CN116042215B - Solid solution type near infrared long afterglow luminescent material and preparation method thereof - Google Patents
Solid solution type near infrared long afterglow luminescent material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 76
- 239000006104 solid solution Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000011651 chromium Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000012984 biological imaging Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium nitrate Inorganic materials [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims 1
- 229910000423 chromium oxide Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000011667 zinc carbonate Substances 0.000 claims 1
- 229910000010 zinc carbonate Inorganic materials 0.000 claims 1
- 235000004416 zinc carbonate Nutrition 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 238000000695 excitation spectrum Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000010431 corundum Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000002284 excitation--emission spectrum Methods 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 230000005284 excitation Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 3
- 239000003550 marker Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/685—Aluminates; Silicates
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
- C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
- C09K11/681—Chalcogenides
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
- C09K11/7702—Chalogenides with zinc or cadmium
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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Abstract
The invention discloses a solid solution type near infrared long afterglow luminescent material, which has the following chemical expression: [ (1-m) Zn 1‑y Ga 2‑a‑x M a O 4 ‑mCdGa 2 O 4 ]:xCr 3+ yR. The invention also provides a preparation method of the solid solution type near-infrared long-afterglow luminescent material. The novel solid solution type near infrared long afterglow luminescent material provided by the invention uses Cr 3+ The ions are activated ions, can be effectively excited by ultraviolet light and visible light, and generate near infrared long afterglow luminescence, and the rest has high brightness and long time. The near infrared long afterglow luminescent material provided by the invention can generate an ultralong afterglow duration of more than 10 hours after being excited by ultraviolet light for 5 minutes, and the afterglow performance is superior to that of the currently commercial ZnGa 2 O 4 :Cr 3+ Near infrared long afterglow luminescent material.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a solid solution type near-infrared long-afterglow luminescent material and a preparation method thereof.
Background
Long-afterglow luminescent materials, also known as light-accumulating luminescent materials, are essentially one of photoluminescent materials, which are capable of storing the energy of external light radiation (e.g. ultraviolet light, visible light, etc.), and slowly releasing the energy stored therein as visible light at room temperature. In recent years, long afterglow luminescent materials have been vigorously developed in the fields of bioimaging, optical information storage, marker tracing and the like. Currently, long afterglow luminescent materials are mainly concentrated in the visible light part, such as green SrAl 2 O 4 :Eu 2+ ,Dy 3+ Blue CaAl 2 O 4 :Eu 2+ ,Nd 3+ Orange Sr 3 SiO 5 :Eu 2+ ,Nd 5+ Red Y 2 O 2 S:Eu 3+ ,Mg 2+ ,Ti 4+ Etc., however, the near infrared band long afterglow luminescent materials are relatively scarce.
From the relative visual sensitivity function, the human eye has different degrees of light sensitivity to different wavelengths, and especially after 700nm light, the sensitivity of the human eye to spectrum is drastically reduced. Compared with the visible long-afterglow luminescent material, the near infrared long-afterglow luminescent material has irreplaceable functions in the aspects of marker tracing, infrared night vision, positioning, national defense, military and the like. Therefore, development of novel near infrared long afterglow luminescent materials with excellent performance is necessary.
Disclosure of Invention
The invention provides a solid solution type near infrared long afterglow luminescent material and a preparation method thereof, which are Cr, aiming at the defects of the prior art 3+ Activated near infrared ultra-long afterglow luminescent material, and the material has a specific ZnGa 2 O 4 :Cr 3 + More excellent long afterglow luminescence performance.
The specific technical scheme is as follows:
one of the purposes of the invention is to provide a solid solution type near infrared long afterglow luminescent material, which has the following chemical expression: [ (1-m) Zn 1-y Ga 2-a-x M a O 4 -mCdGa 2 O 4 ]:xCr 3+ ,yR；
Wherein: m is Al, in, si, ge, sn, sb or Zr; r is Li + 、Na + 、K + 、Sc 3+ 、Y 3+ 、La 3+ 、Ce 3+ 、Pr 3+ 、Nd 3+ 、Sm 3+ 、Gd 3+ 、Tb 3+ 、Dy 3+ 、Ho 3+ 、Er 3+ 、Tm 3+ 、Yb 3+ Or Lu 3+ ；
Wherein: x, y, a, m the molar coefficient is that x is more than or equal to 0.0001 and less than or equal to 0.30,0, y is more than or equal to 0.20, m is more than or equal to 0 and less than or equal to 1.0, and a is more than or equal to 0 and less than or equal to 1.0.
Further, in the formula: x is more than or equal to 0.001 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.05,0.05, m is more than or equal to 1.0, and a is more than or equal to 0 and less than or equal to 0.5.
Still further, wherein: x is more than or equal to 0.01 and less than or equal to 0.10,0, y is more than or equal to 0.03,0.075 and m is more than or equal to 0.75,0 and a is more than or equal to 0.3.
Still further preferably, the solid solution type near infrared long afterglow luminescent material is one or more than two of the following chemical formulas:
[0.9ZnGa 1.99 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.25ZnGa 1.9 O 4 -0.75CdGa 2 O 4 ]:0.1Cr 3+ ；
[0.5ZnGa 1.96 O 4 -0.5CdGa 2 O 4 ]:0.04Cr 3+ ；
[0.85Zn 0.98 Ga 1.98 O 4 -0.15CdGa 2 O 4 ]:0.02Cr 3+ ,0.02Li + ；
[0.925Zn 0.97 Ga 1.99 O 4 -0.075CdGa 2 O 4 ]:0.01Cr 3+ ,0.03Lu 3 ； +
[0.9ZnGa 1.79 Al 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.85ZnGa 1.69 Ge 0.3 O 4 -0.15CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.8ZnGa 1.78 In 0.2 O 4 -0.2CdGa 2 O 4 ]:0.02Cr 3+ ；
[0.9Zn 0.98 Ga 1.79 Ge 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ,0.02La 3+ 。
the second object of the invention is to provide a preparation method of the solid solution type near-infrared long afterglow luminescent material, which comprises the following steps:
(1) Weighing the compounds containing the corresponding elements according to the composition and proportion of the corresponding chemical expression, grinding and uniformly mixing; the compound is one or more than two of carbonate, oxide, basic carbonate, oxalate, nitrate and acetate of corresponding elements;
(2) And sintering for 2-20 hours at 1000-1400 ℃ in air, taking out the sample, and grinding to obtain the solid solution type near infrared long afterglow luminescent material.
Specifically, in step (1): mixing Zn-containing compound, ga-containing compound, M-containing compound, cd-containing compound, cr-containing compound and R-containing compound, and grinding to obtain mixture.
Further, in step (1): the Zn-containing compound is preferably an oxide, carbonate or hydroxycarbonate of zinc.
Further, in step (1): the Cd-containing compound is preferably an oxide or carbonate of cadmium.
Further, in step (1): the M-containing compound is preferably an M-containing oxide or nitrate.
Further, in step (1): the Cr-containing compound is preferably an oxide or nitrate of chromium.
Further, in step (1): the Ga-containing compound is preferably an oxide or nitrate of gallium.
Further, in step (1): the R-containing compound is preferably an R-containing oxide, nitrate or carbonate.
Still further, in step (1): the compound is oxide of corresponding elements.
Further, in step (2): the sintering condition is preferably 1100-1300 ℃ for 3-15 hours.
The invention further aims to provide application of the solid solution type near-infrared long-afterglow luminescent material, and the material has wide application prospects in military, anti-counterfeiting, optical information storage, biological imaging and other aspects.
The beneficial effects of the invention are as follows:
the novel solid solution type near infrared long afterglow luminescent material provided by the invention has the advantages of ZnGa and the like 2 O 4 Solid solution material of the same crystal structure, which is Cr 3+ The ions are active ions, can be effectively excited by ultraviolet light and visible light to generate near infrared long surplusGlow luminescence (wavelength range is 600 nm-800 nm, main peak of afterglow spectrum is near 690 nm), other glow has high brightness and long time. The near infrared long afterglow luminescent material provided by the invention can generate an ultralong afterglow duration of more than 10 hours after being excited by ultraviolet light for 5 minutes, and the afterglow performance is superior to that of the currently commercial ZnGa 2 O 4 :Cr 3+ Near infrared long afterglow luminescent material. The material has wide application prospect in military, anti-counterfeiting, optical information storage, biological imaging and other aspects. In addition, the material preparation process is simple, the product chemical property is stable, the radioactivity is avoided, and the technical popularization is easy.
Drawings
FIG. 1 is an XRD diffraction pattern and standard card (PDF#38-1240) of the novel solid solution type near infrared long afterglow luminescent material prepared in example 1;
FIG. 2 shows the excitation spectrum and the emission spectrum of the novel solid solution type near infrared long afterglow luminescent material prepared in example 1;
FIG. 3 is an afterglow spectrum of a novel solid solution type near infrared long afterglow luminescent material prepared in example 1 after excitation by 254nm ultraviolet light;
FIG. 4 shows a novel solid solution type near infrared long afterglow luminescent material (upper end curve) and ZnGa prepared in example 1 2 O 4 :Cr 3+ (lower end curve) afterglow decay curve after excitation with 254nm ultraviolet light.
Detailed Description
The principles and features of the present invention are described below in connection with examples, which are set forth only to illustrate the present invention and not to limit the scope of the invention. The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material,the molar ratio between them is 0.9:0.9955:0.1:0.005; accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 4 hours at 1300 ℃ in a high-temperature furnace under the air condition, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.9ZnGa ] 1.99 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ 。
The sample obtained in example 1 was subjected to X-ray diffraction analysis using an instrument of Bruker/D8-FOCUS X-Ray Diffractometer, germany, with a radiation source of Cu K.alpha.1 (lambda= 1.5405 nm), scanning range: 2θ=10 o -80 o Scanning speed 10 o /min. FIG. 1 shows XRD diffraction patterns and standard cards of a novel solid solution type near infrared long afterglow luminescent material prepared in example 1 of the present invention, and it can be seen from FIG. 1a that the solid solution type near infrared long afterglow luminescent material prepared in example 1 of the present invention is ZnGa 2 O 4 Crystalline phase, and standard card (ZnGa 2 O 4 PDF # 38-1240).
And (4) performing excitation spectrum, emission spectrum, afterglow spectrum and afterglow attenuation test on the obtained sample, wherein the results are shown in figures 2-4. Wherein FIG. 2 shows the excitation spectrum and the emission spectrum of the long afterglow luminescent material according to the invention as prepared in example 1. As can be seen from the graph, the long afterglow luminescent material provided by the invention can be effectively excited by ultraviolet light and visible light, and the emission spectrum of the long afterglow luminescent material consists of a series of peaks covering 650nm to 800nm (wherein 350nm in the excitation spectrum is an instrument frequency multiplication peak). FIG. 3 shows the afterglow spectrum of the long afterglow luminescent material of example 1 of the invention after excitation by 254nm ultraviolet light, and FIG. 3 shows that the main peak of the afterglow spectrum of the long afterglow luminescent material of example 1 is located near 690nm and is near infrared long afterglow. FIG. 4 is a graph of [0.9ZnGa 1.99 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ (upper end curve) and ZnGa 2 O 4 :Cr 3+ As can be seen from FIG. 4, the long-afterglow luminescent material prepared in example 1 has an afterglow decay curve at 254nm ultraviolet light excitation, at 25After 4nm ultraviolet light excitation, the near infrared long afterglow brightness ratio of ZnGa 2 O 4 :Cr 3+ High afterglow duration ratio of ZnGa 2 O 4 :Cr 3+ And the test results show that the long afterglow luminescent material prepared in example 1 can reach afterglow time of 10 hours.
Example 2
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material, a molar ratio between them was 0.25:0.9875:0.75:0.05, accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 4 hours at 1300 ℃ in a high-temperature furnace under the air condition, naturally cooling to room temperature, and grinding to obtain a light green powder sample, wherein the chemical composition of the light green powder sample is [0.25ZnGa ] 1.9 O 4 -0.75CdGa 2 O 4 ]:0.1Cr 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 5 hours.
Example 3
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material, a molar ratio between them was 0.5:0.99:0.5:0.02, accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Step (1)) The obtained product is put into a corundum crucible, baked for 6 hours at 1250 ℃ in a high temperature furnace under the air condition, naturally cooled to room temperature, and then ground, thus obtaining a white powder sample with the chemical composition of [0.5ZnGa ] 1.96 O 4 -0.5CdGa 2 O 4 ]:0.04Cr 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 6 hours.
Example 4
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), cdO (analytically pure), cr 2 O 3 (99.99%) and Li 2 CO 3 (analytically pure) as starting material, the molar ratio between them being 0.833:0.9915:0.15:0.01:0.01, accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting in a high-temperature furnace at 1200 ℃ for 6 hours under the air condition, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.85Zn ] 0.98 Ga 1.98 O 4 -0.15CdGa 2 O 4 ]:0.02Cr 3+ ,0.02Li + . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ Is excited by 254nm ultraviolet lightThe post-afterglow decay curve was similar to that of example 1 (shown in FIG. 4), and the test results showed that the afterglow time of the sample could reach 11 hours.
Example 5
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), cdO (analytically pure), cr 2 O 3 (99.99%) and Lu 2 O 3 (analytically pure) as starting material, the molar ratio between them being 0.8973:0.9954:0.075:0.005:0.015, accurately weighing the substances, and fully and uniformly grinding the substances in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 8 hours at 1250 ℃ in a high-temperature furnace under the air condition, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.925Zn ] 0.97 Ga 1.99 O 4 -0.075CdGa 2 O 4 ]:0.01Cr 3+ ,0.03Lu 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ The decay curve of the afterglow after excitation by 254nm ultraviolet light is similar to that of example 1 (shown in FIG. 4), and the test results show that the afterglow time of the sample can reach 13 hours.
Example 6
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), al 2 O 3 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material, a molar ratio between them was 0.9:0.9055:0.09:0.1:0.005 accurately weighing the above materials, and placing in an agate mortarFully and uniformly grinding;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 6 hours at 1300 ℃ in a high-temperature furnace, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.9ZnGa ] 1.79 Al 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 8 hours.
Example 7
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), geO 2 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material, a molar ratio between them was 0.85:0.8683:0.255:0.15:0.005, accurately weighing the above materials, and fully and uniformly grinding in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 7 hours at 1300 ℃ in a high-temperature furnace under the air condition, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.85ZnGa ] 1.69 Ge 0.3 O 4 -0.15CdGa 2 O 4 ]:0.01Cr 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 10 hours.
Example 8
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytical grade), in 2 O 3 (analytically pure), cdO (analytically pure) and Cr 2 O 3 (99.99%) as a raw material, a molar ratio between them was 0.8:0.912:0.08:0.2:0.01, accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, roasting for 7 hours at 1300 ℃ in a high-temperature furnace under the air condition, naturally cooling to room temperature, and grinding to obtain a white powder sample, wherein the chemical composition of the white powder sample is [0.8ZnGa ] 1.78 In 0.2 O 4 -0.2CdGa 2 O 4 ]:0.02Cr 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 8 hours.
Example 9
The preparation method of the solid solution type near-infrared long-afterglow luminescent material comprises the following steps:
(1) ZnO (analytically pure), ga 2 O 3 (analytically pure), geO 2 (analytically pure), cdO (analytically pure), cr 2 O 3 (99.99%) and La 2 O 3 (analytically pure) as starting material, the molar ratio between them being 0.882:0.9055:0.18:0.1:0.005:0.01, accurately weighing the materials, and fully and uniformly grinding the materials in an agate mortar;
(2) Placing the product obtained in the step (1) into a corundum crucible, and emptyingRoasting in a high temperature furnace at 1300 deg.c for 7 hr under gas condition, naturally cooling to room temperature, grinding to obtain white powder sample with chemical composition of 0.9Zn 0.98 Ga 1.79 Ge 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ,0.02La 3+ . The excitation spectrum and emission spectrum are similar to those of example 1 (shown in fig. 2). After the sample is excited by 254nm ultraviolet light, the sample emits near infrared long afterglow, similar to that of the example 1 (shown in figure 3), and the main peak of the rest glow spectrum is located near 690 nm; after the sample is excited by 254nm ultraviolet light, the near infrared long afterglow brightness ratio of the sample is ZnGa 2 O 4 :Cr 3+ Bright and duration time ratio ZnGa 2 O 4 :Cr 3+ And the test results show that the afterglow time of the sample can reach 10 hours.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A solid solution type near infrared long afterglow luminescent material, which is characterized by having the following chemical expression: [ (1-m) Zn 1-y Ga 2-a-x M a O 4 -mCdGa 2 O 4 ]:xCr 3+ ,yR；
Wherein: m is Al, in or Ge; r is Li + 、La 3+ Or Lu 3+ ；
Wherein: x, y, a, m the molar coefficient is that x is more than or equal to 0.001 and less than or equal to 0.20, y is more than or equal to 0 and less than or equal to 0.05,0.05, m is more than or equal to 0.75,0 and less than or equal to 0.5.
2. The solid solution-type near-infrared long-afterglow luminescent material according to claim 1, characterized in that: x is more than or equal to 0.01 and less than or equal to 0.10,0, y is more than or equal to 0.03,0.075 and m is more than or equal to 0.75,0 and a is more than or equal to 0.3.
3. The solid solution type near infrared long afterglow luminescent material according to claim 2, characterized by being one or more than two of the following chemical formulas:
[0.9ZnGa 1.99 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.25ZnGa 1.9 O 4 -0.75CdGa 2 O 4 ]:0.1Cr 3+ ；
[0.5ZnGa 1.96 O 4 -0.5CdGa 2 O 4 ]:0.04Cr 3+ ；
[0.85Zn 0.98 Ga 1.98 O 4 -0.15CdGa 2 O 4 ]:0.02Cr 3+ ,0.02Li + ；
[0.925Zn 0.97 Ga 1.99 O 4 -0.075CdGa 2 O 4 ]:0.01Cr 3+ ,0.03Lu 3+ ；
[0.9ZnGa 1.79 Al 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.85ZnGa 1.69 Ge 0.3 O 4 -0.15CdGa 2 O 4 ]:0.01Cr 3+ ；
[0.8ZnGa 1.78 In 0.2 O 4 -0.2CdGa 2 O 4 ]:0.02Cr 3+ ；
[0.9Zn 0.98 Ga 1.79 Ge 0.2 O 4 -0.1CdGa 2 O 4 ]:0.01Cr 3+ ,0.02La 3+ 。
4. a method for preparing the solid solution type near infrared long afterglow luminescent material according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) Weighing the compounds containing the corresponding elements according to the composition and proportion of the corresponding chemical expression, grinding and uniformly mixing; the compound is one or more than two of carbonate, oxide, basic carbonate, oxalate, nitrate and acetate of corresponding elements;
(2) And sintering for 2-20 hours at 1000-1400 ℃ in air, taking out the sample, and grinding to obtain the solid solution type near infrared long afterglow luminescent material.
5. The method according to claim 4, wherein in the step (1):
the Zn-containing compound is zinc oxide, carbonate or basic carbonate;
the Cd-containing compound is an oxide or carbonate of cadmium;
the compound containing M is an oxide or nitrate containing M;
the Cr-containing compound is chromium oxide or nitrate;
the Ga-containing compound is an oxide or nitrate of gallium;
the compound containing R is oxide, nitrate or carbonate containing R.
6. The method according to claim 5, wherein in the step (1): the compound is oxide of corresponding elements.
7. The method according to claim 4, wherein in the step (2): the sintering condition is 1100-1300 ℃ for 3-15 hours.
8. Use of the solid solution type near infrared long afterglow luminescent material according to any one of claims 1 to 3 in military, anti-counterfeiting, optical information storage or biological imaging fields.
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| CN106957646A (en) * | 2017-03-29 | 2017-07-18 | 中国科学院福建物质结构研究所 | A kind of gallate long-persistence nano-luminescent materials and its preparation method and application |
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