WO2019196376A1 - 尖晶石基颜色可调控的上转换发光材料及其制备方法和应用 - Google Patents

尖晶石基颜色可调控的上转换发光材料及其制备方法和应用 Download PDF

Info

Publication number
WO2019196376A1
WO2019196376A1 PCT/CN2018/111310 CN2018111310W WO2019196376A1 WO 2019196376 A1 WO2019196376 A1 WO 2019196376A1 CN 2018111310 W CN2018111310 W CN 2018111310W WO 2019196376 A1 WO2019196376 A1 WO 2019196376A1
Authority
WO
WIPO (PCT)
Prior art keywords
luminescent material
ions
molar ratio
doped
spinel
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.)
Ceased
Application number
PCT/CN2018/111310
Other languages
English (en)
French (fr)
Inventor
孙康宁
成圆
李爱民
葛平慧
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.)
Shandong University
Original Assignee
Shandong University
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 Shandong University filed Critical Shandong University
Publication of WO2019196376A1 publication Critical patent/WO2019196376A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides

Definitions

  • the invention belongs to the technical field of materials science, and particularly relates to a color-controllable up-conversion luminescent material, in particular to a substrate of Zn(Al x Ga 1-x ) 2 O 4 , Yb 3+ , Tm 3+ , Er 3 . + is a doped ion upconversion luminescent composite material and its preparation method and application.
  • Upconversion luminescence is the process of superimposing two or more long-wavelength photons into short-wavelength photons.
  • a notable feature of the up-conversion process is that the absorbed photon energy is much lower than the emitted photon energy and is therefore also referred to as anti-Stokes illumination.
  • the most studied upconversion luminescence refers to photoluminescence that produces visible or ultraviolet light under the excitation of near-infrared or infrared light.
  • the rare-earth ion doped upconversion luminescence has become the focus of research in the field of luminescent materials due to its excellent spectral properties such as narrow spectral spectrum, high luminescent color purity, high conversion efficiency, wide emission area, and long fluorescence lifetime.
  • the rare earth ions commonly used for up-conversion luminescent materials doped mainly include trivalent europium ions (Yb 3+ ), trivalent europium ions (Er 3+ ), trivalent europium ions (Tm 3+ ), and trivalent europium ions (Ho 3+ ). )and many more.
  • Yb 3+ has a simple energy level and a high energy absorption rate, and is usually used as a sensitizer.
  • Er 3+ , Tm 3+ , Ho 3+ and other energy levels are abundant, the fluorescence lifetime is long, and the spectral line is narrow, which is used as an activator.
  • the upconversion luminescence process excited by rare earth ions is generally achieved by an excited state absorption process, an energy transfer process between the sensitizer and activator ions, and a "photon avalanche" process.
  • Both ZnGa 2 O 4 and ZnAl 2 O 4 are complex oxides of a typical spinel structure (AB 2 O 4 ).
  • the unit cell contains 64 tetrahedral sites, 32 octahedral sites and 32 oxygen atoms.
  • cation A occupies 8 tetrahedral positions
  • cation B occupies 16 octahedral positions, which means that there are still many vacancies in the unit cell, which facilitates the entry of doped ions.
  • both ZnGa 2 O 4 and ZnAl 2 O 4 can generate blue light emission without any doping, and at the same time, when doping different rare earth ions, different colors including red, green and yellow are generated.
  • ZnGa 2 O 4 :Er 3+ will produce green luminescence
  • ZnGa 2 O 4 :Eu 3+ will produce red luminescence
  • ZnAl 2 O 4 :Dy 3+ will produce yellow luminescence and so on.
  • a luminescent material when the luminescent material is applied to a fluorescent lacquer, a luminescent dye, or the like, illuminating of a plurality of colors is generally required to enrich the diversity of the fluorescent lacquer and the luminescent dye, and the production and application requirements are better satisfied.
  • a luminescent material can only exhibit luminescence of one color at a time, and luminescence of different colors needs to be achieved by selecting different matrix materials or doping different rare earth ions. Therefore, if a luminescent material can be provided, the regular and controllable multi-color fluorescence can be realized only by changing the raw material composition, which is bound to expand the production and application requirements.
  • the present invention uses ZnGa 2 O 4 , ZnAl 2 O 4 , and Al 3+ ion doped ZnGa 2 O 4 (Zn(Al x Ga 1-x ) 2 O 4 ) as a matrix.
  • a rare earth ion doped with Yb 3+ /Tm 3+ /Er 3+ was used to prepare a spinel-based color-controlled upconversion luminescent material Zn(Al x Ga 1-x ) 2 O 4 : Yb 3+ , Tm 3+ , Er 3+ .
  • the inventors discovered through accident that the color of the up-converting luminescent material can be achieved not only by controlling the doping amount of Al 3+ ions, but also that the luminescent material has high up-conversion efficiency, and the emitted fluorescence is visible to the naked eye and has high intensity. .
  • One of the objects of the present invention is to provide a spinel-based color-regulated up-converting luminescent material.
  • Another object of the present invention is to provide a method of preparing the above-described up-conversion luminescent material.
  • a third object of the present invention is to provide an application of the above-described upconverting luminescent material.
  • the present invention adopts the following technical solutions:
  • a spinel-based color-regulated up-converting luminescent material is provided, the specific chemical formula of the up-converting luminescent material being Zn(Al x Ga 1-x ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ ;
  • each doping ion in the spinel-based color-controllable up-converting luminescent material has its corresponding oxide as a reaction raw material.
  • each of the doped ions corresponding to the oxide in the luminescent material is a reaction raw material, and is prepared by a high-temperature solid phase reaction.
  • the steps of the preparation method are:
  • step S2 mixing and grinding the reaction raw materials in step S1.
  • step S3 Perform a high-temperature solid phase reaction on the uniformly ground raw material powder in the step S2, and the reaction is completed after the natural cooling.
  • the high-temperature solid phase reaction condition is: the heating rate is 4-6 ° C / min (preferably 5 ° C / min), the reaction temperature is 1200 ⁇ 1400 ° C (preferably 1300 ° C), and the reaction time is 1 to 3 h (preferably 2 h);
  • the use of the above-described upconverting luminescent material in the field of upconversion luminescent display includes, but are not limited to, the use of upconverting luminescent materials in fluorescent paints or luminescent dyes.
  • the spinel-based upconversion luminescent material Zn(Al x Ga 1-x ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in the invention can be produced by the human eye under the irradiation of a 980 nm laser lamp. More intense fluorescence is visible. At the same time, by adjusting the doping amount of Al 3+ ions, fluorescence of different colors can be directly obtained.
  • Zn(Al x Ga 1-x ) 2 O 4 is used as a matrix material, and Yb 3+ /Tm3+ / Er 3+ is used as a doped rare earth ion, and the spinel-based upconversion luminescent powder materials are prepared. It has good luminescence intensity. At the same time, the luminescence intensity and up-conversion efficiency of the material are improved after doping into Al 3+ ions.
  • Zn(Al 0.5 Ga 0.5 ) 1.96 O 4 3.5% Yb 3+ , 0.165% Tm 3+ , 0.33% Er 3+ reached its highest level.
  • the luminescent color of the material can be directly regulated.
  • the luminescence of the prepared material first appeared blue shift in Zn(Al 0.5 Ga 0.5 ) 2 O 4 : 3.5% Yb 3+ , 0.165% Tm 3+ , 0.33% Er 3
  • the pure blue luminescence is achieved in the up-conversion luminescent powder, and then, when the doping amount of the Al 3+ ion continues to increase, the luminescence of the prepared material is red-shifted.
  • the regularly controllable multi-color up-conversion luminescent material can be used in the field of color development such as fluorescent paints and luminescent dyes, which expands the color development range of the existing luminescent materials and improves the controllability of color development. Therefore, the spinel-based upconversion luminescent material of the present invention is extremely valuable for industrial mass production and practical application.
  • Example 1 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material ZnGa 2 O 4 :Yb 3+ , Tm 3+ , and Er 3+ prepared in Example 1 of the present invention;
  • Example 2 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material ZnAl 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 2 of the present invention;
  • Example 3 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material Zn(Al 0.1 Ga 0.9 ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 3 of the present invention;
  • Example 4 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material Zn(Al 0.3 Ga 0.7 ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 4 of the present invention;
  • Example 5 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material Zn(Al 0.5 Ga 0.5 ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 5 of the present invention;
  • Example 6 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material Zn(Al 0.7 Ga 0.3 ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 6 of the present invention;
  • Example 7 is an up-conversion emission spectrum of a spinel-based up-converting luminescent powder material Zn(Al 0.9 Ga 0.1 ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ prepared in Example 7 of the present invention;
  • Figure 8 is an emission peak integral area and "green-red ratio” (GRR) of all spinel-based up-converting luminescent powder materials prepared according to the present invention
  • Figure 9 is a CIE chromaticity diagram of all spinel-based upconverting luminescent powder materials prepared in accordance with the present invention.
  • a spinel-based color-controllable up-converting luminescent material is provided, and the specific chemical formula of the up-converting luminescent material is Zn(Al x Ga 1-x ) 2 O 4 :Yb 3 + , Tm 3+ , Er 3+ ;
  • the obtained powder is again ground in an agate grinding jar to obtain fine and uniform Zn(Al x Ga 1-x ) 2 O 4 :Yb 3+ , Tm 3+ , Er 3+ Convert the luminescent powder.
  • the use of the above-described up-converting luminescent material in the field of up-conversion luminescence display is provided.
  • the applications include, but are not limited to, the use of upconverting luminescent materials in fluorescent paints or luminescent dyes.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: ZnGa 1.96 O 4 : Yb 0.035 Tm 0.00165 Er 0.0033 .
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 1, which contains three distinct emission peaks: about 477 nm. Blue emission peak (produced by 1 G 4 ⁇ 3 H 6 emission of Tm 3+ ions), green emission peak at about 526 nm and 549 nm ( 2 H 11/2 ⁇ 4 I 15/2 from Er 3+ ion) And 4 S 3/2 ⁇ 4 I 15/2 emission produced), a red emission peak at about 659 nm (generated by 4 F 9/2 ⁇ 4 I 15/2 emission of Er 3+ ions).
  • the calculated chromaticity coordinates are (0.434, 0.249), and the position marked on the CIE chromaticity map of Fig. 9 is a, showing a pinkish purple color.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: ZnAl 1.96 O 4 : Yb 0.035 Tm 0.00165 Er 0.0033 .
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 2, and the positions of the three distinct emission peaks contained in the figure are unchanged, and implemented.
  • Example 1 is basically the same.
  • the calculated chromaticity coordinates are (0.415, 0.299), and the position marked on the CIE chromaticity map of Fig. 9 is b, which is pink.
  • the rhodium-based upconversion luminescent material ratio (molar ratio) is as follows: Zn(Al 0.1 Ga 0.9 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 .
  • a certain amount of ZnO, Ga 2 O 3 , Al 2 O 3 , Yb 2 O 3 , Tm 2 O 3 and Er 2 O 3 were respectively weighed into a agate grinding tank and mixed with acetone.
  • the grinding aid is continuously ground for 2 hours to obtain a uniformly mixed powder.
  • the mixed powder is heated at 5 ° C / min, and calcined in air at 1300 ° C for 2 h.
  • the powder obtained after cooling with the furnace is again placed in an agate grinding jar. Grinding to obtain Zn(Al 0.1 Ga 0.9 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 up-converting luminescent powder material.
  • the above-mentioned spinel-based upconversion luminescent material Zn(Al 0.1 Ga 0.9 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 3, and the three apparent emission peaks are included in the figure.
  • the position is unchanged, and is basically the same as Embodiment 1.
  • the calculated chromaticity coordinates are (0.243, 0.161), and the position marked on the CIE chromaticity map of Fig. 9 is c, which is purple.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: Zn(Al 0.3 Ga 0.7 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 .
  • a certain amount of ZnO, Ga 2 O 3 , Al 2 O 3 , Yb 2 O 3 , Tm 2 O 3 and Er 2 O 3 were respectively weighed into a agate grinding tank and mixed with acetone.
  • the grinding aid is continuously ground for 2 hours to obtain a uniformly mixed powder.
  • the mixed powder is heated at 5 ° C / min, and calcined in air at 1300 ° C for 2 h.
  • the powder obtained after cooling with the furnace is again placed in an agate grinding jar. Grinding, Zn (Al 0.3 Ga 0.7 ) 1.96 O 4 : Yb 0.035 Tm 0.00165 Er 0.0033 upconversion luminescent powder material was obtained.
  • the above-mentioned spinel-based upconversion luminescent material Zn(Al 0.3 Ga 0.7 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 4, and the three apparent emission peaks are included in the figure.
  • the position is unchanged, and is basically the same as Embodiment 1.
  • the calculated chromaticity coordinates are (0.250, 0.175), and the position marked on the CIE chromaticity map of Fig. 9 is d, which is purple.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: Zn(Al 0.5 Ga 0.5 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 .
  • a certain amount of ZnO, Ga 2 O 3 , Al 2 O 3 , Yb 2 O 3 , Tm 2 O 3 and Er 2 O 3 were respectively weighed into a agate grinding tank and mixed with acetone.
  • the grinding aid is continuously ground for 2 hours to obtain a uniformly mixed powder.
  • the mixed powder is heated at 5 ° C / min, and calcined in air at 1300 ° C for 2 h.
  • the powder obtained after cooling with the furnace is again placed in an agate grinding jar. Grinding to obtain Zn(Al 0.5 Ga 0.5 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 up-converting luminescent powder material.
  • the above-mentioned spinel-based upconversion luminescent material Zn(Al 0.5 Ga 0.5 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 5, and the three apparent emission peaks are included in the figure.
  • the position is unchanged, and is basically the same as Embodiment 1.
  • the calculated chromaticity coordinates are (0.212, 0.187), and the position marked on the CIE chromaticity map of Fig. 9 is e, which is blue.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: Zn(Al 0.7 Ga 0.3 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 .
  • a certain amount of ZnO, Ga 2 O 3 , Al 2 O 3 , Yb 2 O 3 , Tm 2 O 3 and Er 2 O 3 were respectively weighed into a agate grinding tank and mixed with acetone.
  • the grinding aid is continuously ground for 2 hours to obtain a uniformly mixed powder.
  • the mixed powder is heated at 5 ° C / min, and calcined in air at 1300 ° C for 2 h.
  • the powder obtained after cooling with the furnace is again placed in an agate grinding jar. Grinding to obtain Zn(Al 0.7 Ga 0.3 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 up-converting luminescent powder material.
  • the above-mentioned spinel-based upconverting luminescent material Zn(Al 0.7 Ga 0.3 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 6, which shows three distinct emission peaks. The position is unchanged, and is basically the same as Embodiment 1.
  • the calculated chromaticity coordinates are (0.248, 0.199), and the position marked on the CIE chromaticity map of Fig. 9 is f, which is blue-violet.
  • the spinel-based upconversion luminescent material ratio (molar ratio) is as follows: Zn(Al 0.9 Ga 0.1 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 .
  • a certain amount of ZnO, Ga 2 O 3 , Al 2 O 3 , Yb 2 O 3 , Tm 2 O 3 and Er 2 O 3 were respectively weighed into a agate grinding tank and mixed with acetone.
  • the grinding aid is continuously ground for 2 hours to obtain a uniformly mixed powder.
  • the mixed powder is heated at 5 ° C / min, and calcined in air at 1300 ° C for 2 h.
  • the powder obtained after cooling with the furnace is again placed in an agate grinding jar. Grinding to obtain Zn(Al 0.9 Ga 0.1 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033 up-converting luminescent powder material.
  • the above-mentioned spinel-based upconversion luminescent material Zn(Al 0.9 Ga 0.1 ) 1.96 O 4 :Yb 0.035 Tm 0.00165 Er 0.0033
  • the fluorescence spectrum obtained under excitation at 980 nm is shown in Fig. 7, and the three apparent emission peaks are included in the figure.
  • the position is unchanged, and is basically the same as Embodiment 1.
  • the calculated chromaticity coordinates are (0.373, 0.242), and the position marked on the CIE chromaticity map of Fig. 9 is g, which is pinkish purple.

Landscapes

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

Abstract

尖晶石基颜色可调控的上转换发光材料及其制备方法和应用。所述上转换发光材料Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+都具有良好的发光强度，同时，掺杂进Al 3+离子后，材料的发光强度及上转换效率得到了提高，而且，通过控制Al 3+离子的掺杂量，可以直接对材料的发光颜色进行调控。随Al 3+离子的掺杂量的增加，制备所得的材料发光先出现蓝移，随后，Al 3+离子的掺杂量继续增加时，制备所得的材料发光发生红移。这种有规律可控的多色上转换发光材料可用于荧光漆、发光染料等显色领域，扩大了现有发光材料的显色范围，提高了显色的可调控性。

Description

[根据细则37.2由ISA制定的发明名称]　尖晶石基颜色可调控的上转换发光材料及其制备方法和应用 技术领域
本发明属于材料科学技术领域，具体涉及颜色可调控的上转换发光材料，特别涉及一种以Zn(Al xGa 1-x) 2O 4为基体，以Yb 3+,Tm 3+,Er 3+为掺杂离子的上转换发光复合材料及其制备方法和应用。
背景技术
上转换发光是一个叠加两个或两个以上的长波长光子，将其转化为短波长光子的过程。上转换过程的一个显著特点是吸收的光子能量远远低于所发射的光子能量，因此也被称为反斯托克斯发光。一般来说，研究最多的上转换发光是指在近红外或红外光激发下，产生可见光或紫外光的光致发光。其中，稀土离子掺杂的上转换发光由于具备光谱谱宽窄、发光颜色纯度高、转换效率高、发射区宽、荧光寿命长等优异的发光性能，已成为目前发光材料领域研究的重点。
常用于上转换发光材料掺杂的稀土离子主要有三价镱离子(Yb 3+)、三价铒离子(Er 3+)、三价铥离子(Tm 3+)、三价钬离子(Ho 3+)等等。其中，Yb 3+能级简单，能量吸收率高，通常被用做敏化剂。而Er 3+、Tm 3+、Ho 3+等能级丰富，荧光寿命长，发光谱线窄，被用做激活剂。稀土离子激发的上转换发光过程，一般就是通过激发态吸收过程，以及敏化剂和激活剂离子之间的能量传递过程和“光子雪崩”过程实现的。
ZnGa 2O 4及ZnAl 2O 4都属于典型尖晶石结构(AB 2O 4)的复合氧化物。晶胞中含有64个四面体位点，32个八面体位点和32个氧原子。通常，阳离子A占据了8个四面体位置，阳离子B占据了16个八面体位置，这意味着晶胞中还有许多空位存在，有利于掺杂离子的进入。而且研究发现，ZnGa 2O 4和ZnAl 2O 4都可以在没有任何掺杂的情况下产生蓝光发射，同时在掺杂不同的稀土离子时，会产生包括红、绿、黄等不同颜色的发光，比如：ZnGa 2O 4:Er 3+会产生绿色发光，ZnGa 2O 4:Eu 3+会产生红色发光，ZnAl 2O 4:Dy 3+会产生黄色发光等等。
此外，当发光材料应用于荧光漆、发光染料等情况下时，通常需要多种颜色的发光以丰富荧光漆及发光染料等的多样性，更好地满足生产、应用需求。一般来说，一种发光材料最终只能呈现出一种颜色的发光，不同颜色的发光需要通过选择不同的基体材料或者掺杂不同的稀土离子来实现。因此如能提供一种发光材料，仅通过改变原料成分即可实现规律可控的多色荧光，势必能拓展其生产及应用需求。
发明内容
针对上述现有技术存在的问题，本发明以ZnGa 2O 4、ZnAl 2O 4及Al 3+离子掺杂的ZnGa 2O 4(Zn(Al xGa 1-x) 2O 4)做基体，以Yb 3+/Tm 3+/Er 3+为掺杂的稀土离子，从而成功制备出一种尖晶石基颜色可调控的上转换发光材料Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+。发明人通过研究意外发现，所述上转换发光材料发光的颜色不仅可以通过控制Al 3+离子的掺杂量实现，同时所述发光材料的上转换效率高，所发荧光肉眼可见，强度较高。
本发明的目的之一在于提供一种尖晶石基颜色可调控的上转换发光材料。
本发明的目的之二在于提供上述上转换发光材料的制备方法。
本发明的目的之三在于提供上述上转换发光材料的应用。
为实现上述目的，具体的，本发明采用以下技术方案：
本发明的第一个方面，提供一种尖晶石基颜色可调控的上转换发光材料，所述上转换发光材料具体化学式为Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+；
其中，0≤x≤1，Yb 3+/Tm 3+/Er 3+＝21/1/2(摩尔比)。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝0/1。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/0。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/9。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝3/7。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/1。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝7/3。
进一步的，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝9/1。
进一步的，所述尖晶石基颜色可调控的上转换发光材料中的各掺杂离子均以其对应氧化物为反应原料。
本发明的第二个方面，提供上述尖晶石基颜色可调控的上转换发光材料的制备方法，以上转换发光材料中的各掺杂离子对应氧化物为反应原料，采用高温固相反应制备得到。
具体的，所述制备方法步骤为：
S1.按照上转换发光材料各掺杂离子摩尔比，称取相应量的ZnO，Al 2O 3，Ga 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料；
S2.将步骤S1.中各反应原料混合研磨均匀；
S3.对步骤S2.中研磨均匀的原料粉末进行高温固相反应，反应结束自然冷却后即得。
进一步的，所述步骤S3.中高温固相反应条件：升温速率为4～6℃/min(优选为5℃/min)，反应温度为1200～1400℃(优选为1300℃)，反应时间为1～3h(优选为2h)；
本发明的第三个方面，提供上述上转换发光材料在上转换发光显示领域中的应用。具体的，所述应用包括但不限于上转换发光材料在荧光漆/或发光染料中的应用。
本发明的有益技术效果：
本发明中制备的尖晶石基上转换发光材料Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+，在980nm激光灯的照射下，可以产生人体肉眼可见的较为强烈的荧光。同时，通过调整Al 3+离子的掺杂量，可以直接得到不同颜色的荧光。
具体地，本发明中利用Zn(Al xGa 1-x) 2O 4作为基体材料，Yb 3+/Tm3+ /Er 3+作为掺杂稀土离子，制备的尖晶石基上转换发光粉末材料都具有良好的发光强度，同时，掺杂进Al 3+离子后，材料的发光强度及上转换效率得到了提高，在Zn(Al 0.5Ga 0.5) 1.96O 4:3.5％Yb 3+,0.165％Tm 3+,0.33％Er 3+达到最高。而且，通过控制Al 3+离子的掺杂量，可以直接对材料的发光颜色进行调控。随Al 3+离子的掺杂量的增加，制备所得的材料发光先出现蓝移，在Zn(Al 0.5Ga 0.5) 2O 4:3.5％Yb 3+,0.165％Tm 3+,0.33％Er 3+上转换发光粉末中实现纯蓝色发光，随后，Al 3+离子的掺杂量继续增加时，制备所得的材料发光发生红移。这种有规律可控的多色上转换发光材料可用于荧光漆、发光染料等显色领域，扩大了现有发光材料的显色范围，提高了显色的可调控性。因此本发明的尖晶石基上转换发光材料极具有工业大规模生产及实际应用之价值。
附图说明
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。
图1为本发明实施例1制备的尖晶石基上转换发光粉末材料ZnGa 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图2为本发明实施例2制备的尖晶石基上转换发光粉末材料ZnAl 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图3为本发明实施例3制备的尖晶石基上转换发光粉末材料Zn(Al 0.1Ga 0.9) 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图4为本发明实施例4制备的尖晶石基上转换发光粉末材料Zn(Al 0.3Ga 0.7) 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图5为本发明实施例5制备的尖晶石基上转换发光粉末材料Zn(Al 0.5Ga 0.5) 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图6为本发明实施例6制备的尖晶石基上转换发光粉末材料Zn(Al 0.7Ga 0.3) 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图7为本发明实施例7制备的尖晶石基上转换发光粉末材料Zn(Al 0.9Ga 0.1) 2O 4:Yb 3+,Tm 3+,Er 3+的上转换发射光谱；
图8为本发明制备的所有尖晶石基上转换发光粉末材料的发射峰积分面积与“绿红比”(GRR)；
图9为本发明制备的所有尖晶石基上转换发光粉末材料的CIE色度图谱。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
结合具体实例对本发明作进一步的说明，以下实例仅是为了解释本发明，并不对其内容进行限定。如果实施例中未注明的实验具体条件，通常按照常规条件，或按照销售公司所推荐的条件；在本发明没有特别限定，均可通过商业途径购买得到。
本发明的一种具体实施方式中，提供一种尖晶石基颜色可调控的上转换发光材料，所述上转换发光材料具体化学式为Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+；
其中，0≤x≤1，Yb 3+/Tm 3+/Er 3+＝21/1/2(摩尔比)。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝0/1。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/0。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/9。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝3/7。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/1。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝7/3。
本发明的又一具体实施方式中，所述尖晶石基颜色可调控的上转换发光材料，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝9/1。
本发明的又一具体实施方式中，提供上述尖晶石基颜色可调控的上转换发光材料的制备方法，步骤为：
(1)按照上述掺杂摩尔比，称取一定量的ZnO，Al 2O 3，Ga 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料；
(2)将上述称量的原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末；
(3)将上述研磨后的均匀粉末以5℃/min进行升温，在1300℃下，空气中保温煅烧2h；
(4)随炉冷却后，将得到的粉末再次放入玛瑙研磨罐中研磨，得到细腻均匀的Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+上转换发光粉末。
本发明的又一具体实施方式中，提供上述上转换发光材料在上转换发光显示领域中的应用。具体的，所述应用包括但不限于上转换发光材料在荧光漆/或发光染料中的应用。
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案。
实施例1
尖晶石基上转换发光材料配比(摩尔比)如下：ZnGa 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到ZnGa 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料ZnGa 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图1所示，图中包含三个明显的发射峰，分别为：约477nm处的蓝色发射峰(由Tm 3+离子的 1G 4→ 3H 6发射产生)，约526nm和549nm处的绿色发射峰(由Er 3+离子的 2H 11/2→ 4I 15/2和 4S 3/2→ 4I 15/2发射产生)，约659nm处的红色发射峰(由Er 3+离子的 4F 9/2→ 4I 15/2发射产生)。通过计算得到的色度坐标为(0.434,0.249)，标记在图9CIE色度图谱上的位置为a，呈现粉紫色。
实施例2
尖晶石基上转换发光材料配比(摩尔比)如下：ZnAl 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到ZnAl 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料ZnAlGa 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图2所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.415,0.299)，标记在图9CIE色度图谱上的位置为b，呈现粉色。
实施例3
尖晶石基上转换发光材料配比(摩尔比)如下：Zn(Al 0.1Ga 0.9) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却 后得到的粉末再次放入玛瑙研磨罐中研磨，得到Zn(Al 0.1Ga 0.9) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料Zn(Al 0.1Ga 0.9) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图3所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.243,0.161)，标记在图9CIE色度图谱上的位置为c，呈现紫色。
实施例4
尖晶石基上转换发光材料配比(摩尔比)如下：Zn(Al 0.3Ga 0.7) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到Zn(Al 0.3Ga 0.7) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料Zn(Al 0.3Ga 0.7) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图4所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.250,0.175)，标记在图9CIE色度图谱上的位置为d，呈现紫色。
实施例5
尖晶石基上转换发光材料配比(摩尔比)如下：Zn(Al 0.5Ga 0.5) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到Zn(Al 0.5Ga 0.5) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料Zn(Al 0.5Ga 0.5) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图5所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.212,0.187)，标记在图9CIE色度图谱上的位置为e，呈现蓝色。
实施例6
尖晶石基上转换发光材料配比(摩尔比)如下：Zn(Al 0.7Ga 0.3) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到Zn(Al 0.7Ga 0.3) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料Zn(Al 0.7Ga 0.3) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图6所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.248,0.199)，标记在图9CIE色度图谱上的位置为f，呈现蓝紫色。
实施例7
尖晶石基上转换发光材料配比(摩尔比)如下：Zn(Al 0.9Ga 0.1) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033。
按照上述配比分别称取一定量的ZnO，Ga 2O 3，Al 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料放入玛瑙研磨罐中混合，用丙酮作为助磨剂，持续研磨2h，得到混合均匀的粉末，将该混合粉末以5℃/min升温，在1300℃下，空气中保温煅烧2h，随炉冷却后得到的粉末再次放入玛瑙研磨罐中研磨，得到Zn(Al 0.9Ga 0.1) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033上转换发光粉末材料。
上述尖晶石基上转换发光材料Zn(Al 0.9Ga 0.1) 1.96O 4:Yb 0.035Tm 0.00165Er 0.0033在980nm激发下得到的荧光光谱参见图7所示，图中包含的三个明显发射峰的位置不变，与实施例1基本相同。通过计算得到的色度坐标为(0.373,0.242)，标记在图9CIE色度图谱上的位置为g，呈现粉紫色。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种尖晶石基颜色可调控的上转换发光材料，其特征在于，所述上转换发光材料化学式为Zn(Al xGa 1-x) 2O 4:Yb 3+,Tm 3+,Er 3+；
    其中，0≤x≤1，Yb 3+/Tm 3+/Er 3+＝21/1/2(摩尔比)。
  2. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝0/1。
  3. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/0。
  4. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/9。
  5. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝3/7。
  6. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝1/1。
  7. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝7/3。
  8. 如权利要求1所述的上转换发光材料，其特征在于，离子按以下摩尔比掺杂：Yb 3+/Tm 3+/Er 3+＝21/1/2，Al 3+/Ga 3+＝9/1。
  9. 如权利要求1-8任一项所述上转换发光材料的制备方法，其特征在于，以上转换发光材料中的各掺杂离子对应氧化物为反应原料，采用高温固相反应制备得到；
    优选的，所述制备方法为：
    S1.按照上转换发光材料各掺杂离子摩尔比，称取相应量的ZnO，Al 2O 3，Ga 2O 3，Yb 2O 3，Tm 2O 3和Er 2O 3作为反应原料；
    S2.将步骤S1.中各反应原料混合研磨均匀；
    S3.对步骤S2.中研磨均匀的原料粉末进行高温固相反应，反应结束自然冷却后即得；
    优选的，所述步骤S3.中高温固相反应条件：升温速率为4～6℃/min(优选为5℃/min)，反应温度为1200～1400℃(优选为1300℃)，反应时间为1～3h(优选为2h)。
  10. 权利要求1-8任一项所述上转换发光材料和/或权利要求9所述制备方法制备得到的上转换发光材料在上转换发光显示领域中的应用；
    优选的，所述应用包括上转换发光材料在荧光漆/或发光染料中的应用。
PCT/CN2018/111310 2018-04-12 2018-10-23 尖晶石基颜色可调控的上转换发光材料及其制备方法和应用 Ceased WO2019196376A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810327618.7A CN108410451B (zh) 2018-04-12 2018-04-12 一种尖晶石基颜色可调控的上转换发光材料及其制备方法和应用
CN201810327618.7 2018-04-12

Publications (1)

Publication Number Publication Date
WO2019196376A1 true WO2019196376A1 (zh) 2019-10-17

Family

ID=63135326

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/111310 Ceased WO2019196376A1 (zh) 2018-04-12 2018-10-23 尖晶石基颜色可调控的上转换发光材料及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN108410451B (zh)
WO (1) WO2019196376A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108410451B (zh) * 2018-04-12 2020-07-31 山东大学 一种尖晶石基颜色可调控的上转换发光材料及其制备方法和应用
CN110452701B (zh) * 2019-08-21 2022-07-26 哈尔滨学院 基于稀土掺杂上转换纳米晶的混合精细调节色度的方法
CN116904189A (zh) * 2023-07-14 2023-10-20 长春工业大学 一种近红外上转换长余辉发光材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006054203A1 (en) * 2004-11-18 2006-05-26 Philips Intellectual Property & Standards Gmbh Light emitting device with conversion structure
CN101794834A (zh) * 2009-12-14 2010-08-04 湖南共创光伏科技有限公司 设有上转换荧光材料膜层的高效太阳能薄膜电池及其膜层制备方法
WO2014019153A1 (zh) * 2012-07-31 2014-02-06 海洋王照明科技股份有限公司 铝酸锌荧光材料及其制备方法
CN103849384A (zh) * 2012-11-29 2014-06-11 海洋王照明科技股份有限公司 铝酸锌发光材料及其制备方法
CN108410451A (zh) * 2018-04-12 2018-08-17 山东大学 一种尖晶石基颜色可调控的上转换发光材料及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006054203A1 (en) * 2004-11-18 2006-05-26 Philips Intellectual Property & Standards Gmbh Light emitting device with conversion structure
CN101794834A (zh) * 2009-12-14 2010-08-04 湖南共创光伏科技有限公司 设有上转换荧光材料膜层的高效太阳能薄膜电池及其膜层制备方法
WO2014019153A1 (zh) * 2012-07-31 2014-02-06 海洋王照明科技股份有限公司 铝酸锌荧光材料及其制备方法
CN103849384A (zh) * 2012-11-29 2014-06-11 海洋王照明科技股份有限公司 铝酸锌发光材料及其制备方法
CN108410451A (zh) * 2018-04-12 2018-08-17 山东大学 一种尖晶石基颜色可调控的上转换发光材料及其制备方法和应用

Also Published As

Publication number Publication date
CN108410451A (zh) 2018-08-17
CN108410451B (zh) 2020-07-31

Similar Documents

Publication Publication Date Title
Shu et al. NaCaTiTaO6: Sm3+: a novel orange-red-emitting tantalate phosphor with excellent thermal stability and high color purity for white LEDs
Huang et al. Highly efficient Eu3+-activated K2Gd (WO4)(PO4) red-emitting phosphors with superior thermal stability for solid-state lighting
Liang et al. Synthesis and photoluminescence properties of a novel high-efficiency red-emitting Ca2LuSbO6: Eu3+ phosphor for WLEDs
Xiong et al. Photoluminescence characteristics of Sm3+-doped LnBWO6 (Ln= La, Gd and Y) as new orange-red phosphors
Chahar et al. Color tunable nanocrystalline SrGd2Al2O7: Tb3+ phosphor for solid state lighting
Gan et al. Effects of Gd3+ codoping on the enhancement of the luminescent properties of a NaBi (MoO4) 2: Eu3+ red-emitting phosphors
Xia et al. Enhanced photoluminescence and energy transfer performance of Y 3 Al 4 GaO 12: Mn 4+, Dy 3+ phosphors for plant growth LED lights
Zeng et al. Synthesis and luminescence of Pr3+ doped Lu2MoO6 phosphors
Zhang et al. Synthesis, structure, and color-tunable luminescence properties of lanthanide activator ions doped bismuth silicate as single-phase white light emitting phosphors
Zhou et al. Color-tunable luminescence properties and energy transfer of Tb3+/Sm3+ co-doped Ca9La (PO4) 5 (SiO4) F2 phosphors
Li et al. One-step synthesis of Sc2W3O12: Eu3+ phosphors with tunable luminescence for WLED
Xiong et al. White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+= Eu3+, Dy3+) phosphors
Zhang et al. Synthesis and luminescence properties of reddish orthosilicate oxyapatite phosphor LiGd9 (SiO4) 6O2: Sm3+
Guo et al. Color-tunable photoluminescence and energy transfer properties of single-phase Ba10 (PO4) 6O: Eu2+, Mn2+ phosphors
Liu et al. K0. 5La0. 5SrMgWO6: Mn4+: A high-efficiency perovskite structure phosphor for plant cultivation LEDs
Ramakrishna et al. Driving the photoluminescent and structural properties of X2-Y2SiO5 by varying the dopant Dy3+ concentration towards cool WLED applications
Guo et al. Structure and luminescence properties of multicolor phosphor Ba2La3 (SiO4) 3Cl: Tb3+, Eu3+
CN108949166B (zh) 一种上转换率可控的ab2o4基上转换发光材料及其制备方法和应用
Zhang et al. Preparation and luminescence properties of Ba9Y2Si6O24: Sm3+ phosphors with excellent thermal stability for solid-state lightning
WO2019196376A1 (zh) 尖晶石基颜色可调控的上转换发光材料及其制备方法和应用
Dou et al. Emission color tuning via modulating PO43−/VO43− proportion in Gd (PxV1− x) O4: 1 at.% Dy3+: Realization of a promising single-phased white-light-emitting phosphor at x= 0.3
Xiong et al. Novel red emitting LnTaO4: Eu3+ (Ln= La, Y) phosphors for warm white LEDs
Zhang et al. Synthesis and photoluminescence properties of Eu3+-doped Na2YMg2V3O12: A novel red-emitting phosphor for WLEDs
Yuan et al. Multi-mode tunable luminescence in Bi 3+-activated oxyfluoride phosphors for multi-level anti-counterfeiting applications
Zhai et al. Novel square plate-like NaGd (WO4) 2: Tm3+, Dy3+ phosphors: Synthesis, characterization, tunable luminescence properties and energy transfer behaviors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18914344

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18914344

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 23.03.2021)

122 Ep: pct application non-entry in european phase

Ref document number: 18914344

Country of ref document: EP

Kind code of ref document: A1