CN106147764A - A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications - Google Patents
A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications Download PDFInfo
- Publication number
- CN106147764A CN106147764A CN201610420395.XA CN201610420395A CN106147764A CN 106147764 A CN106147764 A CN 106147764A CN 201610420395 A CN201610420395 A CN 201610420395A CN 106147764 A CN106147764 A CN 106147764A
- Authority
- CN
- China
- Prior art keywords
- manganese
- chromium
- emitting film
- substrate
- light
- 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.)
- Pending
Links
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 title claims abstract description 58
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229940000489 arsenate Drugs 0.000 title claims abstract description 58
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010408 film Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 27
- 239000010409 thin film Substances 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052788 barium Inorganic materials 0.000 claims abstract description 17
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 17
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 239000000470 constituent Substances 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims description 24
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 7
- 238000004549 pulsed laser deposition Methods 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- -1 Cr3+ Ion Chemical class 0.000 claims 1
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical class [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 238000001228 spectrum Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 238000000151 deposition Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 238000009832 plasma treatment Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000075 oxide glass Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- XWBKRSAKQYHNRC-UHFFFAOYSA-N [Zr].[As](O)(O)(O)=O Chemical compound [Zr].[As](O)(O)(O)=O XWBKRSAKQYHNRC-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FIJMPJIZAQHCBA-UHFFFAOYSA-N arsanylidynezirconium Chemical compound [Zr]#[As] FIJMPJIZAQHCBA-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/74—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing arsenic, antimony or bismuth
- C09K11/7492—Arsenides; Nitrides; Phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Physical Vapour Deposition (AREA)
- Luminescent Compositions (AREA)
Abstract
A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, its chemical formula is RZr4‑x‑yAs6O24∶xMn4+,yCr3+, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element, in the electroluminescent spectrum (EL) of this manganese-chromium-codoped zirconium arsenate light-emitting film, has the strongest glow peak in 607nm and 629nm position, it is possible to be applied in thin-film electroluminescent displays.The present invention also provides for the preparation method and applications of this manganese-chromium-codoped zirconium arsenate light-emitting film.
Description
[technical field]
The present invention relates to a kind of manganese-chromium-codoped zirconium arsenate light-emitting film, its preparation method, membrane electro luminescent device
And preparation method thereof.
[background technology]
Thin-film electroluminescent displays (TFELD) is owing to its active illuminating, total solids, impact resistance, reaction are fast, visual angle
Greatly, the advantage such as Applicable temperature width, operation be simple, caused and paid close attention to widely, and quickly grown.
Zirconium arsenate luminescent material is the popular research material as LED fluorescent powder.Burst of ultraviolel blue colour fluorescent powder is
Through can as commercial product, and constantly improve in research and development.
[summary of the invention]
Based on this, it is necessary to provide a kind of manganese-chromium-codoped zirconium arsenate luminescence that can be applicable to membrane electro luminescent device
This manganese-chromium-codoped zirconium arsenate light-emitting film electroluminescent device of thin film, its preparation method and preparation method thereof.
A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, its chemical formula is RZr4-x-yAs6O24: xMn4+,yCr3+, wherein,
R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03,
RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
In a preferred embodiment, the thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 50nm～300nm.
The preparation method of a kind of manganese-chromium-codoped zirconium arsenate light-emitting film, comprises the following steps:
According to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5, MnO2With
Cr2O3Powder body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Substrate is loaded in the reative cell of chemical vapor depsotition equipment, and the vacuum of reative cell is set to 1.0 × 10- 3Pa～1.0 × 10-5Pa；
Regulation base target spacing is 45mm～95mm, and substrate temperature is 250 DEG C～750 DEG C, and the flow of working gas is
10sccm～40sccm, operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulsed laser deposition
Obtaining chemical formula is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R selected from magnesium unit
Element, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It it is base
Matter, Mn4+And Cr3+Ion is active element.
In a preferred embodiment, base target spacing is 60mm, and substrate temperature is 500 DEG C, and the flow of working gas is
20sccm, operating pressure is 3Pa, and pulsed laser energy is 150W；
In a preferred embodiment, the thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 50nm～300nm.
A kind of membrane electro luminescent device, substrate that this membrane electro luminescent device includes stacking gradually, anode layer, luminescence
Layer and cathode layer, the material of described luminescent layer is manganese-chromium-codoped zirconium arsenate light-emitting film, this manganese-chromium-codoped zirconium arsenic acid
The chemical formula of salt light-emitting film is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R
Selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03,
RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
The preparation method of a kind of membrane electro luminescent device, comprises the following steps:
The substrate with anode is provided；
Forming luminescent layer on described anode, the material of described luminescent layer is manganese-chromium-codoped zirconium arsenate light-emitting film,
The chemical formula of this manganese-chromium-codoped zirconium arsenate light-emitting film is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenic
Hydrochlorate light-emitting film, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,
0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element；
Form negative electrode on the light-emitting layer.
In a preferred embodiment, the preparation of described luminescent layer comprises the following steps:
According to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5, MnO2With
Cr2O3Powder body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Substrate is loaded in the reative cell of chemical vapor depsotition equipment, and the vacuum of reative cell is set to 1.0 × 10- 3Pa～1.0 × 10-5Pa；
Regulation base target spacing is 45mm～95mm, and substrate temperature is 250 DEG C～750 DEG C, and the flow of working gas is
10sccm～40sccm, operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulsed laser deposition
Obtaining chemical formula is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R selected from magnesium unit
Element, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It it is base
Matter, Mn4+And Cr3+Ion is active element.
Above-mentioned manganese-chromium-codoped zirconium arsenate light-emitting film (RZr4-x-yAs6O24∶xMn4+,yCr3+) electroluminescent spectrum
(EL), in, there is the strongest glow peak in 607nm and 629nm position, it is possible to be applied in thin-film electroluminescent displays.
[accompanying drawing explanation]
Fig. 1 is the structural representation of the membrane electro luminescent device of an embodiment；
Fig. 2 is the electroluminescent spectrogram of the manganese-chromium-codoped zirconium arsenate light-emitting film of embodiment 1 preparation.
[detailed description of the invention]
Below in conjunction with the accompanying drawings with specific embodiment to manganese-chromium-codoped zirconium arsenate light-emitting film, its preparation method and thin film
Electroluminescent device and preparation method thereof is further elucidated with.
The manganese-chromium-codoped zirconium arsenate light-emitting film of one embodiment, its chemical formula is RZr4-x-yAs6O24∶xMn4+,
yCr3+, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤
0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
Preferably, the thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 50nm～300nm, and x is 0.02, and y is 0.03.
It is furthermore preferred that the thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 150nm.
RZr in this manganese-chromium-codoped zirconium arsenate light-emitting film4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
In the electroluminescent spectrum (EL) of this manganese-chromium-codoped zirconium arsenate light-emitting film, have the strongest in 607nm and 629nm wavelength zone
Glow peak, it is possible to be applied in thin-film electroluminescent displays.
The preparation method of above-mentioned manganese-chromium-codoped zirconium arsenate light-emitting film, comprises the following steps:
Step S11, according to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5,
MnO2And Cr2O3Powder body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Substrate is loaded in the reative cell of chemical vapor depsotition equipment, and the vacuum of reative cell is set to 1.0 × 10- 3Pa～1.0 × 10-5Pa。
In the present embodiment, substrate is indium tin oxide glass (ITO), it will be understood that in other embodiments, it is possible to
Think fluorine doped tin oxide glass (FTO), the zinc oxide (AZO) mixing aluminum or indium-doped zinc oxide (IZO)；Substrate priority toluene,
Acetone and EtOH Sonicate clean 5 minutes, and then clean with distilled water flushing, nitrogen sends into reative cell after air-drying；
Preferably, at 1250 DEG C, sintering obtains target；The vacuum of reative cell is 5.0 × 10-4Pa。
Step S13, regulation base target spacing are 45mm～95mm, and substrate temperature is 250 DEG C～750 DEG C, working gas
Flow is 10sccm～40sccm, and operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulse and swashs
It is RZr that light deposition obtains chemical formula4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R select
From magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03,
RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element；
In a preferred embodiment, base target spacing is 60mm, and substrate temperature is 500 DEG C, and the flow of working gas is
20sccm, operating pressure is 3Pa, and pulsed laser energy is 150W；
In a preferred embodiment, the thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 50～300nm；
In a preferred embodiment, working gas is oxygen；
Step S14, carry out chemical gaseous phase deposition and obtain manganese-chromium-codoped zirconium its chemical formula of arsenate light-emitting film and be
RZr4-x-yAs6O24∶xMn4+,yCr3+, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤
X≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
Referring to Fig. 1, the membrane electro luminescent device 100 of an embodiment, this membrane electro luminescent device 100 includes depending on
The substrate 1 of secondary stacking, anode 2, luminescent layer 3 and negative electrode 4.
Substrate 1 is glass substrate.Anode 2 is the tin indium oxide (ITO) being formed in glass substrate.The material of luminescent layer 3
For manganese-chromium-codoped zirconium arsenate light-emitting film, the chemical formula of this manganese-chromium-codoped zirconium arsenate light-emitting film is RZr4-x- yAs6O24∶xMn4+,yCr3+, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤
0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.The material of negative electrode 4 is silver
(Ag)。
The preparation method of above-mentioned membrane electro luminescent device, comprises the following steps:
Step S21, offer have the substrate 1 of anode 2.
In present embodiment, substrate 1 is glass substrate, and anode 2 is the tin indium oxide (ITO) being formed in glass substrate.
It is appreciated that in other embodiments, it is also possible to for fluorine doped tin oxide glass (FTO), the zinc oxide (AZO) or indium-doped of mixing aluminum
Zinc oxide (IZO)；There is substrate 1 priority acetone, dehydrated alcohol and the deionized water ultrasonic cleaning of anode 2 and carry out with to it
Oxygen plasma treatment.
Step S22, on anode 2 formed luminescent layer 3, the material of luminescent layer 3 is that manganese-chromium-codoped zirconium arsenate luminescence is thin
Film, the chemical formula of this manganese-chromium-codoped zirconium arsenate light-emitting film is RZr4-x-yAs6O24∶xMn4+,yCr3+, wherein, R is selected from magnesium
Element, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is
Substrate, Mn4+And Cr3+Ion is active element.
In present embodiment, luminescent layer 3 is prepared by following steps:
First, according to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5, MnO2
And Cr2O3Powder body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Substrate is loaded in the reative cell of chemical vapor depsotition equipment, and the vacuum of reative cell is set to 1.0 × 10- 3Pa～1.0 × 10-5Pa,
Moreover, regulation base target spacing be 45mm～95mm, substrate temperature is 250 DEG C～750 DEG C, the flow of working gas
For 10sccm～40sccm, operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulse laser and sinks
It is long-pending that to obtain chemical formula be RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R be selected from magnesium
Element, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is
Substrate, Mn4+And Cr3+Ion is active element.
In a preferred embodiment, base target spacing is 60mm, and substrate temperature is 500 DEG C, and the flow of working gas is
20sccm, operating pressure is 3Pa, and pulsed laser energy is 150W；
In a preferred embodiment, working gas is oxygen；
Step S23, on luminescent layer 3 formed negative electrode 4.
In present embodiment, the material of negative electrode 4 is silver (Ag), evaporation formed.
It is specific embodiment below.
Embodiment 1
By 1mmol MgO, 3.96mmol ZrO2, 3mmol As2O5, 0.015mmol MnO2With 0.0025mmol Cr2O3
Powder body, after uniformly mixing, sinters a size of diameter 50 at 1250 DEG C, thickness be the ceramic target of 2mm be the shape of cake
Shape, and target is loaded in vacuum cavity, it is ito glass by substrate, successively cleans 5 minutes with toluene, acetone and EtOH Sonicate,
Then clean with distilled water flushing, and carry out oxygen plasma treatment with to it, put into vacuum cavity.Target and the distance of substrate
It is set as 60mm, with mechanical pump and molecular pump, the vacuum of cavity is evacuated to 5.0 × 10-4Pa；Use oxygen as working air current,
Working gas flow is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, pulsed laser energy 150W, starts thin film
Deposition.The thickness deposition of thin film is led to 150nm, the chemistry taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains
Formula is MgZr3.96As6O24∶0.03Mn4+,0.01Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
The chemical general formula of the manganese-chromium-codoped zirconium arsenate light-emitting film obtained in the present embodiment is MgZr3.96As6O24∶
0.03Mn4+,0.01Cr3+, wherein RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
Refer to Fig. 2, Fig. 2 and show the electroluminescence spectrum (EL) of the manganese-chromium-codoped zirconium arsenate light-emitting film obtained.
As seen from Figure 2, in electroluminescence spectrum, there is the strongest glow peak can be applied to electroluminescent of thin film at 607nm and 629nm
In optical display unit.
Embodiment 2
By 1mmol MgO, 3.985mmol ZrO2, 3mmol As2O5, 0.005mmol MnO2And 0.00125mmol
Cr2O3Powder body, after uniformly mixing, sinters a size of diameter 50 at 900 DEG C, and thickness is the ceramic target of 2mm, and by target
Material loads in vacuum cavity, is ito glass by substrate, successively cleans 5 minutes, then with steaming with toluene, acetone and EtOH Sonicate
Distilled water is rinsed well, and carries out oxygen plasma treatment with to it, puts into vacuum cavity.The distance of target and substrate is set as
60mm, is evacuated to 1.0 × 10 with mechanical pump and molecular pump the vacuum of cavity-3Pa；Use oxygen as working air current, work gas
Flow is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, pulsed laser energy 80W, starts the deposition of thin film.
The thickness deposition of thin film to 50nm, the chemical general formula taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains is
MgZr3.985As6O24∶0.01Mn4+,0.005Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
Embodiment 3
By 1mmol MgO, 3.92mmol ZrO2, 3mmol As2O5, 0.025mmol MnO2With 0.0075mmol Cr2O3
Powder body, after uniformly mixing, sinters a size of diameter 50 at 1300 DEG C, and thickness is the ceramic target of 2mm, and by target
Load in vacuum cavity, be ito glass by substrate, successively clean 5 minutes, then with distillation with toluene, acetone and EtOH Sonicate
Water is rinsed well, and carries out oxygen plasma treatment with to it, puts into vacuum cavity.The distance of target and substrate is set as
95mm, is evacuated to 1.0 × 10 with mechanical pump and molecular pump the vacuum of cavity-5Pa；Use oxygen as working air current, work gas
Flow is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, pulsed laser energy 300W, starts the deposition of thin film.
The thickness deposition of thin film to 300nm, the chemical general formula taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains is
MgZr3.92As6O24∶0.05Mn4+,0.03Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
Embodiment 4
By 1mmol CaO, 3.96mmol ZrO2, 3mmol As2O5, 0.015mmol MnO2With 0.0025mmol Cr2O3
Powder body, after uniformly mixing, sinters a size of diameter 50 at 1250 DEG C, and thickness is the ceramic target of 2mm, and by target
Load in vacuum cavity, be ito glass by substrate, successively clean 5 minutes, then with distillation with toluene, acetone and EtOH Sonicate
Water is rinsed well, and carries out oxygen plasma treatment with to it, puts into vacuum cavity.The distance of target and substrate is set as
60mm, is evacuated to 5.0 × 10 with mechanical pump and molecular pump the vacuum of cavity-4Pa；Use oxygen as working air current, work gas
Flow is 20sccm, and pressure is adjusted to 3.0Pa, and underlayer temperature is 500 DEG C, pulsed laser energy 150W, starts the deposition of thin film.
The thickness deposition of thin film to 70nm, the chemical general formula taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains is
CaZr3.96As6O24∶0.03Mn4+,0.01Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
Embodiment 5
By 1mmol CaO, 3.985mmol ZrO2, 3mmol As2O5, 0.005mmol MnO2And 0.00125mmol
Cr2O3Powder body, after uniformly mixing, sinters a size of diameter 50 at 900 DEG C, and thickness is the ceramic target of 2mm, and by target
Material loads in vacuum cavity, is ito glass by substrate, successively cleans 5 minutes, then with steaming with toluene, acetone and EtOH Sonicate
Distilled water is rinsed well, and carries out oxygen plasma treatment with to it, puts into vacuum cavity.The distance of target and substrate is set as
45mm, is evacuated to 1.0 × 10 with mechanical pump and molecular pump the vacuum of cavity-3Pa；Use oxygen as working air current, work gas
Flow is 10sccm, and pressure is adjusted to 0.5Pa, and underlayer temperature is 250 DEG C, pulsed laser energy 80W, starts the deposition of thin film.
The thickness deposition of thin film to 100nm, the chemical general formula taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains is
CaZr3.985As6O24∶0.01Mn4+,0.005Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
Embodiment 6
By 1mmol CaO, 3.92mmol ZrO2, 3mmol As2O5, 0.025mmol MnO2With 0.0075mmol Cr2O3
Powder body, after uniformly mixing, sinters a size of diameter 50 at 1300 DEG C, and thickness is the ceramic target of 2mm, and by target
Load in vacuum cavity, be ito glass by substrate, successively clean 5 minutes, then with distillation with toluene, acetone and EtOH Sonicate
Water is rinsed well, and carries out oxygen plasma treatment with to it, puts into vacuum cavity.The distance of target and substrate is set as
95mm, is evacuated to 1.0 × 10 with mechanical pump and molecular pump the vacuum of cavity-5Pa；Use oxygen as working air current, work gas
Flow is 40sccm, and pressure is adjusted to 5.0Pa, and underlayer temperature is 750 DEG C, pulsed laser energy 300W, starts the deposition of thin film.
The thickness deposition of thin film to 250nm, the chemical general formula taking out the manganese-chromium-codoped zirconium arsenate light-emitting film that sample obtains is
CaZr3.92As6O24∶0.05Mn4+,0.03Cr3+.Last one layer of Ag of evaporation on light-emitting film, as negative electrode.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a manganese-chromium-codoped zirconium arsenate light-emitting film, it is characterised in that its chemical formula is RZr4-x-yAs6O24∶xMn4+,
yCr3+, wherein, R be selected from magnesium elements, calcium constituent, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤
0.03, RZr4As6O24It is substrate, Mn4+And Cr3+Ion is active element.
Manganese-chromium-codoped zirconium arsenate light-emitting film the most according to claim 1, it is characterised in that described manganese-chromium-codoped
The thickness of zirconium arsenate light-emitting film is 50nm～300nm.
3. the preparation method of a manganese-chromium-codoped zirconium arsenate light-emitting film, it is characterised in that comprise the following steps:
According to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5, MnO2And Cr2O3Powder
Body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Substrate is loaded in the reative cell of pulsed laser deposition equipment, and the vacuum of reative cell is set to 1.0 × 10-3Pa～
1.0×10-5Pa；
Regulation base target spacing is 45mm～95mm, and substrate temperature is 250 DEG C～750 DEG C, and the flow of working gas is 10sccm
～40sccm, operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulsed laser deposition
Formula is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R be selected from magnesium elements, calcium
Element, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4 +And Cr3+Ion is active element.
The preparation method of manganese-chromium-codoped zirconium arsenate light-emitting film the most according to claim 3, it is characterised in that described
Base target spacing is 60mm, and substrate temperature is 500 DEG C, and the flow of working gas is 20sccm, and operating pressure is 3Pa, and pulse swashs
Light energy is 150W.
The preparation method of manganese-chromium-codoped zirconium arsenate light-emitting film the most according to claim 3, it is characterised in that described
The thickness of manganese-chromium-codoped zirconium arsenate light-emitting film is 50nm～300nm.
6. a membrane electro luminescent device, substrate that this membrane electro luminescent device includes stacking gradually, anode layer, luminescent layer
And cathode layer, it is characterised in that the material of described luminescent layer is manganese-chromium-codoped zirconium arsenate light-emitting film, and this manganese chromium is co-doped with
The chemical formula of miscellaneous zirconium arsenate light-emitting film is RZr4-x-yAs6O24∶xMn4+,yCr3+, wherein, R is selected from magnesium elements, calcium constituent, strontium
Element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+And Cr3+
Ion is active element.
Membrane electro luminescent device the most according to claim 6, it is characterised in that the thickness of described luminescent layer be 50nm～
300nm。
8. the preparation method of a membrane electro luminescent device, it is characterised in that comprise the following steps:
The substrate with anode is provided；
Forming luminescent layer on described anode, the thin film of described luminescent layer is manganese-chromium-codoped zirconium arsenate light-emitting film, this manganese
The chemical formula of chromium codope zirconium arsenate light-emitting film is RZr4-x-yAs6O24∶xMn4+,yCr3+, wherein, R is selected from magnesium elements, calcium
Element, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+
And Cr3+Ion is active element；
Form negative electrode on the light-emitting layer.
The preparation method of membrane electro luminescent device the most according to claim 8, it is characterised in that the system of described luminescent layer
For comprising the following steps:
According to RZr4-x-yAs6O24∶xMn4+,yCr3+The stoichiometric proportion of each element is by MgO, ZrO2, As2O5, MnO2And Cr2O3Powder
Body, after mixing, at 900 DEG C～1300 DEG C, sintering obtains target；
Described substrate is loaded the reative cell of chemical vapor depsotition equipment, and the vacuum of reative cell is set to 1.0 × 10-3Pa
～1.0 × 10-5Pa；
Regulation base target spacing is 45mm～95mm, and substrate temperature is 250 DEG C～750 DEG C, and the flow of working gas is 10sccm
～40sccm, operating pressure is 0.5Pa～5Pa, and pulsed laser energy is 80W～300W, carries out pulsed laser deposition
Formula is RZr4-x-yAs6O24∶xMn4+,yCr3+Manganese-chromium-codoped zirconium arsenate light-emitting film, wherein, R be selected from magnesium elements, calcium
Element, strontium element, in barium element at least one, 0.01≤x≤0.05,0.005≤y≤0.03, RZr4As6O24It is substrate, Mn4+
And Cr3+Ion is active element.
The preparation method of manganese-chromium-codoped zirconium arsenate light-emitting film the most according to claim 9, it is characterised in that institute
Stating base target spacing is 60mm, and substrate temperature is 500 DEG C, and the flow of working gas is 20sccm, and operating pressure is 3Pa, pulse
Laser energy is 150W.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420395.XA CN106147764A (en) | 2016-06-13 | 2016-06-13 | A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610420395.XA CN106147764A (en) | 2016-06-13 | 2016-06-13 | A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106147764A true CN106147764A (en) | 2016-11-23 |
Family
ID=57353151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610420395.XA Pending CN106147764A (en) | 2016-06-13 | 2016-06-13 | A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106147764A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285965A (en) * | 2023-03-31 | 2023-06-23 | 江西理工大学 | Novel Mn 4+ 、Cr 3+ Co-doped fluoride near infrared fluorescent powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449680A (en) * | 2013-09-25 | 2015-03-25 | 海洋王照明科技股份有限公司 | Fluorine/copper-codoped alkaline earth sulfide light-emitting material, and preparation method and application thereof |
| CN104745184A (en) * | 2013-12-26 | 2015-07-01 | 海洋王照明科技股份有限公司 | Manganese-chromium-codoped zirconium arsenate luminescent film and its preparation method and use |
-
2016
- 2016-06-13 CN CN201610420395.XA patent/CN106147764A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449680A (en) * | 2013-09-25 | 2015-03-25 | 海洋王照明科技股份有限公司 | Fluorine/copper-codoped alkaline earth sulfide light-emitting material, and preparation method and application thereof |
| CN104745184A (en) * | 2013-12-26 | 2015-07-01 | 海洋王照明科技股份有限公司 | Manganese-chromium-codoped zirconium arsenate luminescent film and its preparation method and use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285965A (en) * | 2023-03-31 | 2023-06-23 | 江西理工大学 | Novel Mn 4+ 、Cr 3+ Co-doped fluoride near infrared fluorescent powder and preparation method thereof |
| CN116285965B (en) * | 2023-03-31 | 2023-12-15 | 江西理工大学 | Near infrared fluorescent powder of manganese-chromium co-doped fluoride and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104745187A (en) | Manganese-doped cerium antimonate luminescent film and its preparation method and use | |
| CN106147764A (en) | A kind of manganese-chromium-codoped zirconium arsenate light-emitting film, preparation method and applications | |
| CN103805192A (en) | Samarium-doped rare earth borate luminous film as well as preparation method and application thereof | |
| CN106118650A (en) | HONGGUANG niobium zincate luminescent material, preparation method and applications | |
| CN103421496B (en) | Manganese Ti doped fluorine magnesium germanate luminescence material, preparation method and applications | |
| CN104650884A (en) | Luminescent film, preparation method and application thereof | |
| CN106469781A (en) | A kind of europium terbium codope zirconium stibate light-emitting film, preparation method and applications | |
| CN103805183A (en) | Europium-erbium double-doped zirconium dioxide light-emitting film and preparation method and application thereof | |
| CN102787293A (en) | Manganese-doped aluminosilicate oxynitride luminescent film, preparation method and organic electroluminescent devices thereof | |
| CN103805172A (en) | Cerium-terbium co-doped calcium sulfate luminous film and preparation method and application thereof | |
| CN104178137A (en) | Praseodymium-doped indium silicate luminescent film, preparing method thereof and electroluminescent device | |
| CN103421490B (en) | Cerium dopping alkaline earth lithium borate salt luminescent thin film, preparation method and application thereof | |
| CN104745184A (en) | Manganese-chromium-codoped zirconium arsenate luminescent film and its preparation method and use | |
| CN104659173A (en) | Light-emitting film and preparation method and application thereof | |
| CN103805189A (en) | Manganese-chromium-codoped alkaline earth titanium phosphate light-emitting thin film as well as preparation method and application thereof | |
| CN104140812A (en) | III-group scandium silicate luminescent material co-doped with titanium and manganese, preparing method thereof and applications of the material | |
| CN103820116A (en) | Titanium-manganese codoped yttrium oxide light-emitting film and preparation method thereof, and electroluminescence device | |
| CN103571475A (en) | Titanium manganese-codoped group-III molybdate luminescent material, preparation method and application thereof | |
| CN104212450A (en) | Luminescent film, preparation method and application thereof | |
| CN104449687A (en) | Manganese-titanium co-doped indium fluosilicate luminescent film as well as preparation method and application thereof | |
| CN104212451A (en) | Luminescent film, preparation method and application thereof | |
| CN103571477A (en) | Europium bismuth co-doped Group-III molybdate light-emitting material, preparation method and application thereof | |
| CN104449729A (en) | Samarium-doped rare-earth fluorogallate luminescent thin film, preparation method and application thereof | |
| CN104140810A (en) | Manganese-doped barium nitrosilicate luminescence material, and preparation method and application thereof | |
| CN104277844A (en) | Cerium doped zirconium antimonate luminescent thin film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161123 |