CN116639975A - Blue light excited wide half-width near infrared fluorescent ceramic and preparation method and application thereof - Google Patents
Blue light excited wide half-width near infrared fluorescent ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- -1 gadolinium scandium aluminum Chemical compound 0.000 claims abstract description 10
- 239000002223 garnet Substances 0.000 claims abstract description 10
- 238000004020 luminiscence type Methods 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims abstract description 7
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 3
- 239000011651 chromium Substances 0.000 claims description 40
- 238000000498 ball milling Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 23
- 235000015895 biscuits Nutrition 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 1
- 238000000295 emission spectrum Methods 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
The invention discloses a blue light excited wide half-width near infrared fluorescent ceramic, a preparation method and application thereof, wherein the chemical formula of the near infrared fluorescent ceramic is (Gd) x1‑ Ca x ) 3 (Sc y1‑ Cr y ) 2 (Al 1‑ z Si z ) 3 O 12 Wherein 0.02 is less than or equal tox≤0.06，0.004≤y≤0.012，0.04≤z≤0.12，x:z=1, (1.5-2); the near infrared fluorescent ceramic is prepared by adopting a solid phase reaction method and combining high-temperature sintering. The valence state of Cr ion in the luminescent center of the near infrared fluorescent ceramic is +3, the main peak of the emission spectrum is 780-850nm, the half-width is 240-280nm, and the luminescent center of the near infrared fluorescent ceramic realizes 700-Near infrared luminescence at 950 nm. The near infrared fluorescent ceramic phase structure of the invention is gadolinium scandium aluminum garnet, and has the advantages of high luminous efficiency, half-width of emission spectrum and the like.
Description
Technical Field
The invention relates to the technical field of near infrared luminescent ceramic materials, in particular to a blue light excited wide half-width near infrared fluorescent ceramic, and a preparation method and application thereof.
Background
The near infrared spectrum technology has the advantages of no damage, high response speed and no pollution, and is widely studied in the fields of food detection, medical treatment and the like. The short-wave near-infrared is divided into 780nm to 1100nm, which covers the frequency multiplication and sum frequency characteristic information of the vibration of the hydrogen-containing group (O-H N-H C-H), the light emitting device of the wave band is adopted to irradiate the detection object, the specific substance can absorb the specific light wave band, and the substance and the content can be judged according to the information of the spectrum. Therefore, the short-wave near infrared spectrum technology is increasingly applied, and the deep research of the near infrared luminescent material is of great significance.
The traditional tungsten filament lamp and halogen lamp have large volume, short service life and low efficiency, and limit the light weight, miniaturization and portable development of devices. The LED type near infrared has the advantages of small volume, long service life, high luminous efficiency and the like, but the narrow bandwidth is insufficient to meet the emission spectrum requirement of a near infrared light source. Therefore, development of high-quality and high-performance near infrared fluorescent materials is urgently required. Trivalent Cr is taken as a typical transition metal ion, has outstanding advantages in the aspect of near infrared luminescent materials, has an emission range from dark red to near infrared, has a strong absorption peak in the visible spectrum range (ultraviolet and blue light), and is quite matched with a commercial blue LED chip. In recent years, cr is used 3+ Near infrared fluorescent materials as near infrared light emitting centers have been developed in a remarkable manner. Chinese patent CN111117618B discloses a compound with the chemical formula Gd x3- Re x Sc y z2-- Cr y Al z Ga 3 O 12 Is characterized in that Ga is contained in the core of the patent 3+ The ions occupy the entire tetrahedral sites in the matrix and the octahedral sites thereof contain Sc at the same time 3+ And Al 3+ Therefore, the material has a wide emission spectrum range (700-1000 nm). Chinese patent CN114058372a discloses a chemical formula a y2- Ln y BAl x4- Cr x SiO 12 The patent mainly uses Cr 3+ -Ln 3+ The energy transfer between the two luminescent powders widens the emission range (600 nm-1100 nm). Documents Journal of Luminescence, 2018, 202, 523-531 synthesizeX 3 Sc 2 Ga 3 O 12 (X=lu, Y, gd, la) series near infrared phosphors, the half width of which is extended from 73nm to 145nm by adjusting dodecahedron cations, but the thermal stability thereof is also reduced. Documents Journal of Materials Chemistry C, 2020, 8, 1981-1988 by Ca 2+ -Si 4+ Co-substituted Y 3+ -Al 3+ Y is prepared 3- x Ca x Al x5- Si x O 12 Cr near infrared fluorescent powder, the fluorescent powder emits spectrumThe maximum half-width is 160nm. However, the paper does not make a composition change to the octahedral sites of the matrix.
Chinese patent CN 113213933A discloses a compound of formula Y x z3-- A x Al x y5-- Si x O 12 ：yCr 3+ ，zYb 3+ Is a near infrared fluorescent ceramic. From the aspect of component analysis, the near infrared ceramics disclosed by the patent contain Y element and occupy larger area. Analysis from the luminescence center crystal field environment, in which the main peak of luminescence ion emission is mainly influenced by Y 3+ And the effect of the a ions. Chinese patent CN 113817468A discloses a compound of formula (a x B y ) 2 C 4 D 5 O 18 :aCr 3+ Cr of bRE 3+ The near infrared phosphor doped with cordierite, which is analyzed from the aspect of composition, has 18 oxygen components in total, and can be Cr 3+ Providing a plurality of crystallographic lattice sites, thereby obtaining a wide half-width emission characteristic. Chinese patent CN 113817468A discloses a chemical formula a x B y C z O q D p According to the method of this patent, a wide half-width can be obtained, however, as shown in this patent, the internal quantum efficiency is low (IQE is 14.1%,18.4%, etc.).
In summary, the existing near infrared luminescent materials have the problems of low luminous efficiency, narrow half-width of emission spectrum, neglecting valence state of Cr ions, and the like. Development of broad emission band, cr 3+ The near infrared fluorescent ceramics with stable valence state has important significance.
Disclosure of Invention
In order to solve the problems of thermal quenching and narrow emission spectrum of a near infrared luminescent material, the invention provides a blue light excited wide half-width near infrared fluorescent ceramic, a preparation method and application thereof, wherein the main peak of the emission spectrum of the fluorescent ceramic is 780-850nm under the excitation of blue light, the half-width is 240-280nm, and the valence state of Cr ions in a luminescent center is +3.
To solve the above problemsThe invention provides near infrared fluorescent ceramics for the fields of food detection, medical treatment and the like, which have the characteristics of stable luminescence, high half-width, small thermal quenching and the like, and adopts the following technical scheme: a blue light excited wide half-width near infrared fluorescent ceramic has a chemical formula of (Gd) x1- Ca x ) 3 (Sc y1- Cr y ) 2 (Al z1- Si z ) 3 O 12 WhereinxIs Ca 2+ Doped dodecahedral Gd 3+ The mole percentage of the lattice site is calculated,yis a luminescence center Cr 3+ Doped octahedral Sc 3+ The mole percentage of the lattice site is calculated,zis Si (Si) 4+ Doped tetrahedral Al 3+ Mole percent of lattice site is 0.02-lessx≤0.06，0.004≤y≤0.012，0.04≤z≤0.12，x:z=1 (1.5-2), the ceramic phase structure is gadolinium scandium aluminum garnet structure, cr 3+ To activate ions for luminescence, ca 2+ And Si (Si) 4+ Is to maintain Cr 3+ Charge-stabilized, hybridized luminescent ion surrounding dodecahedral Gd 3+ And tetrahedral Al 3+ Coordination environment, sc 3+ Is an octahedral framework ion.
The invention also provides a preparation method of the infrared fluorescent ceramic, and the preparation process is controllable.
In order to solve the technical problems, the preparation method of the near infrared fluorescent ceramic provided by the invention is a solid phase reaction method combined with high-temperature sintering, and comprises the following specific steps:
(1) According to the chemical formula (Gd x1- Ca x ) 3 (Sc y1- Cr y ) 2 (Al z1- Si z ) 3 O 12 The stoichiometric ratio of each element respectively weighing gadolinium oxide, calcium carbonate, scandium oxide, chromium oxide, aluminum oxide and silicon dioxide with the purity of more than 99.9 percent as raw material powder, whereinxIs Ca 2+ Doped dodecahedral Gd 3+ The mole percentage of the lattice site is calculated,yis a luminescence center Cr 3+ Doped octahedral Sc 3+ The mole percentage of the lattice site is calculated,zis Si (Si) 4+ Doped tetrahedral Al 3+ Mole percent of lattice site is 0.02-lessx≤0.06，0.004≤y≤0.012，0.04≤z≤0.12，x:z=1, (1.5-2); adding raw material powder, a ball milling medium and grinding balls into a ball milling tank for medium-speed ball milling to uniformly mix the mixed powder, adding the grinding balls into the ball milling tank for medium-speed ball milling at a ball milling speed of 90r/min-100r/min for 20h-30h to fully and uniformly mix the mixed powder;
(2) Drying the mixture after ball milling in an oven at 45-50 ℃, and sieving the dried powder with a 50-80 mesh sieve for 1-2 times;
(3) Placing the sieved powder into a mould for forming under the action of pressure to obtain a near infrared fluorescent ceramic biscuit;
(4) Placing the near infrared fluorescent ceramic biscuit in an inert atmosphere for high-temperature sintering at 1460-1480 ℃ for 2-4 hours to obtain unannealed near infrared fluorescent ceramic;
preferably, the ball milling medium is alcohol, the ratio of the alcohol to the raw material powder is 2.5:3.5, and the units are mL and g respectively.
Preferably, the ball milling rotating speed in the step (1) is 95r/min-100r/min, and the ball milling time is 25h-30h.
Preferably, in the step (1), the calcium carbonate and the silicon dioxide are nano powder, and the particle size is 10-20nm.
Preferably, the powder obtained after the mixed powder in the step (2) is dried is screened for 1-2 times through a 50-60-mesh screen.
Preferably, the high-temperature sintering temperature in the step (4) is 1470-1480 ℃, the heat preservation is carried out for 3-4 hours, and the heating rate during high-temperature sintering is 0.1-0.5 ℃/min.
The invention also provides application of the blue light excited wide half-width near infrared fluorescent ceramic.
The wide half-width near infrared fluorescent ceramic realizes near infrared luminescence of 700-950nm under the excitation of a high-power blue LED (2W-30W) or LD (1W-3W).
After the near infrared fluorescent ceramics and the blue light LED or the LD are remotely packaged, a near infrared light emitting device is obtained, and the near infrared light emitting device can be used in the fields of food detection, biomedical treatment and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) Ca provided by the invention 2+ And Si (Si) 4+ The proportion and the dosage can maintain Cr in the crystal structure 3+ The charge is stable, so that the valence state of Cr ions in the luminescent center of the near infrared fluorescent ceramic is +3.
(2) The near infrared fluorescent ceramic provided by the invention has an emission spectrum main peak of 780-850nm and a half-width of 240-280nm under blue light excitation. Ca provided according to the present invention 2+ 、Si 4+ The proportion and the dosage can lead the radii of dodecahedron, octahedron and tetrahedron lattice ions in the ceramic matrix of the gadolinium scandium aluminum garnet structure to be matched, and the dodecahedron Gd around the hybridized luminescent ion is hybridized on the premise of not generating a hetero phase 3+ And tetrahedral Al 3+ The coordination environment expands the half-width of the emission peak of the ceramic.
(3) The near infrared fluorescent ceramic provided by the invention effectively solves the problem of narrow half-width of a near infrared luminescent material, is simple to prepare and controllable in process, and realizes near infrared luminescence of 700-950nm under excitation of a high-power blue LED (2W-30W) or LD (1W-3W).
(4) The near infrared fluorescent ceramic and the LED or LD packaged near infrared light emitting device can be applied to the fields of food detection, biomedical treatment and the like.
Drawings
FIG. 1 is a diagram showing the near infrared fluorescent ceramics prepared in examples 1 to 3 of the present invention.
Fig. 2 is an XRD pattern of the near infrared fluorescent ceramics prepared in examples 1 to 3 of the present invention.
FIG. 3 is a graph showing the emission spectrum of the near infrared fluorescent ceramic prepared in example 3 of the present invention.
FIG. 4 is an SEM image of near infrared fluorescent ceramics prepared in example 3 of the invention.
FIG. 5 is an absorption spectrum of the near infrared fluorescent ceramic of comparative example 1.
FIG. 6 is an absorption spectrum of the near infrared fluorescent ceramic of comparative example 2.
FIG. 7 is an absorption spectrum of the near infrared fluorescent ceramic of comparative example 3.
FIG. 8 is an emission spectrum of the near infrared fluorescent ceramic of comparative example 4.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples. The raw material powders used in the following examples were all commercially available and had purities of more than 99.9%.
Example 1: preparation (Gd) 0.98 Ca 0.02 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.96 Si 0.04 ) 3 O 12 :
(1) Press (Gd) 0.98 Ca 0.02 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.96 Si 0.04 ) 3 O 12 The molar mass ratio of each element in the Gd-Gd composite material is accurately weighed 2 O 3 ，Sc 2 O 3 ，Cr 2 O 3 ，SiO 2 ，Al 2 O 3 Mixing the ball milling medium and the raw material powder according to the ratio of 2.5:3.5 (mL: g), adding a grinding ball, performing medium-speed ball milling in a ball milling tank at the ball milling rotating speed of 90r/min for 30h, and uniformly mixing the mixed powder.
(2) And (3) drying the ball-milled mixture in an oven at 45 ℃, and sieving the dried powder for 2 times through a 50-mesh sieve.
(3) And (3) placing the sieved powder into a mould to be molded under the action of pressure, so as to obtain a near infrared fluorescent ceramic biscuit, wherein the density of the biscuit is 40% of the theoretical density of gadolinium scandium aluminum garnet.
(4) And (3) placing the biscuit in an inert atmosphere for high-temperature sintering, wherein the sintering temperature is 1460 ℃, the heating rate is 0.5 ℃/min, and the temperature is kept for 4 hours to obtain the near infrared fluorescent ceramic.
FIG. 1 shows a ceramic article of this example. The XRD pattern of the ceramic of this example is shown in FIG. 2, which shows that the ceramic is gadolinium scandium aluminum garnet crystal phase. The main peak of the emission spectrum of the ceramic is 780nm, the half-width is 240 nm, and the valence state of Cr ions in the luminescence center is +3.
Example 2: preparation (Gd) 0.96 Ca 0.04 ) 3 (Sc 0.992 Cr 0.008 ) 2 (Al 0.94 Si 0.06 ) 3 O 12
(1) Press (Gd) 0.96 Ca 0.04 ) 3 (Sc 0.992 Cr 0.008 ) 2 (Al 0.94 Si 0.06 ) 3 O 12 The molar mass ratio of each element in the Gd-Gd composite material is accurately weighed 2 O 3 ，Sc 2 O 3 ，Cr 2 O 3 ，SiO 2 ，Al 2 O 3 Mixing the ball milling medium and the raw material powder according to the ratio of 2.5:3.5 (mL: g), adding a grinding ball, performing medium-speed ball milling in a ball milling tank at the ball milling speed of 95r/min for 25h, and uniformly mixing the mixed powder.
(2) The mixture after ball milling is dried in an oven at 48 ℃, and the dried powder is sieved for 2 times by a 70-mesh sieve.
(3) And (3) placing the sieved powder into a mould to be molded under the action of pressure, so as to obtain a near infrared fluorescent ceramic biscuit, wherein the density of the biscuit is 42% of the theoretical density of gadolinium scandium aluminum garnet.
(4) And (3) sintering the biscuit at a high temperature in an inert atmosphere, wherein the sintering temperature is 1470 ℃, the heating rate is 0.4 ℃/min, and the temperature is kept for 3 hours to obtain the near infrared fluorescent ceramic.
As shown in fig. 2, the XRD pattern of the ceramic of this example shows that the ceramic is gadolinium scandium aluminum garnet phase. The main peak of the emission spectrum of the ceramic is 820 nm, the half-width is 265 and nm, and the valence state of Cr ions in the luminescence center is +3. FIG. 1 shows a ceramic article of this example.
Example 3: preparation (Gd) 0.94 Ca 0.06 ) 3 (Sc 0.988 Cr 0.012 ) 2 (Al 0.88 Si 0.12 ) 3 O 12
(1) Press (Gd) 0.94 Ca 0.06 ) 3 (Sc 0.988 Cr 0.012 ) 2 (Al 0.88 Si 0.12 ) 3 O 12 The molar mass ratio of each element in the Gd-Gd composite material is accurately weighed 2 O 3 ，Sc 2 O 3 ，Cr 2 O 3 ，SiO 2 ，Al 2 O 3 Mixing the ball milling medium and the raw material powder according to the ratio of 2.5:3.5 (mL: g), adding the grinding balls, performing medium-speed ball milling in a ball milling tank at the ball milling rotating speed of 100r/min for 20h, and uniformly mixing the mixed powder.
(2) The mixed powder is dried in an oven at 50 ℃ and the dried powder is sieved for 1 time by a 80-mesh sieve. (3) And (3) placing the sieved powder into a mould to be molded under the action of pressure, so as to obtain a near infrared fluorescent ceramic biscuit, wherein the density of the biscuit is 45% of the theoretical density of gadolinium scandium aluminum garnet.
(4) And (3) placing the biscuit in an inert atmosphere for high-temperature sintering, wherein the sintering temperature is 1480 ℃, the heating rate is 0.5 ℃/min, and the temperature is kept for 2 hours to obtain the near infrared fluorescent ceramic.
The XRD pattern of the ceramic of this example is shown in FIG. 2, which shows that the ceramic is gadolinium scandium aluminum garnet phase. Fig. 3 is an emission spectrum of the near infrared fluorescent ceramic. Fig. 4 is a microscopic SEM image of the near infrared fluorescent ceramic. The main peak of the emission spectrum of the ceramic is 850nm, the half-width is 280nm, and the valence state of Cr ions in the luminescence center is +3. FIG. 1 shows a ceramic article of this example.
Comparative example 1: preparation (Gd) 0.96 Ca 0.04 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.96 Si 0.04 ) 3 O 12
Near infrared fluorescent ceramics were prepared according to the procedure of example 1 and the chemical formula of comparative example 1, and it was found that +4 was present in the valence state of Cr ion in the prepared ceramics. Illustrating the charge imbalance in the matrix system. The absorption spectrum of the near infrared fluorescent ceramic in comparative example 1 is shown in fig. 5.
Comparative example 2: preparation (Gd) 0.94 Ca 0.06 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.96 Si 0.04 ) 3 O 12
Near infrared fluorescent ceramics were prepared according to the procedure of example 1 and the chemical formula of comparative example 2, and it was found that +4 was present in the valence state of Cr ion in the prepared ceramics. Illustrating the charge imbalance in the matrix system. The absorption spectrum of the near infrared fluorescent ceramic in comparative example 2 is shown in FIG. 6
Comparative example 3: preparation (Gd) 0.98 Ca 0.02 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.94 Si 0.06 ) 3 O 12
Near infrared fluorescent ceramics were prepared according to the procedure of example 1 and the chemical formula of comparative example 3, and it was found that +4 was present in the valence state of Cr ion in the prepared ceramics. Illustrating the charge imbalance in the matrix system. The absorption spectrum of the near infrared fluorescent ceramic in comparative example 3 is shown in fig. 7.
Comparative example 4: preparation (Gd) 0.7 Ca 0.3 ) 3 (Sc 0.996 Cr 0.004 ) 2 (Al 0.7 Si 0.3 ) 3 O 12
Near infrared fluorescent ceramics were prepared according to the procedure of example 1 and the chemical formula of comparative example 4, and it was found that GdAlO appeared in the prepared ceramics 3 The material has an emission peak half width height of only 96 nm. Illustrating excessive Ca incorporation leading to Gd 3 Sc 2 Al 3 O 12 The system dodecahedron, octahedral and tetrahedral lattice ion radius matching is unstable and cannot promote half-width expansion. The emission spectrum of the near infrared fluorescent ceramic in comparative example 4 is shown in FIG. 8.
The combination of examples and comparative examples 1-4 shows that only suitable Ca is present 2+ 、Si 4+ The proportion and the dosage range can only maintain Cr 3 + Stable and broad half-width emission of ionic valence states.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The blue light excited wide half-width near infrared fluorescent ceramic is characterized by comprising the following chemical formula: (G)d 1-x Ca x ) 3 (Sc 1-y Cr y ) 2 (Al 1-z Si z ) 3 O 12 Wherein x is Ca 2+ Doped dodecahedral Gd 3+ Mole percent of lattice sites, y is the luminescence center Cr 3+ Doped octahedral Sc 3+ Mole percent of lattice sites, z is Si 4+ Doped tetrahedral Al 3+ The mole percentage of lattice sites is more than or equal to 0.02 and less than or equal to 0.06,0.004, y and less than or equal to 0.012,0.04 and less than or equal to 0.12, and x is less than or equal to z=1 (1.5-2), and the ceramic phase structure is a gadolinium scandium aluminum garnet structure.
2. The method for preparing the wide half-width near infrared fluorescent ceramic according to claim 1, which is characterized in that a ceramic block is prepared by sintering at high temperature by adopting a die forming combined with a solid phase reaction method, and specifically comprises the following steps:
(1) According to the chemical formula (Gd 1-x Ca x ) 3 (Sc 1-y Cr y ) 2 (Al 1-z Si z ) 3 O 12 The stoichiometric ratio of each element respectively weighing gadolinium oxide, calcium carbonate, scandium oxide, chromium oxide, aluminum oxide and silicon dioxide with the purity of more than 99.9 percent as raw material powder, adding the raw material powder, a ball milling medium and grinding balls into a ball milling tank for medium-speed ball milling, so that the mixed powder is uniformly mixed;
(2) Drying the mixture subjected to ball milling in an oven and sieving;
(3) Placing the sieved powder into a mould for forming under the action of pressure to obtain a near infrared fluorescent ceramic biscuit;
(4) And placing the biscuit in an inert atmosphere for high-temperature sintering to obtain the near infrared fluorescent ceramic.
3. The method for preparing blue light excited near infrared fluorescent ceramics with wide emission band according to claim 2, wherein the calcium carbonate and the silicon dioxide in the step (1) are nano powder with particle size of 10-50nm.
4. The method for preparing blue light excited near infrared fluorescent ceramics with wide emission band according to claim 2, wherein the ball milling medium in the step (1) is alcohol, and the ratio of the ball milling medium to the raw material powder is 2.5:3.5 (mL: g).
5. The method for preparing the blue light excited near infrared fluorescent ceramic with wide emission band according to claim 2, wherein the ball milling rotating speed in the step (1) is 90r/min-100r/min, and the ball milling time is 20h-30h.
6. The method for preparing blue light excited near infrared fluorescent ceramics with wide emission band according to claim 2, wherein the drying temperature in the step (2) is 45-50 ℃, and the dried powder is sieved for 1-2 times by a 50-80 mesh sieve.
7. The method for preparing blue light excited wide emission band near infrared fluorescent ceramic according to claim 2, wherein the density of the biscuit in the step (3) is 40% -45% of the theoretical density of the near infrared fluorescent ceramic.
8. The method for preparing blue light excited near infrared fluorescent ceramics with wide emission band according to claim 2, wherein the sintering temperature of the high-temperature sintering in the step (4) is 1460-1480 ℃, the temperature is kept for 2-4 h, and the heating rate during the high-temperature sintering is 0.1-0.5 ℃/min.
9. The blue-excited broad emission band near infrared fluorescent ceramic of claim 1, wherein the blue-excitation source is an LED or LD and the luminescence range is 430nm-465nm.
10. The blue light excited wide emission band near infrared fluorescent ceramic obtained by the preparation method of any one of claims 2 to 8, which is applied to a fluorescence conversion near infrared LED/LD device.
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