.
4. The method for preparing a near-infrared luminescent bismuth-doped strontium chloropentaborate crystal according to claim 2 or 3, wherein the boron-containing compound in the step (1) is an oxide of boron or boric acid.
5. The method for preparing the near-infrared luminescent bismuth-doped strontium chloropentaborate crystal according to claim 2 or 3, wherein the chlorine-containing compound in the step (1) is strontium chloride, ammonium chloride or strontium chloride containing crystal water.
6. The method for preparing the near-infrared luminescent bismuth-doped strontium chloropentaborate crystal according to claim 2 or 3, wherein the bismuth-containing compound in the step (1) is bismuth trioxide or bismuth nitrate.
7. The method for preparing the near-infrared luminescent bismuth-doped strontium chloropentaborate crystal according to claim 2 or 3, wherein the reducing atmosphere in the step (3) is carbon monoxide or a mixed gas of hydrogen and nitrogen and hydrogen generated by incomplete combustion of graphite powder.
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| CN102703067A (en) * | 2012-05-08 | 2012-10-03 | 华南理工大学 | Near-infrared-luminescence bismuth-doped barium chloropentaborate crystal and preparation method thereof |
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| M2B5O9Cl:Eu（M=Ca、Sr、Ba）的真空紫外光谱特性研究;尤洪鹏;《中国稀土学会第四届学术会议年会论文集》;20001130;第427页图2 * |
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