WO2022052279A1 - 一种多元硫化物上转换发光材料 - Google Patents

一种多元硫化物上转换发光材料 Download PDF

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WO2022052279A1
WO2022052279A1 PCT/CN2020/126670 CN2020126670W WO2022052279A1 WO 2022052279 A1 WO2022052279 A1 WO 2022052279A1 CN 2020126670 W CN2020126670 W CN 2020126670W WO 2022052279 A1 WO2022052279 A1 WO 2022052279A1
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luminescent material
luminescence
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董斌
罗昔贤
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Dalian Minzu University
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
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    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
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Definitions

  • the invention belongs to the field of new optical function materials, in particular to a multi-component sulfide up-conversion luminescent material.
  • Luminescence can be divided into photoluminescence, electroluminescence, cathodoluminescence, radioluminescence, chemiluminescence, bioluminescence, etc.
  • photoluminescence can be divided into conventional photoluminescence [hereinafter referred to as conventional luminescence] and upconversion. glow.
  • the wavelength of the incident excitation light of conventional luminescence is smaller than the wavelength of the emitted light, which is characterized by high luminous efficiency, and the quantum efficiency can reach or even exceed 100%.
  • upconversion luminescence can convert infrared light into ultraviolet or visible light, and its unique luminescence characteristics can be used in biomedicine, solar cells, infrared anti-counterfeiting, laser display and other fields, thus attracting extensive attention.
  • the realization of up-conversion luminescence requires an activator or an energy transfer process between an activator and a sensitizer, and requires a long lifetime for the intermediate energy level of the luminescent ion.
  • the absorption cross section (11.7 ⁇ 10 -21 cm 2 ) of the Yb ion is larger, the energy level structure is simple, and it is easy to achieve high-concentration doping.
  • the Yb ion is Sensitizers can significantly enhance the upconversion luminescence of materials [(1) F. Auzel, Upconversion and anti–Stokes processes with f and d ions in solids, Chem. Rev., 2004, 104, 139–174].
  • the wavelength of the incident excitation light for upconversion luminescence is larger than the wavelength of the emitted light, it is difficult to achieve high luminous efficiency - so far, the highest quantum efficiency of upconversion luminescent materials has not yet reached 10%, and most of them are only 1% or lower.
  • upconversion luminescent materials in addition to selecting luminescent ions with high-efficiency emission levels, sensitizing ions and suitable excitation channels, it is also necessary to reduce the nonradiative transition probability of the material, and the selection of suitable host materials is Another most direct way to improve upconversion luminous efficiency.
  • the choice of the host lattice can not only determine the relative spatial positions between the dopant ions, but also affect the anion species and coordination numbers around the dopant ions. The interaction between the host lattice and the dopant ions has a great influence on the up-conversion luminescence properties and luminous efficiency of the material.
  • the host material There are two main selection criteria for the host material: (1) Selecting a host material with a small phonon energy can reduce the multi-phonon nonradiative relaxation, prolong the lifetime of the excited state, and then improve the up-conversion luminescence efficiency; (2) Select the crystal structure In the host material with low symmetry, the f-f electric dipole transition of upconversion luminescence is forbidden according to the parity selection rule of the electronic transition of lanthanides, while in the host with low crystal symmetry, due to the The effect of the field odd-order term makes the electric dipole transition of the 4fn configuration possible, which can improve the up-conversion luminescence and luminescence efficiency.
  • Rare earth halides fluorides, chlorides, bromides, iodides, etc. have extremely low phonon energy, and can obtain efficient up-conversion luminescence.
  • the chemical properties of chloride, bromide and iodide are unstable, easy to deliquescence, and the preparation process is complicated, which limits their practical application.
  • Fluoride solves the problem of easy deliquescence to a certain extent, and retains the characteristics of low phonon energy. It is currently the most widely used and studied matrix. Among them, ⁇ -NaYF 4 :Yb,Er and ⁇ -NaYF 4 :Yb,Tm are considered to be the upconversion luminescent materials with the highest luminous efficiency at present [(2)KW D. Biner, G.
  • Rare earth sulfur oxides sulfur oxides not only have low phonon energy, but also have good chemical stability and thermal stability (high melting point: 2000-2200 ° C), strong oxidation resistance, high radiation resistance, It has the advantages of low toxicity and insoluble in water.
  • High-efficiency upconversion luminescence has been obtained in the Y 2 O 2 S host, for example, the up-conversion luminescence brightness of Y 2 O 2 S:Yb,Ho excited at 980 nm may be the highest among known materials [(3)Luo XX, Cao WH, Upconversion luminescence of holmium and ytterbium co–doped yttrium oxysulfide phosphor, Mater. Lett., 2007, 61(17):3696–3700].
  • the rare earth oxysulfide has high covalent bond properties, complex preparation process and difficult production.
  • Oxides have high phonon energy, most of them are non-toxic and have good chemical stability, the preparation process is simple, and the requirements for the production environment are low. In addition, in the oxide single crystal, the activated ion fluorescence spectrum is narrow, the gain is higher, and the hardness, mechanical strength and thermal conductivity are better than those of glass, so the oxide single crystal with stable physical and chemical properties is often used as the matrix of the up-conversion laser material. .
  • Rare earth composite oxides such as Y 2 O 3 /Gd 2 O 3 , Bi 2 O 3 , and phosphates have obtained good up-conversion luminescence properties, but the up-conversion luminescence efficiency is still the lowest among the above three materials.
  • Sulfide is an excellent conventional luminescent material matrix, which has been widely used in photoluminescence, electroluminescence, cathodoluminescence, radioluminescence and other fields.
  • Transition metal sulfides such as ZnS:Cu and ZnS:Ag are excellent conventional photoluminescence, electroluminescence, cathodoluminescence and radioluminescence materials.
  • Alkaline earth metal sulfides such as CaS can be applied to long afterglow materials [(4) Hu Xuefang, Chinese invention patent application, Preparation method of rare earth europium activated calcium sulfide or alkaline earth sulfide red luminescent materials, CN1916109A] and electron capture materials [(5) Zhang Jiahua , Wang Ying, Zhang Xia, etc., Chinese invention patent, a sulfide-based three-doped electron capture material and its preparation method, ZL201210483728.5].
  • Rare earth sulfide is an excellent high-grade pigment, so it is difficult to apply to luminescence [(6) Yuan Haibin, Zhang Jianhui, Yu Ruijin, etc., Synthesis of rare earth sulfides and their UV-vis absorption spectra, J.Rare Earths, 2009 , 27, 308].
  • Alkaline-earth ternary sulfides have suitable band gaps and are excellent conventional luminescent host materials, which can be used in the field of LED lighting [(7) Zhou Mingjie, Wang Ronghao, Chinese invention patent application, an alkaline earth-rare earth ternary Meta-sulfide luminescent material and preparation method thereof, CN104119916A.(8) Hao Chuanxin, Xiong Yongqiang, Chinese invention patent, Ternary sulfide luminescent material doped with metal nanoparticles and preparation method, ZL201310089574.6.(9) Lian Shixun; Tian Keming; Yin Dulin; Li Chengzhi; Zhu Ailing; Liu Limin; Zeng Lihua; Zhang Huajing Chinese invention patent application, Erbium-activated alkaline earth rare earth sulfide red luminescent material CN1919968A.(10) Yuta MM,White W B.Photoluminesenee of
  • Tagiyev BG, Tagiyev OB, Mammadov AI Structural and luminescence properties of Ca x Ba 1-x Ga 2 S 4 : Eu 2+ chalcogenide semiconductor solid solutions, Physica B-Condensed Matter, 2015, 478, 58-62.
  • Guo CF, Zhang CX, Lu YH, etc. Luminescent property s of Eu 2+ and Ho 3+ co-doped CaGa 2 S 4 phosphor, Physica Status Solidi A, 2004, 201, 1588-1593.
  • Rare earth polysulfides have low phonon energy comparable to chlorides, and have good chemical stability.
  • the highest phonon energy of NaYS 2 is 279cm -1 , which is lower than the phonon energy of ⁇ -NaYF 4 (418cm -1 ), which has the highest up-conversion luminescence efficiency, and belongs to a low-symmetry crystal system, which is suitable as an ideal up-conversion host.
  • the condition of the material, the up-conversion luminescent material with it as the host should have higher up-conversion luminous efficiency.
  • Rare earth sulfides have been used in high-grade pigments for a long time, and Yb ion sensitization is commonly used. However, there are very few reports on sulfide-based upconversion luminescence.
  • Higuchi et al. first reported the up-conversion luminescence of Er 3+ ions in Ga 2 S 3 -GeS 2 -La 2 S 3 glasses under excitation at 800 and 980 nm, but their green up-conversion luminescence quantum efficiency is less than half that of fluoride glasses [( 23) H.Higuchi,M.Takahashi,Y.Kawamoto,Optical transitions and frequency upconversion emission of Er 3+ ions in Ga 2 S 3 –GeS 2 –La 2 S 3 glasses,J.Appl.Phys.,1998,83 , 19]. In addition, the study by Pascal et al.
  • the LMCT absorption edge of S 2- ⁇ Yb 3+ is lower than 20000 cm -1 , which is different from 2 H 11/2 , 4 S 3/2 and 4 of Er 3+ .
  • the F 7/2 energy levels overlap, which reduces the luminescence intensity of the Yb 3+ and Er 3+ co-doped NaYS 2 upconversion luminescent materials excited at 980 nm by two orders of magnitude. Therefore, it is generally believed that pure rare earth sulfides are not effective host materials for traditional Yb 3+ sensitized upconversion light emission [(24) Pascal Gerner, Hans U.
  • the present invention provides a multi-component sulfide upconversion luminescent material with high luminous efficiency, which realizes red, green and blue upconversion luminescence and ultraviolet and near-infrared upconversion luminescence through multi-wavelength excitation.
  • the material has the advantages of high up-conversion luminescence brightness, stable chemical properties, and good biocompatibility.
  • the preferred n value is 4.5-5.5
  • the preferred k value is 1.8- 2.2.
  • the upconversion luminescent material with the general formula of mA 2 S ⁇ nBS ⁇ kC 2-x S 3 :D x , when D contains Ho, the optimized x value is 0.02-2, and the excitation wavelength range used is 1100- 1190nm.
  • the upconversion luminescent material with the general formula of mA 2 S ⁇ nBS ⁇ kC 2-x S 3 :D x , when D contains Tm, the optimized x value is 0.01-2, and the excitation wavelength range used is 1180- 1260nm and 760-850nm, these two excitation wavelengths can be used individually or simultaneously.
  • the multicomponent sulfide with mA 2 S ⁇ nBS ⁇ kC 2-x S 3 :D x as the general chemical formula of the present invention has very low phonon energy, and belongs to the crystal system with low symmetry, which is an ideal upper Convert the luminescent host material.
  • ion doping with a suitable concentration since the distance between the doping ions is far greater than that of conventional light-emitting materials, high-concentration doping can be achieved and non-radiative relaxation can be reduced, and its up-conversion luminous efficiency exceeds that of traditional NaYF 4 :Yb,Er , and multi-wavelength excitation can be achieved simultaneously.
  • the infrared light in the range of 1450-1600 nm is the eye-safe wavelength.
  • the invention can also reduce the protection level of the application occasion or do not use protective equipment, expand the application range, and have the highest brightness. This is especially advantageous for applications.
  • FIG. 1 is the emission spectrum of the NaY 0.9 S 2 :Er 0.1 sample of Example 18 of the present invention under excitation at 1550 nm.
  • Fig. 2 is the data graph of NaY 0.9 S 2 :Er 0.1 and NaYF 4 :Yb,Er of Example 18 of the present invention; wherein (a) is a comparison diagram of luminance data, and (b) is luminance with 980 and 1550nm laser excitation power Variation graph; (c) is the photoluminescence photo of NaY 0.9 S 2 :Er 0.1 under the excitation of 980 and 1550 nm lasers.
  • Example 60 of the present invention under excitation at 980nm.
  • Example 4 is the emission spectrum of the NaGd 0.9 S 2 :Er 0.1 @NaGd 0.78 S 2 :Er 0.18 , Ho 0.05 sample of Example 61 of the present invention under excitation at 980 nm.
  • Example 5 is the emission spectrum of NaY 0.8 S 2 :Er 0.10 ,Nd 0.10@NaY 0.89 S 2 :Yb 0.08 ,Nd 0.01 ,Tm 0.02 sample of Example 62 of the present invention under excitation at 980nm.
  • Comparative Example 1 Commercial ⁇ -NaYF 4 :Yb,Er green upconversion luminescent material.
  • Comparative Example 2 Commercial ⁇ -NaYF 4 :Yb,Tm blue upconversion luminescent material.
  • Comparative Example 3 Commercial Y 2 O 3 :Yb,Er red upconversion luminescent material.
  • the sample of the present invention is prepared by the solid-phase reaction method, and the raw materials are weighed according to the molar ratio of the elements.
  • the raw materials can be oxides, carbonates, oxalates, nitrates, vinegars of the elements mentioned in the technical scheme. acid, sulfate.
  • dry mixing method grind and mix evenly, put into crucible, put into high temperature furnace, and calcine at 900-1400 °C for 1-50h in sulfurized atmosphere (such as H 2 S, CS 2 ).
  • the calcination time is adjusted according to the material amount.
  • a small amount of co-solvent such as 0-20wt% of AF and/or BF 2 , including NH 4 Cl, NH 4 F, MgF 2 , CaF 2 , SrF 2 , BaF 2 , etc., can be added to the raw materials, which can significantly increase the brightness. Improve up-conversion luminous efficiency.
  • the present invention measures the luminous brightness or luminous intensity of the sample to evaluate its luminous efficiency.
  • the specific method for measuring the luminous brightness is: place the sample in a black disc with a diameter of 10 mm and a depth of 5 mm, and flatten it with a glass plate to eliminate the influence of scattering.
  • the excitation light source is a semiconductor laser.
  • the brightness of the sample is measured with a luminance meter after irradiating the sample with the laser.
  • the commercial ⁇ -NaYF 4 Yb, Er (green), ⁇ -NaYF 4 : Yb, Tm (blue), Y 2 O 3 : Yb, Er (red) with the highest up-conversion luminous efficiency were used as reference samples during the test. .
  • the method of measuring the luminescence intensity by a spectrometer is used for comparison, and all test conditions are kept the same in a group of examples.
  • Example 1 Using Y2O3 (99.99%), Er2O3 ( 99.99%) as starting materials. According to the chemical formula ratio Y 1.9 S 3 :Er 0.01 , the raw materials were weighed, fully ground for 30 minutes, placed in a quartz tube, and then placed in a resistance furnace. Bring CS 2 bubbles with Ar gas, or directly use H 2 S gas containing Ar carrier gas, then heat the sample to 1050 °C at a speed of 10 °C/min, keep it for 2 hours, and then cool it to room temperature. After grinding obtain the target product. A laser of 1500 nm was used as the excitation source, and compared with Comparative Example 1, the performance indicators are shown in the following table.
  • Examples 2-17 can be obtained.
  • the excitation wavelengths used are in the range of 1450-1600nm, 920-1150nm, 780-860nm. These three excitation wavelengths can be used individually or simultaneously, and the effect is similar to that of using a 1500nm excitation light source.
  • the choice of excitation light source wavelength depends on the application conditions and the laser wavelengths available in batches on the market.
  • infrared light in the 1450–1600 nm range is an eye-safe wavelength and has the highest brightness, which is particularly beneficial for applications.
  • adding a small amount of co-solvent to the raw material such as 0-20wt% of NH 4 Cl, NH 4 F, MgF 2 , CaF 2 , SrF 2 , BaF 2 , etc., can further improve the luminous brightness by 5- 28%, when used in combination, the performance is even better.
  • the physical properties of the material can also be changed by co-doping with other RE ions in combination.
  • the addition of Ho, Tm or Pr can increase the red luminescence component in the luminescence spectrum, increase the color purity of red luminescence by 2-15 times, and its luminescence brightness is 110-180% of that of Comparative Example 3 under the same excitation conditions, At the same time, the color purity of its red emission is 200-300% of that of Comparative Example 3.
  • the addition of Yb, Ce, Sm, Tb, Eu or Nd can significantly increase the thermal performance and change the luminescence color, and the temperature rise of the sample can be more than doubled at the same power density.
  • Y2O3 99.99%
  • Er2O3 99.99%
  • Na2CO3 99.99%) were used as starting materials.
  • the raw materials were weighed according to the chemical formula ratio NaY 0.9 S 2 :Er 0.1 , fully ground for 30 minutes, placed in a quartz tube, and then placed in a resistance furnace.
  • the CS 2 bubbles were brought in with Ar gas, and then the sample was heated to 1050 °C at a speed of 10 °C/min, kept for 2 hours, and then cooled to room temperature, and the target product was obtained after grinding.
  • Fig. 1 is the up-conversion luminescence spectrum of NaY 0.9 S 2 :Er 0.1 sample under excitation at 1550 nm. It can be seen that the sample NaY 0.9 S 2 :Er 0.1 exhibits green emission at 512-578 nm and red emission at 640-698 nm, corresponding to Er 3+ at energy level 4 S 3/2 ⁇ 4 I 15/2 , 2 Transitions of H 11/2 ⁇ 4 I 15/2 and 4 F 9/2 ⁇ 4 I 15/2 .
  • Examples 38-47 can be obtained.
  • Examples 48-59 can be obtained.
  • Example 60 NaY 0.9 S 2 :Er 0.1 @NaY 0.8 S 2 :Yb 0.1 ,Er 0.1
  • Figure 3 is the up-conversion luminescence spectrum of NaY 0.9 S 2 :Er 0.1@NaY 0.8 S 2 :Yb 0.1 ,Er 0.1 sample under excitation at 1550nm.
  • the spectrum consists of two groups of bands in the visible part, the green emission in the 512-578nm band and the red emission in the 640-698nm band, corresponding to 4 S 3/2 ⁇ 4 I 15/2 , 2 H 11 of Er 3+ ions, respectively /2 ⁇ 4 I 15/2 and 4 F 9/2 ⁇ 4 I 15/2 transition.
  • NaY 0.9 S 2 :Er 0.1 @NaY 0.8 S 2 :Yb 0.1 ,Er 0.1 are similar in peak shape, but the relative emission intensities of the red and green light bands are very different. Big difference, NaY 0.9 S 2 :Er 0.1 shows strong green light and weak red light, while NaY 0.9 S 2 :Er 0.1 @NaY 0.8 S 2 :Yb 0.1 ,Er 0.1 shows strong red light and weak green light. Under the same excitation conditions, the thermal capacity of this sample is 3 times that of Example 18, so it can be applied to occasions where both light and thermal effects are required.
  • Example 61 NaGd 0.9 S 2 :Er 0.1 @NaGd 0.78 S 2 :Er 0.18 ,Ho 0.05
  • a certain mass of Y 2 O 3 (99.99%) and Er 2 O 3 (99.99%) were weighed according to the stoichiometric ratio of NaGd 0.9 S 2 : Er 0.1 , and an appropriate amount of water and 6 mol/L hydrochloric acid were added and stirred to form rare earth chlorides.
  • Take an appropriate amount of oleic acid and octadecene weigh a certain amount of sulfur powder and sodium oleate, mix with the above rare earth chloride, and remove water and other low-boiling impurities in a vacuum environment at 120°C. The solution was then rapidly heated to 300°C and held for 1 hour.
  • the samples were washed with water and ethanol for several times and then dried to obtain NaGd 0.9 S 2 :Er 0.1 samples. Weigh Y 2 O 3 (99.99%), Er 2 O 3 (99.99%) and Ho 2 O 3 (99.99%) to prepare rare earth chloride, repeat the above steps and add the prepared NaY 0.9 S 2 :Er 0.1 Into the mixture, the core-shell structure NaGd 0.9 S 2 :Er 0.1 @NaGd 0.78 S 2 :Er 0.18 ,Ho 0.05 sample was formed by incubating at 300°C for 1 hour.
  • Figure 4 is the emission spectrum of NaGd 0.9 S 2 :Er 0.1 @NaGd 0.78 S 2 :Er 0.18 ,Ho 0.05 sample under the excitation of 980nm laser.
  • the emission spectrum in Figure 3 consists of 2 groups of bands: 1) The red emission band located in the 646-666 nm band: there are 3 emission peaks located at 650, 654 and 661 nm, corresponding to the 5 F of Ho 3+ ions 5 ⁇ 5 I 8 transition. 2) Green luminescence band located in the 535-565 nm band: there are two emission peaks located at 543 and 548 nm, corresponding to 5 F 4 ⁇ 5 I 8 and 5 S 2 ⁇ 5 I 8 transitions of Ho 3+ ions.
  • Example 62 NaY 0.8 S 2 : Er 0.10 , Nd 0.10 @NaY 0.89 S 2 : Yb 0.08 , Nd 0.01 , Tm 0.02
  • the samples were washed with water and ethanol for several times and then dried to obtain NaY 0.8 S 2 :Er 0.10 , Nd 0.10 samples.
  • Figure 5 is the emission spectrum of NaY 0.8 S 2 :Er 0.10 ,Nd 0.10@NaY 0.89 S 2 :Yb 0.08 ,Nd 0.01 ,Tm 0.02 sample excited by 980nm laser.
  • the spectrum in the figure consists of 3 groups of bands: 1) the blue luminescence band located in the 460-499 nm band, the peak is located at 476 nm, which belongs to the 1 G 4 ⁇ 3 H 6 transition of Tm 3+ ; 2) is located at 639-654 nm
  • the red light-emitting band in the wavelength band, its peak is located at 650nm, which belongs to the 1 G 4 ⁇ 3 F 4 transition of Tm 3+ ions; 3)
  • the red light-emitting band in the 670-726 nm band, its peak is located at 698 nm, which belongs to Tm 3 + 3F3 ⁇ 3H6 transition of the ion.
  • the blue light emission band is obviously stronger than the two red light emission bands, so NaY 0.8 S 2 :Er 0.10 ,Nd 0.10@NaY 0.89 S 2 :Yb 0.08 ,Nd 0.01 ,Tm 0.02 samples showed bright Blue glow.
  • Example 63 NaY 0.9 S 2 : Er 0.10 @NaY 0.9 S 2 : Yb 0.08 , Nd 0.02
  • the upconversion luminescence spectra of NaY 0.9 S 2 :Er 0.10 @NaY 0.9 S 2 :Yb 0.08 ,Nd 0.02 samples consist of three groups of bands, the green emission in the 510-570 nm band, the red emission in the 640-700 nm band and the 710-
  • the infrared emission at 900 nm corresponds to the transitions of 4 S 3/2 ⁇ 4 I 15/2 , 2 H 11/2 ⁇ 4 I 15/2 and 4 F 9/2 ⁇ 4 I 15/2 of Er 3+ ions, respectively, and 4 F 7/2 / 4 F 5/2 / 4 F 3/2 ⁇ 4 I 9/2 transition of Nd 3+ ions.
  • the NaY 0.9 S 2 :Er 0.10@NaY 0.9 S 2 :Yb 0.08 ,Nd 0.02 sample has a significantly higher heating capacity.
  • Example 64 NaY 0.9 S 2 : Er 0.10 @NaY 0.9 S 2 : Yb 0.08 , Sm 0.02
  • the upconversion luminescence spectrum of NaY 0.9 S 2 :Er 0.10 @NaY 0.9 S 2 :Yb 0.08 ,Sm 0.02 sample consists of three groups of bands, green emission at 550-580nm, red at 580-630nm and 630-675nm emission, corresponding to 4 G 5/2 ⁇ 6 H 5/2 , 4 G 5/2 ⁇ 6 H 7/2 , 4 G 5/2 ⁇ 6 H 9/2 transitions of Sm 3+ ions, respectively.
  • NaY 0.9 S 2 :Er 0.1 sample NaY 0.9 S 2 :Er 0.10@NaY 0.9 S 2 :Yb 0.08 ,Sm 0.02 sample can generate a lot of heat.
  • Example 65 NaY 0.9 S 2 :Er 0.10 @NaY 0.9 S 2 :Eu 0.02
  • the samples were washed with water and ethanol several times and then dried to obtain NaY 0.9 S 2 :Er 0.10 samples. Weigh Y 2 O 3 (99.99%), Yb 2 O 3 (99.99%) and Eu 2 O 3 (99.99%) to prepare rare earth chloride, repeat the above steps and add the prepared NaY 0.9 S 2 :Er 0.10 Into the mixture, the core-shell structure NaY 0.9 S 2 :Er 0.10@NaY 0.9 S 2 :Yb 0.08 ,Eu 0.02 sample was formed at 300°C for 1 hour.
  • the up-conversion luminescence spectrum of NaY 0.9 S 2 :Er 0.10 @NaY 0.9 S 2 :Yb 0.08 ,Eu 0.02 sample consists of three groups of bands, green emission at 510-580nm, red at 580-630nm and 630-675nm emission.
  • the red luminescence of the NaY 0.9 S 2 :Er 0.10@NaY 0.9 S 2 :Yb 0.08 ,Eu 0.02 sample was significantly enhanced.

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Abstract

本发明涉及一种多元硫化物上转换发光材料，属于光功能新材料领域。该材料以多元硫化物为基质，稀土离子为激活剂，材料组成通式为：mA 2S·nBS·kC2-xS3:Dx。本发明提供的上转换发光材料料在750-1650nm近红外光激发下可发射紫外、蓝、蓝绿、绿色、红色及近红外光。本发明提供的上转换发光材料，由于是以声子能和对称性较低的多元硫化物作为基质材料，通过优选稀土离子掺杂入基质材料作为发光中心，具有比工业NaYF4:Yb,Er材料更高的上转换发光效率和安全性，应用范围更广。

Description

一种多元硫化物上转换发光材料 技术领域
本发明属于光功能新材料领域，尤其涉及一种多元硫化物上转换发光材料。
背景技术
发光可以分为光致发光，电致发光，阴极射线发光、放射性发光、化学发光、生物发光等多个种类，其中光致发光又可以分为常规光致发光[以下简称常规发光]和上转换发光。常规发光的入射激发光波长小于发射光波长，其特点是发光效率高，量子效率可以达到甚至超过100％。相对于常规发光，上转换发光能够将红外光转化为紫外或可见光，其独特的发光特性可应用于生物医学、太阳能电池、红外防伪、激光显示等领域，从而受到广泛关注。实现上转换发光需要通过激活剂或激活剂和敏化剂之间的能量传递过程，要求发光离子中间能级有较长的寿命，目前能够在室温下实现上转换发光的元素种类不多，其中大多数为镧系元素。与其他镧系元素相比，Yb离子的吸收截面(11.7×10 -21cm 2)较大且能级结构简单，并且易于实现高浓度掺杂，采用980nm红外光作为激发源时，Yb离子作为敏化剂能够显著增强材料的上转换发光[(1)F.Auzel,Upconversion and anti–Stokes processes with f and d ions in solids,Chem.Rev.,2004,104,139–174]。由于上转换发光的入射激发光波长大于发射光波长，因此很难实现高发光效率——截至目前，上转换发光材料的最高量子效率仍未达到10％，绝大多数只有1％或更低。
要进一步提高上转换发光材料的发光效率，除了选择具有高效率发射能级的发光离子、敏化离子和合适的激发通道以外，还需要降低材料的无辐射跃迁几率，而选择合适的基质材料是另一种提高上转换发光效率最直接的方法。基质晶格的选择不仅可以决定掺杂离子之间的相对空间位置，而且还会影响掺杂离子周围的阴离子种类和配位数。基质晶格与掺杂离子之间的相互作用对材料的上转换发光特性及发光效率有较大影响。基质材料的选择标准主要有两条：(1)选择声子能小的基质材料，可降低多声子无辐射弛豫，延长激发态寿命，进而提高上转换发光效率；(2)选择晶体结构对称性低的基质材料，根据镧系元素电子跃迁的宇称选择定则，其上转换发光的f‐f电偶极跃迁是禁戒的，而在晶体对称性较低的基质中，由于晶体场奇次项的作用，使4f n组态的电偶极跃迁成为可能，从而能够提高上转换发光和发光效率。
根据上述标准，人们筛选出了上转换发光效率高的基质材料：
(1)稀土卤化物：氟化物、氯化物、溴化物、碘化物等具有极低的声子能，可以获得高效的上转换发光。氯化物、溴化物、碘化物的化学性质不稳定，易潮解，且制备流程复杂，限制了它们的实际应用。氟化物在一定程度上解决了易潮解的问题，又保留了声子能较低的 特点，是目前使用最多、研究最广泛的基质。其中，β-NaYF 4:Yb,Er和β-NaYF 4:Yb,Tm被认为是目前发光效率最高的上转换发光材料[(2)K.W.
Figure PCTCN2020126670-appb-000001
D.Biner,G.Frei,H.U.Güdel,M.P.Hehlen,S.R.Lüthi,Hexagonal Sodium Yttrium Fluoride Based Green and Blue Emitting Upconversion Phosphors,Chem.Mater.,2004,16,1244]。但氟化物所需要的制备环境也较为苛刻，并且在生产过程中会腐蚀设备和造成环境污染，。
(2)稀土硫氧化物：硫氧化物不仅有较低的声子能，还具有化学稳定性和热稳定性好(熔点高：2000～2200℃)，抗氧化性强，抗辐射性高、毒性低、不溶于水等优点。在Y 2O 2S基质中已经获得高效率的上转换发光，如980nm激发的Y 2O 2S:Yb,Ho的上转换发光亮度可能是已知材料中最高的[(3)Luo X X,Cao W H,Upconversion luminescence of holmium and ytterbium co–doped yttrium oxysulfide phosphor,Mater.Lett.,2007,61(17):3696–3700]。但稀土硫氧化物的共价键属性高，制备工艺复杂，生产困难。
(3)氧化物：氧化物声子能量较高，大部分无毒且化学稳定性好，制备工艺简单，对于生产环境的要求较低。此外，在氧化物单晶中激活离子荧光谱线较窄，增益较高，且硬度、机械强度和热导性能优于玻璃，因此物化性能稳定的氧化物单晶常用作上转换激光材料的基质。Y 2O 3/Gd 2O 3、Bi 2O 3、磷酸盐等稀土复合氧化物获得了较好的上转换发光特性，但是上转换发光效率在上述三种材料里仍然最低。
硫化物是一种优秀的常规发光材料基质，已经在光致发光、电致发光、阴极射线发光、放射性发光等领域得到广泛应用。过渡金属硫化物如ZnS:Cu和ZnS:Ag是优秀的常规光致发光、电致发光、阴极射线发光和放射性发光材料。碱土金属硫化物如CaS可应用于长余辉材料[(4)胡学芳，中国发明专利申请，稀土铕激活的硫化钙或碱土硫化物红色发光材料制备方法，CN1916109A]和电子俘获材料[(5)张家骅,王英,张霞等,中国发明专利,一种基于硫化物的三掺杂电子俘获材料及其制备方法,ZL201210483728.5]。稀土硫化物则是一种优秀的高档颜料，因此很难应用于发光[(6)袁海滨,张剑辉,余瑞金等,Synthesis of rare earth sulfides and their UV-vis absorption spectra,J.Rare Earths,2009,27,308]。碱土三元硫化物具有合适的带隙，是一类优秀的常规发光基质材料，能够用于LED照明灯领域[(7)周明杰,王荣郝,中国发明专利申请，一种碱土-稀土三元硫化物发光材料及其制备方法，CN104119916A.(8)郝传鑫，熊永强，中国发明专利，掺杂金属纳米粒子的三元硫化物发光材料及制备方法，ZL201310089574.6.(9)廉世勋；田科明；尹笃林；李承志；朱爱玲；刘利民；曾立华；张华京中国发明专利申请,铒激活的碱土稀土硫化物红色发光材料CN1919968A.(10)Yuta M M,White W B.Photolumineseenee of sulfide phosphors with the MB 2S 4composition.J.Electrochem.Soc.1992,139,2347-2352.(11)廉世勋,田科明,尹笃林等,一类新的红色荧光粉 MY 2S 4:Er 3+(M＝Sr 2+,Ba 2+)的合成与表征,高等学校化学学报.2007,28,1024-1026.(12)赵君风,陈茜,荣春英等,白光LED用黄色荧光粉Ba(Y 1-0.5x-yAl y) 2S 4:xHo 3+的合成和发光特性.无机化学学报.2011,27,1363-1367.(13)徐剑,张剑辉,张新民等,Ga 2S 3:Eu 2+和SrGa 2+xS 4+y:Eu 2+系列荧光粉的发光性能研究,中国稀土学报,2003,21,635-638.(14)Tagiev BG,Abushov SA,Tagiev OB,Photoluminescence of CaGa 2S 4:Pr Polycrystals,Optics and Spectroscopy,2016,120,403-407.(15)Tagiyev BG,Tagiyev OB,Mammadov AI,Structural and luminescence properties of Ca xBa 1-xGa 2S 4:Eu 2+chalcogenide semiconductor solid solutions,Physica B-Condensed Matter,2015,478,58-62.(16)Guo CF,Zhang CX,Lu YH等,Luminescent properties of Eu 2+and Ho 3+co-doped CaGa 2S 4phosphor,Physica Status Solidi A,2004,201,1588-1593.(17)郭峰,张纯祥,吕玉华等,Ho 3+对CaGa 2S 4:Eu 2+发光性能的影响,中国稀土学报,2004,22,591-595.]、光纤放大器[(18)S.D.Setzler,P.G.Schunemann,T.M.Pollak,Calcium Gallium sulphide(CaGa 2S 4)as a high gain erbium host,US6714578 B2,2002]、电致发光[(19)Mitsuhiro Kawanishi,Noboru Miura,Hironaga Matsumoto等,New red-emitting CaY 2S 4:Eu thin-film electroluminescent devices,Jap.J.Appl.Phys.Part 2-Letters,2003,42,(1A-B),L42-L43.(20)Mamoru Kitaura,Senku Tanaka,Minoru Itoh等,Excitation process of Ce 3+and Eu 2+ions doped in SrGa 2S 4crystals under the condition of multiplication of electronic excitations,J.Lumin.,2016,172,243-248]或激光[(21)Kim MY,Baik SJ,Kim WT等,Optical properties of undoped and Co 2+-,Ho 3+-,Er 3+-,and Tm 3+-doped CaGa 2S 4,CaGa 2Se 4,CaIn 2S 4,and CaIn 2Se 4single crystals,J.Korean Phys.Soc.,2003,43,128-134.(22)Nostrand MC,Page RH,Payne SA等.Room-temperature laser action at 4.3-4.4μm in CaGa 2S 4:Dy 3+,Optics Letters,1999,24,1215-1217]。
稀土多元硫化物具有和氯化物相当的低声子能，且有很好的化学稳定性。如NaYS 2的最高声子能为279cm -1，低于目前上转换发光效率最高的β-NaYF 4(418cm -1)的声子能，且属于低对称性晶系，符合作为理想上转换基质材料的条件，以其为基质的上转换发光材料应具有更高的上转换发光效率。长期以来，稀土硫化物一直被用于高档颜料，而且在常用Yb离子敏化然而，有关硫化物基质上转换发光的报道非常少。
Higuchi等人首先报道了800和980nm激发下Er 3+离子在Ga 2S 3–GeS 2–La 2S 3玻璃的上转换发光，但其绿色上转换发光量子效率小于氟化物玻璃的一半[(23)H.Higuchi,M.Takahashi,Y.Kawamoto,Optical transitions and frequency upconversion emission of Er 3+ions in Ga 2S 3–GeS 2–La 2S 3glasses,J.Appl.Phys.,1998,83,19]。另外，Pascal等人的研究表明，在纯硫化物中，S 2-→Yb 3+的LMCT吸收边低于20000cm -1，与Er 3+的 2H 11/2、 4S 3/2和 4F 7/2能级重叠，使980nm激发的Yb 3+和Er 3+共掺杂的NaYS 2上转换发光材料发光强度下降了两个数量级。 因此，人们普遍认为纯稀土硫化物不是传统Yb 3+敏化上转换发光的有效基质材料[(24)Pascal Gerner,Hans U.Güdel,Absorption and upconversion light emission properties of Er 3+and Yb 3+/Er 3+codoped NaYS 2,Chem.Phys.Lett.,413(2005)105–109.(25)张继森，张立国，任建岳等,室温下Yb 3+和Er 3+掺杂的NaYS 2粉末材料的Stocks和Anti-Stocks发光,发光学报,2013,34(7),824-828]。
发明内容
针对以上现有技术的不足，本发明提供一种高发光效率的多元硫化物上转换发光材料，通过多波长激发，实现红、绿、蓝三基色上转换发光及紫外、近红外上转换发光。该材料具有上转换发光亮度高、化学性质稳定、且生物相容性好等优点。
本发明的技术方案如下：
一种多元硫化物上转换发光材料，以多元硫化物为基质，稀土离子为激活剂，其组成通式为：mA 2S·nBS·kC 2-xS 3:D x，其中A为Li、Na、K、Rb、Cs中的一种或两种以上，B为Be、Mg、Sr、Ba、Zn、Cd、Cs中的一种或两种以上；C为La、Gd、Lu、Y、Sc、Al、Ga、Bi中的一种或两种以上；D为Ho、Er、Tm、Pr中的一种或两种以上，且在D中共掺杂Mo、W、Ce、Sm、Tb、Yb、Eu或Nd；m，n，k，x为摩尔分数，m＝0-2，n＝0-6，k＝0.3-2.5，x＝0.0001-2；该材料在750-1650nm近红外光激发下可发射紫外、蓝、蓝绿、绿色、红色及近红外光。
(1)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，当m＝0-0.2，n＝0-0.1时，优选的k值为0.9-1.1。
(2)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，当n＝0-0.1时，优选的m值为0.8-1.2，同时，优选的k值为0.4-0.6。
(3)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，当m＝0-0.2时，优选的n值为0.8-1.2，同时优选的k值为0.8-1.2。
组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，当m＝0-0.2时，优选的n值为4.5-5.5，同时优选的k值为1.8-2.2。
(4)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，D含有Er时，优选的x值为0.05-2，激发波长范围为1450-1600nm，920-1150nm，780-860nm，可以单独或同时采用这三个激发波长。
(5)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，D含有Ho时，优化的x值为0.02-2，采用的激发波长范围为1100-1190nm。
(6)组成通式为mA 2S·nBS·kC 2-xS 3:D x的上转换发光材料，D含有Tm时，优化的x值为0.01-2，采用的激发波长范围为1180-1260nm和760-850nm，可以单独或同时采用这两个 激发波长。
本发明的有益效果是：
本发明的以mA 2S·nBS·kC 2-xS 3:D x为化学通式的多元硫化物具有很低的声子能，且属于低对称性的晶系，是一类理想的上转换发光基质材料。在优选合适浓度的离子掺杂情况下，由于掺杂离子之间间距远超常规发光材料，能够实现高浓度掺杂及降低无辐射弛豫，其上转换发光效率超过传统NaYF 4:Yb,Er，且可同时实现多波长激发。特别是1450–1600nm区间范围的红外光是人眼安全波长，采用这个波段的光源为激发源时，本发明还可以减轻应用场合的防护等级或不使用防护设备，拓展应用范围，而且亮度最高，这对应用特别有利。
附图说明
图1是本发明实施例18的NaY 0.9S 2:Er 0.1样品在1550nm激发下的发射光谱。
图2是本发明实施例18的NaY 0.9S 2:Er 0.1和NaYF 4:Yb,Er的数据图；其中(a)为亮度数据对比图，(b)为亮度随980和1550nm激光器激发功率的变化曲线图；(c)为NaY 0.9S 2:Er 0.1在980和1550nm激光器激发下的发光照片。
图3是本发明实施例60的NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1样品在980nm激发下的发射光谱。
图4是本发明实施例61的NaGd 0.9S 2:Er 0.1@NaGd 0.78S 2:Er 0.18,Ho 0.05样品在980nm激发下的发射光谱。
图5是本发明实施例62的NaY 0.8S 2:Er 0.10,Nd 0.10@NaY 0.89S 2:Yb 0.08,Nd 0.01,Tm 0.02样品在980nm激发下的发射光谱。
具体实施方式
以下通过具体实施例来说明本发明的多元硫化物的不同组成及其发光性能。
对比实施例1：商业β-NaYF 4:Yb,Er绿色上转换发光材料。
对比实施例2：商业β-NaYF 4:Yb,Tm蓝色上转换发光材料。
对比实施例3：商业Y 2O 3:Yb,Er红色上转换发光材料。
本发明的样品采用固相反应法制备，按照所组成的元素的摩尔比秤取原料，原料可以是技术方案中所提到的元素的氧化物、碳酸盐、草酸盐、硝酸盐、醋酸盐、硫酸盐。采用干混法，研细并混合均匀，装入坩埚，放入高温炉中，在硫化气氛中(如H 2S、CS 2)于900-1400℃煅烧1-50h。煅烧时间根据物料量来调节。为了提高亮度，可在原料中加入少量助溶剂，如0-20wt％的AF和/或BF 2，包括NH 4Cl、NH 4F、MgF 2、CaF 2、SrF 2、BaF 2等，可以显著提高上转换发光效率。
本发明对样品的发光亮度或发光强度进行测量以评价其发光效率。发光亮度的测量具体 方法是：将样品置于直径10mm，深5mm的黑色圆盘中，用玻璃片压平，以消除散射造成的影响。激发光源为半导体激光器，对于可见光样品，将激光器照射样品后用亮度计测量样品亮度。测试时采用目前上转换发光效率最高的商业β-NaYF 4:Yb,Er(绿色)、β-NaYF 4:Yb,Tm(蓝色)、Y 2O 3:Yb,Er(红色)为参考样品。对于不可见样品，则采用光谱仪测量发光强度的方法进行对比，在一组实施例中所有测试条件保持一致。
实施例1：使用Y 2O 3(99.99％)，Er 2O 3(99.99％)作为初始原料。根据化学式配比Y 1.9S 3:Er 0.01称取原料，充分研磨30分钟，放置于石英管中，再将石英管置于电阻炉内。以Ar气带入CS 2气泡，或直接采用含Ar载气的H 2S气体，然后以10℃/min的速度将样品加热到1050℃，保温2个小时，然后冷却到室温，经研磨后得到目标产物。采用1500nm的激光器为激发源，与对比实施例1进行对比，其性能指标见下表。
采用相似的方法，可以得到实施例2-实施例17。
序号 m n k x 相对亮度
对比实施例1         100
实施例1 0 0 C＝Y，k＝1 0.01 89
实施例2 0 0 C＝Y，k＝0.9 0.05 127
实施例3 0 0 C＝Y，k＝1 0.10 133
实施例4 0 0 C＝Y，k＝1.1 0.15 136
实施例5 0 0 C＝Y，k＝1 0.20 138
实施例6 0 0 C＝Y，k＝1 0.40 102
实施例7 A＝Li，m＝0.05 0 C＝Y，k＝1 0.20 165
实施例8 A＝Na，m＝0.10 0 C＝Y，k＝1 0.20 157
实施例9 A＝K，m＝0.20 0 C＝Y，k＝1 0.20 153
实施例10 0 B＝Mg，n＝0.02 C＝Y，k＝1.1 0.20 146
实施例11 0 B＝Ca，n＝0.04 C＝Y，k＝1 0.20 144
实施例12 0 B＝Sr，n＝0.08 C＝Y，k＝1 0.20 141
实施例13 A＝Li，m＝0.05 B＝Mg，n＝0.02 C＝Y，k＝0.9 0.20 169
实施例14 A＝Na，m＝0.05 B＝Mg，n＝0.02 C＝Gd，k＝1 0.20 147
实施例15 A＝K，m＝0.05 B＝Mg，n＝0.02 C＝Lu，k＝1 0.20 172
实施例16 A＝Li，m＝0.05 B＝Mg，n＝0.02 C＝La，k＝1 0.20 153
实施例17 A＝Li，m＝0.05 B＝Mg，n＝0.02 C＝Sc，k＝1 0.20 148
采用实施例1-17相似的方法，还可以得到在实施例1-17中未列举的其他参数对发光颜色、发光强度和热性能的影响。当A＝Rb或Cs时，与A＝K有相似的结果，但Rb和Cs价格较贵。当A组合使用时，性能会更佳，如A＝Li和K的组合，可使产物粒径更均匀，在保持发光强度不变的情况下，还可以适当降低反应温度50-100℃。当B＝Be、Ba或Cd时，与B＝Ca有相似的结果，但考虑到环保要求，含这些元素的产品在应用时可能会遇到困难。当B＝Zn时，要控制载气气氛的流量和还原性。当C＝Al、Ga或Bi时，通常用于替换不超过30％的La、Gd、Lu、Y或Sc，这时可提高发光强度约5-13％。当D＝Er时，采用的激发波长范围为 1450–1600nm，920-1150nm，780-860nm，可以单独或同时采用这三个激发波长，其效果与采用1500nm激发光源相似。激发光源波长的选择取决于应用条件和市场可批量提供的激光波长。对于发光亮度来说，使用1450–1600nm波长范围的红外光>使用920-1150nm波长范围的红外光>使用780-860nm波长范围的红外光。特别是1450–1600nm区间范围的红外光是人眼安全波长，而且亮度最高，这对应用特别有利。在上述实施例中，在原料中加入少量助溶剂，如0-20wt％的NH 4Cl、NH 4F、MgF 2、CaF 2、SrF 2、BaF 2等，还可以使发光亮度进一步提高5-28％，组合使用，性能更加。
当RE＝Er时，通过与其他RE离子的组合共掺杂，还可以改变材料的物理性能，如发光颜色，吸热性能。如额外添加少量(x＝0.01-0.3)的Mo和W，可显著降低发光光谱中的红色发光成分，可使绿色发光的色纯度提高2-10倍。而添加Ho、Tm或Pr，可使发光光谱中的红色发光成分增加，可使红色发光的色纯度提高2-15倍，其发光亮度是相同激发条件下对比实施例3的110-180％，同时其红色发光的色纯度是对比实施例3的200-300％。而添加Yb、Ce、Sm、Tb、Eu或Nd可使热性能显著增加并改变发光颜色，相同功率密度时可使样品的温升提高一倍以上。
当RE＝Ho时，激发波长可更换到1100–1190nm，其绿色发光的色纯度比RE＝Er提高150％以上；当RE＝Tm时，激发波长可更换到1180–1260nm和760-850nm，其蓝色发光的亮度是相同激发条件下对比实施例2的150-300％，从而拓宽应用范围。进一步与其他RE组合，可得到全色发光，或调节色纯度。
当m，n，k，x值超出实施例1-17范围时，如m＝0.2-2，n＝0.1-6，k＝0.3-0.9，k＝1.1-2.5，x＝0.2-2，样品同样有不错的发光效果，但发光强度比相同条件下的实施例1-17有5-53％的下降。
实施例18：NaY 0.9S 2:Er 0.1
使用Y 2O 3(99.99％)，Er 2O 3(99.99％)，Na 2CO 3(99.99％)作为初始原料。根据化学式配比NaY 0.9S 2:Er 0.1称取原料，充分研磨30分钟，放置于石英管中，再将石英管置于电阻炉内。以Ar气带入CS 2气泡，然后以10℃/min的速度将样品加热到1050℃，保温2个小时，然后冷却到室温，经研磨后得到目标产物。
图1为在1550nm激发下，NaY 0.9S 2:Er 0.1样品的上转换发光光谱。可以看出，样品NaY 0.9S 2:Er 0.1呈现位于512-578nm波段的绿色发射和640-698nm的红色发射，分别对应Er 3+在能级 4S 3/2→ 4I 15/2, 2H 11/2→ 4I 15/2和 4F 9/2→ 4I 15/2的跃迁。
为了进一步评价NaY 0.9S 2:Er 0.1的上转换发光性能，比较了在相同功率的980和1550nm激发下，相对于对比实施例1，NaY 0.9S 2:Er 0.1样品的发光亮度数据(图2)。在1550nm激发 下，NaY 0.9S 2:Er 0.1具有很高的上转换发光效率，其亮度为980nm激发下的～60倍，甚至是商业NaYF 4:Yb,Er在980nm激发下的亮度的2倍以上。
采用相似的方法，可以得到实施例19-实施例37。
序号 m n k x 相对亮度
对比实施例1         100
实施例19 A＝0.8Li 0 C＝Y，k＝0.4 0.01 155
实施例20 A＝0.8Na 0 C＝Y，k＝0.4 0.05 172
实施例21 A＝0.8K 0 C＝Y，k＝0.4 0.10 225
实施例22 A＝0.4Na，0.4K 0 C＝Y，k＝0.4 0.50 210
实施例23 A＝0.1Li，0.7Na 0 C＝Y，k＝0.4 1.00 183
实施例24 A＝0.8Na 0 C＝Y，k＝0.4 2.00 160
实施例25 A＝0.8Na 0 C＝Y，k＝0.5 0.10 262
实施例26 A＝0.8Na 0 C＝Y，k＝0.6 0.10 215
实施例27 A＝1.0Na 0 C＝Y，k＝0.4 0.10 245
实施例28 A＝1.0Na 0 C＝Y，k＝0.5 0.10 289
实施例29 A＝1.0Na 0 C＝Y，k＝0.6 0.10 230
实施例30 A＝1.2Na 0 C＝Y，k＝0.6 0.10 196
实施例31 A＝0.8Na B＝Ca，0.01 C＝Y，k＝0.4 0.50 272
实施例32 A＝0.8Na B＝Mg，0.05 C＝Y，k＝0.5 0.50 277
实施例33 A＝0.8Na B＝Sr，0.1 C＝Y，k＝0.6 0.50 251
实施例34 A＝1.0Na B＝Ca，0.1 C＝Y，k＝0.4 0.50 295
实施例35 A＝1.0Na B＝Ca，0.1 C＝La，k＝0.4 0.50 295
实施例36 A＝1.0Na B＝Ca，0.1 C＝Gd，k＝0.5 0.50 299
实施例37 A＝1.0Na B＝Ca，0.1 C＝Lu，k＝0.6 0.50 258
采用实施例19-37相似的方法，还可以得到在实施例19-37中未列举的其他参数对发光颜色、发光强度和热性能的影响。其效果与实施例1-17后面列举的例子相似，但发光强度比
实施例1-17后面列举的提高12-35％。
采用实施例19-37相似的方法，可以得到实施例38-实施例47。
序号 m n k x 相对亮度
对比实施例1         100
实施例38 0 B＝0.8Ca C＝Y，k＝0.8 0.01 105
实施例39 0 B＝0.7Ca，0.1Mg C＝Y，k＝1.0 0.05 132
实施例40 0 B＝0.8Sr C＝Y，k＝1.0 0.10 169
实施例41 0 B＝1.0Ca C＝Y，k＝1.2 0.50 155
实施例42 0 B＝1.2Ca C＝Y，k＝1.0 1.00 118
实施例43 0 B＝0.8Ca C＝Y，k＝1.0 2.00 105
实施例44 A＝0.05Na B＝1.0Ca C＝Y，k＝1.05 0.20 183
实施例45 A＝0.1Li B＝1.0Sr C＝La，k＝1.0 0.20 207
实施例46 A＝0.2K B＝1.0Ca C＝Gd，k＝1.0 0.20 214
实施例47 A＝＝0.02Na，0.03K B＝1.0Ca C＝Lu，k＝1.3 0.20 196
采用实施例38-47相似的方法，还可以得到在实施例38-47中未列举的其他参数对发光 颜色、发光强度和热性能的影响。其效果与实施例1-17后面列举的相似，但发光强度比实施例1-17后面列举的提高7-23％。
采用实施例38-47相似的方法，可以得到实施例48-实施例59。
序号 m n k x 相对亮度
对比实施例1         100
实施例48 0 B＝4.5Ca C＝Y，k＝1.8 0.01 132
实施例49 0 B＝5.0Sr C＝Y，k＝2.0 0.05 151
实施例50 0 B＝5.5Ba C＝Y，k＝2.2 0.10 243
实施例51 0 B＝4.5Ca C＝Y，k＝2.0 0.50 190
实施例52 0 B＝5.0Sr C＝Y，k＝2.0 1.00 214
实施例53 0 B＝5.5Ba C＝Y，k＝2.0 2.00 88
实施例54 A＝Li，m＝0.05 B＝4.5Ca C＝Y，k＝2.0 0.20 294
实施例55 A＝Na，m＝0.10 B＝5.0Sr C＝Y，k＝2.0 0.20 287
实施例56 A＝K，m＝0.20 B＝5.5Ba C＝Y，k＝2.0 0.20 276
实施例57 A＝0.02Li，0.03Na B＝0.2Mg,4.5Ca C＝La，k＝2.0 0.20 325
实施例59 0 B＝5.0Ca C＝Gd，k＝2.0 0.20 236
实施例59 0 B＝5.0Ca C＝Lu，k＝2.0 0.20 198
采用实施例48-59相似的方法，还可以得到在实施例48-59中未列举的其他参数对发光颜色、发光强度和热性能的影响。其效果与实施例1-17后面列举的相似。
实施例60：NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1
按NaY 0.9S 2:Er 0.1的化学计量比称取一定质量的Y 2O 3(99.99％)和Er 2O 3(99.99％)，加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaY 0.9S 2:Er 0.1样品。称取Y 2O 3(99.99％)，Yb 2O 3(99.99％)和Er 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.9S 2:Er 0.1加入到混合物中，在300℃下保温1个小时形成核-壳结构NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1样品。
图3为在1550nm激发下，NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1样品的上转换发光光谱。光谱在可见光部分由两组谱带组成，位于512-578nm波段的绿色发射和640-698nm波段的红色发射，分别对应Er 3+离子的 4S 3/2→ 4I 15/2, 2H 11/2→ 4I 15/2和 4F 9/2→ 4I 15/2的跃迁。与NaY 0.9S 2:Er 0.1样品相比，NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1在峰型上比较相似，但其红、绿光波段的相对发射强度有很大不同，NaY 0.9S 2:Er 0.1呈现绿光强红光弱，而NaY 0.9S 2:Er 0.1@NaY 0.8S 2:Yb 0.1,Er 0.1则是红光强绿光弱。在相同激发条件下，该样品的致热能力是实施例18的3倍，因而可以应用于同时需要光和热效应的场合。
实施例61：NaGd 0.9S 2:Er 0.1@NaGd 0.78S 2:Er 0.18,Ho 0.05
按NaGd 0.9S 2:Er 0.1的化学计量比称取一定质量的Y 2O 3(99.99％)和Er 2O 3(99.99％)，加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaGd 0.9S 2:Er 0.1样品。称取Y 2O 3(99.99％)，Er 2O 3(99.99％)和Ho 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.9S 2:Er 0.1加入到混合物中，在300℃下保温1个小时形成核-壳结构NaGd 0.9S 2:Er 0.1@NaGd 0.78S 2:Er 0.18,Ho 0.05样品。
图4为NaGd 0.9S 2:Er 0.1@NaGd 0.78S 2:Er 0.18,Ho 0.05样品在980nm激光器激发下的发射光谱。图3中的发射谱由2组谱带组成：1)位于646～666nm波段内的红色发光带：存在3个发射峰，分别位于650、654和661nm处，对应于Ho 3+离子的 5F 5→ 5I 8跃迁。2)位于535～565nm波段内的绿色发光带：存在2个发射峰，分别位于543和548nm，对应于Ho 3+离子的 5F 4→ 5I 8和 5S 2→ 5I 8跃迁。
实施例62：NaY 0.8S 2:Er 0.10,Nd 0.10@NaY 0.89S 2:Yb 0.08,Nd 0.01,Tm 0.02
按NaY 0.8S 2:Er 0.10,Nd 0.10的化学计量比称取一定质量的Y 2O 3(99.99％),Er 2O 3(99.99％)和Nd 2O 3(99.99％)加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaY 0.8S 2:Er 0.10,Nd 0.10样品。称取Y 2O 3(99.99％)，Yb 2O 3(99.99％)和Tm 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.8S 2:Er 0.10,Nd 0.10加入到混合物中，在300℃下保温1个小时形成核-壳结构NaY 0.8S 2:Er 0.10,Nd 0.10@NaY 0.89S 2:Yb 0.08,Nd 0.01,Tm 0.02样品。
图5为NaY 0.8S 2:Er 0.10,Nd 0.10@NaY 0.89S 2:Yb 0.08,Nd 0.01,Tm 0.02样品在980nm激光器激发下的发射光谱。图中光谱由3组谱带组成：1)位于460～499nm波段内的蓝色发光带，其峰值位于476nm处，属于Tm 3+的 1G 4→ 3H 6跃迁；2)位于639～654nm波段内的红色发光带，其峰值位于650nm处，属于Tm 3+离子的 1G 4→ 3F 4跃迁；3)位于670～726nm波段内的红色发光带，其峰值位于698nm处，属于Tm 3+离子的 3F 3→ 3H 6跃迁。其中，蓝光发射带要明显强于两个红光发射带，所以在肉眼观察下NaY 0.8S 2:Er 0.10,Nd 0.10@NaY 0.89S 2:Yb 0.08,Nd 0.01,Tm 0.02样品显示了明亮的蓝色发光。
实施例63：NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Nd 0.02
按NaY 0.9S 2:Er 0.10的化学计量比称取一定质量的Y 2O 3(99.99％)和Er 2O 3(99.99％)，加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温 至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaY 0.9S 2:Er 0.10样品。称取Y 2O 3(99.99％)，Yb 2O 3(99.99％)和Nd 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.9S 2:Er 0.10加入到混合物中，在300℃下保温1个小时形成核-壳结构NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Nd 0.02样品。
NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Nd 0.02样品的上转换发光光谱由三组谱带组成，位于510-570nm波段的绿色发射，640-700nm波段的红色发射和710-900nm的红外发射，分别对应Er 3+离子的 4S 3/2→ 4I 15/2, 2H 11/2→ 4I 15/2和 4F 9/2→ 4I 15/2的跃迁，及Nd 3+离子的 4F 7/2/ 4F 5/2/ 4F 3/2→ 4I 9/2跃迁。与NaY 0.9S 2:Er 0.1样品相比，NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Nd 0.02样品的致热能力明显提高。
实施例64：NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Sm 0.02
按NaY 0.9S 2:Er 0.10的化学计量比称取一定质量的Y 2O 3(99.99％)和Er 2O 3(99.99％)，加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaY 0.9S 2:Er 0.10样品。称取Y 2O 3(99.99％)，Yb 2O 3(99.99％)和Sm 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.9S 2:Er 0.10加入到混合物中，在300℃下保温1个小时形成核-壳结构NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Sm 0.02样品。
NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Sm 0.02样品的上转换发光光谱由三组谱带组成，位于550-580nm波段的绿色发射，580-630nm和630-675nm波段的红色发射，分别对应Sm 3+离子的 4G 5/2→ 6H 5/2, 4G 5/2→ 6H 7/2， 4G 5/2→ 6H 9/2跃迁。与NaY 0.9S 2:Er 0.1样品相比，NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Sm 0.02样品的可产生大量热量。
实施例65：NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Eu 0.02
按NaY 0.9S 2:Er 0.10的化学计量比称取一定质量的Y 2O 3(99.99％)和Er 2O 3(99.99％)，加入适量水和6mol/L的盐酸搅拌形成稀土氯化物。取适量油酸和十八烯，称取一定量硫粉和油酸钠，与上述稀土氯化物混合，真空环境下120℃去除水和其他低沸点杂质。随后将溶液迅速升温至300℃，保温1个小时。用水和乙醇多次洗涤样品后烘干，得到NaY 0.9S 2:Er 0.10样品。称取Y 2O 3(99.99％)，Yb 2O 3(99.99％)和Eu 2O 3(99.99％)制备形成稀土氯化物，重复上述步骤并将制得的NaY 0.9S 2:Er 0.10加入到混合物中，在300℃下保温1个小时形成核-壳结构NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Eu 0.02样品。
NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Eu 0.02样品的上转换发光光谱由三组谱带组成，位于510-580nm波段的绿色发射，580-630nm和630-675nm波段的红色发射。与NaY 0.9S 2:Er 0.1 样品相比，NaY 0.9S 2:Er 0.10@NaY 0.9S 2:Yb 0.08,Eu 0.02样品的红色发光显著增强。
采用相似方法，可以得到Pr、Tb等共掺杂的上转换发光样品。
以上所述仅是本发明的优选实施方案，本发明的保护范围并不局限于上述实施范例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (9)

  1. 一种多元硫化物上转换发光材料，其特征在于，所述的多元硫化物上转换发光材料的组成通式为：mA 2S·nBS·kC 2-xS 3:D x，其中A为Li、Na、K、Rb、Cs中的一种或两种以上，B为Be、Mg、Sr、Ba、Zn、Cd、Cs中的一种或两种以上；C为La、Gd、Lu、Y、Sc、Al、Ga、Bi中的一种或两种以上；D为Ho、Er、Tm、Pr中的一种或两种以上，且在D中共掺杂Mo、W、Ce、Sm、Tb、Yb、Eu或Nd；m，n，k，x为摩尔分数，m＝0-2，n＝0-6，k＝0.3-2.5，x＝0.0001-2。
  2. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，当m＝0-0.2，n＝0-0.1时，k值为0.9-1.1。
  3. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，当n＝0-0.1时，m值为0.8-1.2，k值为0.4-0.6。
  4. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，当m＝0-0.2，n值为0.8-1.2时，k值为0.8-1.2。
  5. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，当m＝0-0.2，n值为4.5-5.5时，k值为1.8-2.2。
  6. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，D含有Er时，x值为0.05-2，激发波长范围为1450-1600nm、920-1150nm或780-860nm，采用所述的激发波长中的一种或两种以上。
  7. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，D含有Ho时，x值为0.02-2，采用的激发波长范围为1100-1190nm。
  8. 根据权利要求1所述的一种多元硫化物上转换发光材料，其特征在于，D含有Tm时，x值为0.01-2，激发波长范围为1180-1260nm和760-850nm，单独或同时采用两个激发波长。
  9. 根据权利要求1-8所述的一种多元硫化物上转换发光材料，其特征在于，所述的材料在750-1650nm近红外光激发下发射紫外、蓝、蓝绿、绿色、红色及近红外光。
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