(19)
(11)EP 2 915 865 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
28.06.2017 Bulletin 2017/26

(21)Application number: 12887517.6

(22)Date of filing:  31.10.2012
(51)Int. Cl.: 
C09K 11/84  (2006.01)
C09K 11/87  (2006.01)
C09K 11/78  (2006.01)
C09K 11/02  (2006.01)
(86)International application number:
PCT/CN2012/083883
(87)International publication number:
WO 2014/067114 (08.05.2014 Gazette  2014/19)

(54)

SULFUR OXIDE LUMINESCENT MATERIAL AND PREPARATION METHOD THEREFOR

LUMINESZENTES SCHWEFELOXIDMATERIAL UND HERSTELLUNGSVERFAHREN DAFÜR

SUBSTANCE LUMINESCENTE À BASE D'OXYDE DE SOUFRE ET SON PROCÉDÉ DE PRÉPARATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(43)Date of publication of application:
09.09.2015 Bulletin 2015/37

(73)Proprietors:
  • Ocean's King Lighting Science&Technology Co., Ltd.
    Shenzhen, Guangdong 518054 (CN)
  • Shenzhen Ocean's King Lighting Engineering Co. Ltd.
    Guangdong 518054 (CN)

(72)Inventors:
  • ZHOU, Mingjie
    Shenzhen Guangdong 518054 (CN)
  • WANG, Rong
    Shenzhen Guangdong 518054 (CN)

(74)Representative: Johnson, Richard Alan et al
Mewburn Ellis LLP City Tower 40 Basinghall Street
London EC2V 5DE
London EC2V 5DE (GB)


(56)References cited: : 
EP-A1- 0 491 406
CN-A- 102 061 168
JP-A- 2011 066 227
US-A1- 2002 105 266
WO-A1-2011/120227
CN-A- 102 337 136
US-A- 3 989 977
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] The present invention relates to the field of luminescent material, particularly to a sulfur oxide luminescent material and preparation method therefor.

    BACKGROUND OF THE INVENTION



    [0002] In recent years, field emission devices have attracted much attention due to the advantages, such as low operating voltage, low power consumption, no deflection coil, no X-ray radiation, radiation resistance and magnetic interference resistance, etc. By exciting the luminescent material using field emission cathode ray, field emission light source of high luminance and good color rendering properties can be obtained, which can be applied to professional lighting, display, instructions, general lighting and other fields. Similar to the working principle of conventional cathode-ray tube (CRT), such field emission display lights and forms images by electron beam bombarding on red, green blue trichromatic fluorescent powders. Field emission display has potential advantages in luminance, visual angle, response time, working temperature range, power consumption and other aspects.

    [0003] Sulfur oxides have becoming important hosts for luminescent material activated by rare earth elements, due to good chemical stability, poorly soluble in water, high melting point, strong resistance to oxidation, high light-absorption efficiency and non-toxic. A sulfur oxide doped with europium Ln2O2S:Eu3+ is an important red luminescent material having excellent properties and widely used. However, low luminescent efficiency of the traditional sulfur oxide luminescent material limits its further application.

    SUMMARY OF THE INVENTION



    [0004] In view of this, it is necessary to provide a sulfur oxide luminescent material having relatively high luminescent efficiency.

    [0005] A sulfur oxide luminescent material having a general chemical formula of Ln2-xO2S:Eux3+@My, where Eu3+ is doped in Ln2-xO2S; Ln2-xO2S:Eux3+ has a porous structure, and @ is coating; Ln is selected from Y, Gd and La; M is at least one of Ag, Au, Pt, Pd and Cu nanoparticles; x is in a range of 0<x≤0.2; y is a molar ratio of M to Ln2-xO2S:Eux3+ and y is in a range of 0<y≤1×10-2.

    [0006] In one embodiment, x is in a range of 0.001<×≤0.1.

    [0007] In another embodiment, y is in a range of 1×10-5≤y≤1×10-3.

    [0008] By coating a metal nanoparticle M, the sulfur oxide luminescent material forms a core-shell structure, where M is an inner core and porous material of Ln2-xO2S:Eux3+ is an outer shell. The structure improves internal quantum efficiency of the sulfur oxide luminescent material. Meanwhile, the luminescent efficiency of the material is greatly increased under same excitation conditions due to plasma effect of metal, and the wavelength of emitting light remains unchanged. There is enough space between the inner core and the outer shell so reducing the amount of rare earth element of the outer shell and reducing the costs.

    [0009] In addition, it is necessary to provide a method for preparing a sulfur oxide luminescent material having relatively high luminescent efficiency.

    [0010] A method for preparing a sulfur oxide luminescent material, comprising:

    mixing and reacting a solution of salt containing metal M with an additive and a reducing agent to prepare a colloid containing M, wherein the metal M is at least one of Ag, Au, Pt, Pd and Cu nanoparticles;

    adding the colloid containing M to an ethanol solution of sucrose or glucose to obtain a mixed solution, then heating the mixed solution at 120°C-200°C to form a solution of C@M, and centrifuging the solution of C@M, washing and drying to obtain C@M nanospheres; @ is coating M with C (carbon), and a molar ratio of M to C from sucrose or glucose is in a range of 5×10-4-5×10-2;

    adding the C@M nanospheres to a solution of Ln3+ and Eu3+ according to a molar ratio of Ln3+ to Eu3+ to M which is (2-x):x:y; regulating the pH value of the solution to 2-3, followed by adding oxalic acid and regulating the pH value to 8-9 to obtain a liquid suspension of Ln2(C2O4)3:Eu3+@C@M; separating the liquid suspension to obtain Ln2(C2O4)3:Eu3+@C@M solid; Ln3+ is Y3+, Gd3+ or La3+, and x is in a range of 0<x≤0.2, y is in a range of 0<y≤1×10-2; and,

    mixing sulfur powders with the Ln2(C2O4)3:Eu3+@C@M solid according to a molar ratio of S to Ln3+ which is 1:(2-x), followed by adding a fluxing agent and calcining at 1000°C-1450°C to obtain a sulfur oxide luminescent material having a general chemical formula of Ln2-xO2S:Eux3+@My; Eu3+ is doped in Ln2-xO2S to form Ln2-xO2S:Eux3+ having a porous structure, and @ is coating.



    [0011] In one embodiment, solute of the solution of salt containing metal M is at least one of PdCl2·2H2O, AuCl3·HCl·4H2O, H2PtCl6·H2O, AgNO3 and Cu(NO3)2; solvent of the solution is deionized water or ethanol; a concentration of the solution is in a range of 1×10-3-5×10-2mol/L.

    [0012] In another embodiment, the additive is at least one of polyvinylpyrrolidone, sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate; a concentration of the additive is in a range of 1×10-4g/mL-5×10-2g/mL to the colloid containing M.

    [0013] In yet another embodiment, the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride; a molar ratio of the reducing agent to M is in a range of 3.6:1-18:1.

    [0014] In still another embodiment, the solution of Ln3+ and Eu3+ is a mixed solution of Ln(NO3)3 and Eu(NO3)3.

    [0015] In another embodiment, the fluxing agent is anhydrous sodium carbonate (Na2CO3); a molar ratio of the fluxing agent to the sulfur powder is in a range of 1:100-1:10.

    [0016] The method for preparing a sulfur oxide luminescent material involves preparing a colloid containing metal nanoparticles, then coating carbon on the metal nanoparticles by a hydrothermal method using sucrose or glucose as starting material, followed by preparing precursor powders by precipitating Ln3+ and Eu3+ using a oxalic acid. After that, the precursor powders, sulfur powders and an additive are mixed and calcined to obtain a sulfur oxide luminescent material containing metal nanoparticles inside. During the calcination process, carbon is released by being converted into CO2. The method for preparing a sulfur oxide luminescent material is simple, easy to control, low cost and suitable for industrial production. The obtained sulfur oxide luminescent material has high luminescent efficiency and a broad application prospect.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0017] 

    Fig. 1 is a flow diagram showing the preparation of the sulfur oxide luminescent material according to one embodiment of the present invention;

    Fig. 2 is cathodoluminescence spectra of Ln1.92O2S:Eu0.083+@Ag2.5×10-4 luminescent material coating metal nanoparticles Ag (curve 1), compared with Ln1.92O2S:Eu0.083+ luminescent material without coating metal nanoparticles (curve 2), under 1.5kv voltage, according to Example 4.


    DETAILED DESCRIPTION OF ILLUSTRATED EMBODIMENTS



    [0018] Further description of the sulfur oxide luminescent material and preparation method therefor will be illustrated, which combined with preferred embodiments and the drawings.

    [0019] In one embodiment, a sulfur oxide luminescent material has a general chemical formula of Ln2-xO2S:Eux3+@My, where Eu3+ is doped in Ln2-xO2S. Ln2-xO2S:Eux3+ has a porous structure, and @ is coating; that is, M is located in pores of the Ln3-xO2S:Eux3+. Ln is selected from Y, Gd and La, and M is at least one of Ag, Au, Pt, Pd and Cu nanoparticles. X is in a range of 0<x≤0.2, and y is a molar ratio of M to Ln2-xO2S:Eux3+ in a range of 0<y≤1×10-2.

    [0020] Furthermore, in another preferred embodiment, x is in a range of 0.001≤x≤0.1, and y is in a range of 1×10-5≤y≤1×10-3.

    [0021] By coating a metal nanoparticle M, the sulfur oxide luminescent material forms a core-shell structure, where M is an inner core and porous material of Ln2-xO2S:Eux3+ is an outer shell. The structure improves internal quantum efficiency of the sulfur oxide luminescent material. Meanwhile, the luminescent efficiency of the material is greatly increased under same excitation conditions due to plasma effect of metal, and the wavelength of emitting light remains unchanged. There is enough space between the inner core and the outer shell so reducing the amount of rare earth element of the outer shell and reducing the costs.

    [0022] In addition, one embodiment of a preparation of the sulfur oxide luminescent material having relatively high luminescent efficiency is provided. As shown in Fig. 1, the preparation comprises step S110, S120, S130 and S140.

    [0023] Step S110: mixing and reacting a solution of salt containing metal M with an additive and a reducing agent to prepare a colloid containing M.

    [0024] Solute of the solution of salt containing metal M is at least one of PdCl2·2H2O, AuCl3·HCl·4H2O, H2PtCl6·6H2O, AgNO3 and Cu(NO3)2; solvent of the solution is deionized water or ethanol. In this embodiment, concentration of the solution of salt containing metal M is in a range of 1×10-3-5×10-2mol/L. Metal M obtained herein is at least one of Ag, Au, Pt, Pd and Cu.

    [0025] The additive is at least one of polyvinylpyrrolidone, sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate; a concentration of the additive is in a range of 1×10-4g/mL-5×10-2g/mL to the colloid containing M.

    [0026] The reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride; a molar ratio of the reducing agent to M is in a range of 3.6:1-18:1.

    [0027] Step S120: adding the colloid containing M to an ethanol solution from sucrose or glucose to obtain a mixed solution, then heating the mixed solution at 120°C-200°C to form a solution of C@M, and centrifuging the solution of C@M, washing and drying to obtain C@M nanospheres. Herein, the notation of @ is coating M with C, and a molar ratio of M to C from sucrose or glucose is in a range of 5×10-4-5×10-2.

    [0028] Step S130: adding the C@M nanospheres to a solution of Ln3+ and Eu3+ according to a molar ratio of Ln3+ to Eu3+ to M (2-x):x:y; regulating the pH value of the solution to 2-3, followed by adding a precipitant of oxalic acid and regulating the pH value to 8-9 to obtain a liquid suspension of Ln2(C2O4)3:Eu3+@C@M; separating the liquid suspension to obtain Ln2(C2O4)3:Eu3+@C@M solid.

    [0029] Herein, Ln3+ is Y3+, Gd3+ or La3+. X is in a range of 0<x≤0.2, and y is in a range of 0<y<1×10-2. The solution of Ln3+ and Eu3+ is mixed solution of Ln(NO3)3 and Eu(NO3)3. The solution could be prepared by dissolving oxides of Ln and oxides of Eu in nitric acid, or by dissolving nitrates of Ln and nitrates of Eu in water.

    [0030] Step S140: mixing sulfur powders with the Ln2(C2O4)3:Eu3+@C@M solid according to a molar ratio of S to Ln3+ 1:(2-x), followed by adding a fluxing agent and calcining at 1000°C-1450°C to obtain a sulfur oxide luminescent material having a general chemical formula of Ln2-xO2S:Eux3+@My. During the calcination process, carbon in the C@M is released by being converted into CO2. In the obtained material of Ln2-xO2S:Eux3+@My, Eu3+ is doped in Ln2-xO2S, and Ln2-xO2S:Eux3+ has a porous structure. The notation of @ is coating. M is located in pores of the Ln2-xO2S:Eux3+.

    [0031] In this embodiment, the fluxing agent is anhydrous sodium carbonate (Na2CO3); a molar ratio of the fluxing agent to the sulfur powder is in a range of 1:100-1:10.

    [0032] The method for preparing a sulfur oxide luminescent material involves preparing a colloid containing metal nanoparticles, then coating carbon on the metal nanoparticles by a hydrothermal method using sucrose or glucose as starting material, followed by preparing precursor powders by precipitating Ln3+ and Eu3+ using a oxalic acid. After that, the precursor powders, sulfur powders and an additive are mixed and calcined to obtain a sulfur oxide luminescent material containing metal nanoparticles inside. During the calcination process, carbon is released by being converted into CO2. The method for preparing a sulfur oxide luminescent material is simple, easy to control, low cost and suitable for industrial production. The obtained sulfur oxide luminescent material has high luminescent efficiency and a broad application prospect.

    [0033] Further description of the sulfur oxide luminescent material and preparation method therefor will be illustrated, which combined with preferred embodiments and their performance tests.

    Example 1



    [0034] A sulfur oxide luminescent material having a general chemical formula of La1.9O2S:Eu0.13+@Pd1×10-5 was prepared. The notation of @ was coating the latter with the former.

    [0035] Preparation of colloid containing Pd nanoparticles. 0.22 mg of palladium chloride (PdCl2·2H2O) was dissolved in 19 mL of deionized water, followed by adding 11.0 mg of sodium citrate and 4.0 mg of sodium dodecyl sulfate while magnetically stirring to obtain a mixed solution. 3.8 mg of sodium borohydride were dissolved in 10 mL of deionized water to obtain a solution of sodium borohydride having a concentration of 1×10-2mol/L. While stirring, 1 mL of the solution of sodium borohydride was rapidly added to the mixed solution. The reaction was conducted for 20 minutes to produce 20 mL of colloid containing Pd nanoparticles having a concentration of 5×10-5 mol/L.

    [0036] Preparation of C@Pd nanospheres. 4 g of glucose were dissolved in 32 mL of anhydrous ethanol to prepare an ethanol solution of glucose. 8 mL of the colloid were added to the ethanol solution of glucose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 120°C for 36 hours to prepare a solution of C@Pd. The solution of C@Pd was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol twice, and then dried at 60°C to obtain C@Pd nanospheres.

    [0037] Preparation of precursor powders. 15.4753 g of lanthanum oxide (La2O3) and 0.8797 g of europium oxide (Eu2O3) were completely dissolved in nitric acid to prepare 250 mL of a solution of La3+ and Eu3+. 10 mL portions of the solution of La3+ and Eu3+ were added to a beaker by using a pipette, and then 0.0016 g of the C@Pd nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 2 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 9 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 6 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for twice. The solid matters were dried at 60°C to obtain precursor powders.

    [0038] Preparation of La1.9O2S:Eu0.13+@Pd1×10-5. The precursor powders were mixed with 0.1282 g of sulfur powders and 0.0042 g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1000°C for 10 hours. The mixture was then cooled and grinded to obtain a luminescent material of La1.9O2S:Eu0.13+@Pd1×10-5.

    Example 2



    [0039] A sulfur oxide luminescent material having a general chemical formula of Gd1.8O2S:Eu0.23+@Au1×10-2 was prepared. The notation of @ was coating the latter with the former.

    [0040] Preparation of colloid containing Au nanoparticles. 20.6 mg of chloroauric acid (AuCl3·HCl·4H2O) were dissolved in 16.8 mL of deionized water, followed by adding 14 mg of sodium citrate and 6 mg of cetyl trimethyl ammonium bromide while magnetically stirring to obtain a mixed solution. 1.9 mg of sodium borohydride /was dissolved in 10 mL of deionized water to obtain a solution of sodium borohydride having a concentration of 5×10-3mol/L. 17.6 mg of ascorbic acid were dissolved in 10 mL of deionized water to obtain a solution of ascorbic acid having a concentration of 1×10-2mol/L. While stirring, 0.08 mL of the solution of sodium borohydride was added to the mixed solution. After 5 minutes, 3.12 mL of the solution of ascorbic acid was added to the mixed solution. The reaction was conducted for 20 minutes to produce 20 mL of colloid containing Au nanoparticles having a concentration of 5×10-3 mol/L.

    [0041] Preparation of C@Au nanospheres. 0.0389g of sucrose was dissolved in 24 mL of anhydrous ethanol to prepare an ethanol solution of sucrose. 16 mL of the colloid were added to the ethanol solution of sucrose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 160°C for 20 hours to prepare a solution of C@Au. The solution of C@Au was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol for three times, and then dried at 80°C to obtain C@Au nanospheres.

    [0042] Preparation of precursor powders. 9 mL portions of a solution of gadolinium nitrate at 0.8mol/L, and 2 mL portions of a solution of europium nitrate at 0.4 mol/L were added to a beaker by using a pipette, and then 0.96 g of the C@Au nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 3 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 8 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 2 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for twice. The solid matters were dried at 80°C to obtain precursor powders.

    [0043] Preparation of Gd1.8O2S:Eu0.23+@Au1×10-2. The precursor powders were mixed with 0.1282 g of sulfur powders and 0.0084g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1450°C for 2 hours. The mixture was then cooled and grinded to obtain a luminescent material of Gd1.8O2S:Eu0.23+@Au1×10-2.

    Example 3



    [0044] A sulfur oxide luminescent material having a general chemical formula of Gd1.999O2S:Eu0.0013+@Pt5×10-3 was prepared. The notation of @ was coating the latter with the former.

    [0045] Preparation of colloid containing Pt nanoparticles. 25.9 mg of chloroplatinic acid (H2PtCl6·H2O) were dissolved in 17 mL of deionized water, followed by adding 40.0 mg of sodium citrate and 60.0 mg of sodium dodecyl sulfonate while magnetically stirring to obtain a mixed solution. 1.9 mg of sodium borohydride was dissolved in 10 mL of deionized water to obtain a solution of sodium borohydride having a concentration of 5×10-3mol/L. 10 mL of a solution of hydrazine hydrate having a concentration of 5×10-2mol/L were prepared. While stirring, 0.4 mL of the solution of sodium borohydride was added to the mixed solution. After 5 minutes, 2.6 mL of the solution of hydrazine hydrate was added to the mixed solution. The reaction was conducted for 40 minutes to produce 20 mL of colloid containing Pt nanoparticles having a concentration of 2.5×10-3 mol/L.

    [0046] Preparation of C@Pt nanospheres. 0.0023g of glucose was dissolved in 30 mL of anhydrous ethanol to prepare an ethanol solution of glucose. 10 mL of the colloid were added to the ethanol solution of glucose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 150°C for 10 hours to prepare a solution of C@Pt. The solution of C@Pt was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol twice, and then dried at 70°C to obtain C@Pt nanospheres.

    [0047] Preparation of precursor powders. 19.99 mL portions of a solution of gadolinium nitrate (Gd(NO3)3) at 0.5mol/L, and 0.5 mL portions of a solution of europium nitrate (Eu(NO3)3) at 0.01mol/L were added to a beaker by using a pipette, and then 0.024g of the C@Pt nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 2.5 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 8.5 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 4 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for twice. The solid matters were dried at 65°C to obtain precursor powders.

    [0048] Preparation of Gd1.999O2S:Eu0.0013+@Pt5×10-3. The precursor powders were mixed with 0.1602g of sulfur powders and 0.0530g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1250°C for 6 hours. The mixture was then cooled and grinded to obtain a luminescent material of Gd1.999O2S:Eu0.0013+@Pt5×10-3.

    Example 4



    [0049] A sulfur oxide luminescent material having a general chemical formula of Y1.92O2S:Eu0.083+@Ag2.5×10-4 was prepared. The notation of @ was coating the latter with the former.

    [0050] Preparation of colloid containing Ag nanoparticles. 3.4mg of silver nitrate (AgNO3) was dissolved in 18.4 mL of deionized water, followed by adding 42mg of sodium citrate to obtain a mixed solution. 5.7mg of sodium borohydride were dissolved in 10 mL of deionized water to obtain a solution of sodium borohydride having a concentration of 1.5×10-2mol/L. While stirring, 1.6 mL of the solution of sodium borohydride was rapidly added to the mixed solution. The reaction was conducted for 10 minutes to produce 20 mL of colloid containing Ag nanoparticles having a concentration of 1×10-3mol/L.

    [0051] Preparation of C@Ag nanospheres. 5g of glucose was dissolved in 35 mL of anhydrous ethanol to prepare an ethanol solution of glucose. 5 mL of the colloid were added to the ethanol solution of glucose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 180°C for 24 hours to prepare a solution of C@Ag. The solution of C@Ag was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol for twice, and then dried at 60°C to obtain C@Ag nanospheres.

    [0052] Preparation of precursor powders. 19.99 mL portions of a solution of yttrium nitrate (Y(NO3)3) at 0.4mol/L, and 3.2 mL portions of a solution of europium nitrate (Eu(NO3)3) at 0.1mol/L were added to a beaker by using a pipette, and then 0.0016g of the C@Ag nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 3 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 8 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 4 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for three times. The solid matters were dried at 60°C to obtain precursor powders.

    [0053] Preparation of Y1.92O2S:Eu0.083+@Ag2.5×10-4. The precursor powders were mixed with 0.1282 g of sulfur powders and 0.0212g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1200°C for 5 hours. The mixture was then cooled and grinded to obtain a luminescent material of Y1.92O2S:Eu0.083+@Ag2.5×10-4.

    [0054] Fig. 2 is cathodoluminescence spectra of Y1.92O2S:Eu0.083+@Ag2.5×10-4 luminescent material coating metal nanoparticles Ag (curve 1), compared with Y1.92O2S:Eu0.083+ luminescent material without coating metal nanoparticles (curve 2), under 1.5kv voltage, according to this embodiment. It can be seen from Fig. 2 that the emission peak shown at about 626nm, luminescent intensity of the luminescent material coating metal nanoparticles is increased by 25%.

    Example 5



    [0055] A sulfur oxide luminescent material having a general chemical formula of La1.85O2S:Eu0.153+@Cu1×10-4 was prepared. The notation of @ was coating the latter with the former.

    [0056] Preparation of colloid containing Cu nanoparticles. 1.6mg of copper nitrate (Cu(NO3)2) was dissolved in 16 mL of deionized water, followed by adding 12mg of polyvinylpyrrolidone (PVP) while magnetically stirring to obtain a mixed solution. 0.4mg of sodium borohydride was dissolved in 10 mL of ethanol to obtain a solution of sodium borohydride having a concentration of 1×10-3mol/L. While stirring, 4 mL of the solution of sodium borohydride was rapidly added to the mixed solution. The reaction was conducted for 10 minutes to produce 20 mL of colloid containing Cu nanoparticles having a concentration of 4×10-4mol/L.

    [0057] Preparation of C@Cu nanospheres. 6g of sucrose was dissolved in 39.5 mL of anhydrous ethanol to prepare an ethanol solution of sucrose. 0.5 mL of the colloid was added to the ethanol solution of sucrose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 200°C for 5 hours to prepare a solution of C@Cu. The solution of C@Cu was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol for twice, and then dried at 75°C to obtain C@Cu nanospheres.

    [0058] Preparation of precursor powders. 18.5 mL portions of a solution of lanthanum nitrate (La(NO3)3) at 0.4mol/L, and 5 mL portions of a solution of europium nitrate (Eu(NO3)3) at 0.3mol/L were added to a beaker by using a pipette, and then 0.0048g of the C@Cu nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 3 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 9 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 6 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for twice. The solid matters were dried at 70°C to obtain precursor powders.

    [0059] Preparation of La1.85O2S:Eu0.153+@Cu1×10-4. The precursor powders were mixed with 0.1282 g of sulfur powders and 0.0106g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1350°C for 4 hours. The mixture was then cooled and grinded to obtain a luminescent material of La1.85O2S:Eu0.153+@Cu1×10-4.

    Example 6



    [0060] A sulfur oxide luminescent material having a general chemical formula of Y1.95O2S:Eu0.053+@(Ag0.5/Au0.5)1.25×10-3 was prepared. The notation of @ was coating the latter with the former. "/" means the coexistence of the two matters.

    [0061] Preparation of colloid containing Ag and Au nanoparticles. 6.2 mg of chloroauric acid (AuCl3·HCl·4H2O) and 2.5 mg of silver nitrate were dissolved in 28 mL of deionized water, followed by adding 22mg of sodium citrate and 20mg of polyvinylpyrrolidone (PVP) while magnetically stirring to obtain a mixed solution. 5.7mg of sodium borohydride were dissolved in 10 mL of deionized water to obtain a solution of sodium borohydride having a concentration of 1.5×10-2mol/L. While stirring, 2 mL of the solution of sodium borohydride was rapidly added to the mixed solution. The reaction was conducted for 20 minutes to produce 30 mL of colloid containing Ag and Au nanoparticles having a concentration of 1×10-3mol/L.

    [0062] Preparation of C@(Ag/Au) nanospheres. 5.705g of sucrose was dissolved in 30 mL of anhydrous ethanol to prepare an ethanol solution of sucrose. 10 mL of the colloid were added to the ethanol solution of sucrose to prepare a mixed solution. The mixed solution was transferred to a 50-mL polytetrafluoroethylene-lined reactor, and then heated at 140°C for 15 hours to prepare a solution of C@(Ag/Au). The solution of C@(Ag/Au) was separated by centrifuging to obtain solid matters. The solid matters were washed with deionized water and anhydrous ethanol for twice, and then dried at 80°C to obtain C@(Ag/Au) nanospheres.

    [0063] Preparation of precursor powders. 19.5 mL portions of a solution of yttrium nitrate (Y(NO3)3) at 0.4mol/L, and 3.2 mL portions of a solution of europium nitrate (Eu(NO3)3) at 0.1mol/L were added to a beaker by using a pipette, and then 0.0012g of the C@(Ag/Au) nanospheres was added to prepare a mixed solution. The pH value of the mixed solution was regulated to 3 by dripping nitric acid into the mixed solution. After that, a precipitant of oxalic acid was added to the mixed solution. The pH value of the mixed solution was then regulated to 8 by dripping ammonia water. The mixed solution was thoroughly stirred and reacted. A liquid suspension of products was obtained after conducting the reaction for 4 hours. The suspension was filtrated and washed with deionized water and anhydrous ethanol for twice. The solid matters were dried at 60°C to obtain precursor powders.

    [0064] Preparation of Y1.95O2S:Eu0.053+@(Ag0.5/Au0.5)1.25×10-3. The precursor powders were mixed with 0.1282 g of sulfur powders and 0.0127g of anhydrous sodium carbonate (Na2CO3) to obtain a mixture. The mixture was grinded and placed in a crucible of aluminium oxide, followed by being calcining at 1100°C for 8 hours. The mixture was then cooled and grinded to obtain a luminescent material of Y1.95O2S:Eu0.053+@(Ag0.5/Au0.5)1.25×10-3.

    [0065] While the present invention has been described with reference to particular embodiments, it will be understood that the embodiments are illustrative and that the invention scope is not so limited. Alternative embodiments of the present invention will become apparent to those having ordinary skill in the art to which the present invention pertains. Such alternate embodiments are considered to be encompassed within the scope of the present invention.


    Claims

    1. A sulfur oxide luminescent material having a general chemical formula of Ln2-xO2S:Eux3+@My, wherein Eu3+ is doped in Ln2-xO2S; Ln2-xO2S:Eux3+ has a porous structure, and @ is coating; Ln is selected from Y, Gd and La; M is at least one of Ag, Au, Pt, Pd and Cu nanoparticles; x is in a range of 0<x≤0.2; y is a molar ratio of M to Ln2-xO2S:Eux3+ and y is in a range of 0<y≤1×10-2.
     
    2. The sulfur oxide luminescent material according to claim 1, wherein x is in a range of 0.001≤x≤0.1.
     
    3. The sulfur oxide luminescent material according to claim 1, wherein y is in a range of 1≤10-5≤y≤1≤10-3.
     
    4. A method for preparing a sulfur oxide luminescent material, comprising:

    mixing and reacting a solution of salt containing metal M with an additive and a reducing agent to prepare a colloid containing M, wherein the metal M is at least one of Ag, Au, Pt, Pd and Cu nanoparticles;

    adding the colloid containing M to an ethanol solution of sucrose or glucose to obtain a mixed solution, then heating the mixed solution at 120°C-200°C to form a solution of C@M, and centrifuging the solution of C@M, washing and drying to obtain C@M nanospheres; @ is coating M with C, and a molar ratio of M to C from sucrose or glucose is in a range of 5≤10-4-5≤10-2;

    adding the C@M nanospheres to a solution of Ln3+ and Eu3+ according to a molar ratio of Ln3+ to Eu3+ to M which is (2-x):x:y; regulating the pH value of the solution to 2-3, followed by adding oxalic acid and regulating the pH value to 8-9 to obtain a liquid suspension of Ln2(C2O4)3:Eu3+@C@M; separating the liquid suspension to obtain Ln2(C2O4)3:Eu3+@C@M solid; Ln3+ is Y3+, Gd3+ or La3+, and x is in a range of 0<x≤0.2, y is in a range of 0<y≤1≤10-2; and,

    mixing sulfur powders with the Ln2(C2Oa)3:Eu3+@C@M solid according to a molar ratio of S to Ln3+ which is 1:(2-x), followed by adding a fluxing agent and calcining at 1000°C-1450°C to obtain a sulfur oxide luminescent material having a general chemical formula of Ln2-xO2S:Eux3+@My; Eu3+ is doped in Ln2-xO2S to form Ln2-xO2S:Eux3+ having a porous structure, and @ is coating.


     
    5. The method for preparing a sulfur oxide luminescent material according to claim 4, wherein solute of the solution of salt containing metal M is at least one of PdCl2·H2O, AuCl3·HCl·4H2O, H2PtCl6·6H2O, AgNO3 and Cu(NO3)2; solvent of the solution is deionized water or ethanol; a concentration of the solution is in a range of 1×10-3-5×10-2mol/L.
     
    6. The method for preparing a sulfur oxide luminescent material according to claim 4, wherein the additive is at least one of polyvinylpyrrolidone, sodium citrate, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfonate; a concentration of the additive is in a range of 1×10-4g/mL-5×10-2g/mL to the colloid containing M.
     
    7. The method for preparing a sulfur oxide luminescent material according to claim 4, wherein the reducing agent is at least one of hydrazine hydrate, ascorbic acid, sodium citrate and sodium borohydride; a molar ratio of the reducing agent to M is in a range of 3.6:1-18:1.
     
    8. The method for preparing a sulfur oxide luminescent material according to claim 4, wherein the solution of Ln3+ and Eu3+ is a mixed solution of Ln(NO3)3 and Eu(NO3)3.
     
    9. The method for preparing a sulfur oxide luminescent material according to claim 4, wherein the fluxing agent is anhydrous sodium carbonate; a molar ratio of the fluxing agent to the sulfur powder is in a range of 1:100-1:10.
     


    Ansprüche

    1. Lumineszierendes Schwefeloxidmaterial mit einer allgemeinen chemischen Formel von Ln2-xO2S:Eux3+@My, worin Eu3+ in Ln2-xO2S dotiert ist; Ln2-xO2S:Eux3+ eine poröse Struktur aufweist und @ eine Beschichtung ist; Ln aus Y, Gd und La ausgewählt ist; M zumindest ein Material ausgewählt aus Ag-, Au-, Pt-, Pd- und Cu-Nanopartikeln ist; x im Bereich von 0 < x ≤ 5 0,2 liegt; y ein Molverhältnis von M zu Ln2-xO2S:Eux3+ ist und im Bereich von 0 < y ≤ 1x10-2 liegt.
     
    2. Lumineszierendes Schwefeloxidmaterial nach Anspruch 1, worin x im Bereich von 0,001 ≤ x ≤ 0,1 liegt.
     
    3. Lumineszierendes Schwefeloxidmaterial nach Anspruch 1, worin y im Bereich von 1x10-5 ≤ y ≤ 1x10-3 liegt.
     
    4. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials, wobei das Verfahren Folgendes umfasst:

    das Mischen und Umsetzen einer Lösung eines das Metall M enthaltenden Salzes mit einem Additiv und einem Reduktionsmittel zur Herstellung eines M-hältigen Kolloids, worin das Metall M zumindest ein Material ausgewählt aus Ag-, Au-, Pt-, Pd- und Cu-Nanopartikeln ist;

    das Zusetzen des M-hältigen Kolloids zu einer Ethanollösung von Saccharose oder Glukose zum Erhalt eines Lösungsgemischs, anschließend das Erhitzen des Lösungsgemischs auf 120 bis 200 °C zur Bildung einer Lösung von C@M und das Zentrifugieren der Lösung von C@M, das Waschen und Trocknen zum Erhalt von C@M-Nanokügelchen; worin @ eine Beschichtung von M mit C ist und das Molverhältnis von M zu C aus Saccharose oder Glukose im Bereich von 5x10-4 bis 5x10-2 liegt;

    das Zusetzen von C@M-Nanokügelchen zu einer Lösung von Ln3+ und Eu3+ gemäß einem Molverhältnis von Ln3+ zu Eu3+ zu M, das (2-x):x:y entspricht; das Regulieren des pH-Werts der Lösung auf 2 bis 3 gefolgt vom Zusetzen von Oxalsäure und dem Regulieren des pH-Werts auf 8 bis 9 zum Erhalt einer flüssigen Suspension von Ln2(C2O4)3:Eu3+@C@M; das Abscheiden der flüssigen Suspension zum Erhalt eines Ln2(C2O4)3:Eu3+@C@M-Feststoffs; worin Ln3+ Y3+, Gd3+ oder La3+ ist und x im Bereich von 0 < x ≤ 0,2 liegt und y im Bereich von 0 < y ≤ 1x10-2 liegt; und

    das Mischen von Schwefelpulvern mit dem Ln2(C2O4)3:Eu3+@C@M-Feststoff gemäß einem Molverhältnis von S zu Ln3+, das 1:(2-x) entspricht, gefolgt vom Zusetzen eines Flussmittels und dem Kalzinieren bei 1.000 bis 1.450 °C zum Erhalt eines lumineszierenden Schwefeloxidmaterials mit einer allgemeinen chemischen Formel Ln2-xO2S:Eux3+@My, worin Eu3+ in Ln2-xO2S dotiert ist, um Ln2-xO2S:Eux3+ zu bilden, das eine poröse Struktur aufweist, und @ eine Beschichtung ist.


     
    5. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials nach Anspruch 4, worin der Gelöststoff der Lösung des das Metall M enthaltenden Salzes zumindest einer ausgewählt aus PdCl2-2H2O, AuCl3-HCl-4H2O, H2PtCl6·6H2O, AgNO3 und Cu(NO3)2 ist; das Lösungsmittel der Lösung entionisiertes Wasser oder Ethanol ist; die Konzentration der Lösung im Bereich von 1x10-3 bis 5x10-2 mol/l liegt.
     
    6. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials nach Anspruch 4, worin das Additiv zumindest eines ausgewählt aus Polyvinylpyrrolidon, Natriumcitrat, Cetyltrimethylammoniumbromid, Natriumdodecylsulfat und Natriumdodecylsulfonat ist; wobei die Konzentration des Additivs im Bereich von 1x10-4 g/ml bis 5x10-2 g/ml zu dem M-hältigen Kolloid liegt.
     
    7. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials nach Anspruch 4, worin das Reduktionsmittel zumindest eines ausgewählt aus Hydrazinhydrat, Ascorbinsäure, Natriumcitrat und Natriumborhydrid ist, wobei das Molverhältnis des Reduktionsmittels zu M im Bereich von 3,6:1 bis 18:1 liegt.
     
    8. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials nach Anspruch 4, worin die Lösung von Ln3+ und Eu3+ ein Lösungsgemisch von Ln(NO3)3 und Eu(NO3)3 ist.
     
    9. Verfahren zur Herstellung eines lumineszierenden Schwefeloxidmaterials nach Anspruch 4, worin das Flussmittel wasserfreies Natriumcarbonat ist, wobei das Molverhältnis des Flussmittels zu dem Schwefelpulver im Bereich von 1:100 bis 1:10 liegt.
     


    Revendications

    1. Matériau luminescent à base d'oxyde de soufre de formule chimique générale Ln2-xO2S:Eux3+@My dans laquelle Eu3+ est dopé dans Ln2-xO2S ; Ln2-xO2S:Eux3+ a une structure poreuse, et @ est un revêtement ; Ln est choisi parmi Y, Gd et La ; M est au moins l'un parmi Ag, Au, Pt, Pd et Cu sous la forme de nanoparticules ; x est situé dans la plage 0 < x ≤ 0,2 ; y est le rapport molaire de M à Ln2-xO2S:Eux3+ et y est situé dans la plage 0 < y ≤ 1 x 10-2.
     
    2. Matériau luminescent à base d'oxyde de soufre selon la revendication 1, dans lequel x est situé dans la plage 0,001 ≤ x ≤ 0,1.
     
    3. Matériau luminescent à base d'oxyde de soufre selon la revendication 1, dans lequel y est situé dans la plage 1 x 10-5 ≤ y ≤ 1 x 10-3.
     
    4. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre, comprenant :

    le mélange et la réaction d'une solution d'un sel contenant un métal M avec un additif et un agent réducteur pour préparer un colloïde contenant M, le métal M étant au moins l'un parmi Ag, Au, Pt, Pd et Cu sous la forme de nanoparticules ;

    l'addition du colloïde contenant M à une solution éthanolique de saccharose ou de glucose pour que soit obtenue une solution mixte, puis le chauffage de la solution mixte à 120°C-200°C pour former une solution de C@M, et la centrifugation de la solution de C@M, le lavage et le séchage pour que soient obtenues des nanosphères de C@M ; @ étant un revêtement de M avec C, et le rapport molaire de M à C provenant du saccharose ou du glucose étant situé dans la plage allant de 5 x 10-4 à 5 x 10-2 ;

    l'addition des nanosphères de C@M à une solution de Ln3+ et Eu3+ conformément à un rapport molaire de Ln3+ à Eu3+ à M qui est de (2-x)/x/y ; la régulation de la valeur de pH de la solution à 2-3, suivie de l'addition d'acide oxalique et de la régulation de la valeur de pH à 8-9 pour que soit obtenue une suspension liquide de Ln2(C2O4)3:Eu3+@C@M ; la séparation de la suspension liquide pour que soit obtenu du Ln2(C2O4)3:Eu3+@C@M solide ; Ln3+ étant Y3+, Gd3+ ou La3+, et x étant situé dans la plage 0 < x ≤ 0,2, y étant situé dans la plage 0 < y ≤ 1 x 10-2 ; et

    le mélange de poudres de soufre avec le solide Ln2(C2O4)3:Eu3+@C@M conformément à un rapport molaire de S à Ln3+ qui est de 1/(2-x), suivi de l'addition d'un fondant et de la calcination à 1000°C-1450°C pour que soit obtenu un matériau luminescent à base d'oxyde de soufre de formule chimique générale Ln2-xO2S:Eux3+@My ; Eu3+ étant dopé dans Ln2-xO2S pour former Ln2-xO2S:Eux3+ ayant une structure poreuse, et @ étant un revêtement.


     
    5. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre selon la revendication 4, dans lequel le soluté de la solution de sel contenant le métal M est au moins l'un parmi PdCl2•2H2O, AuCl3•HCl•4H2O, H2PtCl6•6H2O, AgNO3 et Cu(NO3)2 ; le solvant de la solution est de l'eau désionisée ou de l'éthanol ; et la concentration de la solution est située dans la plage allant de 1 x 10-3 à 5 x 10-2 mol/l.
     
    6. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre selon la revendication 4, dans lequel l'additif est au moins l'un parmi la polyvinylpyrrolidone, le citrate de sodium, le bromure de cétyltriméthylammonium, le dodécylsulfate de sodium et le dodécylsulfonate de sodium ; et la concentration de l'additif est située dans la plage allant de 1 x 10-4 g/ml à 5 x 10-2 g/ml par rapport au colloïde contenant M.
     
    7. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre selon la revendication 4, dans lequel l'agent réducteur est au moins l'un parmi l'hydrazine hydratée, l'acide ascorbique, le citrate de sodium et le borohydrure de sodium ; et le rapport molaire de l'agent réducteur à M est situé dans la plage allant de 3,6/1 à 18/1.
     
    8. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre selon la revendication 4, dans lequel la solution de Ln3+ et Eu3+ est une solution mixte de Ln(NO3)3 et Eu(NO3)3.
     
    9. Procédé pour préparer un matériau luminescent à base d'oxyde de soufre selon la revendication 4, dans lequel le fondant est le carbonate de sodium anhydre ; et le rapport du fondant à la poudre de soufre est situé dans la plage allant de 1/100 à 1/10.
     




    Drawing