CN111690400A - Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof - Google Patents

Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof Download PDF

Info

Publication number
CN111690400A
CN111690400A CN201910190087.6A CN201910190087A CN111690400A CN 111690400 A CN111690400 A CN 111690400A CN 201910190087 A CN201910190087 A CN 201910190087A CN 111690400 A CN111690400 A CN 111690400A
Authority
CN
China
Prior art keywords
cspbbr
quantum dot
rare earth
caal
long afterglow
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
Application number
CN201910190087.6A
Other languages
Chinese (zh)
Other versions
CN111690400B (en
Inventor
陈学元
宫仲亮
郑伟
高宇
委娇娇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Institute of Research on the Structure of Matter of CAS
Original Assignee
Fujian Institute of Research on the Structure of Matter of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujian Institute of Research on the Structure of Matter of CAS filed Critical Fujian Institute of Research on the Structure of Matter of CAS
Priority to CN201910190087.6A priority Critical patent/CN111690400B/en
Publication of CN111690400A publication Critical patent/CN111690400A/en
Application granted granted Critical
Publication of CN111690400B publication Critical patent/CN111690400B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/664—Halogenides
    • C09K11/665—Halogenides with alkali or alkaline earth metals
    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

A rare earth-quantum dot long afterglow composite luminescent material and a preparation method and application thereof. The composite material consists of a rare earth long afterglow luminescent material and quantum dots. The composite material is simple to prepare, and only the rare earth long afterglow luminescent material and the quantum dots need to be coated into a film by spin coating or directly mixed. By regulating the type and proportion of the rare earth long afterglow luminescent material and the quantum dots, the composite material can realize high-efficiency long afterglow luminescence in the full visible spectrum. The composite material overcomes the defects that the afterglow emission half-peak width of the traditional rare earth long afterglow material is large and the luminous wave band is limited by the material, and realizes the continuous adjustment of the visible light wave band. The invention finely regulates and controls the afterglow spectrum of the material, and the composite material can be applied to the fields of biological monitoring, biological imaging, optical coding, anti-counterfeiting, display and the like.

Description

Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a quantum dot-rare earth long afterglow composite luminescent material and a preparation method and application thereof.
Background
The long afterglow luminescent material is one kind of photoluminescent material with stored excited high energy photon and released slowly in the form of light after the excitation is stopped for long time light emission. The long afterglow material is widely applied to the fields of safety identification, information display, anti-counterfeiting, stress detection, biological imaging and the like. (reference: B.K. Gupta et al., J.appl.Phys.2015,117,243104)
The rare earth long afterglow luminescent material is a novel environment-friendly energy-saving material, has high luminous brightness, long afterglow time and good chemical stability, and is widely concerned at home and abroad. By using the unique electronic structure and rich transition energy level of rare earth, the rare earth long afterglow material can produce multi-color luminescence in visible light wave band. The other glow light wavelengths can be finely regulated by regulating the compositions of the rare earth ions and the matrix ions, which requires a great deal of attempts to different rare earth ions and doping concentrations thereof. In addition, due to the energy level structure characteristics of rare earth ions, the rare earth long afterglow material has different afterglow duration and half peak width, so that narrow-band emission of the whole visible spectrum section cannot be realized, and the freedom degree of light emission regulation is limited.
Disclosure of Invention
In order to overcome the defects of the rare earth long afterglow luminescent material in application, the invention provides a quantum dot-rare earth long afterglow composite luminescent material, which is mainly formed by blending the rare earth long afterglow luminescent material and quantum dots.
According to the embodiment of the invention, the mole ratio of the rare earth long afterglow luminescent material and the quantum dots in the composite material is 1 (0.001-1000), preferably 1 (0.01-100), further preferably 1 (0.01-20), for example (5-20) to 1.
According toIn an embodiment of the present invention, the substrate of the rare earth long persistence luminescent material is selected from one, two or more of oxides, fluorides, sulfides, halides, nitrides, phosphides, arsenides, selenides, tellurides, aluminum oxides, fluorohalides, sulfur oxides, silicon oxides, vanadates, phosphates, borates, silicates, aluminates, germanates, tungstates, molybdates, titanates, sulfates, tantalates, niobates, chromates, gallates; preferably at least one of an oxide and a sulfur oxide; for example from CaAl2O4、SrAl2O4One or two of them;
according to an embodiment of the present invention, the rare earth active ion of the rare earth long afterglow material is selected from Er3+、Tm3+、Ho3 +、Pr3+、Gd3+、Ce3+、Nd3+、Tb3+、Eu2+、Sm3+、Dy3+、Mn2+、Cr3+One or a combination of several of them; preferably Eu2+、Nd3+、Dy3+、Tm3+、Sm3+One or a combination of several of them; more preferably Eu2+、Nd3+、Dy3+One, or a combination of two or more thereof.
According to an embodiment of the present invention, the rare earth long persistent luminescent material is selected from the group including, but not limited to, the following compounds: CaAl2O4:Eu2+,Nd3+(CAO)，SrAl2O4:Eu2+,Dy3+，CaAl2O4:Eu2+，CaAl2O4:Tb3+，Ca12Al14O33:Eu2 +,Nd3+，CaAl2O4:Tb3+，BaAl2O4:Ce3+,Dy3+，SrAl4O7:Eu2+,Dy3+，CaxSr1-xAl2O4:Eu2+,Nd3+(wherein 0)<x<1)，MgAl2O4:Ce3+，SrAl2O4:Eu2+，CdSiO3:Sm3+，Ca2Al2SiO7:Ce3+，CaAl2Si2O8:Eu2+,Dy3+，MAl2O4:Eu2+,Dy3+,Nd3+(M ═ Sr or Ca), CdSiO3:Sm3+，CaMgSi2O6:Eu2+,Dy3+，Sr3MgSi2O8:Eu2+,Dy3 +，Sr2MgSi2O7:Eu2+,Dy3+，Sr2SiO4:Eu2+,Dy3+，CaTiO3:Pr3+，ZnS:Eu2+，CaS:Bi3+,Tm3+。
According to an embodiment of the present invention, the size of the rare earth long afterglow luminescent material can be in the nanometer scale, the micron scale or the crystal form of the bulk material.
According to the embodiment of the invention, the surface property of the rare earth long afterglow luminescent material can be oil soluble, water soluble or both oil and water insoluble.
According to the embodiment of the invention, the rare earth long afterglow luminescent material sample comprises a solution, a powder, a film and a block thereof, and preferably the solution, the powder and the film thereof.
According to an embodiment of the present invention, the quantum dot is selected from at least one of a halide perovskite quantum dot, an oxide quantum dot, a sulfide quantum dot, a selenide quantum dot, a telluride quantum dot, a nitride quantum dot, a phosphide quantum dot, an arsenide quantum dot, a carbon quantum dot, a carbide quantum dot, a silicon quantum dot, a silicide quantum dot, a germanium quantum dot, a germanide quantum dot, and a core-shell structure or a heterojunction formed on the basis of the quantum dot.
According to an embodiment of the present invention, the quantum dots are preferably CdS, CdSe, InP, CuInS2Or CdS, CdSe, InP, ZnS, CuInS2A core-shell structure or a heterojunction formed on the basis of the quantum dots, or organic-inorganic hybrid perovskite quantum dots and all-inorganic perovskite quantum dots.
According toIn an embodiment of the present invention, the quantum dots are selected from the group including, but not limited to: CsPbCl3、CsPbCl1.5Br1.5、CsPbCl1Br2、CsPbBr3、CsPbBr2I1、CsPbBr1.5I1.5、CsPbBr1I2、CsPbI3、CdSe、InP@ZnS。
According to embodiments of the present invention, the surface properties of the quantum dots may be oil soluble, water soluble, or both oil and water insoluble.
According to an embodiment of the invention, the quantum dot sample comprises a solution, powder, film, bulk thereof, preferably a solution, powder and film sample.
According to an embodiment of the present invention, the quantum dot-rare earth long afterglow composite luminescent material is selected from the group consisting of, but not limited to, the following composite materials: CaAl2O4:Eu2+,Nd3+-CsPbCl3、CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5、CaAl2O4:Eu2+,Nd3+-CsPbCl2Br1、CaAl2O4:Eu2+,Nd3+-CsPbCl1Br2、CaAl2O4:Eu2+,Nd3+-CsPbBr3、CaAl2O4:Eu2+,Nd3+-CsPbBr2I1、CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5、CaAl2O4:Eu2+,Nd3+-CsPbBr1I2、CaAl2O4:Eu2+,Nd3+-CsPbI3、CaAl2O4:Eu3+,Nd3+-CsPbBr2.3I0.7、SrAl2O4:Eu2+,Dy3+-CsPbBr2I1、SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5、SrAl2O4:Eu2+,Dy3+-CsPbBr1I2、SrAl2O4:Eu2+,Dy3+-CsPbI3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr2I1、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1I2、Sr4Al14O25:Eu2+,Dy3+-CsPbI3、Sr2MgSi2O7:Eu2 +,Dy3+-CsPbBr3、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr2I1、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1I2、Sr2MgSi2O7:Eu2+,Dy3+-CsPbI3、Sr2SiO4:Eu2+,Dy3+-CsPbBr2I1、Sr2SiO4:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2SiO4:Eu2+,Dy3+-CsPbBr1I2、Sr2SiO4:Eu2+,Dy3 +-CsPbI3、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr3、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr2I1、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1I2、Sr3MgSi2O8:Eu2+,Dy3+-CsPbI3，Sr3MgSi2O8:Eu2+,Dy3+-InP@ZnS。
The invention also provides a preparation method of the quantum dot-rare earth long afterglow composite luminescent material, which comprises the following steps: the rare earth long afterglow luminescent material and the quantum dots are coated into a film by spin coating or are directly mixed to obtain the quantum dot-rare earth long afterglow composite luminescent material.
According to the embodiment of the invention, the mixing form comprises the steps of mixing the rare earth long afterglow luminescent material, the solution of the quantum dots, mixing the powder, laminating the thin film and blending to prepare the thin film.
According to the embodiment of the invention, the mole ratio of the rare earth long afterglow luminescent material and the quantum dots is 1 (0.001-1000), preferably 1 (0.01-100), and more preferably 1 (0.01-20).
According to an exemplary embodiment of the present invention, the preparation method comprises the steps of: respectively dispersing the rare earth long afterglow material and the quantum dots in Polydimethylsiloxane (PDMS) or polymethyl methacrylate (PMMA), and carrying out fractional spin coating and solidification to obtain the quantum dot-rare earth composite long afterglow composite luminescent material.
The invention also provides the application of the quantum dot-rare earth long afterglow composite luminescent material, which comprises the aspects of biological detection, biological imaging, optical coding, anti-counterfeiting, display, photoelectric detector and solar spectrum conversion. Preferably for display, optical coding and multiple security.
The invention has the beneficial effects that:
(1) the composite material of the invention obtains continuous adjustment of narrow-band emission of visible spectrum under the excitation of ultraviolet light, and breaks through the bottleneck that only broadband emission exists when a long afterglow material is used alone.
(2) The composite material of the invention consists of two parts of rare earth long afterglow luminescent material and quantum dots: the rare earth long afterglow luminescent material releases the energy stored by the defects in a luminescent form, and the quantum dots absorb the released light energy to realize the continuous luminescence of the quantum dots. The radiation energy transfer (or radiation reabsorption) breaks through the limit of the distance between the conventional Fluorescence Resonance Energy Transfer (FRET) donor and acceptor; the synthetic method is simple and convenient, and is easy to popularize and prepare in a large scale.
(3) The luminescent wavelength range of the quantum dots in the composite material is 420-1500nm, preferably 450-700 nm; the long-afterglow luminescence of the whole visible spectrum can be continuously regulated and controlled by regulating the types and the number of the rare earth long-afterglow luminescent materials and the quantum dots, which cannot be realized by the traditional long-afterglow luminescent materials.
(4) By changing the types and the number of the rare earth long afterglow materials and the quantum dots, the afterglow spectrum of the materials can be finely regulated, so that countless identifiable optical labels are constructed, and the application prospect of the optical labels in the fields of optical coding, multiple anti-counterfeiting, display and the like is expanded.
Drawings
FIG. 1 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbX3(wherein X is one or two halogens) CsPbCl in the composite material3，(b)CsPbCl1.5Br1.5，(c)CsPbBr3，(d)CsPbBr1.5I1.5，(e)CsPbI3Transmission electron micrograph and (f) X-ray powder diffraction pattern of perovskite quantum dots.
FIG. 2 corresponds to CsPbCl in example 13，CsPbCl2Br1，CsPbCl1.5Br1.5，CsPbCl1Br2，CsPbBr3，CsPbBr2I1，CsPbBr1.5I1.5，CsPbBr1I2，CsPbI3Fluorescence emission spectrum (excitation wavelength of 365nm) and absorption spectrum (dotted line indicates absorption curve and solid line indicates emission curve in fig. 2) of perovskite quantum dots.
FIG. 3 corresponds to CsPbCl in example 13，CsPbCl1.5Br1.5，CsPbBr3，CsPbBr2I1，CsPbBr1.5I1.5，CsPbI3The fluorescence lifetime of the perovskite quantum dots is shown, and the excitation wavelength is 375 nm.
FIG. 4 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbX3(wherein X is one or two halogens) a film of a composite material of (a) CAO and (b) CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.5The molar ratio of (c) CaAl to (12: 1)2O4:Eu2+,Nd3+-CsPbBr3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr3The molar ratio of (d) CaAl to (14: 1)2O4:Eu2+,Nd3+-CsPbBr2I1(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2I1The molar ratio of (e) CaAl to (15: 1)2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1.5I1.5The molar ratio of (a) to (b) is 18:1 and (f) CaAl2O4:Eu2+,Nd3+-CsPbI3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbI3Molar ratio 20:1) photographs under normal light (first row) and photographs of afterglow emitted light (second row) (where first row a is white, b is pale green, c is pale yellow, d is orange, e is dark red, f is dark red; the second row a is blue-violet emission, b is blue emission, c is green emission, d is orange emission, e is red emission, and f is dark red emission.
FIG. 5 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbX3(wherein X is one or two halogens) a film of a composite material of (a) CAO and (b) CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.5The molar ratio of (c) CaAl to (12: 1)2O4:Eu2+,Nd3+-CsPbCl1Br2(CaAl in composite Material)2O4:Eu2 +,Nd3+With CsPbCl1Br2The molar ratio of (d) CaAl to (12: 1)2O4:Eu2+,Nd3+-CsPbBr3(CaAl in composite Material)2O4:Eu2 +,Nd3+And CsPbBr3The molar ratio of (e) CaAl to (14: 1)2O4:Eu2+,Nd3+-CsPbBr2.3I0.7(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2.3I0.7The molar ratio of 14:1), (f) CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2I1The molar ratio of (g) CaAl to (15: 1)2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1.5I1.5The molar ratio of 18:1), (h) CaAl2O4:Eu2+,Nd3+-CsPbBr1I2(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1I2A molar ratio of 20:1) and (i) CaAl2O4:Eu2+,Nd3+-CsPbI3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbI3Molar ratio of 20:1) (left diagram), afterglow decay curve (middle diagram) and its CIE color coordinate position (right diagram).
FIG. 6 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbCl2Br1Afterglow spectra of composites with different composition ratios, wherein the CAO content was fixed at 0.2mmol (0 denotes a composite sample prepared using 0. mu. mol CsPbCl2Br1 and 0.2mmol CAO; 1 denotes a sample prepared using 1. mu. mol CsPbCl2Br1Composite samples prepared with 0.2mmol of CAO, and so on).
FIG. 7 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbBr1.5I1.5Afterglow spectrum of composite materials with different composition ratios, wherein CAO content is fixed at 0.2mmol (0 means using 0. mu. mol CsPbBr)1.5I1.5Composite samples prepared with 0.2 mmolCAO; 2 denotes the use of 2. mu. molCsPbBr1.5I1.5Composite samples prepared with 0.2 mmole cao, and so on).
FIG. 8 corresponds to CaAl in example 12O4:Eu2+,Nd3+-CsPbX3(wherein X is one or two halogens) a film of a composite material of (a) CAO and (b) CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.5The molar ratio of (c) CaAl to (12: 1)2O4:Eu2+,Nd3+-CsPbBr3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr3The molar ratio of (d) CaAl to (14: 1)2O4:Eu2+,Nd3+-CsPbBr2I1(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2I1The molar ratio of (e) CaAl to (15: 1)2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1.5I1.5The molar ratio of (a) to (b) is 18:1 and (f) CaAl2O4:Eu2+,Nd3+-CsPbI3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbI3Molar ratio of 20:1) fluorescence lifetime of CAO measured at 100K, excitation wavelength 375nm, and monitoring wavelength 440 nm.
FIG. 9 shows the results of example 1 wherein (a) CAO and (b) CaAl are used2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.5The molar ratio of (c) CaAl to (12: 1)2O4:Eu2+,Nd3+-CsPbBr3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr3The molar ratio of (d) CaAl to (14: 1)2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1.5I1.5The molar ratio is 18:1), the test range is 200K-550K, and the heating rate is 30K-min.
FIG. 10 corresponds to CaAl in example 12O4:Eu2+,Nd3+Sensitization of perovskite quantum dots by radiative energy transfer process is indicative of the intent.
FIG. 11 is a graph of the afterglow luminescence spectra of several composites prepared in example 2, wherein a is SrAl2O4 Eu2+,Dy3 +B is SrAl2O4:Eu2+,Dy3+-CsPbBr3(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr3The molar ratio is 8:1), c is SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr2I1The molar ratio is 9:1), d is SrAl2O4: Eu2+,Dy3+-CsPbBr1.5I1.5(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1.5I1.5The molar ratio is 10:1), e is SrAl2O4:Eu2+,Dy3+-CsPbBr1I2(detection result of SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1I2 molar ratio was 10: 1).
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention, but should not be construed as limiting the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Instruments and devices:
the product of the embodiment of the invention is characterized by powder diffraction, and the model of the instrument is MiniFlex2, the manufacturer is Rigaku, and the radiation wavelength of the copper target is 0.154187 nm.
The product of the embodiment of the invention is used for X-ray energy spectrum analysis, and the model of the instrument is JEM-2010, and the manufacturer is JEOL.
The type of an instrument used for transmission electron microscope detection of the product in the embodiment of the invention is TECNAI G2F20, FEI.
The product of the embodiment of the invention is characterized by ultraviolet visible absorption spectrum, and the model of the used instrument is Lambda365, and the manufacturer is Perkin-Elmer.
The product of the embodiment of the invention is used for fluorescence emission spectroscopy and fluorescence life characterization, the model of the used instrument is FLS980, the manufacturer is Edinburgh, and the excitation light source is a xenon lamp and a 390nm LD pulse laser.
CsPbX as used in the present application3The preparation method of (wherein X is one or two halogens) comprises the following steps:
the CsPbX3The (X ═ Cl, Br, I) quantum dots can be prepared by the hot injection method. Mixing Cs2CO3、Pb(CH3COO)2Dissolving in mixed solvent of octadecene, oleic acid and oleylamine, injecting HX (X ═ Cl, Br, I) solvent at high temperature to obtain CsPbX3And (4) quantum dots. The emission spectrum of the light source is continuously adjustable between the range of 400-700 nm. Specific preparation methods are listed below.
Preparation example 1 CsPbCl3Preparation of perovskite quantum dots
Weighing 0.5mmol of lead acetate and 0.1mmol of cesium carbonate, adding 1mL of oleic acid, 1mL of oleylamine, 1mL of tri-n-octylphosphine and 10mL of octadecene, introducing nitrogen, heating to 120 ℃, and keeping the temperatureForming a transparent solution A after 10 minutes, and then heating to 180 ℃; injecting 124 μ L hydrochloric acid into the solution A quickly, preserving the temperature for 10 seconds, and cooling to room temperature quickly by using an ice bath (the cooling speed is about 10-15 ℃/second); centrifugation was followed by washing with 10mL of cyclohexane and 10mL of acetone 1 time, and the precipitate was dispersed in 30mL of cyclohexane to give CsPbCl3Perovskite quantum dots.
Preparation example 2 CsPbCl1.5Br1.5Preparation of perovskite quantum dots
Weighing 0.5mmol of lead acetate and 0.05mmol of cesium carbonate, adding 0.5mL of oleic acid, 0.5mL of oleylamine and 6mL of octadecene, introducing nitrogen, heating to 120 ℃, keeping the temperature for 30 minutes to form a transparent solution A, and then heating to 190 ℃; rapidly injecting 62 mu L of hydrochloric acid and 87 mu L of hydrogen bromide into the solution A, preserving the temperature for 5 seconds, and rapidly cooling to room temperature by using an ice water bath; centrifugation was followed by 1 washing with 5mL cyclohexane and 5mL acetone, and the precipitate was dispersed in 30mL cyclohexane to give CsPbCl1.5Br1.5Perovskite quantum dots.
Preparation example 3 CsPbBr3Preparation of perovskite quantum dots
Weighing 0.5mmol of lead acetate and 0.08mmol of cesium carbonate, adding 1.5mL of oleic acid, 1.5mL of oleylamine and 8mL of octadecene, introducing nitrogen, heating to 120 ℃, keeping the temperature for 30 minutes to form a transparent solution A, and then heating to 170 ℃; 173 mul of hydrogen bromide is injected into the solution A quickly, the temperature is kept for 10 seconds, and the solution A is cooled to room temperature quickly by an ice bath (the cooling speed is about 10-15 ℃/s); centrifugation followed by 1 wash with 5mL cyclohexane and 5mL acetone, and dispersion of the precipitate in 30mL cyclohexane gave CsPbBr3Perovskite quantum dots.
Preparation example 4CsPbBr2I1Preparation of perovskite quantum dots
Weighing 0.5mmol of lead acetate and 0.2mmol of cesium acetate, adding 1.5mL of oleic acid, 1.5mL of oleylamine and 10mL of octadecene, introducing nitrogen, heating to 120 ℃, keeping the temperature for 40 minutes to form a transparent solution A, and then heating to 160 ℃; injecting 116 mul hydrogen bromide and 66 mul hydrogen iodide into the solution A, keeping the temperature for 10 seconds, and cooling to room temperature rapidly by ice bath; the precipitate was dispersed in 30m by centrifugation and then washed 1 time with 1mL of cyclohexaneIn L cyclohexane to obtain CsPbBr2I1Perovskite quantum dots.
Referring to the method of the preparation example, the following quantum dots were also prepared by changing the molar ratio of halogen to other raw materials: CsPbBr1.5I1.5、CsPbI3、CsPbCl2Br1、CsPbCl1Br2、CsPbBr1.5I1.5、CsPbBr1I2、CsPbCl1.5Br1.5、CsPbBr2.3I0.7。
Example 1 CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5Preparation of
Weighing CaAl ground to submicron level2O4:Eu2+,Nd3+(CAO) 0.24mmol of rare earth long afterglow luminescent material and 0.1g of polydimethylsiloxane (Doccorning 184(PDMS)) are mixed uniformly, placed in a glove box, air in the mixture is pumped out, then the mixture is spin-coated on a quartz plate and placed in a drying oven at 90 ℃ for 30mins to obtain cured CaAl2O4:Eu2+,Nd3+A film. Then weighing CsPbCl1.5Br1.520 mu mol of polydimethylsiloxane (Dowcorn 184)0.1g, uniformly mixing, pumping air out, and spin-coating on CaAl2O4:Eu2+,Nd3+Placing the film on a drying oven at 90 ℃ for 30mins again to obtain solidified CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.5Molar ratio 12:1) film.
The following composites were also prepared with reference to the method of example 1 above: CaAl2O4:Eu2+,Nd3+-CsPbBr3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr3Molar ratio of 14:1), CaAl2O4:Eu2+,Nd3+-CsPbBr2I1(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2I1Molar ratio of 15:1), CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1.5I1.518:1) molar ratio of CaAl2O4:Eu2+,Nd3+-CsPbI3(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbI3Molar ratio of 20:1), CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1.5Br1.512:1) molar ratio of CaAl2O4:Eu2+,Nd3+-CsPbCl1Br2(CaAl in composite Material)2O4:Eu2+,Nd3+With CsPbCl1Br212:1) molar ratio of CaAl2O4:Eu2+,Nd3+-CsPbBr2.3I0.7(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr2.3I0.7Molar ratio of 14:1), CaAl2O4:Eu2+,Nd3+-CsPbBr1I2(CaAl in composite Material)2O4:Eu2+,Nd3+And CsPbBr1I2The molar ratio was 20: 1).
Example 2 SrAl2O4:Eu2+,Dy3+-CsPbBr3Preparation of
Weighing SrAl which is ground to submicron level2O4:Eu2+,Dy3+Rare earth long afterglow luminescent material (SrAl)2O4Middle Eu2 +,Dy3+The doping content is 3 percent) of 0.08mmol and 0.1g of polydimethylsiloxane (Doccorning 184(PDMS)), the materials are uniformly mixed, the mixture is placed in a glove box, the air in the mixture is pumped out, then the mixture is coated on a quartz plate in a spin coating mode, the mixture is placed in a drying oven at 90 ℃ for 30mins at constant temperature, and the cured product is obtainedSrAl of (1)2O4:Eu2+,Dy3+A film. Then weighing CsPbBr 310 mu mol of polydimethylsiloxane (Dowcorn 184)0.1g, uniformly mixing, pumping air out, and spin-coating SrAl2O4:Eu2+,Dy3+Placing the film on a drying oven at the temperature of 90 ℃ for 30mins again to obtain the solidified SrAl2O4:Eu2+,Dy3+-CsPbBr3(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr3Molar ratio 8:1) film. The following composite materials were also prepared by the method of reference example 2: SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr2I1Molar ratio of 9:1), SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1.5I1.5Molar ratio of 10:1), SrAl2O4:Eu2+,Dy3+-CsPbBr1I2(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1I2The molar ratio was 10: 1).
Example 3 Performance testing
CsPbX3Transmission electron micrograph (fig. 1a) and X-ray powder diffraction pattern (fig. 1b) of (X ═ Cl, Br, I) quantum dots indicate that such quantum dots are cubic phase structures, have good dispersibility and crystallization, and have particle size of about 10 to 16 nm. Fluorescence and absorption spectra (FIG. 2) show that CsPbX is excited by UV light3The perovskite quantum dots have narrow-band emission, the half-peak width of the perovskite quantum dots is 9-31nm, and the absorption range is wide. FIG. 3 shows CsPbX3The fluorescence lifetime of the perovskite quantum dots is 7.7-103 ns. CaAl prepared in the above examples2O4:Eu2+,Nd3+-CsPbX3The composite film photograph (figure 4) and the afterglow luminescent photograph show that the composite material can continuously present bright after being irradiated by ultraviolet lightThe continuous adjustable luminescence of blue-violet, green and red, and the corresponding afterglow luminescence spectrogram, afterglow decay curve and color coordinate graph (figure 5) illustrate that the composite material film prepared by the embodiment inherits the narrower emission peak width and the afterglow luminescence duration of the perovskite quantum dot to be more than 8 h. The color gamut range of several composite materials can reach 130% of NTSC color gamut standard (i.e. the result obtained by calculating the integral of the area formed by the color coordinate position of the afterglow luminescence wavelength of the thin film compared with the integral area formed by the NTSC tristimulus value). CaAl prepared in the above examples2O4:Eu2+,Nd3+-CsPbCl2Br1The afterglow spectrum (FIG. 6) of the composite materials (CAO 0.2mmol) with different composition ratios shows CsPbCl in the composite material2Br1Increase of the ratio, CsPbCl2Br1Absorb more of the CAO's luminescence and thus dominate. CaAl prepared in the above examples2O4:Eu2+,Nd3+-CsPbBr1.5I1.5The afterglow spectrum (FIG. 7) of the composite materials (CAO 0.2mmol) with different composition ratios shows that CsPbBr is varied with the composite materials1.5I1.5The ratio is increased, and the afterglow luminescence of the CAO can be completely absorbed so as to present the fluorescence emission of the perovskite quantum dots. CaAl prepared in the above examples2O4:Eu2+,Nd3+-CsPbX3The fluorescence lifetime of the CAO measured at 100K temperature of the thin film of the composite material (fig. 8) indicates that the fluorescence lifetime of the CAO in the composite material is not changed basically, which indicates that there is no resonance energy transfer between the CAO and the perovskite quantum dots, but a simple radiation re-absorption process. The pyroelectric Spectroscopy (FIG. 9) shows that CaAl prepared in the above example is monitored2O4:Eu2+,Nd3+-CsPbX3CsPbX in composite material3The variation trend of the emission peak intensity of the quantum dots along with the temperature is found, CsPbX3Compared with the thermolysis spectrogram of CAO, the thermolysis curve has no obvious change, which shows that CsPbX3The quantum dots can realize efficient absorption of CAO luminescence. Fig. 10 is a schematic diagram of the principle of radiation reabsorption between the long persistence luminescent material and the quantum dots.
Example 4: SrAl2O4:Eu2+,Dy3+-CsPbX3(wherein X is one or two halogens) luminescent property of composite material
FIG. 11 shows SrAl2O4:Eu2+,Dy3+-CsPbX3The composite material inherits the narrower emission peak width of the quantum dot and the afterglow luminescence detection result of the long afterglow luminescence material. Wherein a is SrAl2O4:Eu2+,Dy3+B is SrAl2O4:Eu2+,Dy3 +-CsPbBr3(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr3The molar ratio is 8:1), c is SrAl2O4:Eu2+,Dy3+-CsPbBr2I1(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr2I1The molar ratio is 9:1), d is SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1.5I1.5The molar ratio is 10:1), e is SrAl2O4:Eu2 +,Dy3+-CsPbBr1I2(SrAl in the composite Material)2O4:Eu2+,Dy3+And CsPbBr1I2The detection result of the molar ratio of 10: 1).
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The quantum dot-rare earth long afterglow composite luminescent material is characterized in that the composite material is mainly formed by blending the rare earth long afterglow luminescent material and quantum dots.
2. The quantum dot-rare earth long afterglow composite luminescent material of claim 1, wherein the molar ratio of the rare earth long afterglow luminescent material to the quantum dots in the composite material is 1 (0.001-1000).
3. The quantum dot-rare earth long afterglow composite luminescent material according to claim 1 or 2, wherein the rare earth long afterglow luminescent material is selected from the group comprising but not limited to the following substances: CaAl2O4:Eu2+,Nd3+(CAO)，SrAl2O4:Eu2+,Dy3+，CaAl2O4:Eu2+，CaAl2O4:Tb3+，Ca12Al14O33:Eu2+,Nd3+，CaAl2O4:Tb3+，BaAl2O4:Ce3+,Dy3+，SrAl4O7:Eu2+,Dy3+，CaxSr1-xAl2O4:Eu2+,Nd3+(wherein 0)<x<1)，MgAl2O4:Ce3+，SrAl2O4:Eu2+，CdSiO3:Sm3+，Ca2Al2SiO7:Ce3+，CaAl2Si2O8:Eu2+,Dy3+，MAl2O4:Eu2+,Dy3+,Nd3+(M ═ Sr or Ca), CdSiO3:Sm3+，CaMgSi2O6:Eu2+,Dy3+，Sr3MgSi2O8:Eu2+,Dy3+，Sr2MgSi2O7:Eu2+,Dy3+，Sr2SiO4:Eu2+,Dy3+，CaTiO3:Pr3+，ZnS:Eu2+，CaS:Bi3+,Tm3+。
4. The quantum dot-rare earth long persistence composite luminescent material according to any one of claims 1 to 3, wherein the quantum dot is selected from at least one of a halide perovskite quantum dot, an oxide quantum dot, a sulfide quantum dot, a selenide quantum dot, a telluride quantum dot, a nitride quantum dot, a phosphide quantum dot, an arsenide quantum dot, a carbon quantum dot, a carbide quantum dot, a silicon quantum dot, a silicide quantum dot, a germanium quantum dot, a germanide quantum dot, and a core-shell structure or a heterojunction formed on the basis of the quantum dot.
5. The quantum dot-rare earth long afterglow composite luminescent material of any one of claims 1 to 4, wherein the quantum dot is CdS, CdSe, InP, CuInS2Or CdS, CdSe, InP, ZnS, CuInS2A core-shell structure or a heterojunction formed on the basis of the quantum dots, or organic-inorganic hybrid perovskite quantum dots and all-inorganic perovskite quantum dots.
6. The quantum dot-rare earth long afterglow composite luminescent material of any one of claims 1 to 5, wherein the quantum dot is selected from the group comprising but not limited to the following: CsPbCl3、CsPbCl1.5Br1.5、CsPbCl1Br2、CsPbBr3、CsPbBr2I1、CsPbBr1.5I1.5、CsPbBr1I2、CsPbI3、CdSe、InP@ZnS。
7. The quantum dot-rare earth long afterglow composite luminescent material of any one of claims 1 to 6, wherein the quantum dot-rare earth long afterglow composite luminescent material is selected from the composite materials including but not limited to: CaAl2O4:Eu2+,Nd3+-CsPbCl3、CaAl2O4:Eu2+,Nd3+-CsPbCl1.5Br1.5、CaAl2O4:Eu2+,Nd3+-CsPbCl2Br1、CaAl2O4:Eu2+,Nd3 +-CsPbCl1Br2、CaAl2O4:Eu2+,Nd3+-CsPbBr3、CaAl2O4:Eu2+,Nd3+-CsPbBr2I1、CaAl2O4:Eu2+,Nd3+-CsPbBr1.5I1.5、CaAl2O4:Eu2+,Nd3+-CsPbBr1I2、CaAl2O4:Eu2+,Nd3+-CsPbI3、CaAl2O4:Eu3+,Nd3+-CsPbBr2.3I0.7、SrAl2O4:Eu2+,Dy3+-CsPbBr2I1、SrAl2O4:Eu2+,Dy3+-CsPbBr1.5I1.5、SrAl2O4:Eu2+,Dy3+-CsPbBr1I2、SrAl2O4:Eu2+,Dy3+-CsPbI3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr3、Sr4Al14O25:Eu2+,Dy3+-CsPbBr2I1、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr4Al14O25:Eu2+,Dy3+-CsPbBr1I2、Sr4Al14O25:Eu2+,Dy3+-CsPbI3、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr3、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr2I1、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2MgSi2O7:Eu2+,Dy3+-CsPbBr1I2、Sr2MgSi2O7:Eu2+,Dy3+-CsPbI3、Sr2SiO4:Eu2+,Dy3+-CsPbBr2I1、Sr2SiO4:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr2SiO4:Eu2+,Dy3+-CsPbBr1I2、Sr2SiO4:Eu2+,Dy3+-CsPbI3、Sr3MgSi2O8:Eu2+,Dy3 +-CsPbBr3、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr2I1、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1.5I1.5、Sr3MgSi2O8:Eu2+,Dy3+-CsPbBr1I2、Sr3MgSi2O8:Eu2+,Dy3+-CsPbI3，Sr3MgSi2O8:Eu2+,Dy3+-InP@ZnS。
8. The preparation method of the quantum dot-rare earth long afterglow composite luminescent material of any one of claims 1 to 7, characterized by comprising the following steps: the rare earth long afterglow luminescent material and the quantum dots are coated into a film by spin coating or are directly mixed to obtain the quantum dot-rare earth long afterglow composite luminescent material.
9. The method of claim 8, comprising the steps of: the rare earth long afterglow material and the quantum dots are dispersed in Polydimethylsiloxane (PDMS) or polymethyl methacrylate (PMMA), and the quantum dot-rare earth long afterglow composite luminescent material can be obtained by fractional spin coating and solidification.
10. The use of the quantum dot-rare earth long afterglow composite luminescent material of any one of claims 1 to 7, characterized in that the luminescent material is used for biological detection, biological imaging, optical coding, anti-counterfeiting, display, photoelectric detector, and solar spectrum conversion.
CN201910190087.6A 2019-03-13 2019-03-13 Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof Active CN111690400B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910190087.6A CN111690400B (en) 2019-03-13 2019-03-13 Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910190087.6A CN111690400B (en) 2019-03-13 2019-03-13 Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111690400A true CN111690400A (en) 2020-09-22
CN111690400B CN111690400B (en) 2021-12-14

Family

ID=72475715

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910190087.6A Active CN111690400B (en) 2019-03-13 2019-03-13 Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111690400B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112251224A (en) * 2020-10-26 2021-01-22 陕西科技大学 Long afterglow luminescent material surface loaded CsPbX3Preparation method of (1)
CN114045165A (en) * 2021-12-03 2022-02-15 福州大学 Method for realizing multi-color variable pattern by long afterglow/quantum dot composite luminescent material
CN116814253A (en) * 2023-06-19 2023-09-29 华北水利水电大学 Hydrophobically modified long afterglow fluorescent powder and application thereof in self-luminous high-strength cement-based material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110121260A1 (en) * 2005-01-20 2011-05-26 Samsung Electronics Co., Ltd. Quantum dot phosphor for light emitting diode and method of preparing the same
CN106838668A (en) * 2016-12-30 2017-06-13 上海科润光电技术有限公司 A kind of long range infrared laser illuminating device
CN110746957A (en) * 2018-07-24 2020-02-04 Tcl集团股份有限公司 Long-afterglow composite material based on quantum dots and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110121260A1 (en) * 2005-01-20 2011-05-26 Samsung Electronics Co., Ltd. Quantum dot phosphor for light emitting diode and method of preparing the same
CN106838668A (en) * 2016-12-30 2017-06-13 上海科润光电技术有限公司 A kind of long range infrared laser illuminating device
CN110746957A (en) * 2018-07-24 2020-02-04 Tcl集团股份有限公司 Long-afterglow composite material based on quantum dots and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEI ZHENG ET AL.: "Near-infrared-triggered photon upconversion tuning in all-inorganic cesium lead halide perovskite quantum dots", 《NATURE COMMUNICATIONS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112251224A (en) * 2020-10-26 2021-01-22 陕西科技大学 Long afterglow luminescent material surface loaded CsPbX3Preparation method of (1)
CN114045165A (en) * 2021-12-03 2022-02-15 福州大学 Method for realizing multi-color variable pattern by long afterglow/quantum dot composite luminescent material
CN116814253A (en) * 2023-06-19 2023-09-29 华北水利水电大学 Hydrophobically modified long afterglow fluorescent powder and application thereof in self-luminous high-strength cement-based material

Also Published As

Publication number Publication date
CN111690400B (en) 2021-12-14

Similar Documents

Publication Publication Date Title
US8017972B2 (en) Multilayered white light emitting diode using quantum dots and method of fabricating the same
Wu et al. Long afterglow phosphorescent materials
Peng et al. Synthesis of SrAl2O4: Eu, Dy phosphor nanometer powders by sol–gel processes and its optical properties
Zhai et al. Blue–green afterglow of BaAl2O4: Dy3+ phosphors
CN111690400B (en) Quantum dot-rare earth long afterglow composite luminescent material and preparation method and application thereof
Guo et al. Luminescent properties of Sr2SiO4: Eu2+ nanorods for near-UV white LED
JP2009504809A (en) Photonic material with regularly arranged cavities
Yang et al. Lead oxide enables lead volatilization pollution inhibition and phase purity modulation in perovskite quantum dots embedded borosilicate glass
KR101792800B1 (en) Color tunable upconversion nanophosphor and method of fabricating the same
Lin et al. Sol–gel synthesis and characterization of Zn2SiO4: Mn phosphor films
Wang et al. Long persistent luminescence and traps distribution of Tb3+ doped calcium gallium germanate
KR101616363B1 (en) Multicolor tunable nanophosphor and its synthesis method and transparent polymer composite including the nanophosphor
Gupta et al. A Novel near white light emitting nanocrystalline Zn2P2O7: Sm3+ derived using citrate precursor route: Photoluminescence spectroscopy
Zheng et al. Luminescence properties of composite material Sr2MgSi2O7: Eu2+, Dy3+/light conversion agent with multilayer structure
Ramteke et al. Eu3+ and Dy3+-activated LaAlO3 phosphor for solid-state lighting
Ali et al. Energy transfer between Ce and Sm co-doped YAG nanocrystals for white light emitting devices
Lin et al. Dense nanosized europium silicate clusters induced light emission enhancement in Eu-doped silicon oxycarbide films
Huang et al. Luminescence improvement of Y2O2S: Tb3+, Sr2+, Zr4+ white-light long-lasting phosphor via Eu3+ addition
Wang et al. Long persistent luminescence property of green emitting Sr3Ga4O9: Tb3+ phosphor for anti-counterfeiting application
Yang et al. Preparation and luminescence properties of a white emitting long afterglow luminous fiber based on FRET
CN104334683A (en) Phosphors of rare earth and transition metal doped Ca1+xSr1-xGayIn2-ySzSe3-zF2, methods of manufacturing and applications
Guo et al. A building-block strategy for dynamic anti-counterfeiting by using (Ba, Sr) Ga2O4: Sm3+ new red persistent luminescent phosphor as an important component
Švančárek et al. Photoluminescence of (ZnO) XZ (SiO2) Y:(MnO) Z green phosphors prepared by direct thermal synthesis: The effect of ZnO/SiO2 ratio and Mn2+ concentration on luminescence
Archana et al. Influence of rare earth substitution on structure, photoluminescence emission properties and Judd-Ofelt analysis of ZnS: Eu3+ red phosphors
Martínez-Martínez et al. Blue–green–red luminescence from CeCl3-and MnCl2-doped hafnium oxide layers prepared by ultrasonic spray pyrolysis

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
GR01 Patent grant