CN117701277A - Broadband far-infrared fluorescent powder and preparation method and application thereof - Google Patents
Broadband far-infrared fluorescent powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a broadband far-infrared fluorescent powder and a preparation method and application thereof, wherein the broadband far-infrared fluorescent powder has a chemical general formula as follows: m is M a N(Ge/Ti/Sn) b B 4 O 36 :xCr 3+ ，M＝Li/Na/K，N＝Al 20‑c (Ga/In) c ，0.02<x<0.32，0<a<1.2，0<b<1，0<c<20. The excitation spectrum of the fluorescent powder can be matched with near ultraviolet and commercial GaN blue LEDs; the emission spectrum is 650-900nm; the fluorescent lamp has excellent luminous heat stability at the working temperature of 150 ℃; the spectrum regulation and control can be realized by controlling the proportion of N element; the enhancement of luminous intensity and zero thermal quenching performance can be realized by controlling the proportion of Ge/Ti/Sn elements;the lamp encapsulated by the broadband far-infrared fluorescent powder can be applied to the plant illumination fields such as rice seedling raising and light supplementing.
Description
Technical Field
The invention relates to the technical field of luminescent materials and preparation thereof, in particular to ultraviolet-blue light excited broadband far-infrared fluorescent powder and a preparation method and application thereof.
Background
The rapid emergence of biological lighting technology has become a new growth point in the lighting industry, a typical representative of which is plant lighting technology. The illumination is taken as an indispensable part in the growth and development of plants, and the agricultural yield and quality increase or other specific production purposes can be realized by regulating and controlling the environmental element, such as: regulating flowering phase, prolonging fresh-keeping period, etc. However, currently, commercial red phosphors, such as fluoride KSF: mn 4+ Or nitride CaAlSiN 3 :Eu 2+ The far-red light band is lacking. Although the overlapping degree of far-red light wave band and photosynthetic effective radiation wave band is low, the combination of far-red light and short-wave light can enhance the photosynthesis of plants, and the far-red light has important regulation and control functions on various plant physiological phenomena (sprouting, flowering, negative-avoiding reaction and the like) based on the dynamic balance of photosensitive pigments. Therefore, research on the far-red fluorescent material with high luminous efficiency and high thermal stability has important significance for modern agricultural production.
The far-red light activator commonly used in the current luminescent materials is Cr 3+ Since the 3d3 electronic structure of the ion is easily influenced by the environment of a crystal field, the far-red light-near infrared emission of 650-1200nm can be realized by selecting proper matrix materials and modification strategies. But in a weaker crystal field environment, cr 3+ The emission energy level of the ions is coupled with the matrix to a high degree, and the non-radiative transition probability is high at high temperature, so that the luminous thermal stability is low. In view of the long time required for operation of the light supplementing lamp, this is certainly true for Cr 3+ Application belt for activating fluorescent powderSevere challenges are presented. In the prior study, cr with high luminous efficiency and high thermal stability 3+ The active luminescent material often contains rare earth element or Ge 4+ As this contributes to obtaining a thermodynamically stable, structurally stable compound. The stable structure with high compactness can reduce non-radiative transition of the fluorescent powder and improve the luminescence property and thermal quenching resistance of the fluorescent powder. Therefore, based on the above knowledge, it is necessary to screen a material which is simple to synthesize, inexpensive in raw materials, high in structural stability and can accommodate Cr 3+ Ion doped matrix material to obtain high light efficiency and high stability far-red light. Wherein, the aluminum borate material has the characteristics of simple preparation, cheaper raw materials, high Debye temperature and wide band gap. Its high debye temperature means high structural stability, while the wide band gap indicates that the material is more difficult to produce luminescence thermal quenching by thermo-electric dissociation mechanism. This suggests that aluminoborate materials are ideal substrates for preparing high light efficiency, high thermal stability phosphors.
Disclosure of Invention
The invention aims to provide broadband far-red light fluorescent powder with tunable spectrum and excellent thermal stability.
The invention further aims at providing a preparation method of the broadband far-infrared fluorescent powder.
The invention also aims at providing an application of the broadband far-infrared fluorescent powder.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a broadband far-red fluorescent powder has a chemical general formula: m is M a N(Ge/Ti/Sn) b B 4 O 36 :xCr 3+ ；
Wherein M is one element of Li, na, K (m=li/Na/K); n=al 20 -c(Ga/In) c ；0.02<x<0.32，0<a<1.2，0<b<1，0<c<20。
The broadband far-red fluorescent powder can realize the regulation and control of the emission spectrum and half-peak width of the material by regulating the size of a/b. By adjusting the size of a, the crystal structure of the material can be improved to enhance the luminous intensity of the material. Secondly, by adjusting the size of b, the enhancement of the luminous intensity and the thermal stability of the material can be realized, and zero thermal quenching at the working temperature of 150 ℃ can be realized at most; finally, the widening and the red shift of the spectrum can be realized by regulating and controlling the size of c.
Preferably, the broadband far-red fluorescent powder has an excitation spectrum of 320-680nm and shows a broadband far-red light emission spectrum of 650-900 nm. The excitation spectrum of the broadband far-infrared fluorescent powder is 320-680nm, and the broadband far-infrared fluorescent powder is matched with near ultraviolet light and commercial GaN blue light LEDs; the emission spectrum is 650-900nm, and has good matching with the absorption spectrum of the plant photosensitive pigment; the range of both excitation and emission spectra is relatively broad.
Preferably, the broadband far-red fluorescent powder keeps 90% of luminous intensity at room temperature under the working temperature of 150 ℃, has excellent light effect and can realize zero thermal quenching.
Preferably, the preparation method of the broadband far-infrared fluorescent powder comprises the following steps:
s1: according to the chemical general formula M a N(Ge/Ti/Sn) b B 4 O 36 :xCr 3+ Proportioning, namely weighing raw materials of oxide and carbonate of M, N according to a molar ratio of a chemical formula, adding alcohol as a dispersing agent, grinding and uniformly mixing to obtain a mixture for later use;
s2: sintering the mixture obtained in the step S1 at a high temperature, and cooling to obtain a sample;
s3: and (3) taking out the sample obtained in the step (S2), and grinding uniformly to obtain the broadband far-infrared fluorescent powder.
Specifically, in the step S1, the mass of the B-element-containing compound is 5-7 times of the normal stoichiometric amount. Because the melting point of the B-element-containing compound is lower, the B-element-containing compound is easy to volatilize at high temperature, and the B-element-containing compound is excessively added as a substance synthesis fluxing agent, so that the luminous performance of the material is improved. The remaining elements are calculated according to the normal stoichiometric ratio.
Specifically, in the step S2, the reaction temperature range of high-temperature sintering is 1400-1500 ℃ and the reaction time range is 5-8h. The high-temperature sintering is sintering in a muffle furnace.
A lamp is a lamp encapsulated by the broadband far-red fluorescent powder, and is applied to the field of plant illumination.
The preparation method of the broadband far-infrared fluorescent powder is simple, the synthesis temperature is low, the raw materials are low in price, the large-scale production is convenient, the broadband far-infrared fluorescent powder can be applied to rice seedling raising scenes, and the seedling quality is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the broadband far-infrared fluorescent powder has excitation peaks in ultraviolet and blue light areas, and can be well matched with commercial ultraviolet or blue light chips;
2. the broadband far-infrared fluorescent powder has an emission spectrum of 650-900nm and well covers the absorption spectrum of the plant spectral pigment;
3. the broadband far-red fluorescent powder is almost in zero thermal quenching at the working temperature of 150 ℃, and has stable luminescence;
4. the broadband far-red fluorescent powder can realize spectrum tuning of 730-770nm by adjusting the substitution amount of N element, thereby widening the application scene of the far-red fluorescent powder;
5. the broadband far-infrared fluorescent powder has the advantages of low price of raw materials, simple synthesis process, low synthesis temperature, stable chemical performance, no pollution and convenience for mass production.
6. The broadband far-infrared fluorescent powder can be packaged into a plant illumination lamp, is applied to rice seedling raising scenes, and improves seedling quality.
Drawings
FIG. 1 is a sample Li prepared in example 1 of the present invention 1.2 Al 20-x B 4 O 36 :xCr 3+ An X-ray powder diffraction pattern of (2);
FIG. 2 is a sample Li prepared in example 1 of the present invention a Al 19.84 B 4 O 36 :0.16Cr 3+ An X-ray powder diffraction pattern of (2);
FIG. 3 is a sample Li prepared in example 1 of the present invention 1.2 Al 19.84 B 4 O 36 :0.16Cr 3+ Is provided, the excitation and emission spectra of (a);
FIG. 4 is a diagram of the present inventionExample 1 preparation of sample Li x Al 19.84 B 4 O 36 :0.16Cr 3+ Is provided, the excitation and emission spectra of (a);
FIG. 5 is a sample Li prepared in example 1 of the present invention 1.2 Al 19.84 B 4 O 36 :0.16Cr 3+ A plot of fluorescence emission spectrum versus integrated intensity (integrated range: 650-900 nm) versus test temperature (excitation wavelength 397 nm);
FIG. 6 is a sample Li prepared in example 2 of the present invention 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c=0-20);
FIG. 7 is a sample Li prepared in example 2 of the present invention 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c=0-20);
FIG. 8 is a sample Li prepared in example 3 of the present invention 1.2 Al 19.84-x Ge b B 4 O 36 :0.16Cr 3+ Is a spectrum of the emission spectrum of (a);
FIG. 9 is a sample Li prepared in example 3 of the present invention 1.2 Al 19.84-b Ge b B 4 O 36 :0.16Cr 3+ A plot of fluorescence emission spectrum versus integrated intensity (integrated range: 650-900 nm) versus test temperature (excitation wavelength 397 nm);
FIG. 10 is a sample Li prepared in example 3 of the present invention 1.2 Al 18.84 GeB 4 O 36 :0.16Cr 3+ A quantum efficiency map of (2);
FIG. 11 shows plant height and stem base width of rice seedlings under different light qualities according to example 4 of the present invention;
FIG. 12 shows enzyme contents of rice seedlings under different light qualities according to example 4 of the present invention;
FIG. 13 is a plot of the end points of rice seedlings under different light qualities according to example 4 of the present invention.
Detailed Description
The invention is further elucidated below in connection with specific embodiments and with fig. 1-13. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. While the present disclosure has been described in terms of embodiments, not every embodiment is intended to be a separate embodiment, and the description is for clarity only, and the disclosure is not limited to the embodiments shown and described herein, as such, may be practiced otherwise, and as appropriate, in various embodiments, as may be appreciated by those skilled in the art.
Example 1
This example is prepared according to the following method 1.2 Al 20-x B 4 O 36 :xCr 3+ (x= 0.02,0.04,0.08,0.16,0.24,0.32) and Li a Al 19.84 B 4 O 36 :0.16Cr 3+ (a= 0,0.4,0.8,1.2,1.6) phosphor.
The preparation process of the fluorescent powder comprises the following steps: the preparation method comprises the steps of taking aluminum oxide (99.99%), boric acid (99.9%), chromium oxide (99.9%), lithium carbonate (99.9%) as raw materials, weighing other raw materials except 5 times of excessive boric acid according to stoichiometric ratio, dripping a proper amount of alcohol as a dispersing agent, grinding for 20min, mixing uniformly, putting into a corundum crucible, putting into a muffle furnace, sintering at 1400 ℃ for 6 hours, cooling, grinding a product, and sieving with a 200-mesh screen to obtain the broadband far-infrared light emitting fluorescent powder.
FIGS. 1 and 2 show Li 1.2 Al 20-x B 4 O 36 :xCr 3+ (x= 0.02,0.04,0.08,0.16,0.24,0.32) and Li a Al 19.84 B 4 O 36 :0.16Cr 3+ The XRD pattern of the (a= 0,0.4,0.8,1.2,1.6) fluorescent powder has a peak shape well matched with a standard card, and the successful synthesis of the broadband far-infrared light emitting fluorescent powder is proved.
FIG. 3 is Li 1.2 Al 19.84 B 4 O 36 :0.16Cr 3+ The fluorescent powder can be effectively excited by near ultraviolet light and blue light through excitation and emission spectrum; the fluorescent powder emission spectrum consists of a narrow peak at 696nm and a broad peak at 700-900 nm.
FIG. 4 is Li a Al 19.84 B 4 O 36 :0.16Cr 3+ Emission spectrum of phosphor, visible Li 2 CO 3 The luminous intensity of the fluorescent powder is effectively improved.
FIG. 5 is Li 1.2 Al 19.84 B 4 O 36 :0.16Cr 3+ The emission spectrum of the fluorescent powder at different temperatures and the intensity contrast diagram thereof show that the material can keep 90.1% of the temperature (25 ℃) at the working temperature of 150 ℃, which shows that the material has excellent thermal stability and great application potential.
Example 2
This example is prepared according to the following method 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c= 0,4,8,12,16,20) phosphor.
Li 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c=0, 4,8,12,16, 20) phosphor preparation
The preparation process comprises the following steps: lithium carbonate (99.9%), alumina (99.99%), gallium oxide (99.99%) are used as raw materials, and the raw materials are weighed according to a certain proportion:
| lithium carbonate | Alumina oxide | Gallium oxide | Boric acid | |
| a＝0 | 0.0359g | 0.7833g | 0g | 1g |
| a＝1 | 0.0359g | 0.7420g | 0.0757g | 1g |
| a＝2 | 0.0359g | 0.7008g | 0.1516g | 1g |
| a＝3 | 0.0359g | 0.6596g | 0.2274g | 1g |
| a＝4 | 0.0359g | 0.6183g | 0.3031g | 1g |
| a＝5 | 0.0359g | 0.5771g | 0.3789g | 1g |
Weighing 0.0098g of chromium oxide as an activator, dripping a proper amount of alcohol as a dispersing agent, grinding for 15min, mixing uniformly, loading into a corundum crucible, and sintering in a muffle furnace at 1400 DEG CAfter cooling for 6 hours, grinding the product, and sieving the product with a 200-mesh sieve to obtain the broadband far-red light emitting fluorescent powder Li 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c＝0,4,8,12,16,20)。
As shown in FIG. 6, li is 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c (c= 0,4,8,12,16,20) the XRD pattern of the phosphor, the peak shape matched well with the standard card, shows successful synthesis of broadband far-red emitting phosphor.
FIG. 7 is Li 1.2 N 19.84 B 4 O 36 :0.16Cr 3+ ，N＝Al 20-c Ga c The emission spectrum of the (c= 0,4,8,12,16,20) phosphor shows that as the Ga element ratio increases, the peak at 696nm decreases, the broad peak red shifts (730-770 nm), and an increase in the half-peak width of the spectrum is exhibited.
Example 3
This example is prepared according to the following method 1.2 Al 19.84-b Ge b B 4 O 36 :0.16Cr 3+ (b=0, 1) phosphor.
Li 1.2 Al 19.84-x Ge x B 4 O 36 :0.16Cr 3+ (b=0, 1) phosphor preparation process: weighing raw materials of lithium carbonate (99.9%), germanium oxide (99.9%), aluminum oxide (99.99%) and chromium oxide (99.9%), dripping a proper amount of alcohol as a dispersing agent, grinding for 15min, mixing uniformly, loading into a corundum crucible, placing into a muffle furnace, sintering at 1400 ℃ for 6 hours, cooling, grinding the product, and sieving with a 200-mesh screen to obtain the broadband far-infrared light emitting fluorescent powder Li 1.2 Al 19.84- b Ge b B 4 O 36 :0.16Cr 3+ (b＝0，1)。
As shown in fig. 8, the addition of germanium oxide effectively increases the luminous intensity of the phosphor.
FIG. 9 is Li 1.2 Al 19.84-b Ge b B 4 O 36 :0.16Cr 3+ (b=0, 1) the temperature of the phosphor depends onThe addition of the germanium oxide improves the luminescence thermal stability of the broadband far-red light emitting fluorescent powder according to the emission spectrum. At the working temperature of 150 ℃, the fluorescent powder almost does not generate luminescence thermal quenching and has zero thermal quenching performance.
FIG. 10 is Li 1.2 Al 18.84 GeB 4 O 36 :0.16Cr 3+ The quantum efficiency of the fluorescent powder reaches 98.6%, and the fluorescent powder has high luminous quantum efficiency.
Example 4
In this example, the fluorescent powder-encapsulated lamp obtained in example 3 was used for demonstration of rice seedling raising applications according to the following method.
The rice seedling raising and light supplementing process comprises the following steps: selecting Xiangzao indica type 45 as a light supplementing exemplary variety, sterilizing with 5% sodium hypochlorite solution, selecting full seeds without plant diseases and insect pests, placing in a 37 ℃ incubator for 24 hours to promote germination, and sowing on a seedling raising tray. After sowing, the lamp packaged by the fluorescent powder obtained in example 3 was used for light supplementing-R group (red light), B group (blue light), RB group (red+blue), RBF group (red+blue+far red), and far red light of RBF group was obtained by using the far red fluorescent powder obtained in example 3. In the light supplementing process, consistency of light intensity ((100+/-5 mu molm-2/s-1), light period (8:00-24:00) and humidity (70% +/-5%) is guaranteed, and after light supplementing is carried out for 30 days, agronomic characters and physiological indexes of seedlings are detected.
FIG. 10 shows the plant height and the stem base width of rice seedlings under different light quality, and it can be seen that the rice seedlings are long under red light, short and strong under blue light, and the addition of far-red light improves the plant height and the stem base width of the rice seedlings.
FIG. 11 shows the enzyme content of rice seedlings under different light conditions, with higher seedling peroxidase content in red light and lower seedling peroxidase content in blue light, and the other groups are not significantly different from the red light group. The far-red light can effectively improve the content of catalase in seedlings, and the phenomenon shows that the far-red light can enhance the stress resistance of plants.
Fig. 12 shows the leaf angle state of rice seedlings under different light quality, the seedling fiber length under red light, the third leaf under blue light, the combination of blue and red light shows a larger leaf angle, and the leaf angle reaches the maximum after far-red light is added. The comparison shows that far-red light can promote the development of rice seedlings.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. A broadband far-infrared fluorescent powder is characterized by having a chemical general formula: m is M a N(Ge/Ti/Sn) b B 4 O 36 :xCr 3+ ；
Wherein M is one element of Li, na and K;
N＝Al 20-c (Ga/In) c ；
0.02<x<0.32，0<a<1.2，0<b<1，0<c<20。
2. the broadband far-red fluorescent powder according to claim 1, wherein the excitation spectrum thereof is 320-680nm, and the broadband far-red light emission spectrum thereof is 650-900 nm.
3. The broadband far-infrared fluorescent powder according to claim 1, which maintains a luminous intensity of 90% at room temperature at an operating temperature of 150 ℃.
4. A method for preparing the broadband far-infrared fluorescent powder according to any one of claims 1 to 3, comprising the steps of:
s1: according to the chemical general formula M a N(Ge/Ti/Sn) b B 4 O 36 :xCr 3+ Proportioning, namely weighing raw materials of an oxide and carbonate of M, N according to a molar ratio of a chemical formula, adding alcohol as a dispersing agent, grinding and uniformly mixing to obtain a mixture for later use;
s2: sintering the mixture obtained in the step S1 at a high temperature, and cooling to obtain a sample;
s3: and (3) taking out the sample obtained in the step (S2), and grinding uniformly to obtain the broadband far-infrared fluorescent powder.
5. The method of producing a broadband far-infrared phosphor according to claim 4, wherein in the step S1, the mass of the B element-containing compound is 5 to 7 times the normal stoichiometric amount.
6. The method for preparing broadband far infrared fluorescent powder according to claim 4, wherein in the step S2, the reaction temperature of high-temperature sintering is 1400-1500 ℃ and the reaction time is 5-8h.
7. A luminaire, characterized in that it is a luminaire employing a broadband far-red phosphor package according to any one of claims 1-6.
8. A luminaire as claimed in claim 7, characterized in that it is applied in the field of plant lighting.
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