CN114806564A - Trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material, preparation method and LED light source thereof - Google Patents
Trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material, preparation method and LED light source thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 66
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 40
- 239000011737 fluorine Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910001430 chromium ion Inorganic materials 0.000 title claims abstract description 19
- 239000011651 chromium Substances 0.000 claims abstract description 97
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- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- C09K11/75—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth containing antimony
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Abstract
The invention discloses a trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding an Na source, and continuously stirring to form a mixed solution; putting the mixed solution into a reaction device for reaction, washing and drying to obtain Cr 3+ Doping a fluorine antimonate near-infrared fluorescent material; the Cr is 3+ The chemical composition of the doped fluorine antimonate near-infrared fluorescent material is as follows: NaSbF 4 ：xCr 3+ And x is 0.5 to 5%. The invention provides Cr 3+ The fluorine antimonate doped near-infrared fluorescent material has high fluorescence quantum efficiency and absorption efficiency, and the preparation method is simple and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to a trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material, a preparation method and an LED light source thereof.
Background
The near infrared spectrum technology has different scattering spectrum shapes and intensities for substances, and can be widely applied to the fields of biomedical imaging, food detection, night vision imaging and the like. At present, commercial near-infrared light sources mainly comprise tungsten halogen lamps, near-infrared LEDs and infrared lasers. However, the conventional tungsten halide has a broad emission spectrum, but has the disadvantages of large volume, slow response, low efficiency, short service life, a large amount of visible light in the spectrum, and the like. The near-infrared LED and the infrared laser have the characteristics of small volume and high efficiency, but the near-infrared LED and the infrared laser have narrow emission band, unstable emission wavelength and poor luminous thermal stability, and cannot be widely applied to the technical field of near-infrared spectroscopy. With the rapid development of the LED technology, the near-infrared light source can be realized by exciting the near-infrared fluorescent powder by using the high-efficiency blue LED chip. The LED light source (pc-LED) based on the fluorescent powder conversion has the advantages of wide emission spectrum bandwidth, controllable adjustment, high thermal stability, high efficiency, low cost and the like, and shows wide application prospect. At present, the broadband near-infrared pc-LED technology is in a primary stage, photoelectric conversion efficiency is low, output power is low, an emission band is not wide enough, the wide application of near infrared cannot be met, and the development of an efficient broadband near-infrared fluorescent material is the key for solving the problems.
Disclosure of Invention
The technical problem to be solved by the invention is to provide trivalent chromium ions (Cr) 3+ ) The preparation method of the doped fluorine antimonate near-infrared fluorescent material adopts a hydrothermal method, is simple to operate, has easily obtained raw materials and low cost, and is suitable for industrial large-scale production.
The technical problem to be solved by the present invention is to provide a trivalent chromium ion (Cr) 3+ ) Fluorine antimonate doped near-infrared fluorescent material, and Cr thereof 3+ Doped with fluoroantimonateThe infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm to emit broadband near-infrared light with the wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and the quantum efficiency is 53-55%.
The invention also provides an LED light source, wherein the electro-optic conversion efficiency is 9-12% under 100mA, and the LED light source is a broadband near-infrared LED light source.
In order to solve the technical problem, the invention provides Cr 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding an Na source, and continuously stirring to form a mixed solution;
putting the mixed solution into a reaction device for reaction, washing and drying to obtain Cr 3+ Doping a fluorine antimonate near-infrared fluorescent material;
the Cr is 3+ The chemical composition of the doped fluorine antimonate near-infrared fluorescent material is as follows: NaSbF 4 ：xCr 3+ ，x＝0.5～5％。
Preferably, the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the amount of the HF solution is 0.7-0.9 g/mL.
Preferably, in the Sb source and the Na source, the molar ratio of Sb to Na is 1: (1-3);
in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005-0.05): 1.
preferably, the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 ；
The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 ；
The Na source is NaF or NaHF 2 And Na 2 CO 3 One of (1);
the mass fraction of the HF solution is 20-60 wt%.
Preferably, the mixed solution is put into a high-pressure reaction kettle, reacted for 6 to 15 hours at the temperature of 180-220 ℃, cooled, washed and dried to obtain a finished product.
Preferably, in the washing and drying process, deionized water is adopted for washing for 1-3 times, then an organic solvent is used for washing for 1-2 times so as to remove residual reaction liquid on the surface, and then drying is completed at the temperature of 50-100 ℃.
In order to solve the problems, the invention also provides Cr 3+ The fluorine-doped antimonate near-infrared fluorescent material is prepared by the preparation method.
Preferably, the Cr is 3+ The fluorine-doped antimonate near-infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm to emit broadband near-infrared light with the wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and the quantum efficiency is 53-55%.
In order to solve the above problems, the present invention also provides an LED light source, which is manufactured by the following method: adding the above Cr 3+ Uniformly mixing the doped fluorine antimonate near-infrared luminescent fluorescent material with epoxy resin to obtain a mixed material;
and coating the mixed material on a blue LED chip, and curing to obtain a finished product.
Preferably, the Cr is 3+ Doping fluorine antimonate near-infrared luminescent fluorescent material and epoxy resin according to the proportion of 1: (1-4) in a mass ratio.
The implementation of the invention has the following beneficial effects:
the invention provides Cr 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material has the advantages of simple process, short period, low cost, high yield and easy large-scale production. Prepared Cr 3+ The fluorine-doped antimonate near-infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm to emit broadband near-infrared light with the wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and the quantum efficiency is 53-55%. Adding the Cr 3+ The doped fluorine antimonate near-infrared fluorescent material is made into an LED light source, the electro-optic conversion efficiency of the LED light source is 9-12% under 100mA, the LED light source is a broadband near-infrared LED light source, and the wide application prospect is achieved in the near-infrared imaging field.
Drawings
FIG. 1 is a drawing showing a preparation process of example 1 of the present inventionThe obtained NaSbF 4 :0.5％Cr 3+ XRD spectrogram of the near-infrared fluorescent material;
FIG. 2 shows NaSbF prepared in example 1 of the present invention 4 :0.5％Cr 3+ Excitation and emission spectrograms of the near-infrared fluorescent material;
FIG. 3 shows NaSbF samples prepared in example 4 of the present invention 4 :3％Cr 3+ A quantum efficiency map of the near-infrared fluorescent material;
FIG. 4 is an electroluminescence spectrum of an LED light source prepared from the near-infrared fluorescent materials prepared in examples 1 to 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
In order to solve the above technical problems, the present invention provides a trivalent chromium ion (Cr) 3+ ) The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
s1, dissolving the Sb source and the Cr source in the HF solution, stirring until the Sb source and the Cr source are dissolved, adding the Na source, and continuously stirring to form a mixed solution;
s2, loading the mixed solution into a reaction device for reaction, washing and drying to obtain Cr 3+ Doping a fluorine antimonate near-infrared fluorescent material;
the Cr is 3+ The chemical composition of the doped fluorine antimonate near-infrared fluorescent material is as follows: NaSbF 4 ：xCr 3+ ，x＝0.5～5％。
ABCF in the prior art 6: xCr 3+ Is relatively common Cr 3+ Doped near-infrared fluorescent materials, wherein A represents alkali metals, B represents alkaline earth metals, and C represents elements of a third main group or a third subgroup. Most of the near-infrared fluorescent materials belong to a double-perovskite structure, B 2+ And C 3+ Ions all adopt octahedral coordination, Cr 3+ Ions tend to occupy both sites simultaneously, so that the distance between two luminescent centers is too close, causing fluorescence quenching.
The invention adopts the fluorine antimonate NaSbF 4 In the structure of (1), Sb 3+ Ion and 6 fluorine ionsCoordination forming distorted octahedra with large distance between octahedra, Na + The ions adopt nine coordination. Cr (chromium) component 3+ Ions occupying Sb only 3+ Lattice site, high fluorescence quenching concentration and high fluorescence quantum efficiency, [ SbF 6 ]The octahedron is seriously distorted and can greatly inhibit Cr 3+ The forbidden transition law of electrons on the outer layer of d3 of the ion obtains larger fluorescence quantum efficiency and absorption efficiency.
In step S1, the ratio of the sum of the amounts of the Sb source, the Cr source and the Na source added to the amount of the HF solution is preferably 0.7 to 0.9 g/mL. It should be noted that, the ratio of the sum of the added amounts of the Sb source, the Cr source and the Na source to the amount of the HF solution is less than 0.7g/mL, a hetero phase occurs, and the luminous efficiency of the sample is reduced; the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the amount of the HF solution is more than 0.9g/mL, so that a hetero phase appears, the luminous efficiency of the sample is reduced, and the crystallinity of the sample is reduced. More preferably, the ratio of the sum of the addition amounts of the Sb source, the Cr source and the Na source to the amount of the HF solution is 0.8 g/mL.
Preferably, in the Sb source and the Na source, the molar ratio of Sb to Na is 1: (1-3), specifically, the molar ratio of Sb to Na is less than 1: 1, will result in the generation of Sb-containing element impurity phase; the molar ratio of Sb to Na is more than 1: 3, leading to the generation of Na element-containing hetero-phase. More preferably, the molar ratio of Sb to Na is 1: 1.
preferably, in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005-0.05): 1, in particular, the molar ratio of Cr to Sb is less than 0.005: 1, will result in NaSbF 4 :Cr 3+ The luminous efficiency of the fluorescent powder is very low; the molar ratio of Cr to Sb is more than 0.05: 1, will result in NaSbF 4 :Cr 3+ The phosphor is concentration quenched and Na is produced 3 CrF 6 And (3) impurity phase. More preferably, the molar ratio of Cr to Sb is (0.01-0.03): 1.
preferably, the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 (ii) a The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 (ii) a The Na source is NaF or NaHF 2 And Na 2 CO 3 One of (1); the HF solutionThe mass fraction of the liquid is 20-60 wt%. More preferably, the Sb source is Sb 2 O 3 (ii) a The Cr source is Cr (NO) 3 ) 3 ·9H 2 O; the Na source is NaHF 2 . The mass fraction of the HF solution is 25-35 wt%.
In the step S2, compared with the method of co-precipitation in the prior art to prepare the near-infrared fluorescent material, the method of hydrothermal preparation of the near-infrared fluorescent material of the present invention has the advantages of simple process, short period, low cost, high yield, and easy mass production. In addition, the solvent is single in the preparation process, only HF solution is needed, impurities are not easy to generate, and the prepared finished product has pure crystalline phase.
Preferably, the mixed solution is put into a high-pressure reaction kettle, reacted for 6 to 15 hours at the temperature of 180-220 ℃, cooled, washed and dried to obtain a finished product. More preferably, the reaction is carried out for 10-12h at 200-220 ℃, and then the product is obtained after cooling, washing and drying.
It should be noted that technical difficulties exist in the post-treatment process during the preparation process. After the hydrothermal reaction is finished, NaSb needs to be washed and removed 1-x F 4 :xCr 3+ HF solution remained on the surface of the near-infrared fluorescent material, but the HF solution is directly added with an organic solvent for washing, so that the surface appearance of a product is easily influenced, the product tends to be fluffy, and the luminous efficiency is influenced. On the other hand, due to NaSbF 4 The solubility of (A) is higher, and the NaSbF can be caused by directly adding a large amount of deionized water for washing 4 Dissolving and precipitating CrF 3 . Therefore, the composition of the washing solution used in the washing process has a large impact on the properties of the final product. Preferably, in the washing and drying process, deionized water is firstly adopted for washing for 1-3 times, then an organic solvent is used for washing for 1-2 times so as to remove residual reaction liquid on the surface, and then drying is completed at the temperature of 50-100 ℃. Preferably, the organic solvent is ethanol or acetone, and the drying is completed at the temperature of 70-80 ℃.
In conclusion, the Cr prepared by the preparation method 3+ The doped fluorine antimonate near-infrared fluorescent material can be excited by blue light or green light with the wavelength of 400-650nm to emit broadband near-infrared light with the wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and quanta are formed in the fluorescent materialThe efficiency is 53-55%.
Correspondingly, the invention also provides an LED light source which is prepared by adopting the following method: adding the above Cr 3+ Uniformly mixing the doped fluorine antimonate near-infrared luminescent fluorescent material with epoxy resin to obtain a mixed material; and coating the mixed material on a blue LED chip, and curing to obtain a finished product. Preferably, the Cr is 3+ Doping fluorine antimonate near-infrared luminescent fluorescent material and epoxy resin according to the proportion of 1: (1-4) in a mass ratio. The electro-optic conversion efficiency of the LED light source is 9-12% under 100mA, the broadband near-infrared LED light source is provided, and the broadband near-infrared LED light source has a wide application prospect in the field of near-infrared imaging.
The invention is further illustrated by the following specific examples:
example 1
Cr (chromium) 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
mixing 0.024g Cr (NO) 3 )·9H 2 O，1.74g Sb 2 O 3 Dissolved in 3mL of 49 wt% HF solution, stirred until completely dissolved, and then 0.4199g of NaHF was added 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220 ℃ for 10h, cooling to room temperature, centrifugally washing with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, filtering, and drying at 70 ℃ for 8 hours to obtain NaSbF 4 :0.5％Cr 3+ 。
Example 2
Cr (chromium) 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
mixing 0.024g Cr (NO) 3 )·9H 2 O，1.74g Sb 2 O 3 Dissolving the NaSbF into 3mL of HF solution with the mass concentration of 20 wt%, stirring until the NaSbF is completely dissolved, adding 0.4199g of NaF, continuously stirring for 30min, transferring the NaSbF into a high-pressure reaction kettle, reacting at 200 ℃ for 10h, cooling to room temperature, centrifugally washing with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, filtering, and drying at 80 ℃ for 8 hours to obtain NaSbF 4 :0.5％Cr 3+ 。
Example 3
Cr (chromium) 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
0.048g of Cr (NO) 3 )·9H 2 O，1.731g Sb 2 O 3 Dissolved in 3mL of a 30 wt% HF solution, stirred to complete dissolution, and then 0.6199g of NaHF was added 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220 ℃ for 10h, cooling to room temperature, centrifugally washing with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, filtering, and drying at 70 ℃ for 8 hours to obtain NaSbF 4 :1％Cr 3+ 。
Example 4
Cr (chromium) 3+ The preparation method of the doped fluorine antimonate near-infrared fluorescent material comprises the following steps:
0.144g of Cr (NO) 3 )·9H 2 O，1.696g Sb 2 O 3 Dissolved in 3mL of 49 wt% HF solution, stirred until completely dissolved, and then 0.6199g of NaHF was added 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220 ℃ for 10h, cooling to room temperature, centrifugally washing with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, filtering, and drying at 70 ℃ for 8 hours to obtain NaSbF 4 :3％Cr 3+ 。
Example 5
Cr (chromium) 3+ The preparation method of the fluorine antimonate doped near-infrared fluorescent material comprises the following steps:
0.24g of Cr (NO) 3 )·9H 2 O，1.661g Sb 2 O 3 Dissolved in 3mL of 49 wt% aqueous HF solution, stirred to complete dissolution, and then 0.6199g of NaHF was added 2 Stirring for 30min, transferring to a high-pressure reaction kettle, reacting at 220 ℃ for 10h, cooling to room temperature, centrifugally washing with deionized water for 2 times, centrifugally washing with absolute ethyl alcohol for 1 time, filtering, and drying at 70 ℃ for 8 hours to obtain NaSbF 4 :5％Cr 3+ 。
Cr obtained in example 1 3+ XRD test and excitation and emission spectrum evaluation are carried out on the doped fluorine antimonate near-infrared fluorescent material, and FIG. 1 shows that Cr prepared in example 1 is 3+ XRD spectrogram of doped fluorine antimonate near-infrared fluorescent powder prepared fromAs can be seen in FIG. 1, the XRD diffraction peaks of the samples obtained are consistent with those of standard card JCPDS No.34-0428, which shows that NaSbF is obtained 4 :0.5％Cr 3+ Is a pure phase.
FIG. 2 shows Cr obtained in example 1 3+ Excitation and emission spectrograms of the fluorine antimonate doped near-infrared fluorescent powder, wherein the excitation spectrum of a sample consists of two broad peaks of 428nm and 600nm, the strongest excitation is positioned at 428nm, the emission is broad-peak near-infrared light of 700-900nm, and the strongest emission wavelength is 762 nm.
Meanwhile, NaSbF prepared in example 4 was used 4 :3％Cr 3+ The near infrared fluorescent material is tested, FIG. 3 is a fluorescence quantum efficiency graph, and from FIG. 3, NaSbF 4 :3％Cr 3+ The fluorescence quantum efficiency of (2) was 54.5%.
Then, Cr obtained in examples 1 to 5 was added 3+ The method for preparing the LED light source by doping the fluorine antimonate comprises the following steps:
0.2g of epoxy resin and 0.1g of Cr obtained in examples 1 to 5 3+ And fully and uniformly mixing the doped fluorine antimonate near-infrared fluorescent material, coating the mixture on a blue light GaN chip, placing the blue light GaN chip in a vacuum drying oven, drying the blue light GaN chip for 30min at the temperature of 60 ℃, transferring the blue light GaN chip to an oven, and drying the blue light GaN chip for 4h at the temperature of 120 ℃ to obtain the LED light source. FIG. 4 is the electroluminescence spectrum of the LED light source at a drive current of 100 mA. As can be seen from FIG. 4, NaSbF obtained in example 4 was compared with examples 1 to 3 and example 5 4 :3％Cr 3+ The near-infrared fluorescent material has better luminous intensity.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material is characterized by comprising the following steps:
dissolving an Sb source and a Cr source in an HF solution, stirring until the Sb source and the Cr source are dissolved, adding an Na source, and continuously stirring to form a mixed solution;
putting the mixed solution into a reaction device for reaction, washing and drying to obtain Cr 3+ Doping a fluorine antimonate near-infrared fluorescent material;
the Cr is 3+ The chemical composition of the doped fluorine antimonate near-infrared fluorescent material is as follows: NaSbF 4 ：xCr 3+ ，x＝0.5～5％。
2. The method for preparing a trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material according to claim 1, wherein the ratio of the sum of the amounts of the Sb source, the Cr source and the Na source added to the amount of the HF solution used is 0.7 to 0.9 g/mL.
3. The method for preparing a trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material according to claim 1, wherein, in the Sb source and the Na source, the molar ratio of Sb to Na is 1: (1-3);
in the Cr source and the Sb source, the molar ratio of Cr to Sb is (0.005-0.05): 1.
4. the method for preparing the trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material according to claim 1, wherein the Sb source is Sb 2 O 3 Or Sb (CH) 3 COO) 3 ；
The Cr source is Cr (NO) 3 ) 3 ·9H 2 O or Cr 2 O 3 ；
The Na source is NaF or NaHF 2 And Na 2 CO 3 One of (1);
the mass fraction of the HF solution is 20-60 wt%.
5. The method for preparing the trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material according to claim 1, wherein the mixed solution is put into a high-pressure reaction kettle, reacted at the temperature of 180 ℃ and 220 ℃ for 6-15h, cooled, washed and dried to obtain the finished product.
6. The method for preparing a trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material according to claim 1, wherein in the washing and drying process, deionized water is used for washing for 1-3 times, an organic solvent is used for washing for 1-2 times to remove residual reaction liquid on the surface, and then drying is performed at a temperature of 50-100 ℃.
7. A trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material is characterized by being prepared by the preparation method of the trivalent chromium ion doped fluorine antimonate near-infrared fluorescent material according to any one of claims 1 to 6.
8. The trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material of claim 1, wherein the trivalent chromium ion doped fluoroantimonate near-infrared fluorescent material can be excited by blue light or green light with a wavelength of 400-650nm to emit broadband near-infrared light with a wavelength of 700-900nm, the strongest wavelength is 760-770 nm, the half-peak width is 110-120 nm, and the quantum efficiency is 53-55%.
9. An LED light source, characterized in that, the LED light source is manufactured by the following method:
uniformly mixing the trivalent chromium ion doped fluorine antimonate near-infrared luminescent fluorescent material of claim 7 or 8 with epoxy resin to obtain a mixed material;
and coating the mixed material on a blue LED chip, and curing to obtain the LED light source.
10. The LED light source of claim 9 wherein the trivalent chromium ion doped fluoroantimonate near-infrared luminescent fluorescent material and the epoxy are present in a ratio of 1: (1-4) in a mass ratio.
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