CN115572600B - Sm (Sm) 2+ Activated broadband near infrared luminescent material and preparation method and application thereof - Google Patents
Sm (Sm) 2+ Activated broadband near infrared luminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Sm 2+ Activated broadband near infrared luminescent material, and preparation method and application thereof. The chemical composition of the luminescent material is M 1‑x‑y Al 3‑z Si 3+z O 4‑z N 5‑z :Sm x, Ln 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 Ba, sr, ca, mg; ln is one or more elements of Bi, yb, eu, nd, gd, tb, dy, ho, er, tm, pr; wherein x is more than or equal to 0.001 and less than or equal to 0.2, and y is more than or equal to 0 and less than or equal to 0.1. Compared with the prior art, the near infrared luminescent material provided by the invention adopts Sm 2+ As an activation center, it has a completely new chemical composition. The luminescent material can be efficiently excited by light in the wavelength range of 240-640 nm, so that 650-1000 nm broadband near infrared light is emitted, and ultraviolet light, violet-blue light, green light and red light can be converted into near infrared light by the luminescent material. The near infrared fluorescent powder provided by the invention has the advantages of convenience in synthesis and stable chemical performance, and is suitable for the fields of biological imaging, plant growth illumination, white light LEDs, solar batteries and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to a broadband near infrared luminescent material with a novel activation center, and a preparation method and application thereof.
Background
In recent years, the advantages of good spectrum easy adjustment and simple preparation process of the inorganic luminescent material are widely applied to the fields of LEDs and the like. Near infrared luminescent materials (emission wavelength longer than 650 nm) have been attracting attention in recent years for their potential application value in promoting plant illumination, rapid detection of foods, bio-imaging, and the like [ non-patent document 1]. For plant growth, near infrared around 730nm can be absorbed by Phytochrome (PFR) of the plant, promoting plant growth. In addition, near infrared light has also shown great potential in medical imaging and the like in recent years, and near infrared light having different projection ratios with respect to near infrared light around 780nm is utilized to be able to well show the rough distribution of human palm blood vessels using a near infrared camera, thereby showing strong competitiveness [ non-patent documents 2,3]. Therefore, the development of the novel near infrared luminescent material with high efficiency and stability has important significance.
The excitation center can be selected from Eu in principle of luminescence, which is expected to obtain near infrared luminescent material with emission peak of more than 650nm 2+ ，Cr 3+ And Mn of 4+ Etc. For example, report of non-patent document 4Eu of the channel 2+ Activated SrY 2 S 4 After the material is irradiated by 465nm blue light to store energy, the material can emit deep red light with a peak value of 640 nm; also as reported in non-patent document 5, cr 3+ At Mg 2 GeO 4 The emission peak is tuned from 940nm to 1100nm by weakening the crystal field strength in the matrix. With Cr 3+ Is similar to the luminescence mechanism of Mn 4+ It also readily exhibits deep red and near infrared luminescence upon entering the hexacoordinated octahedral lattice site, as in Na 2 SiF 6 :Mn 4+ And Ca 14 Al 10 Zn 6 O 35 Mn is observed in the matrix 4+ Near-infrared luminescence by occupying hexacoordinated octahedral lattice [ non-patent documents 6,7]. However, the lack of the type of the activation center of the near infrared luminescent material is still significant, so that the development of a new near infrared activation center is also important for the development of near infrared luminescent materials. At present with Sm 2+ There are few reports in the related patent literature of near infrared light emitting materials as activation centers, and only some oxide phosphors exhibiting mainly linear emission (such as the linear emission of patent literature 1) have insufficient emission wavelength [ non-patent literature 8]. In addition, most of the common near infrared fluorescent powder uses oxide, sulfide and fluoride as matrixes, and the matrix structure generally has the problem of relatively unstable, which restricts the development of the near infrared fluorescent powder. And near infrared fluorescent powder using nitrogen oxides with stable structure as a matrix is rarely reported. Sm was observed in the case of the nitrogen oxide luminescent material reported in patent document 1 2+ Long wavelength emission of (c). It should be noted, however, that the material has an emission wavelength peak of 682nm and is derived from Sm 2+ Is a transition of f-f. It is known that the f-f transition luminescence efficiency of rare earth ions is low if Sm can be adjusted 2+ The emission probability of the 5d transition back to the ground state is larger than that of the 4f excited state energy level transition back to the ground state, thereby realizing Sm 2+ The emission based on d-f transition is expected to greatly improve the luminous efficiency of the material and regulate the luminous wavelength of the material, which is good for Sm 2+ The development of the application of activated broadband emission near infrared luminescent materials is of great importance.
Non-patent document 1: R.J.Xie.light-Emitting Diodes: bright NIR-Emitting Phosphor Making Light Sources Smarter.light Sci appl.2020,9:155.
Non-patent document 2: S.J.Dhoble, R.Priya, N.S.Dhoble, O.P.Pandey.Short review on recent progress in Mn 4+ -activated oxide phosphors for indoor plant light-emitting diodes.Luminescence.2021,36(3),560-575.
Non-patent document 3: L.L.Zhang, D.D.Wang, Z.D.Hao, X.Zhang, G.H.Pan, H.J.Wu, J.H.Zhang.Cr 3+ -doped broadband NIR garnet phosphor with enhanced luminescence and its application in NIR spectroscopy.Adv.Opt.Mater.2019,7(12),1900185.
Non-patent document 4: J.Mckittrick, L.E.Shea-Rohwer. Review: down Conversion Materials for Solid-State lighting. J.Am. Ceram. Soc.,2014,97 (5): 1327-1352.
Non-patent document 5: H.Cai, S.Q.Liu, Z.Song, Q.L.Liu.Tuning Luminescence from NIR-I to NIR-II in Cr 3+ -Doped Olivine Phosphors for Nondestructive Analysis.J.Mater.Chem.C.2021,9(16),5469-5477.
Non-patent document 6: M.G.Brik, A.M.Srivastava.On the optical properties of the Mn 4+ ion in solids.J.Lumin.,2013,133:69-72.
Non-patent document 7: W.Lu, W.Lv, Q.Zhao, M.Jiao, B.Shao, H.You.A Novel Efficient Mn 4+ Activated Ca 14 Al 10 Zn 6 O 35 Phosphor:Application in Red-Emitting and White LEDs.Inorg.Chem.,2014,53(22):11985-11990.
Non-patent document 8: T.Zheng, M.Runowski, P.S.Lis,V.Lavin.Huge Enhancement of Sm 2+ Emission via Eu 2+ Energy Transfer in a SrB 4 O 7 Pressure Sensor.J.Mater.Chem.C,2020,8(14):4810-4817.
Patent document 1: lv Ying, li Yunkai, fan Saiting, zhao Ning, xue Yan A Sm 2+ ActivatedNear infrared luminescent material and preparation method and application thereof: 202210566931.2
Disclosure of Invention
In view of the background art, the invention mainly provides the nitrogen oxide matrix near-infrared luminescent material which has the advantages of simple synthesis method, high efficiency and convenient industrialized production, and is simultaneously applicable to a plurality of fields such as plant growth illumination, white light LEDs, biological imaging, solar cells and the like, and the 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. The composition is shown as a formula (I):
M 1-x-y Al 3-z Si 3+z O 4-z N 5-z :Sm x ,Ln 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) is characterized in that M in the chemical composition formula at least comprises one or more of Ba, sr and Ca elements.
(3) The method for preparing a near infrared luminescent material according to (1) or (2), wherein the M precursor, the Sm precursor, the Ln precursor, the Al precursor and the Si precursor react at a high temperature of 1200-1800 ℃ in a reducing atmosphere according to a certain chemical dosage ratio; or sintering under reducing atmosphere to obtain Sm and Ln doped M metal silicate compound, and then reacting with Si and Al precursors in certain stoichiometric ratio at 1200-1800 deg.C under reducing atmosphere.
(4) The M precursor is one or more of M carbonate, M oxalate, M nitrate, M sulfate, M chloride and M oxide;
(5) The Sm precursor is one or more of Sm carbonate, sm oxide, sm sulfide, sm halide, sm boride, sm oxalate and Sm nitrate;
(6) The Ln precursor is one or more of carbonate of Ln, oxide of Ln, sulfide of Ln, chloride of Ln, oxalate of Ln and nitrate of Ln;
(7) The Al precursor is one or more of an oxide of Al, a nitride of Al, a chloride of Al, a nitrate of Al and a carbonate of Al;
(8) The Si precursor is one or more of Si oxide and Si nitride; preferably, the reducing atmosphere is one of nitrogen, argon-hydrogen mixed gas or nitrogen-hydrogen mixed gas.
Preferably, the temperature of the high-temperature reaction is 1300-1700 ℃; the high-temperature reaction time is 2-12 h.
The invention also discloses application of the near infrared luminescent material in biological imaging, plant growth illumination, white light LED and solar battery.
The invention provides a broadband near infrared luminescent material with a novel luminescent center and a preparation method thereof. The near infrared luminescent material has a novel luminescent center and a brand new chemical composition, and meanwhile, no related literature reports the luminescent characteristics. In addition, compared with the traditional near infrared luminescent material, the broadband near infrared luminescent material is prepared by Sm 2+ As the activation center, sm 2 + Broadband near infrared luminescent materials as active centers have been rarely reported. In addition, the near infrared luminescent material takes oxynitride as a matrix, so that the near infrared luminescent material has good stability and can be suitable for scenes under special conditions (such as high temperature and high humidity).
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 a normalized emission spectrum at 450nm excitation and a normalized excitation spectrum monitored at 764nm of the near infrared luminescent material obtained in example 2 of the present invention;
FIG. 3 is a graph of normalized emission intensity measured at different temperatures for example 2;
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 a graph of emission intensity versus example 10 and example 8;
FIG. 6 is a graph of normalized excitation and emission spectra of example 11;
FIG. 7 is a graph showing the peak position contrast of the emission of example 14, example 15, example 8, example 2, example 16, and example 17 under excitation with 450nm blue light.
Detailed Description
The technical solutions in the embodiments of the present invention will be described in detail below in conjunction with the embodiments of the present invention, and the described embodiments are only some, but not all embodiments of the present invention. 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), siO 2 (analytical grade) and Sm 2 O 3 (analytically pure) molar ratio of 1.88:1:0.06, respectively taking materials, grinding the raw materials in an agate mortar, mixing, drying, loading into a corundum crucible, and placing in a high-temperature furnace, and adding 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 2 hours, and cooling to room temperature along with a furnace after the reaction to obtain Sm 2+ Doped Ba 2 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 、Al 2 O 3 AlN has a molar ratio of 1.7:1.3333:3.4, grinding and mixing in an agate mortar again, drying, loading into a boron nitride crucible, placing into a high temperature furnace, and adding 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 after the reaction technology, taking out, and grinding in an agate mortar to obtain the required near infrared luminescent material.
The near infrared luminescent material obtained in example 1 was subjected to optical performance analysis by using a fluorescence spectrometer, and showed broadband emission with a peak value of about 760nm under excitation of ultraviolet light of 450nm, which indicates that the near infrared luminescent material can be excited by ultraviolet light to emit deep red light, i.e., the luminescent material can convert ultraviolet light into deep red light.
Example 2
BaCO is carried out 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 0.64:1.2:1:0.08:1.7:1.3333:3.4, respectively taking materials, grinding and mixing the raw materials in an agate mortar, drying, loading into a boron nitride crucible, and placing into a high-temperature furnace in 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 after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped with 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. The spectrum belongs to monoclinic space group P2 1 And has a chemical composition of BaAl 3 Si 3 O 4 N 5 Is substantially identical to the standard profile (ICSD # 186416) and no distinct peaks were observed.
The near infrared luminescent 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 450nm blue excitation is at 764nm. It is indicated that the near infrared luminescent material may be excited by blue light to emit deep red light, i.e. the luminescent material is capable of converting blue light into deep red light.
By performing the thermal stability test on example 2, the sample chemistry of example 2 was stable compared to other oxide, fluoride phosphors, and the normalized stability emission spectra are shown in fig. 3.
Example 3
SrCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytical grade)、Al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 1.96:1:0.02:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then loading the raw materials into a boron nitride crucible, and placing the boron nitride crucible in a high-temperature furnace in 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 after the reaction is finished, taking out, grinding in an agate mortar to obtain Sm 2+ Doped near infrared luminescent material.
The near infrared luminescent material obtained in example 3 was analyzed by a fluorescence spectrometer, and the emission peak under 365nm ultraviolet excitation was located at 762nm. It is indicated that the luminescent material may be excited by ultraviolet light to emit deep red light, i.e. the near infrared luminescent material is capable of converting ultraviolet light into deep red light.
Example 4
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), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 1.44:0.4:1:0.08:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then loading the raw materials into a boron nitride crucible, and placing the boron nitride crucible in a high-temperature furnace in 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 after the reaction is finished, taking out, grinding in an agate mortar to obtain Sm 2+ Doped 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 are P2 1 And has a chemical composition of BaAl 3 Si 3 O 4 N 5 Is substantially identical to the standard profile (ICSD # 186416) without significant impurity peaks being observed.
The luminescent material obtained in example 4 was analyzed by a fluorescence spectrometer, and the emission peak under excitation of 450nm blue light was at 762nm, which was different from the sample of example 2 in terms of the emission peak position, and was not different. It is indicated that the luminescent material may be excited by blue light to emit deep red light, i.e. the luminescent material is capable of converting blue light into deep red light.
Examples 5 to 7
BaCO is carried out 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 1.84:1:0.08:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then loading the raw materials into a boron nitride 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 =5: 95 And H) 2 Ar gas mixture (gas volume content ratio is H) 2 : ar=5: 95 Sintering at 1600 ℃ for 4 hours at the gas flow rate of 100mL/min, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain 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 BaAl 3 Si 3 O 4 N 5 Standard profile (ICSD # 186416) was consistent and no distinct hetero-peaks were observed.
The luminescent materials obtained in examples 5 to 7 were analyzed by a fluorescence spectrometer, and their emission spectra were obtained under excitation with 450nm blue light. The emission spectrum patterns of example 5, example 6 and example 7 were not significantly changed in shape from those of fig. 2.
Example 8
BaCO is carried out 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 0.68:1.2:1:0.06:1.7:1.3333:3.4, respectively mixing the above raw materialsGrinding in agate mortar, drying, loading into boron nitride crucible, and heating in 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 1550 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped with 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 BaAl 3 Si 3 O 4 N 5 Standard profile (ICSD # 186416) was consistent and no distinct hetero-peaks were observed.
The luminescent material obtained in example 8 was analyzed by a fluorescence spectrometer, and its emission spectrum was obtained under excitation with 450nm blue light, which was not significantly changed from that of fig. 2.
Example 9
According to BaCO 3 (analytically pure), caCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 0.64:1.2:1:0.08:1.7:1.3333:3.4, grinding and mixing the raw materials in an agate mortar, drying, loading into a boron nitride crucible, placing into a high-temperature furnace, and adding H 2 Ar gas mixture (gas volume content ratio is H) 2 : ar=5: 95, gas flow rate of 100 mL/min) at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped with 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 BaAl 3 Si 3 O 4 N 5 Standard profile (ICSD # 186416) was consistent and no distinct hetero-peaks were observed.
The luminescent material obtained in example 9 was analyzed by fluorescence spectrometer, and its emission spectrum obtained under excitation with 450nm blue light was not significantly changed compared with fig. 2.
Example 10
According to BaCO 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytically pure), bi 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 0.64:1.2:1:0.06:0.02:1.7:1.3333:3.4, grinding and mixing the raw materials in an agate mortar, drying, loading into a boron nitride crucible, and placing into a high-temperature furnace in 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 1550 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ 、Bi 3+ Doped 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 BaAl 3 Si 3 O 4 N 5 Standard profile (ICSD # 186416) was consistent and no distinct hetero-peaks were observed.
The luminescent material obtained in example 10 was analyzed by a fluorescence spectrometer, and its emission spectrum obtained under excitation by 450nm ultraviolet light was not significantly changed as compared with example 8, except that the emission intensity was enhanced, as shown in fig. 5.
Example 11
According to BaCO 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytically pure) in a molar ratio of 0.68:1.2:1:0.06 grinding and mixing the above materials in agate mortar, drying, loading into corundum crucible, and placing in high temperature furnace, under 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 2 hours, cooling to room temperature along with a furnace after the reaction is finished, and taking out to obtain Sm 2+ Doped (Ba, sr) 2 SiO 4 Precursor materials. Then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding in an agate mortar, drying, loading into a boron nitride crucible, and placing into a 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 1550 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped near infrared luminescent material.
The luminescent material obtained in example 11 was analyzed by a fluorescence spectrometer, and as shown in fig. 6, the emission spectrum thereof obtained under excitation with 450nm blue light was not significantly changed from that of example 8.
Example 12
BaCO is carried out 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytically pure) in a molar ratio of 1.56:0.4:1:0.02 grinding and mixing the above materials in agate mortar, drying, loading into corundum crucible, and placing in high temperature furnace, under H 2 /N 2 Mixed gas (gas content ratio is H) 2 ：N 2 =5: 95, gas flow rate of 100 mL/min) at 1300 ℃ for 2 hours, cooling to room temperature along with a furnace after the reaction is finished, and taking out to obtain Sm 2+ Doped (Ba, sr) 2 SiO 4 Precursor materials. Then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding in an agate mortar, drying, loading into a boron nitride crucible, and placing into a 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 1600 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped near infrared luminescent material.
The luminescent material obtained in example 12 was analyzed by fluorescence spectrometer, and its emission spectrum obtained under excitation of 450 blue light was not significantly changed compared with fig. 2.
Example 13
BaCO is carried out 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical grade) and Bi 2 O 3 (analytically pure) in a molar ratio of 0.64:1.2:1:0.06:0.02, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then loading the raw 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 1300 ℃ for 2 hours, cooling to room temperature along with a furnace after the reaction is finished, and taking out to obtain Sm 2+ 、Bi 3+ Doped (Ba, sr) 2 SiO 4 A precursor. Then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding in an agate mortar, drying, loading into a boron nitride crucible, and placing into a high-temperature furnace, at 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 luminescent material obtained in example 13 was analyzed by a fluorescence spectrometer, and its emission spectrum obtained under excitation with 450nm blue light was not significantly changed as compared with example 10.
Examples 14 to 17
BaCO is carried out 3 (analytically pure), srCO 3 (analytically pure), siO 2 (analytically pure), sm 2 O 3 (analytical purity), si 3 N 4 (analytically pure), al 2 O 3 (analytically pure) and AlN (analytically pure) in a molar ratio of 0.76:1.2:1:0.02:1.7:1.3333:3.4, 0.72:1.2:1:0.04:1.7:1.3333:3.4, 0.6:1.2:1:0.10:1.7:1.3333:3.4, 0.56:1.2:1:0.12:1.7:1.3333:3.4 (example 14, example 15, example 16, example 17, respectively) the above raw materials were ground and mixed in an agate mortar, dried, and then charged into a boron nitride crucible,in a high temperature furnace, in 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 after the reaction is finished, taking out, grinding in an agate mortar to obtain the required Sm 2+ Doped with near infrared luminescent material.
The luminescent materials obtained in examples 14 to 17 were analyzed by a fluorescence spectrometer, and their emission spectra were obtained under excitation with 450nm blue light, with the exception of the shift in emission peak position, which was not significantly changed from that of fig. 2.
From the above, it can be seen that the near infrared luminescent material of this study can be excited by light in the wavelength range of 240 to 640nm, thereby emitting broadband near infrared light having d-f transition characteristics of 650 to 1000 nm. Typically, sm 2+ Exhibits only f-f linear emission because f-f transition is lower in the excited state energy level and is more easily observed, and is more observed in the halogen alkaline earth metal compound (e.g., caF 2 :Sm 2+ ,BaClF:Sm 2+ Etc.), such materials are poorly water stable. Also, as previously described, such emission is inefficient, the emission location is fixed and not long enough (typically the emission peak is less than 700 nm), and near infrared emission at longer wavelengths cannot be achieved. In view of the above, the present study focused on Sm 2+ The micro-environment regulation of (2) improves the emission position and efficiency through matrix selection, anion and cation replacement and other optimization, and Sm is realized in nitrogen oxide for the first time 2+ Near infrared emission mainly based on d-f broadband at room temperature, and realizes the regulation and control of broadband emission peak from 752nm to 770 nm. The research is not only beneficial to Sm 2+ The active luminescent material exploration plays an important role in the practical application of the near infrared luminescent material.
In addition, the invention adopts Sm 2+ The nitrogen oxide broadband near infrared luminescent material prepared as an activation center can solve the problems of few luminescent centers (commonly found in Cr at present) existing in the research of the existing near infrared luminescent material 3+ 、Eu 2+ 、Fe 3+ And Mn of 4+ ) Low efficiency and poor physical and chemical stability, thereby promoting the near-nitrogen oxideInfrared luminescent materials are being developed in the application fields of white light LEDs, biological imaging, plant illumination, night surveillance, etc.
Claims (10)
1. The near infrared luminescent material is characterized by comprising the following preparation method:
according to BaCO 3 Analytically pure, siO 2 Analytical purity and Sm 2 O 3 Analytically pure, molar ratio 1.88:1:0.06, taking materials respectively; grinding the above materials in agate mortar, mixing, drying, charging into corundum crucible, and heating in H furnace 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, sintering at 1300 ℃ for 2 hours under the gas flow rate of 100mL/min, and cooling to room temperature along with a furnace after the reaction to obtain Sm 2+ Doped Ba 2 SiO 4 A precursor; then the precursor is combined with Si 3 N 4 、Al 2 O 3 AlN has a molar ratio of 1.7:1.3333:3.4, grinding and mixing in an agate mortar again, drying, putting into a boron nitride crucible again, putting into a high temperature furnace, and adding H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, sintering for 4 hours at 1600 ℃ at the gas flow rate of 100mL/min, cooling to room temperature along with a furnace after the reaction is finished, taking out, and grinding in an agate mortar to obtain the required near infrared luminescent material.
2. The near infrared luminescent material is characterized by comprising the following preparation method:
BaCO is carried out 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity were in terms of molar ratio of 0.64:1.2:1:0.08:1.7:1.3333:3.4, respectively taking materials; grinding the above materials in agate mortar, drying, adding into boron nitride crucible, and heating in H furnace 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, gas flow rate of 100In mL/min, the reaction is carried out for 4 hours at 1600 ℃, after the reaction is finished, the mixture is cooled to room temperature along with a furnace, taken out and ground in an agate mortar to obtain the required Sm 2+ Doped with near infrared luminescent material.
3. The near infrared luminescent material is characterized by comprising the following preparation method:
SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity were in terms of molar ratio of 1.96:1:0.02:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then charging the raw materials into a boron nitride crucible, and placing the boron nitride crucible in a high-temperature furnace at H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, at a gas flow rate of 100mL/min, carrying out high-temperature reaction at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain Sm 2+ Doped near infrared luminescent material.
4. The near infrared luminescent material is characterized by comprising the following preparation method:
according to BaCO 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity at a molar ratio of 1.44:0.4:1:0.08:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then charging the raw materials into a boron nitride crucible, and placing the boron nitride crucible in a high-temperature furnace at H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, at a gas flow rate of 100mL/min, carrying out high-temperature reaction at 1600 ℃ for 4 hours, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain Sm 2+ Doped near infrared luminescent material.
5. The near infrared luminescent material is characterized by comprising the following preparation method:
BaCO is carried out 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity were in terms of molar ratio of 1.84:1:0.08:1.7:1.3333:3.4, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then charging the raw materials into a boron nitride crucible, and respectively adding pure nitrogen and H into a high-temperature furnace 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95 and H 2 Ar gas mixture, the gas volume content ratio is H 2 : ar=5: 95, sintering at 1600 ℃ for 4 hours in a gas flow rate of 100mL/min, cooling to room temperature along with a furnace after the reaction is finished, taking out, grinding in an agate mortar to obtain Sm 2+ Doped near infrared luminescent material.
6. The near infrared luminescent material is characterized by comprising the following preparation method:
BaCO is carried out 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity were in terms of molar ratio of 0.68:1.2:1:0.06:1.7:1.3333:3.4, grinding and mixing the raw materials in an agate mortar, drying, then charging into a boron nitride crucible, and placing in a high-temperature furnace at H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1550 ℃, the reaction is cooled to room temperature along with a furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ Doped with near infrared luminescent material.
7. The near infrared luminescent material is characterized by comprising the following preparation method:
according to BaCO 3 Analytically pure CaCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity at a molar ratio of 0.64:1.2:1:0.08:1.7:1.3333:3.4, grinding and mixing the raw materials in an agate mortar, drying, then charging into a boron nitride crucible, charging into a high temperature furnace, charging into H 2 The volume content ratio of the Ar mixed gas is H 2 : ar=5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1600 ℃, the reaction is cooled to room temperature along with the furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ Doped with near infrared luminescent material.
8. The near infrared luminescent material is characterized by comprising the following preparation method:
according to BaCO 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, bi 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity at a molar ratio of 0.64:1.2:1:0.06:0.02:1.7:1.3333:3.4, grinding and mixing the raw materials in an agate mortar, drying, then charging into a boron nitride crucible, and placing in a high-temperature furnace at H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1550 ℃, the reaction is cooled to room temperature along with a furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ 、Bi 3+ Doped near infrared luminescent material.
9. The near infrared luminescent material is characterized by comprising the following preparation method:
according to BaCO 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, molar ratio 0.68:1.2:1:0.06 grinding and mixing the above materials in agate mortar, drying, charging into corundum crucible, and charging into H in high temperature furnace 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, sintering at 1300 ℃ for 2 hours in the gas flow rate of 100mL/minWhen the reaction is finished, cooling the mixture to room temperature along with a furnace, and taking out the mixture to obtain Sm 2+ Doped (Ba, sr) 2 SiO 4 A precursor material; then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding and mixing uniformly in an agate mortar, drying, then putting into a boron nitride crucible, putting into a high-temperature furnace, and adding H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1550 ℃, the reaction is cooled to room temperature along with a furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ Doped near infrared luminescent material.
10. The near infrared luminescent material is characterized by comprising the following preparation method:
BaCO is carried out 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure in molar ratio 1.56:0.4:1:0.02 grinding and mixing the above materials in agate mortar, drying, charging into corundum crucible, and heating in H furnace 2 /N 2 Mixed gas with the gas content ratio of H 2 ：N 2 =5: 95, sintering for 2 hours at 1300 ℃ in a gas flow rate of 100mL/min, cooling to room temperature along with a furnace after the reaction is finished, and taking out to obtain Sm 2+ Doped (Ba, sr) 2 SiO 4 A precursor material; then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding and mixing uniformly in an agate mortar, drying, then putting into a boron nitride crucible, putting into a high-temperature furnace, and adding H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1600 ℃, the reaction is cooled to room temperature along with the furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ Doped near infrared luminescent material;
or;
BaCO is carried out 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytical purity and Bi 2 O 3 Analytically pure in molar ratio 0.64:1.2:1:0.06:0.02, respectively taking the raw materials, grinding and mixing the raw materials uniformly in an agate mortar, drying the raw materials, then charging the raw materials into a corundum crucible, and placing the corundum crucible in a high-temperature furnace in H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, sintering for 2 hours at 1300 ℃ in a gas flow rate of 100mL/min, cooling to room temperature along with a furnace after the reaction is finished, and taking out to obtain Sm 2+ 、Bi 3+ Doped (Ba, sr) 2 SiO 4 A precursor; then the precursor is combined with Si 3 N 4 、Al 2 O 3 And AlN in a molar ratio of 1.7:1.3333:3.4, grinding and mixing uniformly in an agate mortar, drying, then putting into a boron nitride crucible, putting into a high-temperature furnace, and adding H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, sintering for 4 hours at 1600 ℃ under the gas flow rate of 100mL/min, cooling to room temperature along with a furnace, taking out, and grinding to obtain the required near infrared luminescent material;
or;
BaCO is carried out 3 Analytically pure SrCO 3 Analytically pure, siO 2 Analytical grade, sm 2 O 3 Analytically pure, si 3 N 4 Analytically pure, al 2 O 3 Analytical purity and AlN analytical purity were in terms of mole ratio of 0.76:1.2:1:0.02:1.7:1.3333:3.4, 0.72:1.2:1:0.04:1.7:1.3333:3.4, 0.6:1.2:1:0.10:1.7:1.3333:3.4, 0.56:1.2:1:0.12:1.7:1.3333:3.4, respectively taking materials, grinding and mixing the raw materials in an agate mortar, drying, then charging into a boron nitride crucible, and placing in a high-temperature furnace at H 2 /N 2 The volume content ratio of the mixed gas is H 2 ：N 2 =5: 95, the gas flow rate is 100mL/min, the reaction is carried out for 4 hours at 1600 ℃, the reaction is cooled to room temperature along with the furnace after the reaction is finished, the mixture is taken out, and the mixture is ground in an agate mortar to obtain the required Sm 2+ Doped with near infrared luminescent material.
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| CN102181285A (en) * | 2011-03-08 | 2011-09-14 | 中国科学技术大学 | Silica nitride fluorescent powder and preparation method thereof |
| CN114058371A (en) * | 2021-12-10 | 2022-02-18 | 南昌工程学院 | Yellow light long afterglow luminescent material and preparation method and application thereof |
| CN114907841A (en) * | 2022-05-23 | 2022-08-16 | 南昌工程学院 | Sm 2+ Activated near-infrared luminescent material and preparation method and application thereof |
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| CN102181285A (en) * | 2011-03-08 | 2011-09-14 | 中国科学技术大学 | Silica nitride fluorescent powder and preparation method thereof |
| CN114058371A (en) * | 2021-12-10 | 2022-02-18 | 南昌工程学院 | Yellow light long afterglow luminescent material and preparation method and application thereof |
| CN114907841A (en) * | 2022-05-23 | 2022-08-16 | 南昌工程学院 | Sm 2+ Activated near-infrared luminescent material and preparation method and application thereof |
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