CN114907841B - Sm (Sm) 2+ Activated near infrared luminescent material, preparation method and application thereof - Google Patents
Sm (Sm) 2+ Activated near infrared luminescent material, preparation method and application thereof Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/77066—Aluminium Nitrides or Aluminium Oxynitrides
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Abstract
The invention provides a Sm 2+ Activated near infrared luminescent material, and preparation method and application thereof are provided. The chemical composition of the fluorescent powder is M 1‑x‑y Al 1‑z Si 5+z O 2‑z N 7‑z :Sm x, Bi y ,K y The method comprises the steps of carrying out a first treatment on the surface of the Wherein M is one or more elements of Mg, ca, sr, ba; wherein x is more than or equal to 0.001 and less than or equal to 0.2, y is more than or equal to 0 and less than or equal to 0.1, and z is more than or equal to 0 and less than or equal to 0.1. Compared with the prior art, the invention has brand new chemical composition, and uses Sm 2+ As an activator, the fluorescent powder can be excited by light in the wavelength range of 240-600 nm to emit near infrared light with the peak wavelength of 650-850 nm and the peak wavelength of 682nm, so that the fluorescent material can convert ultraviolet light, violet-blue light, green light and red light into near infrared light. The synthesis method is simple, has stable chemical performance, and is suitable for application scenes of white light LEDs, plant growth illumination, solar cells or biological markers.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to a near infrared luminescent material, a preparation method and application thereof.
Background
The inorganic luminescent material is widely applied to the fields of LEDs and the like due to the advantages of good spectrum easy adjustment and simple preparation process. Near infrared luminescent materials (emission wavelength of more than 650 nm) have been attracting attention in recent years for their potential application value in promoting plant illumination and the like [ refer to non-patent document 1]. For plant growth, near infrared light of 640-660nm is used for carbohydrate synthesis and near infrared light of 660-730nm can be absorbed by phytochromes (phytochromes), which is beneficial to accelerating plant growth. In addition, near infrared light has recently shown great potential for applications in food rapid detection, medical imaging, iris recognition, night vision monitoring, and the like and has shown strong competitiveness [ refer to non-patent documents 2,3]. Therefore, the development of the efficient and stable near infrared luminescent material has important significance.
In terms of luminescence principle, the activation ion can be Eu, which is aimed to obtain near infrared luminescent material with emission peak larger than 650nm 2+ ,Cr 3+ And Mn of 4+ Etc. For example, eu reported in non-patent document 3 2+ The activated CaS material can exhibit near infrared light emission characteristics with a peak value of 650nm after energy storage by uv irradiation; cr as reported in non-patent document 4 3+ At Ca 3 Sc 2 Si 3 O 12 Broadband emission (from) from 700 to 900nm is exhibited in the matrix due to the smaller crystal field strength (Dq/B.apprxeq.2.25) 4 T 2 - 4 A 2 ). With Cr 3+ Similar luminescence mechanism, mn 4+ Deep red and near infrared luminescence are also readily exhibited in the lattice site of hexacoordinated octahedra, as in K 2 AlF 6 :Mn 4+ And (Ca, sr) 14 Zn 6 Ga 10 O 35 Mn is observed in the matrix 4+ Near infrared luminescence of (1) [ refer to non-patent documents 5,6 ]]. In non-patent document 7, cr is systematically introduced 3+ And Mn of 4+ Related research work that exhibited deep red or near infrared light. However, the problem of lack of the corresponding activation center species is remarkable, so that the development of new near infrared activation centers is also important for the development of near infrared luminescent materials, and Sm 2+ There are few reports in the patent literature of near infrared luminescent materials as luminescent centers. In addition, the development of the near infrared fluorescent powder is restricted by the problem that the common near infrared fluorescent powder basically takes oxides, sulfides and fluorides as matrixes and the relative instability of the matrixes is limited, wherein the nitrogen oxides with stable structures are taken as matrixesReports are made.
Non-patent document 1: GN A De Guzman, S F Hu, R-S Liu.engineering Applications of Near-Infrared Phosphors: review and Future Perspectives [ J ]. J.Chin.chem.Soc.,2020, 68 (2): 206-215.
Non-patent document 2: ghong, J C Lee, J T Robinson, et al multifunctional In Vivo Vascular Imaging using Near-Infrared II Fluorescence [ J ]. Nat.Med.,2012,18 (12): 1841-1846.
Non-patent document 3: R-J Xie. Light-Emitting Diodes: bright NIR-Emitting Phosphor Making Light Sources Smarter [ J ]. Light Sci Appl,2020,9:155.
Non-patent document 4: l Yao, Q Shao, X Xu, et al Broadband Emission of Single-Phase Ca 3 Sc 2 Si 3 O 12 :Cr 3+ /Ln 3+ (Ln=Nd,Yb,Ce)Phosphors for Novel Solid-State Light Sources with Visible to Near-Infrared Light Output[J].Ceram.Int.,2019,45(11):14249-14255.
Non-patent document 5: e Song, J Wang, J Shi, et al Highly Efficient and Thermally Stable K 3 AlF 6 :Mn 4+ as a Red Phosphor for Ultra-High-Performance Warm White Light-Emitting Diodes[J].ACS Applied Materials&Interfaces,2017,9(10):8805-12.
Non-patent document 6: y Wu, Y Lv, K Ruan, et al A Far-Red Emission (Ca, sr) 14 Zn 6 Ga 10 O 35 :Mn 4+ Phosphor for Potential Application in Plant-Growth LEDs[J].Dalton Trans.,2018,47(43):15574-15582.
Non-patent document 7: s Adachi. Review-Mn 4+ vs Cr 3+ :A Comparative Study as Activator Ions in Red and Deep Red-Emitting Phosphors[J].ECS J.Solid State Sci.Tech.,2020,9(2):026003.
Disclosure of Invention
In view of the above background art, the present invention aims to provide a simple, efficient and industrially advantageous near infrared luminescent material of nitrogen oxide suitable for white light LED, plant growth illumination, iris recognition, solar cell and for biological marker, and a preparation method thereof.
The present invention is a result of a series of studies based on the above knowledge, and thereby succeeded in providing a near infrared light emitting material. Namely, the composition is shown as formula (I):
M 1-x-y Al 1-z Si 5+z O 2-z N 7-z :Sm x ,Bi y ,K y (I);
(1) In the above (I), x is not less than 0.001 and not more than 0.2, y is not less than 0 and not more than 0.1, and z is not less than 0 and not more than 0.1.M is one or more elements of Mg, ca, sr, ba,
(2) Wherein, the near infrared luminescent material in the formula (I) and M in the chemical composition formula at least contains Ba or Sr element.
(3) The method for preparing a near infrared luminescent material according to (1) or (2), wherein the M precursor, the Sm precursor, the Bi precursor, the K precursor, the Al precursor and the Si precursor are calcined in a reducing atmosphere at 1200-1800 ℃ according to a certain chemical dose ratio; or sintering under reducing atmosphere to obtain Sm 2+ 、Bi 3+ 、K + The doped M metal silicate compound is then sintered again with the stoichiometric Si and Al precursors in a reducing atmosphere at 1200 to 1800 ℃;
wherein at least one nitrogen-containing compound is selected from the M precursor, sm precursor, bi precursor, K precursor, al precursor and Si precursor.
(4) The M precursor is one or more of carbonate of M, oxide of M, nitride of M, oxalate of M and nitrate of M;
(5) The Sm precursor is one or more of Sm carbonate, sm oxide, sm oxalate and Sm nitrate;
(6) The Bi precursor is one or more of Bi carbonate, bi oxide, bi oxalate and Bi nitrate;
(7) The K precursor is one or more of K carbonate, K oxide, K oxalate, K nitrate and K hydroxide;
(8) The Al precursor is one or more of an oxide of Al, a nitride of Al and a nitrate of Al;
(9) The Si precursor is one or more of Si oxide and Si nitride; preferably, the reducing atmosphere is ammonia gas or nitrogen-hydrogen mixed gas.
Preferably, the high-temperature sintering temperature is 1300-1700 ℃; the high-temperature sintering time is 2-10 h.
The invention also discloses application of any near infrared luminescent material in white light LEDs, plant growth illumination, solar cells and biological markers.
The invention provides a near infrared luminescent material, a preparation method and application thereof. The near infrared luminescent material has brand new chemical composition and no related literature reports the luminescent characteristics. In addition, compared with the traditional near infrared luminescent material, the near infrared luminescent material adopts Sm 2+ As an activator, sm 2+ Near infrared luminescent materials as activators have been recently reported. In addition, the fluorescent powder taking the oxynitride as the matrix generally has good stability, so that the prepared near infrared luminescent material can be suitable for some special conditions (such as high temperature and high humidity) and scenes on white light LEDs, plant growth illumination, solar cells and biological markers.
Drawings
FIG. 1 is an X-ray diffraction chart of a near infrared light emitting material obtained in example 2 of the present invention;
FIG. 2 is an emission spectrum of the near infrared light emitting material obtained in example 2 of the present invention under 341nm excitation and an excitation spectrum at a monitoring wavelength of 682 nm;
FIG. 3 is a graph of the relative emission intensity of example 2 after various times of treatment in water;
FIG. 4 is an X-ray diffraction chart of the near infrared light emitting material obtained in example 4 of the present invention;
FIG. 5 is an emission spectrum of the near infrared light emitting material obtained in example 4 under excitation of 341nm and an excitation spectrum at a monitoring wavelength of 682 nm;
fig. 6 is a graph of emission intensity comparison after correction of example 13 and example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
According to BaCO 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytical grade) and Sm 2 O 3 (analytically pure) molar ratio of 1.54:0.4:1:0.03, respectively taking materials, grinding, mixing, drying, loading into corundum crucible, and placing in high temperature furnace, at H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ Doped Ba 1.6 Sr 0.4 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 AlN is as follows, according to mole ratio 1:3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 4 hours at 1600 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The fluorescent material obtained in example 1 was analyzed by a fluorescence spectrometer, and the emission peak under 341nm ultraviolet excitation was 682nm, so that the fluorescent powder could be excited by ultraviolet light to emit near infrared light, thereby converting ultraviolet light into near infrared light.
Example 2
According to BaCO 3 (analytically pure), siO 2 (analytical grade) and Sm 2 O 3 (analytically pure) molar ratio of 1.76:1:0.12, respectively taking materials, grinding, mixing, drying, and loading into corundum crucible, whereinIn a high temperature furnace, H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ Doped Ba 2 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 AlN is as follows, according to mole ratio 1:3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 4 hours at 1600 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The material obtained in example 2 was analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 1. Querying an international crystallography database to confirm that the spectrum and the monoclinic space group are Imm2 (44) and the chemical composition is BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent material obtained in example 2 was analyzed by a fluorescence spectrometer, and its normalized excitation and emission spectrum is shown in fig. 2, and the emission peak under 341nm ultraviolet excitation is 682nm. The fluorescent powder can be excited by ultraviolet light to emit near infrared light, so that the fluorescent material can convert the ultraviolet light into the near infrared light.
The stability test of example 2 shows that the powder stability was not good enough compared to other oxides, fluoride fluorescence powder (as reported in non-patent reference Journal of Materials Chemistry C,2022,10 (18): 7049, K) 2 SiF 4 :Mn 4+ The dark red luminescent material, after being soaked in water for 60 minutes, has the luminous intensity reduced to 27 percent, the sample of the example 2 has stable chemical property, the normalized luminous intensity is adopted for comparison to determine the stability data of the material, the sample has no obvious luminous intensity change after being soaked in water for 72 hours, and the sample has good water stability.
Example 3
According to SrCO 3 (analytically pure), siO 2 (analytical grade) and Sm 2 O 3 (analytically pure) molar ratio of 1.94:1:0.03, respectively taking materials, grinding, mixing, drying, loading into corundum crucible, and placing in high temperature furnace, at H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ Doped Sr 2 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 And AlN is 1 according to the mole ratio: 3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 4 hours at 1600 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The fluorescent material obtained in example 3 was analyzed by a fluorescence spectrometer, and the emission peak under excitation by ultraviolet light at 341nm was found to be 682nm. The fluorescent powder can be excited by ultraviolet light to emit near infrared light, so that the fluorescent material can convert the ultraviolet light into the near infrared light.
Example 4
According to BaCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure) and AlN (analytically pure) molar ratio of 1.76:1:0.12:3:2, respectively taking materials, grinding, mixing and drying the materials uniformly, then loading the materials into a corundum crucible, and placing the corundum crucible in a high-temperature furnace and H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace, taking out, grinding to obtain the required Sm 2+ Doped with near infrared luminescent material.
The material obtained in example 4 was analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 4. Querying in International Crystal database to confirm that the spectrum and space group belonging to monoclinic system areImm2 (44) and of chemical composition BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent material obtained in example 4 was analyzed by a fluorescence spectrometer, and the emission peak under 341nm ultraviolet excitation was 682nm, which was different from the sample of example 2 in terms of the emission intensity, as shown in FIG. 5. The fluorescent powder can be excited by ultraviolet light to emit near infrared light, so that the fluorescent material can convert the ultraviolet light into the near infrared light.
Examples 5 to 7
According to BaCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure) and AlN (analytically pure) molar ratio of 1.88:1:0.06:3:2, respectively taking materials, grinding, mixing and drying the materials uniformly, then loading the materials into a corundum crucible, and respectively adding pure nitrogen and H into a high-temperature furnace 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =10: 90 And H) 2 Ar gas mixture (gas volume content ratio is H) 2 : ar=5: 95 Sintering for 4 hours at 1600 ℃ in 100mL/min at the gas flow rate, cooling to room temperature along with a furnace, taking out, grinding to obtain the required Sm 2+ Doped near infrared luminescent material.
The materials obtained in examples 5 to 7 were analyzed by X-ray diffraction to confirm the diffraction pattern of the sample and BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent materials obtained in examples 5 to 7 were analyzed by a fluorescence spectrometer, and their emission spectra were obtained under excitation with ultraviolet light of 341 nm. The emission patterns of example 5, example 6 and example 7 were not significantly changed from those of fig. 2, indicating that all of the 3 reducing atmospheres could successfully obtain near infrared luminescent materials.
Example 8
According to BaCO 3 (analytically pure), siO 2 (analytical grade) and Sm 2 O 3 (analytically pure) molar ratio of 1.96:1:0.02, respectivelyTaking materials, grinding, mixing, drying, loading into corundum crucible, and placing in high temperature furnace, at H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ Doped Ba 2 SiO 4 Precursor materials. Then the precursor is combined with Si 3 N 4 And AlN is 1 according to the mole ratio: 3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 6 hours at 1550 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The material obtained in example 8 was analyzed by X-ray diffraction to confirm the diffraction pattern of the sample and BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent material obtained in example 8 was analyzed by a fluorescence spectrometer, and the emission spectrum thereof obtained under excitation by ultraviolet light at 341nm was not significantly changed from that of fig. 2.
Example 9
According to BaCO 3 (analytically pure), caCO 3 (analytically pure), sm 2 O 3 (analytical grade) and SiO 2 (analytically pure) molar ratio of 1.52:0.4:0.03:1, respectively taking materials, grinding, mixing, drying, loading into corundum crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ Doped Ba 1.6 Ca 0.4 SiO 4 Precursor materials. Then the precursor is combined with Si 3 N 4 And AlN is 1 according to the mole ratio: 3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio)Examples are H 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 6 hours at 1550 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The material obtained in example 9 was analyzed by X-ray diffraction to confirm the diffraction pattern of the sample and BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent material obtained in example 9 was analyzed by a fluorescence spectrometer, and the emission spectrum thereof obtained under excitation by ultraviolet light at 341nm was not significantly changed from that of fig. 2.
Example 10
According to BaCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), bi 2 O 3 (analytically pure) and AlN (analytically pure) molar ratio of 1.68:1:0.12:3:0.04:2, respectively taking materials, grinding, mixing and drying the materials uniformly, then loading the materials into a corundum crucible, and placing the corundum crucible in a high-temperature furnace and H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace, taking out, grinding to obtain the required Sm 2+ Doped with near infrared luminescent material.
The material obtained in example 10 was analyzed by X-ray diffraction to confirm the diffraction pattern of the sample and BaAlSi 5 O 2 N 7 Standard profile (ICSD # 240276) was consistent and no distinct hetero-peaks were observed.
The fluorescent material obtained in example 10 was analyzed by a fluorescence spectrometer, and its emission spectrum obtained under excitation with ultraviolet light at 341nm was not significantly changed, except for the difference in emission intensity, as compared with fig. 2.
Example 11
According to BaCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical grade) and Bi 2 O 3 (analytically pure) molar ratio of 1.8:1:0.06:0.04, respectively taking the materials and grinding the materialsGrinding, mixing, drying, loading into corundum crucible, and heating in high temperature furnace at H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ And Bi (Bi) 3+ Doped Ba 2 SiO 4 Precursor materials. Then the precursor is combined with Si 3 N 4 And AlN is 1 according to the mole ratio: 3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 6 hours at 1550 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The fluorescent material obtained in example 11 was analyzed by a fluorescence spectrometer, and its emission spectrum obtained under excitation with ultraviolet light at 341nm was not significantly changed, except for the difference in emission intensity, as compared with fig. 2.
Example 12
According to BaCO 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure) and AlN (analytically pure) molar ratio of 1.36:0.4:1:0.12:3:2, respectively taking materials, grinding, mixing and drying the materials uniformly, then loading the materials into a corundum crucible, and placing the corundum crucible in a high-temperature furnace and H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace, taking out, grinding to obtain the required Sm 2+ Doped with near infrared luminescent material.
The fluorescent material obtained in example 12 was analyzed by a fluorescence spectrometer, and its emission spectrum obtained under 341nm ultraviolet excitation was not significantly changed as compared with fig. 2.
Example 13
According to BaCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytically pure), K 2 CO 3 (analytically pure), and Bi 2 O 3 (analytically pure) molar ratio of 1.72:1:0.06:0.04:0.04, respectively taking materials, grinding, mixing, drying, loading into corundum crucible, and placing into high temperature furnace at H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 3 hours, and cooling to room temperature along with a furnace to obtain Sm 2+ 、Bi 3+ And K + Doped Ba 2 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 And AlN is 1 according to the mole ratio: 3:2, grinding, mixing, drying, loading into boron nitride crucible, placing into high temperature furnace, and adding into H 2 /N 2 Mixed gas (gas volume content ratio is H) 2 :N 2 =5: 95, the gas flow rate is 100 mL/min), sintering for 6 hours at 1600 ℃, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material.
The fluorescent material obtained in example 13 was analyzed by a fluorescence spectrometer, and as shown in fig. 6, the emission spectrum thereof was obtained under excitation with ultraviolet light of 341nm as compared with example 2, with no significant change except that the emission intensity was stronger than that of example 2.
In addition, the invention adopts Sm 2+ The nitrogen oxide near infrared luminescent material prepared by activation can solve the problems of few luminescent centers (commonly found in Cr at present) in the research of the existing near infrared luminescent material 3+ And Mn of 4+ ) The problems of low efficiency and poor physical and chemical stability are solved, so that the development of the nitrogen oxide near infrared luminescent material in the application fields of special environments (high temperature and high humidity), plant illumination, biological imaging, white light LEDs and the like is promoted.
Claims (9)
1. A near infrared luminescent material, as shown in formula (I):
M 1-x-y Al 1-z Si 5+z O 2-z N 7-z :Sm x, Bi y ,K y (I);
wherein M is at least one element of Sr and Ba; sm is Sm 2+ ;
0.001 ≤ x ≤ 0.2,0≤ y≤ 0.1,0 ≤ z ≤ 0.1。
2. A process for preparing near infrared light-emitting material as claimed in claim 1, wherein,
mixing the M precursor, the Sm precursor, the Bi precursor, the K precursor, the Al precursor and the Si precursor, performing high-temperature solid-phase reaction to obtain the near-infrared luminescent material,
wherein at least one nitrogen-containing compound is selected from the M precursor, the Sm precursor, the Bi precursor, the K precursor, the Al precursor and the Si precursor;
the high temperature solid phase reaction is carried out in a reducing atmosphere.
3. The method for preparing near infrared luminescent material as claimed in claim 1, wherein the method comprises the steps of synthesizing Sm, bi and K doped silicate containing M, mixing with Al precursor and Si precursor, and performing high temperature solid phase reaction to obtain near infrared luminescent material;
wherein at least one nitrogen-containing compound is contained in the Sm, bi and K doped M-containing silicate, al precursor and Si precursor;
the high temperature solid phase reaction is carried out in a reducing atmosphere.
4. A process according to claim 3, wherein,
the method comprises the following steps: mixing the M precursor, the Sm precursor, the Bi precursor and the K precursor, sintering at high temperature in a reducing atmosphere to obtain the M-containing silicate doped with Sm, bi and K, mixing with the Al precursor and the Si precursor, and sintering for the second time in the reducing atmosphere to obtain the high-temperature-resistant ceramic material.
5. The method according to claim 2 or 4, wherein the purity of the M precursor, sm precursor, bi precursor, K precursor, al precursor, and Si precursor is not lower than 99.5%.
6. The preparation method according to claim 2 or 3, wherein the temperature of the high-temperature solid phase reaction is 1200-1800 ℃; the high-temperature solid phase reaction time is 2-10 h.
7. The method according to claim 6, wherein the reducing atmosphere is ammonia gas, argon hydrogen gas or a mixed gas of nitrogen and hydrogen gas.
8. The preparation method according to claim 2 or 4, characterized in that it has at least one of the following technical characteristics:
the M precursor is one or more of carbonate of M, oxide of M, nitride of M, oxalate of M and nitrate of M;
the Sm precursor is one or more of Sm carbonate, sm oxide, sm oxalate and Sm nitrate;
the Bi precursor is one or more of Bi carbonate, bi oxide, bi oxalate and Bi nitrate;
the K precursor is one or more of K carbonate, K oxide, K oxalate, K nitrate and K hydroxide;
the Al precursor is one or more of an oxide of Al, a nitride of Al and a nitrate of Al;
the Si precursor is one or more of Si oxide and Si nitride.
9. Use of the near infrared luminescent material according to claim 1 or the near infrared luminescent material prepared by the preparation method according to any one of claims 2 to 8 in white light LEDs, plant growth lighting, solar cells and biomarkers.
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