CN116333736A - Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof - Google Patents
Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof Download PDFInfo
- Publication number
- CN116333736A CN116333736A CN202310338114.6A CN202310338114A CN116333736A CN 116333736 A CN116333736 A CN 116333736A CN 202310338114 A CN202310338114 A CN 202310338114A CN 116333736 A CN116333736 A CN 116333736A
- Authority
- CN
- China
- Prior art keywords
- near infrared
- luminescent material
- infrared light
- solution
- conversion luminescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 82
- 230000007547 defect Effects 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- -1 rare earth ions Chemical class 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 46
- 150000002500 ions Chemical class 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 238000004020 luminiscence type Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000007704 transition Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 229910052691 Erbium Inorganic materials 0.000 description 16
- 239000004065 semiconductor Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052775 Thulium Inorganic materials 0.000 description 6
- 230000005284 excitation Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
- C09K11/777—Oxyhalogenides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7701—Chalogenides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a near infrared light-induced defect enhanced up-conversion luminescent material and a preparation method thereof, wherein the luminescent material has a general formula of Bi/Bi (m‑x) O n Br q xRE, under the irradiation of near infrared laser, the surface of the material is light-induced to form oxygen vacancy defects in situ, and the existing oxygen vacancies can effectively expand the response range of light and can be used for preparing Bi m O n Br q The intermediate energy level of the defect is formed between the valence band and the conduction band, which is beneficial to realizing the transition of electrons from the valence band to the intermediate energy band to the conduction band while increasing the near infrared light absorption, promoting the electrons to be transferred to the luminous energy level of rare earth ions through the defect energy level, and finally realizing the up-conversion luminescence enhancement. The up-conversion nano luminescent material can effectively avoid the decrease of fluorescence intensity caused by defects, and effectively enhance the up-conversion luminescence intensity by reasonably utilizing the defects; the preparation method of the material has simple process and low energy consumption, and has industrial and market application and popularization prospects.
Description
Technical Field
The invention belongs to the technical field of up-conversion nano materials, and particularly relates to a near infrared light-induced defect enhanced up-conversion luminescent material and a preparation method thereof.
Background
The rare earth ion doped up-conversion luminescent material can convert long-wavelength near infrared light into short-wavelength visible or ultraviolet emitted light, and the unique luminescent phenomenon makes the material show great application prospect in the fields of three-dimensional display, RGB three-primary color printing, optical anti-counterfeiting, optical temperature sensing, biological imaging, photodynamic therapy and the like. The rare earth ions and the semiconductor material are good luminescent materials, and the effective combination of the rare earth ions and the semiconductor material provides a new opportunity for developing novel high-efficiency luminescent materials or laser devices. Among the numerous semiconductor materials, bismuth oxybromide (Bi m O n Br q ) Semiconductor materials are receiving much attention due to their unique physical properties and layered structure, and when combined with rare earth ions, can produce luminescence phenomena and rules completely different from conventional luminescent host materials. Structurally, bi m O n Br q From interleaved [ Bi ] 2 O 2 ]Layer and Br atomic layer composition, wherein Bi atoms and O atoms are bonded by strong covalent bonds, and Br atomic layer is bonded to [ Bi ] 2 O 2 ]The atomic layers are connected through Van der Waals force; such weak van der Waals forces cause Bi to be m O n Br q Is easily dissociated in the c-axis direction to form an ultra-thin two-dimensional structure, which easily causes ordered loss of atoms to generate defects. Up-conversion luminescent nano material doped with rare earthThe increase in surface defects increases the probability of non-radiative transitions, resulting in a decrease in luminous intensity. Because the defects of the materials are unavoidable, how to reasonably utilize the defects to improve the luminous efficiency of the rare earth up-conversion luminous material through material design has become a research hot spot at present.
Oxygen vacancies are a typical crystal defect created by the detachment of surface oxygen atoms. In the previous study, we successfully synthesized Er containing oxygen defects by adopting a tea polyphenol assisted hydrothermal method 3+ Doping Bi 3 O 4 Br nano-sheet, which realizes Er by adjusting oxygen vacancy concentration 3+ Ion up-conversion luminescence enhancement [ Unveiling the mechanisms of defects induced upconversion luminescence enhancement in Er ] 3+ ～sensitized 2D Bi 3 O 4 Br nanosheets》，Ceramics International，2023，49，12012～12020]. However, this method of chemically constructing oxygen vacancies has a relatively large influence on the morphology of the material, since the concentration of oxygen vacancies is not easily controlled. Although the annealing in the reducing atmosphere can effectively introduce defects, the defects of serious lattice distortion, high energy consumption, complex operation and the like exist. In order to solve the problems, the invention dopes Bi in rare earth m O n Br q On the basis of the nano material, the Bi ions in the material are reduced by using a reducing agent to form Bi metal simple substance. Due to the existence of Bi metal, under the irradiation of 980nm near infrared light, the plasma resonance effect (SPR) of the Bi metal generates higher heat energy, so that the lattice oxygen is stimulated to escape to generate oxygen vacancy defects. The method for generating oxygen vacancies in situ by near infrared laser irradiation can realize effective regulation and control of the concentration of the oxygen vacancies by changing the excitation power or irradiation time of a near infrared laser. The generated oxygen vacancies further promote the absorption of near infrared light by the material and enhance the up-conversion luminescence by means of the defect energy levels. In addition, 980nm near infrared light is used as one of important excitation light sources for rare earth up-conversion luminescence, the prepared material can realize luminescence under the irradiation of the same laser light source and adjust the luminescence intensity and color by generating oxygen vacancies in situ, and the material has important application prospect in the fields of anti-counterfeiting and display. The related preparation method has low energy consumption and operationThe method is simple and convenient, and can realize effective regulation and control of defect concentration while ensuring stable crystal structure.
Accordingly, in order to solve the above-mentioned problems, a near-infrared light-induced defect enhanced up-conversion luminescent material and a method for preparing the same are proposed herein.
Disclosure of Invention
In order to solve the technical problems, the invention designs a near infrared light-induced defect enhanced up-conversion luminescent material and a preparation method thereof, wherein oxygen vacancy defects are generated in situ by near infrared laser induction so as to improve up-conversion luminescence intensity; the Bi metal is utilized to promote the absorption of the material to near infrared light; providing heat energy through 980nm laser irradiation to promote defect increase, and then introducing defect energy level; bi/Bi under continuous irradiation (m-x) O n Br q The proper defect concentration of xRE gradually enhances the fluorescence intensity, and the fluorescence intensity is stable after 20 min.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a near infrared light-induced defect enhanced up-conversion luminescent material, characterized in that the material has a chemical formula: bi/Bi (m-x) O n Br q :xRE；
m, n, q=1-12, RE is rare earth element including one or more of Yb, er, tm and Ho, and x=0.5-10%.
Another object of the present invention is to provide a method for preparing a near infrared light induced defect enhanced up-conversion luminescent material, which is characterized by comprising the following steps:
step1: the molar ratio of Bi ion, br ion and RE ion is (m-x): q: x, and Bi (NO) 3 ) 3 Solution, RE (NO) 3 ) 3 Mixing the solution with bromine compound solution, adding the mixture into the mixed solution of glycol and deionized water, stirring uniformly at room temperature, adjusting the pH value to 1-13, mixing the raw materials uniformly, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, heating to 140-220 ℃ at a constant speed, and reacting for 1-72 h;
step2: washing the reaction product obtained in Step1 with deionized water and ethanol, drying, putting the dried product into deionized water, adding 5-60 mmol of reducing agent, adjusting pH to be acidic, reacting for 5-120 min at 60-80 ℃, washing and drying to obtain the target material.
Further, RE (NO) as described in Step1 3 ) 3 A solution prepared by the method comprising: RE (RE) 2 O 3 Dissolving rare earth raw material in nitric acid solution at 170-200 ℃ to prepare RE (NO) 3 ) 3 A solution.
Further, the bromine compound solution described in Step1 is one or more of KBr, naBr, CTAB solutions.
Further, the pH value in Step1 is adjusted by using concentrated ammonia water, sodium hydroxide and/or dilute nitric acid.
Further, in the mixed solution described in Step1, the molar ratio of ethylene glycol to deionized water is 1:1.
Further, in Step2, dilute nitric acid is used for adjusting the pH, and ph=1 to 5.
Further, the reducing agent in Step2 is one or more of sodium hypophosphite, sodium borohydride or ethylene glycol.
The beneficial effects of the invention are as follows:
the up-conversion nano luminescent material can effectively avoid the decrease of fluorescence intensity caused by defects, and effectively enhance the up-conversion luminescence intensity by reasonably utilizing the defects; bi/Bi prepared by the method (m-x) O n Br q The xRE material is a nano sheet, so that defect concentration can be increased under the excitation of a 980nm laser, further, rare earth up-conversion luminescence is enhanced, and along with the change of the irradiation time of the 980nm laser, defect concentration regulation and control can be realized, and further, rare earth up-conversion luminescence is regulated and controlled; the preparation method of the material has simple process and low energy consumption, and has industrial and market application and popularization prospects.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of Bi/Bi prepared 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ XRD pattern of the material;
FIG. 2 is a diagram of Bi/Bi prepared 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ Temperature-changing EPR spectrum of the material;
FIG. 3 is a diagram of Bi/Bi prepared 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ Fluorescence spectrum of the material.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described 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
Near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 3.99 O 5 Br 2 :0.5％Yb 3+ /0.5％Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) The Yb is weighed according to the proportion of Bi ions, br ions, yb ions and Er ions of 3.99:2:0.005:0.005 in mole ratio 2 O 3 ，Er 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, er (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、CTAB、Yb(NO 3 ) 3 、Er(NO 3 ) 3 Adding the mixture into a solution of glycol and deionized water in a ratio of 1:1, uniformly stirring, adjusting the pH value to 9-10, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) WashingWashing and drying, adding the sample into deionized water, adding 5-50 mmol of reducer sodium hypophosphite, adjusting pH to 1-5, reacting in a water bath kettle at 80 ℃ for 5-30 min, washing and drying to obtain the compound Bi/Bi 3.99 O 5 Br 2 :0.5％Yb 3 + /0.5％Er 3+ Bi is doped with rare earth ions of (2) 4 O 5 Br 2 A semiconductor light emitting material.
Example 2
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 2.985 O 4 Br:1％Yb 3+ /0.5％Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) The Yb is weighed according to the proportion of Bi ions, br ions, yb ions and Er ions of 3.985:2:0.01:0.005 in mole ratio 2 O 3 ，Er 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, er (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Er(NO 3 ) 3 Adding the mixture into a solution of glycol and deionized water in a ratio of 1:1, uniformly stirring, adjusting the pH value to 10-11, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 5-50 mmol of reducer sodium hypophosphite, adjusting pH to 1-5, reacting in a water bath kettle at 80 ℃ for 5-30 min, washing and drying to obtain the compound Bi/Bi 2.985 O 4 Br:1％Yb 3+ /0.5％Er 3+ Bi is doped with rare earth ions of (2) 3 O 4 Br semiconductor light emitting material.
Example 3
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 3.89 O 5 Br 2 :10％Yb 3+ /1％Tm 3 + The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) According to the mole ratio of Bi ion, br ion, yb ion and Tm ion of 389:2:0.1:0.01, and Yb is weighed according to the proportion 2 O 3 ，Tm 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, tm (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Tm(NO 3 ) 3 Adding the mixture into a solution of glycol and deionized water in a ratio of 1:1, uniformly stirring, adjusting the pH value to 9-10, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 5-50 mmol of reducing agent sodium borohydride, reacting for 10-30min, washing and drying to obtain Bi/Bi 3.89 O 5 Br 2 :10％Yb 3+ /1％Tm 3+ Bi is doped with rare earth ions of (2) 4 O 5 Br 2 A semiconductor light emitting material.
Example 4
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 0.89 OBr:10％Yb 3+ /1％Tm 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) Yb was weighed according to the molar ratio of Bi ion, br ion, yb ion and Tm ion of 0.89:1:0.1:0.01 2 O 3 ，Tm 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, tm (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Tm(NO 3 ) 3 Adding the mixture into a solution of glycol and deionized water in a ratio of 1:1, uniformly stirring, adjusting the pH value to 5-7, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 10-80 reducing agent glycol, uniformly heating to 140-180 ℃ in a hydrothermal kettle, reacting for 3-18h, washing and drying to obtain the Bi/Bi compound 0.89 OBr:10％Yb 3+ /1％Tm 3+ Is doped with the rare earth ions of BiOBr semiconductor luminescent material.
Example 5
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) The Yb is weighed according to the proportion of Bi ions, br ions, yb ions and Er ions of 3.975:2:0.02:0.005 in mole ratio 2 O 3 ，Er 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, er (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Er(NO 3 ) 3 Adding the mixture into a solution of glycol and deionized water in a ratio of 1:1, uniformly stirring, adjusting the pH value to 9-10, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 5-50 mmol of reducer sodium hypophosphite, adjusting pH to 1-5, reacting in a water bath kettle at 80 ℃ for 5-30 min, washing and drying to obtain the compound Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ Bi is doped with rare earth ions of (2) 4 O 5 Br 2 A semiconductor light emitting material.
The chemical formula obtained in this example is Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ As can be seen from FIG. 1, the position and relative intensity of the diffraction peak of the near infrared light induced defect enhanced up-conversion luminescent material are substantially consistent with those of the standard card, indicating Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ Is a pure phase structure; in addition, the diffraction peak of the material is sharp and has higher intensity, which indicates that the crystallinity is higher and the crystallization quality is good.
The chemical formula obtained in this example is Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ The temperature-changing EPR spectrum of the near-infrared light-induced defect enhancement up-conversion luminescent material is shown in figure 2, and as can be seen from figure 2, the near-infrared light-induced defect enhancement up-conversion luminescent material is irradiated under 980nm laser, and the signal value of the oxygen vacancy defect is gradually enhanced along with the increase of irradiation time, which shows that Bi/Bi is 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ Defect enhancement is achieved under near infrared laser irradiation.
The chemical formula obtained in this example is Bi/Bi 3.975 O 5 Br 2 :2％Yb 3+ /0.5％Er 3+ The fluorescence spectrum of the rare earth ion doped bismuth oxychloride semiconductor luminescent material under 980nm excitation is shown in figure 3, and the spectrum shows that Er is obtained from figure 3 3+ Characteristic emission peak of ions, red light with the wavelength of 650-690 nm 4 F 9/2 → 4 /I 15/2 Energy level transition generation; and the luminous intensity is gradually enhanced along with the increase of the irradiation time; luminous intensity 0<5<10<15<20min。
Example 6
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 0.985 OBr:1％Yb 3+ /0.5％Er 3 + The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) The Yb is weighed according to the proportion of Bi ions, br ions, yb ions and Er ions of 0.985:1:0.01:0.005 in mole ratio 2 O 3 ，Er 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, er (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、NaBr、Yb(NO 3 ) 3 、Er(NO 3 ) 3 Adding the mixture into deionized water, uniformly stirring, adjusting the pH value to 5-7, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) After washing and drying, the sample is added for dissociationAdding 5-50 mmol of reducer sodium hypophosphite into the sub-water, adjusting pH to be 1-5, reacting for 5-30 min in a water bath kettle at 80 ℃, washing and drying to obtain the compound with the chemical formula Bi/Bi 0.985 OBr:1％Yb 3+ /0.5％Er 3+ Is doped with the rare earth ions of BiOBr semiconductor luminescent material.
Example 7
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 0.94 OBr:5％Yb 3+ /1％Ho 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) The Yb is weighed according to the proportion of Bi ions, br ions, yb ions and Ho ions of 0.94:1:0.05:0.01 in terms of mole ratio 2 O 3 ，Ho 2 O 3 The two rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, ho (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Ho(NO 3 ) 3 Adding the mixture into deionized water, uniformly stirring, adjusting the pH value to 5-7, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 5-50 mmol of reducer sodium hypophosphite, adjusting pH to 1-5, reacting in a water bath kettle at 80 ℃ for 5-30 min, washing and drying to obtain the compound Bi/Bi 0.94 OBr:5％Yb 3+ /1％Ho 3+ Is doped with the rare earth ions of BiOBr semiconductor luminescent material.
Example 8
The near infrared light induced defect enhanced up-conversion luminescent material chemical Bi/Bi 0.84 OBr:10％Yb 3+ /5％Ho 3+ /1％Tm 3+ The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the material comprises the following steps:
(1) Yb was weighed according to the molar ratio of Bi ion, br ion, yb ion, ho ion and Tm ion of 0.84:1:0.1:0.05:0.01 2 O 3 ，Ho 2 O 3 ，Tm 2 O 3 Three rare earth materials are dissolved in nitric acid solution at 170-200 ℃ to prepare Yb (NO) 3 ) 3 Solution, ho (NO) 3 ) 3 And Tm (NO) 3 ) 3 A solution. The Bi (NO) is weighed according to the proportion 3 ) 3 、KBr、Yb(NO 3 ) 3 、Ho(NO 3 ) 3 And Tm (NO) 3 ) 3 Adding the mixture into deionized water, uniformly stirring, adjusting the pH value to 5-7, uniformly mixing the raw materials, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, uniformly heating to 140-180 ℃, and reacting for 3-18 h.
(2) Washing and drying, adding the sample into deionized water, adding 5-50 mmol of reducer sodium hypophosphite, adjusting pH to 1-5, reacting in a water bath kettle at 80 ℃ for 5-30 min, washing and drying to obtain the compound Bi/Bi 0.84 OBr:10％Yb 3+ /5％Ho 3+ /1％Tm 3+ Is doped with the rare earth ions of BiOBr semiconductor luminescent material.
Claims (8)
1. A near infrared light induced defect enhanced up-conversion luminescent material, characterized in that the material has a chemical formula: bi/Bi (m-x) O n Br q :xRE；
m, n, q=1-12, RE is rare earth element including one or more of Yb, er, tm and Ho, and x=0.5-10%.
2. The method for preparing the near infrared light induced defect enhanced up-conversion luminescent material according to claim 1, comprising the steps of:
step1: the molar ratio of Bi ion, br ion and RE ion is (m-x): q: x, and Bi (NO) 3 ) 3 Solution, RE (NO) 3 ) 3 Mixing the solution with bromine compound solution, adding the mixture into the mixed solution of glycol and deionized water, stirring uniformly at room temperature, adjusting the pH value to 1-13, mixing the raw materials uniformly, adding the mixture into a hydrothermal kettle, wherein the filling degree of the hydrothermal kettle is 0.4-0.8, heating to 140-220 ℃ at a constant speed, and reacting for 1-72 h;
step2: washing the reaction product obtained in Step1 with deionized water and ethanol, drying, putting the dried product into deionized water, adding 5-60 mmol of reducing agent, adjusting pH to be acidic, reacting for 5-30 min at 60-80 ℃, washing and drying to obtain the target material.
3. The method for preparing near infrared light-induced defect enhanced up-conversion luminescent material according to claim 2, wherein RE (NO 3 ) 3 A solution prepared by the method comprising: RE (RE) 2 O 3 Dissolving rare earth raw material in nitric acid solution at 170-200 ℃ to prepare RE (NO) 3 ) 3 A solution.
4. The method of claim 2, wherein the bromine compound solution in Step1 is one or more of KBr, naBr, CTAB solutions.
5. The method for preparing the near infrared light induced defect enhanced up-conversion luminescent material according to claim 2, wherein the method comprises the following steps: and the pH value is regulated by using concentrated ammonia water, sodium hydroxide and/or dilute nitric acid in Step 1.
6. The method for preparing the near infrared light induced defect enhanced up-conversion luminescent material according to claim 2, wherein the method comprises the following steps: in the mixed solution described in Step1, the molar ratio of the glycol to the deionized water is 1:1.
7. The method for preparing the near infrared light induced defect enhanced up-conversion luminescent material according to claim 2, wherein the method comprises the following steps: in Step2, dilute nitric acid is used for adjusting the pH, and the pH=1-5.
8. The method for preparing the near infrared light induced defect enhanced up-conversion luminescent material according to claim 2, wherein the method comprises the following steps: the reducing agent in Step2 is one or more of sodium hypophosphite, sodium borohydride or ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338114.6A CN116333736B (en) | 2023-03-31 | 2023-03-31 | Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338114.6A CN116333736B (en) | 2023-03-31 | 2023-03-31 | Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116333736A true CN116333736A (en) | 2023-06-27 |
| CN116333736B CN116333736B (en) | 2024-05-28 |
Family
ID=86883841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310338114.6A Active CN116333736B (en) | 2023-03-31 | 2023-03-31 | Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116333736B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117089347A (en) * | 2023-08-25 | 2023-11-21 | 昆明理工大学 | Heterojunction interface electric field enhanced up-conversion luminescent material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618284A (en) * | 2012-03-15 | 2012-08-01 | 吉林大学 | Bioluminescent nanoparticle with 800-nanometer strong near infrared up-conversion emission characteristic and application thereof |
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
| CN109943336A (en) * | 2019-03-27 | 2019-06-28 | 昆明理工大学 | A kind of rare earth ion doped bismuth oxychloride semiconductor material and preparation method thereof |
| CN109971479A (en) * | 2019-03-27 | 2019-07-05 | 昆明理工大学 | A kind of rare earth ion doped BiOX up-conversion luminescent material and preparation method thereof |
| CN111185184A (en) * | 2020-01-19 | 2020-05-22 | 浙江树人学院（浙江树人大学） | Preparation method of bismuth ferrite visible-light-driven photocatalyst and application of bismuth ferrite visible-light-driven photocatalyst in photocatalytic performance |
| CN113755170A (en) * | 2021-10-11 | 2021-12-07 | 江西乾照光电有限公司 | Rare earth ion doped bismuth silicate up-conversion luminescent material and preparation method thereof |
-
2023
- 2023-03-31 CN CN202310338114.6A patent/CN116333736B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618284A (en) * | 2012-03-15 | 2012-08-01 | 吉林大学 | Bioluminescent nanoparticle with 800-nanometer strong near infrared up-conversion emission characteristic and application thereof |
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
| CN109943336A (en) * | 2019-03-27 | 2019-06-28 | 昆明理工大学 | A kind of rare earth ion doped bismuth oxychloride semiconductor material and preparation method thereof |
| CN109971479A (en) * | 2019-03-27 | 2019-07-05 | 昆明理工大学 | A kind of rare earth ion doped BiOX up-conversion luminescent material and preparation method thereof |
| CN111185184A (en) * | 2020-01-19 | 2020-05-22 | 浙江树人学院（浙江树人大学） | Preparation method of bismuth ferrite visible-light-driven photocatalyst and application of bismuth ferrite visible-light-driven photocatalyst in photocatalytic performance |
| CN113755170A (en) * | 2021-10-11 | 2021-12-07 | 江西乾照光电有限公司 | Rare earth ion doped bismuth silicate up-conversion luminescent material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| YONGJIN LI等: "Investigation on the upconversion emission in 2D BiOBr:Yb3+/Ho3+ nanosheets", SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, vol. 150, pages 135 - 141 * |
| YONGJIN LI等: "Modulating Photon Harvesting Through Constructing Oxygen Vacancies-Rich 0D/2D Plasmonic Bi/Bismuth Oxybromide Upconversion Nanosheets Toward Improved Solar Photocatalysis", SOL. RRL, vol. 5, pages 2100619 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117089347A (en) * | 2023-08-25 | 2023-11-21 | 昆明理工大学 | Heterojunction interface electric field enhanced up-conversion luminescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116333736B (en) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guan et al. | Multicolor tunable luminescence and paramagnetic properties of NaGdF 4: Tb 3+/Sm 3+ multifunctional nanomaterials | |
| CN109943336B (en) | Rare earth ion doped bismuth oxychloride semiconductor material and preparation method thereof | |
| Tan et al. | Influence of carbon templates and Yb3+ concentration on red and green luminescence of uniform Y2O3: Yb/Er hollow microspheres | |
| Zheng et al. | Multicolor tunable luminescence and laser-sensitization induced upconversion enhancement in Ln-doped Gd 2 O 3 crystals for anti-counterfeiting | |
| CN116333736B (en) | Near infrared light-induced defect enhanced up-conversion luminescent material and preparation method thereof | |
| Yang et al. | Controlled morphology and EDTA-induced pure green upconversion luminescence of Er 3+/Ho 3+-Yb 3+ co-doped NaCe (MoO 4) 2 phosphor | |
| Pavitra et al. | Pump power induced tunable upconversion emissions from Er 3+/Tm 3+/Yb 3+ ions tri-doped SrY 2 O 4 nanocrystalline phosphors | |
| Jadhav et al. | Enhanced down and upconversion emission for Li+ co-doped Gd2O3: Er3+ nanostructures | |
| Lim | Microwave sol–gel derived NaCaGd (MoO4) 3: Er3+/Yb3+ phosphors and their upconversion photoluminescence properties | |
| Guo et al. | Strategy to enhance the red-emission of CaWO4: Eu3+ phosphors assisted by poly acrylic acid (PAA) | |
| Hao et al. | YBO3: Ce3+, Yb3+ based near-infrared quantum cutting phosphors: Synthesis and application to solar cells | |
| Zhang et al. | Novel bismuth silicate based upconversion phosphors: Facile synthesis, structure, luminescence properties, and applications | |
| Jiang et al. | Facile one-step hydrothermal synthesis and luminescence properties of Eu3+-doped NaGd (WO4) 2 nanophosphors | |
| Li et al. | Synthesis, characterization and upconversion emission properties of the nanocrystals of Yb3+/Er3+-codoped YF3–YOF–Y2O3 system | |
| Lian et al. | Synthesis and optical properties of (Gd1− x, Eux) 2O2SO4 nano-phosphors by a novel co-precipitation method | |
| Li et al. | Enhanced near-infrared quantum cutting in CaMoO4: Yb3+ phosphors induced by doping with Li+ ions for improving solar cells efficiency | |
| Zheng et al. | Morphology evolution, tunable multicolor and enhanced upconversion luminescence via Li+ doping in Yb3+/Tm3+/Ho3+ tri-doped NaYF4 microcrystals | |
| Cheng et al. | Down-conversion emission of Ce3+-Tb3+ co-doped CaF2 hollow spheres and application for solar cells | |
| Gao et al. | Surface radiation-regulation effect in Eu (BA) 3Phen doped polyacrylonitrile nanofibers | |
| Zhai et al. | Synthesis and luminescent properties of NaLa (MoO 4) 2: Eu 3+, Tb 3+ phosphors by microwave-assisted sol–gel method | |
| Huang et al. | Synthesis and luminescence properties of a novel yellow–white emitting NaLa (MoO4) 2: Dy3+, Li+ phosphor | |
| Huerta et al. | Role of Li+ ion in improved crystallization and the luminescence enhancement of up and down conversion process in Er3+/Yb3+ doped in Y4O (OH) 9NO3 and Y2O3 nanoparticles | |
| CN116554874A (en) | Preparation method of perovskite fluorescent material capable of regulating and controlling luminous efficiency | |
| Liu et al. | Facile synthesis and multicolor luminescence properties of Gd4O3F6: Ln3+ (Ln= Eu, Tb, Dy, Sm, Ho, Tm, Yb/Er, Yb/Ho) microcrystals | |
| Song et al. | SrWO4: Er3+/Yb3+ nanorods: Synthesis and upconversion luminescence |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |