CN111171811A - Near-infrared luminescent material, preparation method thereof and LED device thereof - Google Patents
Near-infrared luminescent material, preparation method thereof and LED device thereof Download PDFInfo
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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
- C09K11/685—Aluminates; Silicates
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- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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 near-infrared luminescent material, a preparation method thereof and an LED device thereof. The chemical formula of the luminescent material is as follows: AMAlF6：xCr3+Wherein A is alkali metal, M is alkaline earth metal, and x is more than or equal to 0.0001 and less than or equal to 30 at.%; it can be effectively excited in 360-500nm range and can emit near infrared light of 700-1000 nm. The luminescent material can be synthesized by a solid phase method or a coprecipitation method, and has the advantages of simple preparation process, environmental protection and low cost. The LED device is obtained by packaging the luminescent material and the purple light or blue light chip, and can be used as a near-infrared light source for the fields of analysis and detection, iris recognition, automobile sensing, security and the like.
Description
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to a near-infrared luminescent material, a preparation method thereof and an LED device thereof.
Background
The near-infrared light region is a non-visible light region discovered earlier by people, and due to the fact that the early technical level is not high and is influenced by frequency doubling and frequency combination, the detection result is subjected to spectrum overlapping and complex analysis, and research and application of near-infrared light are limited to a certain extent. In the 60's of the 20 th century, the appearance of commercial instruments and a great deal of work done by Norris and other people, the theory that the content of substances and a plurality of different wavelength absorption peaks in a near-infrared region are in a linear relation is put forward, and the NIR diffuse reflection technology is utilized to measure components such as moisture, protein, fat and the like in agricultural products, so that the near-infrared spectrum technology is widely applied to agricultural and sideline product analysis. However, in the middle and later period of the 60 s, with the appearance of various new analysis technologies, the defects of low sensitivity and poor anti-interference performance are exposed by the classical near infrared spectrum analysis technology, so that people are indifferent to the application of the technology in analysis and detection, and the near infrared spectrum enters a silent period.
The successful application of multivariate calibration technology, an important component of chemometrics generated in the 70 s, in spectral analysis, promotes the popularization of near infrared spectroscopy. In the late 80 s, the rapid development of computer technology drives the development of digitization and chemometrics of analytical instruments, good effects of spectral information extraction and background interference are achieved by a chemometrics method, and the special characteristics of near infrared spectrum in a sample measuring technology are added, so that people know the value of the near infrared spectrum again, and the application and research of the near infrared spectrum in various fields, such as medicine, pharmacology, molecular cell biology and the like, are accelerated. Hospitals in the united states are trying to use a novel instrument to help nurses find blood vessels on the arms of patients by detecting the positions of blood vessels by means of near infrared rays harmless to the human body and projecting the distribution images of blood vessels on the arms in real time so as to allow medical staff to accurately find the position of needle discharge and avoid the occurrence of "no needle left". In addition, the luminescent material used for the near-infrared fluorescence mark is located in a near-infrared region, the biological molecules do not self-illuminate in the region, signal interference on detection due to spectral overlapping does not occur, the near-infrared fluorescence mark can be excited by visible light with shorter wavelength, so that high sensitivity is obtained by avoiding the dispersity of excitation light, the penetration depth of near-infrared light in biological living tissue is large, optical signals can be generated in deep tissue, and the tissue hardly has any influence, so that more biological information can be obtained, and the method plays a positive role in further promoting the development of technologies such as medical imaging, tumor treatment and the like.
Because the spectral distribution of sunlight and the response spectrum of the battery are not completely synchronous, the solar battery mainly absorbs near infrared light with longer wavelength, and ultraviolet and blue-green light with short wavelength occupying most of sunlight are difficult to be absorbed by the solar battery, so that the phenomenon of spectral mismatch is caused, and the great loss of sunlight energy is caused. Patent document CN 102618285a reports a down-conversion near-infrared luminescent material used in a solar cell, which adopts a down-conversion material to convert short-wavelength light in sunlight into long-wavelength light through quantum cutting, so as to greatly eliminate the phenomenon of spectrum mismatch, improve the utilization rate of sunlight, and thus indirectly improve the photoelectric conversion efficiency of the solar cell.
Besides, the near infrared light can be used for biological recognition, such as fingerprint recognition, iris recognition, face recognition and the like. A novel broadband infrared LED derived from an Oselan photoelectric semiconductor successfully creates a broadband near-infrared LED capable of emitting light with a wavelength ranging from 650nm to 1050nm by applying a fluorescent powder technology to an infrared emitter, develops an infrared spectrum technology suitable for the consumer product market, and is applied to the fields of food industry, agriculture and the like to detect the contents of moisture, fat, carbohydrate, sugar and protein in food. Therefore, research and development of the near-infrared fluorescent powder become a new direction for research and development personnel to actively research in the current industry, more choices are provided for the field of near-infrared luminescent materials, and the research and development of the near-infrared luminescent powder have great research significance for the research of the near-infrared luminescent materials.
Disclosure of Invention
The invention provides a near-infrared luminescent material, the chemical composition of which is AMAlF6：xCr3+Wherein A is an alkali metal, M is an alkaline earth metal, Cr3+Is a luminous central ion, and x is more than or equal to 0.0001 and less than or equal to 30at percent.
The luminescent material can be excited by a purple light or blue light LED chip within the range of 360-500nm, near infrared light with the wavelength range of 700-1000nm is emitted, and the peak value is about 800 nm.
According to an embodiment of the present invention, a is selected from one or a combination of Li, Na, K, Rb, Cs, and M is selected from one or a combination of Mg, Ca, Sr, Ba.
The invention also provides a preparation method of the luminescent material, which comprises the following steps:
according to the formula AMAlF6：xCr3+Respectively weighing a compound containing A ions, a compound containing M ions, a compound containing Al ions and a compound containing Cr ions according to the stoichiometric ratio of the elements, dissolving the compounds in a solvent, adding HF into the obtained solution, and precipitating to obtain the luminescent material.
According to an embodiment of the present invention, the a ion-containing compound is selected from one or two or more of a carbonate, an oxide, a chloride, a fluoride, a nitrate, or a sulfate of a ion; the M ion-containing compound is selected from one or more than two of carbonate, oxide, chloride, fluoride, nitrate or sulfate of M ions; the compound containing Al ions is Al (NO)3)3·9H2O、AlCl3、AlF3Or Al2(SO4)3One or more than two of the above; the compound containing Cr ions is Cr (NO)3)3·9H2O、CrCl3、CrF3Or Cr2(SO4)3One kind or two or more kinds of them.
According to an embodiment of the present invention, the solvent is preferably an acid, such as one of hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid; preferably, the acid is hydrochloric acid.
According to an embodiment of the invention, the HF is an aqueous solution of HF, preferably having a concentration of at least 5 wt.%, preferably at least 15 wt.%.
According to an embodiment of the present invention, preferably, HF is slowly added to the solution, for example, at a rate of 0.001 to 20mL/min, preferably 0.1 to 10 mL/min.
According to an embodiment of the present invention, the solution containing the precipitate obtained in the above method is centrifuged, filtered, and dried to obtain the light-emitting material. Preferably, the drying temperature is at least 30 ℃, more preferably, the drying temperature is at least 50 ℃. The drying time is at least 2h, more preferably at least 4 h. Preferably, the precipitate is washed after filtration, for example with alcohol or acetone; for example, 2-3 times.
According to an embodiment of the present invention, the preparation method comprises, for example, the steps of:
(1) according to the formula AMAlF6：xCr3+Respectively weighing a compound containing A ions, a compound containing M ions, a compound containing Al ions and a compound containing Cr ions according to the stoichiometric ratio of the elements, wherein x is more than or equal to 0.0001 and less than or equal to 30 at%, and dissolving the compounds in an acid solution to prepare a clear solution;
(2) slowly dropwise adding an HF aqueous solution into the clear solution prepared in the step (1) to gradually separate out a precipitate;
(3) and (3) centrifugally filtering the solution containing the precipitate in the step (2), cleaning the precipitate, and drying in a drying box to obtain the luminescent material.
Further, the present invention also provides another preparation method of the luminescent material, comprising the following steps:
according to the formula AMAlF6：xCr3+The stoichiometric ratio of each element in the raw materials is obtained by respectively weighing AF and MF2、AlF3、CrF3And after mixing, heating to a high temperature in the atmosphere of air or a fluorine/nitrogen mixed gas, keeping the temperature for a period of time, and naturally cooling to obtain the luminescent material.
According to an embodiment of the present invention, the volume content of the fluorine gas in the fluorine/nitrogen mixed gas atmosphere is 1% to 40%, preferably 5% to 20%.
According to an embodiment of the invention, the elevated temperature is at least 300 ℃, preferably at least 500 ℃, preferably at least 700 ℃.
According to an embodiment of the invention, the constant temperature is for a period of at least 2h, preferably at least 6 h.
The invention also provides the application of the luminescent material, which can be used as a near-infrared luminescent material in various fields using near-infrared light sources, such as detection, marking, identification, photoelectric equipment and the like.
According to an embodiment of the present invention, the luminescent material of the present invention is used in an LED.
Further, the invention also provides an LED device which comprises at least one luminescent material.
According to an embodiment of the present invention, the LED device further comprises an LED chip, which may be a violet or blue LED chip, preferably a 450nm blue LED chip.
The LED device is excited by a 360-500nm purple light or blue light LED chip, can obtain near infrared light with the emission wavelength of 700-1000nm, and can be used as a near infrared light source.
The invention also provides application of the LED device as a near-infrared light source in the fields of analysis and detection, iris recognition, automobile sensing and security.
Has the advantages that:
(1) the invention provides a luminescent material, which is prepared from Cr3+Is a luminous center ion, and can effectively emit near infrared light of 700-1000nm under the excitation of light of 360-500 nm.
(2) The luminescent material is synthesized by adopting a coprecipitation method or a solid phase method, and the method has the advantages of low raw material cost, simple process, easy operation and the like, and is easy to realize the large-scale preparation of the luminescent material.
(3) The luminescent material provided by the invention can be effectively excited by the existing commercial purple light and blue light LED chips, and the LED device can be obtained by packaging, so that the commercialization of the near infrared light LED device can be realized.
Drawings
FIG. 1 is an XRD spectrum of a luminescent material prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of the luminescent material prepared in example 1 of the present invention.
FIG. 3 shows the excitation and emission spectra of the luminescent material prepared in example 1 of the present invention.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Examples 1 to 9: AMAlF6：xCr3+Preparation of luminescent materials
Examples 1-9 were synthesized using a coprecipitation method, differing only in the kind and amount of the raw materials, and the kind and amount of the raw materials used are listed in table 1.
The synthesis comprises the following specific steps: dissolving A ion-containing compound and M ion-containing compound in hydrochloric acid (36 wt.%), stirring for 1-10min to obtain clear solution, and adding Al (NO)3)3·9H2O and Cr (NO)3)3·9H2And adding O into the solution, continuously stirring for 10min, slowly dropwise adding an HF (40 wt.%) aqueous solution into the solution at a speed of 0.1mL/min, gradually precipitating out of the solution, filtering the solution containing the precipitate, washing the precipitate for 2-3 times by using acetone, and drying the washed precipitate in an oven at 140 ℃ for 4h to obtain a luminescent material sample. Spectral characteristics of the sample were measured by FLS980 (edinburgh instruments) fluorescence spectrometer, and phase analysis and scanning electron microscopy were performed on the sample by X-ray diffractometer (DMAX 2500PC, japan science) and scanning electron microscopy (FE-SEM, hitachi SU1510, japan).
Table 1 examples 1-9 preparation parameters
XRD analysis of the samples synthesized by the coprecipitation method showed all phases, as shown in the XRD pattern of the example 1 sample in FIG. 1, which matches the standard card PDF # 48-1640. FIG. 2 is an SEM image of the sample of example 1, showing that the sample has a uniform particle size distribution and a particle size of 1-5 μm. FIG. 3 is a graph of the excitation and emission spectra of the sample of example 1, showing that the sample has a broad excitation peak at 360-500nm and emits a broadband near infrared light of 700-1000 nm.
Examples 10 to 18: AMAlF6：xCr3+Preparation of luminescent materials
Examples 10 to 18 were synthesized by the solid phase method, and only differences were found in the kinds and amounts of the raw materials, and the kinds and amounts of the raw materials used are shown in Table 2.
Firstly, AF and MF are respectively weighed according to stoichiometric ratio2、AlF3、CrF3Uniformly mixing, heating to a certain temperature in air atmosphere, keeping the temperature constant for a period of time, naturally cooling, and grinding the sample to obtain AMAlF6：Cr3+A luminescent material.
TABLE 2 EXAMPLES 10-18 preparation parameters
Example 19: preparation of LED device
The luminescent material synthesized in the above embodiments 1 to 18, but not limited to the above near-infrared phosphor, is mixed with silica gel, and then packaged with a blue LED chip to obtain an LED device emitting near-infrared light, which can be applied to various analytical detection devices as a near-infrared light source.
The above examples illustrate embodiments of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The near-infrared luminescent material has the chemical composition of AMAlF6：xCr3+Wherein A is an alkali metal, M is an alkaline earth metal, Cr3+Is a luminous central ion, and x is more than or equal to 0.0001 and less than or equal to 30at percent.
2. The luminescent material according to claim 1, wherein the luminescent material can be excited by violet or blue LED chips in a wavelength range of 360-500nm to emit near-infrared light with a wavelength range of 700-1000nm and a peak value of about 800 nm.
3. A luminescent material as claimed in claim 1 or 2, wherein a is selected from one of Li, Na, K, Rb, Cs or a combination thereof, and M is selected from one of Mg, Ca, Sr, Ba or a combination thereof.
4. A method for preparing a luminescent material as claimed in any one of claims 1 to 3, comprising the steps of:
according to the formula AMAlF6：xCr3+Respectively weighing a compound containing A ions, a compound containing M ions, a compound containing Al ions and a compound containing Cr ions according to the stoichiometric ratio of the elements, dissolving the compounds in a solvent, adding HF into the obtained solution, and precipitating to obtain the luminescent material.
5. The production method according to claim 4, wherein the A ion-containing compound is one or more selected from a carbonate, an oxide, a chloride, a fluoride, a nitrate, and a sulfate of the A ion; the M ion-containing compound is selected from one or more than two of carbonate, oxide, chloride, fluoride, nitrate or sulfate of M ions; the compound containing Al ions is Al (NO)3)3·9H2O、AlCl3、AlF3Or Al2(SO4)3One or more than two of the above; the compound containing Cr ions is Cr (NO)3)3·9H2O、CrCl3、CrF3Or Cr2(SO4)3One kind or two or more kinds of them.
6. The method according to claim 4 or 5, characterized in that it comprises the steps of:
(1) according to the formula AMAlF6：xCr3+Respectively weighing a compound containing A ions, a compound containing M ions, a compound containing Al ions and a compound containing Cr ions according to the stoichiometric ratio of the elements, wherein x is more than or equal to 0.0001 and less than or equal to 30 at%, and dissolving the compounds in an acid solution to prepare a clear solution;
(2) slowly dropwise adding an HF aqueous solution into the clear solution prepared in the step (1) to gradually separate out a precipitate;
(3) and (3) centrifugally filtering the solution containing the precipitate in the step (2), cleaning the precipitate, and drying in a drying box to obtain the luminescent material.
7. A method for preparing a luminescent material as claimed in any one of claims 1 to 3, comprising the steps of:
according to the formula AMAlF6：xCr3+The stoichiometric ratio of each element in the raw materials is obtained by respectively weighing AF and MF2、AlF3、CrF3And after mixing, heating and keeping the temperature for a period of time in the atmosphere of air or fluorine/nitrogen mixed gas to obtain the luminescent material.
8. Use of the luminescent material according to any one of claims 1 to 3 as a near-infrared luminescent material in the field of detection, labeling, identification, optoelectronic devices using a near-infrared light source; for example in LEDs.
9. An LED device comprising at least one luminescent material according to any one of claims 1 to 3.
10. The use of the LED device of claim 9 as a near infrared light source in the fields of analytical testing, iris recognition, automotive sensing, and security.
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| CN113444522A (en) * | 2021-05-21 | 2021-09-28 | 江西理工大学 | Cr (chromium)3+Doped novel fluoride near-infrared fluorescent material, preparation method and luminescent light source thereof |
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