WO2013000111A1 - 钛掺杂三元系硅酸盐薄膜及其制备方法和应用 - Google Patents

钛掺杂三元系硅酸盐薄膜及其制备方法和应用 Download PDF

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WO2013000111A1
WO2013000111A1 PCT/CN2011/076446 CN2011076446W WO2013000111A1 WO 2013000111 A1 WO2013000111 A1 WO 2013000111A1 CN 2011076446 W CN2011076446 W CN 2011076446W WO 2013000111 A1 WO2013000111 A1 WO 2013000111A1
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titanium
silicate film
doped ternary
powder
doped
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PCT/CN2011/076446
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English (en)
French (fr)
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周明杰
王平
陈吉星
钟铁涛
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海洋王照明科技股份有限公司
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Priority to US14/129,668 priority Critical patent/US20140166932A1/en
Priority to PCT/CN2011/076446 priority patent/WO2013000111A1/zh
Priority to JP2014517372A priority patent/JP5728618B2/ja
Priority to EP11868779.7A priority patent/EP2725082B1/en
Priority to CN201180070933.2A priority patent/CN103534333B/zh
Publication of WO2013000111A1 publication Critical patent/WO2013000111A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/10—Screens on or from which an image or pattern is formed, picked up, converted or stored
    • H01J29/18—Luminescent screens
    • H01J29/20—Luminescent screens characterised by the luminescent material
    • 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
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/676—Aluminates; Silicates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source

Definitions

  • the invention belongs to the field of semiconductor optoelectronic materials, and in particular relates to a titanium doped ternary silicate film and a preparation method and application thereof.
  • Thin film electroluminescent display Due to its advantages of active illumination, full solidification, impact resistance, fast response, large viewing angle, wide applicable temperature and simple process, it has attracted wide attention and developed rapidly.
  • Monochrome TFELD with ZnS:Mn as the luminescent layer It has matured and commercialized. At present, TEFLD's research focuses on the improvement of blue light brightness to achieve color and full-color TFELD.
  • rare earth ion doped silicate phosphors have been deeply studied, and good red to blue excitation can be obtained.
  • rare earths are expensive, and silicates are prepared into thin film electroluminescent materials. At times, the film quality is often low and the performance is poor, which limits further applications.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior art, and to provide a titanium doped ternary silicate film, a preparation method and application thereof.
  • Another object of an embodiment of the present invention is to provide a method for preparing the above titanium doped ternary silicate film.
  • Another object of embodiments of the present invention is to provide the use of the above titanium doped ternary silicate film in field emission devices, cathode ray tubes and/or electroluminescent devices.
  • the embodiment of the present invention is achieved by the first aspect, wherein a titanium-doped ternary silicate film having a general formula of Ca 2-x MgSi 2 O 7 is provided. : xTi 4+ , where x is 0.00017 to 0.0256.
  • An embodiment of the present invention provides a method for preparing the above titanium-doped ternary silicate film, which comprises the following steps:
  • CaO powder, MgO powder, SiO 2 powder and TiO 2 powder are mixed according to a molar ratio (2-x): 1: 2: x, and sintered as a target, wherein x is 0.00017-0.0256;
  • the target is placed in a magnetron sputtering chamber, vacuumed, and the working pressure is set to 0.2 Pa to 4 Pa, and a mixed gas of inert gas and hydrogen gas is introduced, and the mixed gas flow rate is 15 sccm to 35 sccm, and the substrate temperature to 250 o C ⁇ 750 o C, the sputtering power of 30 W ⁇ 200 W, sputtering to obtain a titanium doped ternary silicate film.
  • the titanium-doped ternary silicate film of the embodiment of the present invention obtains a film having high luminous intensity, thermal stability and chemical stability by Ti-doped ternary silicate.
  • the above preparation method adopts a magnetron sputtering method, which has the advantages of high deposition rate, good film adhesion, easy control, and large-area deposition. Further, the film exhibits the advantages of high stability and long life in the application of optoelectronic semiconductors.
  • FIG. 1 is a flow chart showing a method of preparing a titanium-doped ternary silicate film according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view of a titanium-doped ternary silicate film according to an embodiment of the present invention as an electroluminescent device as a light-emitting layer;
  • Example 3 is a graph showing the electroluminescence spectrum of a titanium-doped ternary silicate film prepared in Example 1 of the present invention.
  • Example 4 is an XRD spectrum of a titanium-doped ternary silicate film prepared in Example 1 of the present invention.
  • the embodiment of the present invention is achieved by the first aspect, wherein a titanium-doped ternary silicate film having a general formula of Ca 2-x MgSi 2 O 7 is provided. : xTi 4+ , where x is 0.00017 to 0.0256. Preferably, x is from 0.001 to 0.008.
  • the silicate matrix has high chemical stability and thermal stability, and the high-purity silica raw material is cheap and easy to obtain, and is an ideal matrix material. Compared with the rare earth, Ti is inexpensive, and a small amount of doping in the matrix material Ca 2 MgSi 2 O 7 can obtain high-intensity luminescence.
  • Another object of the present invention is to provide a method for preparing a titanium-doped ternary silicate film according to an embodiment of the present invention. Referring to FIG. 1, the method includes the following steps:
  • S01 CaO powder, MgO powder, SiO 2 powder and TiO 2 powder are mixed according to a molar ratio (2-x): 1: 2: x, and sintered as a target, wherein x is 0.00017 to 0.0256 ;
  • S02 loading the target into a magnetron sputtering chamber, evacuating, setting a working pressure of 0.2 Pa to 4 Pa, and introducing a mixed gas of inert gas and hydrogen gas, and the flow rate of the mixed gas is 15 sccm to 35 sccm.
  • the bottom temperature is 250 o C to 750 o C, and the sputtering power is 30 W to 200 W.
  • the titanium doped ternary silicate film is sputtered.
  • step S01 CaO powder, MgO powder, SiO 2 powder, and TiO 2 powder are weighed and uniformly mixed, and sintered as a target.
  • the sintering temperature is 1250 o C.
  • the purity of the above powder is preferably greater than 99.99%.
  • the molar ratio of each component in the mixture is CaO: MgO: SiO 2 : TiO 2 is (2-x): 1: 2: x, wherein x is 0.00017 to 0.0256.
  • the content of the matrix component and the doping element is an important factor affecting the properties and structure of the film.
  • Doping metal ions have an effect on the structure of the material. Foreign metal ions enter the crystal lattice and partially distorted the crystal structure. Therefore, if the doping amount is too large, the lattice distortion will be too large, and the ion ordering in the crystal lattice will be disturbed. The formation of a heterophase in the material will seriously weaken the material properties, and if the doping is too small, the luminescent properties will be lowered.
  • the value of x is from 0.001 to 0.008.
  • the substrate is a hard substrate such as sapphire, quartz glass, or silicon wafer. Ultrasonic washing with acetone, absolute ethanol and deionized water before use. Substrates, such as ITO glass substrates, may also be selected for further application.
  • the distance between the target and the substrate is preferably from 45 mm to 95 mm. More preferably, the distance of the target from the substrate is 60 mm.
  • the vacuum of the chamber is pumped to 1.0 ⁇ 10 -3 Pa to 1.0 ⁇ 10 -5 Pa or more, preferably 6.0 ⁇ 10 -4 Pa, using a mechanical pump or a molecular pump.
  • the working gas in the sputtering chamber is a mixed gas of an inert gas and hydrogen gas, wherein the volume percentage of hydrogen is from 1% to 15%, preferably from 3% to 8%.
  • the mixed gas has a flow rate of 20 sccm to 30 sccm, an operating pressure of 1.5 Pa to 2.5 Pa, a substrate temperature of 400 o C to 600 o C, and a sputtering power of 100 W to 140 W. Further, annealing the obtained titanium-doped ternary silicate film can improve the performance of the film.
  • the titanium-doped ternary silicate film prepared under the above specific process conditions is annealed, and the annealing treatment comprises a process of heating the titanium-doped ternary silicate film to an annealing temperature and maintaining the temperature.
  • the annealing temperature is 500 o C to 800 o C.
  • the annealing temperature is 550 o C to 650 o C.
  • the annealing environment may be an inert gas such as nitrogen, argon or the like, or vacuum annealing.
  • the annealing treatment is annealed in a 0.01 Pa vacuum furnace.
  • the annealing temperature is not too fast or too slow, and the heating rate is from 1 o C/min to 10 o C/min. Preferably, the heating rate is from 5 o C/min to 8 o C/min. After heating to the annealing temperature, it is maintained for 1 h to 3 h, preferably for 2 h. Annealing improves the crystal quality of the film, increases the film, and improves the luminous efficiency of the film.
  • Embodiments of the present invention also provide the use of the above titanium-doped ternary silicate film in a field emission device, a cathode ray tube, and/or an electroluminescent device.
  • an electroluminescent device as an example, referring to FIG. 2, a titanium-doped ternary silicate thin film electroluminescent device using the above embodiment is shown, which comprises a glass base layer 21, an anode 22, and a light-emitting layer which are sequentially stacked. 23. And cathode 24.
  • the anode 22 may be indium tin oxide (abbreviated as ITO), and the light-emitting layer 23 may comprise a titanium-doped ternary silicate film in the embodiment of the present invention; the cathode 24 may be, but not limited to, metal Ag.
  • the thin film electroluminescent device structure is represented as: glass/ITO/titanium doped ternary silicate film/Ag.
  • Each layer may be formed by a conventional method. For example, a glass substrate with an ITO layer may be used, and the titanium-doped ternary silicate film may be sputtered by a magnetron sputtering method, and then the Ag layer may be evaporated.
  • Embodiments of the present invention provide a titanium-doped ternary silicate film obtained by doping a small amount of titanium to obtain a titanium-doped ternary silicate film having high crystallinity.
  • the preparation method of the titanium-doped ternary silicate film adopts a magnetron sputtering method to realize high light-emitting intensity and stable performance while maintaining a good service life.
  • annealing the titanium-doped ternary silicate film obtained by sputtering using a mixed gas of an inert gas and hydrogen the light-emitting efficiency of the film can be improved, and a film having excellent performance can be obtained with a small amount of doping. There is a strong emission in the blue zone.
  • the CaO powder, the MgO powder, the SiO 2 powder and the TiO 2 powder having a purity of 99.99% were mixed, and the molar ratio of each component in the mixture was CaO: MgO: SiO 2 : TiO 2 was 1.994: 1: 2: 0.006, the mass of CaO powder is 111.6 g, the mass of MgO powder is 40 g, the mass of SiO 2 powder is 120 g, and the mass of TiO 2 powder is 0.48 g.
  • the ceramic target of 50 ⁇ 2 mm is sintered at a high temperature of 1250 o C, and the target is placed in a vacuum chamber.
  • the glass substrate with ITO was ultrasonically cleaned with acetone, absolute ethanol and deionized water, and subjected to oxygen plasma treatment, and placed in a vacuum chamber. Set the distance between the target and the substrate to 60 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 5.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 5% (volume percentage).
  • gas flow rate 25 sccm the pressure was adjusted to 2.0 Pa
  • the substrate temperature was set to 500 o C
  • the sputtering power was adjusted to 120 W, obtained by sputtering a titanium doped ternary silicate film.
  • the obtained film sample had the chemical formula Ca 1.994 MgSi 2 O 7 : 0.006 Ti 4+ .
  • the CaO powder, the MgO powder, the SiO 2 powder and the TiO 2 powder having a purity of 99.99% were mixed, and the molar ratio of each component in the mixture was CaO: MgO 5 : SiO 2 : TiO 2 was 1.9997: 1: 2 : 0.0003, the mass of the CaO powder is 111.98 g, the mass of the MgO powder is 40 g, the mass of the SiO 2 powder is 120 g, and the mass of the TiO 2 powder is 0.024 g.
  • 900 o C to a sintering temperature ⁇ 50 ⁇ 2 mm of the ceramic target, and the target material into a vacuum chamber.
  • the sapphire substrate was ultrasonically cleaned with acetone, absolute ethanol and deionized water, rinsed with deionized water, and finally dried with high temperature nitrogen and placed in a vacuum chamber. Set the distance between the target and the substrate to 45 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 1.0 ⁇ 10 -3 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 1% (volume percentage).
  • gas flow rate of 10 sccm a pressure was adjusted to 0.2 Pa
  • the substrate temperature was set to 250 o C
  • the sputtering power was adjusted to 30 W, obtained by sputtering a titanium doped ternary silicate film.
  • the obtained film sample had a chemical formula of Ca 1.9997 MgSi 2 O 7 : 0.0003 Ti 4+ .
  • the CaO powder, the MgO powder, the SiO 2 powder and the TiO 2 powder having a purity of 99.99% were mixed, and the molar ratio of each component in the mixture was CaO: MgO: SiO 2 : TiO 2 was 1.995: 1: 2: 0.005, the mass of the CaO powder is 111.72 g, the mass of the MgO powder is 40 g, the mass of the SiO 2 powder is 120 g, and the mass of the TiO 2 powder is 0.4 g. After uniformly mixed, 1300 o C to a sintering temperature ⁇ 50 ⁇ 2 mm of the ceramic target, and the target material into a vacuum chamber.
  • the sapphire substrate was ultrasonically cleaned with acetone, absolute ethanol and deionized water, rinsed with deionized water, and finally dried with high temperature nitrogen and placed in a vacuum chamber. Set the distance between the target and the substrate to 95 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 1.0 ⁇ 10 -5 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 1% (volume percentage). , gas flow rate 35 sccm, the pressure was adjusted to 4.0 Pa, the substrate temperature was set to 750 o C, the sputtering power was adjusted to 200 W, obtained by sputtering a titanium doped ternary silicate film.
  • the obtained film sample had a chemical formula of Ca 1.95 MgSi 2 O 7 : 0.05Ti 4+ .
  • the CaO powder, the MgO powder, the SiO 2 powder and the TiO 2 powder having a purity of 99.99% were mixed, and the molar ratio of each component in the mixture was CaO: MgO: SiO 2 : TiO 2 was 1.99983: 1: 2: 0.00017, the mass of the CaO powder is 111.99 g, the mass of the MgO powder is 40 g, the mass of the SiO 2 powder is 120 g, and the mass of the TiO 2 powder is 0.0136 g.
  • the sapphire substrate was ultrasonically cleaned with acetone, absolute ethanol and deionized water, rinsed with deionized water, and finally dried with high temperature nitrogen and placed in a vacuum chamber. Set the distance between the target and the substrate to 50 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 8.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 3% (volume percentage).
  • gas flow rate 15 sccm the pressure was adjusted to 2.5 Pa
  • the substrate temperature was set to 400 o C
  • the sputtering power was adjusted to 100 W, obtained by sputtering a titanium doped ternary silicate film.
  • the obtained titanium-silicate doped ternary films annealed in an argon atmosphere, wherein the annealing temperature is 650 o C, a heating rate of 4 o C / min, holding time of 2.5 h.
  • the obtained film sample had a chemical formula of Ca 1.99983 MgSi 2 O 7 : 0.00017 Ti 4+ .
  • the CaO powder, the MgO powder, the SiO 2 powder and the TiO 2 powder having a purity of 99.99% were mixed, and the molar ratio of each component in the mixture was CaO: MgO: SiO 2 : TiO 2 was 1.9744: 1: 2: 0.0256, the mass of the CaO powder is 110.57 g, the mass of the MgO powder is 40 g, the mass of the SiO 2 powder is 120 g, and the mass of the TiO 2 powder is 2.048 g. After uniformly mixed, 1200 o C to a sintering temperature ⁇ 50 ⁇ 2 mm of the ceramic target, and the target material into a vacuum chamber.
  • the sapphire substrate was ultrasonically cleaned with acetone, absolute ethanol and deionized water, rinsed with deionized water, and finally dried with high temperature nitrogen and placed in a vacuum chamber. Set the distance between the target and the substrate to 70 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 7.0 ⁇ 10 -4 Pa, and the mixed gas of argon and hydrogen is introduced into the vacuum chamber, wherein the hydrogen content is 8% (volume percentage).
  • gas flow rate 30 sccm the pressure was adjusted to 1.5 Pa
  • the substrate temperature was set to 600 o C
  • the sputtering power was adjusted to 140 W, obtained by sputtering a titanium doped ternary silicate film.
  • the obtained titanium-doped ternary silicate film was annealed in argon gas, wherein the annealing temperature was 550 o C, the heating rate was 8 o C/min, and the holding time was 1.5 h.
  • the obtained film sample had the chemical formula Ca 1.9744 MgSi 2 O 7 : 0.0256Ti 4+ .
  • Example 3 is an electroluminescence spectrum of a titanium-doped ternary silicate film prepared in Example 1 of the present invention, which is at 480 There is a strong blue light emission peak at nm, indicating that the titanium-doped ternary silicate is a good blue light material.
  • Example 4 is an XRD spectrum of a titanium-doped ternary silicate film prepared in Example 1 of the present invention.
  • Control standard and JCPDS In the standard card, the characteristic peak in the figure is the crystallization peak of the matrix silicate, and there are no diffraction peaks of doping elements and other impurities.

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Abstract

提供一种钛掺杂三元系硅酸盐薄膜，所述钛掺杂三元系硅酸盐薄膜的通式为Ca2-xMgSi2O7：xTi4+，其中，x取值为0.00017～0.0256。还提供上述钛掺杂三元系硅酸盐薄膜的制备方法以及采用此方法获得的钛掺杂三元系硅酸盐薄膜在场发射器件、阴极射线管和/或电致发光器件中的应用。

Description

钛掺杂三元系硅酸盐薄膜及其制备方法和应用 技术领域
本发明属于半导体光电材料领域，具体涉及一种钛掺杂三元系硅酸盐薄膜及其制备方法和应用。
 背景技术
薄膜电致发光显示器(TFELD) 由于其主动发光、全固体化、耐冲击、反应快、视角大、适用温度宽、工序简单等优点，已引起了广泛的关注，且发展迅速。以ZnS:Mn为发光层的单色TFELD 已发展成熟并已实现商业化。目前，TFELD 的研究重点是蓝光亮度的提高，从而实现彩色及至全色TFELD。
在发光体系材料中，稀土离子掺杂硅酸盐类荧光粉已经得到深入的研究，能够得到良好的红光到蓝光的激发，但是，稀土价格昂贵，硅酸盐在制备成薄膜电致发光材料时，往往薄膜质量低，性能差，限制了进一步的应用。
 技术问题
本发明所要解决的技术问题在于克服现有技术之缺陷，提供一种钛掺杂三元系硅酸盐薄膜及其制备方法和应用。
本发明实施例的另一目的在于提供上述钛掺杂三元系硅酸盐薄膜的制备方法。
本发明实施例的另一目的在于提供上述钛掺杂三元系硅酸盐薄膜在场发射器件、阴极射线管和/或电致发光器件中的应用。
技术解决方案
本发明实施例是这样实现的，第一方面提供一种钛掺杂三元系硅酸盐薄膜，所述钛掺杂三元系硅酸盐薄膜的通式为Ca2-xMgSi2O7: xTi4+，其中，x取值为0.00017～0.0256。
本发明实施例在于提供上述钛掺杂三元系硅酸盐薄膜的制备方法，其包括如下步骤：
将CaO粉体、MgO粉体、SiO2粉体和TiO2粉体按照摩尔比（2-x）: 1: 2: x混合，烧结作为靶材，其中，x取值为0.00017～0.0256；
将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2 Pa～4 Pa，通入惰性气体和氢气的混合气体，混合气体流量为15 sccm～35 sccm，衬底温度为250oC～750oC，溅射功率为30 W～200 W，溅射得钛掺杂三元系硅酸盐薄膜。
 有益效果
本发明实施例的钛掺杂三元系硅酸盐薄膜，通过Ti掺杂三元系硅酸盐，获得发光强度高，热稳定性和化学稳定性好的薄膜。上述制备方法采用磁控溅射法，其具有沉积速率高、薄膜附着性好、易控制并能实现大面积沉积等优点。进一步，该薄膜在光电半导体的应用中表现出稳定性高、寿命长的优势。
附图说明
图1是本发明实施例的钛掺杂三元系硅酸盐薄膜的制备方法的流程图；
图2是以本发明实施例的钛掺杂三元系硅酸盐薄膜作为做发光层的电致发光器件的结构示意图；
图3是本发明实施例1制备的钛掺杂三元系硅酸盐薄膜电致发光光谱图。
图4是本发明实施例1制备的钛掺杂三元系硅酸盐薄膜XRD谱图。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明作进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例是这样实现的，第一方面提供一种钛掺杂三元系硅酸盐薄膜，所述钛掺杂三元系硅酸盐薄膜的通式为Ca2-xMgSi2O7: xTi4+，其中，x取值为0.00017～0.0256。优选地，x取值为0.001～0.008。
硅酸盐基质具有较高的化学稳定性和热稳定性，而且高纯二氧化硅原料价廉易得，是一种理想的基质材料。相对于稀土而言，Ti价格低廉，少量的掺杂于基质材料Ca2MgSi2O7中便可以获得高强度的发光。
本发明实施例的另一目的在于提供本发明实施例的钛掺杂三元系硅酸盐薄膜的制备方法，请参阅图1，其包括如下步骤：
S01：将CaO粉体、MgO粉体、SiO2粉体和TiO2粉体按照摩尔比（2-x）: 1: 2: x混合，烧结作为靶材，其中，x取值为0.00017～0.0256；
S02：将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2 Pa～4 Pa，通入惰性气体和氢气的混合气体，混合气体流量为15 sccm～35 sccm，衬底温度为250oC～750oC，溅射功率为30 W～200 W，溅射得钛掺杂三元系硅酸盐薄膜。
步骤S01中，称取CaO粉体、MgO粉体、SiO2粉体和TiO2粉体，并将其均匀混合，烧结作为靶材。例如在900oC～1300oC温度下烧结，制成大约Ф 50×2 mm的陶瓷靶材。优选地，烧结温度为1250oC。上述粉体的纯度优选大于99.99%。混合物中各组份的摩尔比为CaO: MgO: SiO2: TiO2为（2-x）: 1: 2: x，其中，x取值为0.00017～0.0256。基体成分和掺杂元素的含量是影响薄膜性能和结构的重要因素。掺杂金属离子对材料结构有影响，外来金属离子进入晶格，使晶体结构发生部分畸变，因此，掺杂量过大，会导致晶格畸变过大，扰乱晶格中的离子有序化或导致材料中生成杂相，会使材料性能严重弱化，掺杂过少，则其发光性能会降低。优选地，所述x取值为0.001～0.008。
步骤S02中，衬底为蓝宝石、石英玻璃、硅片等硬质衬底。使用前用丙酮、无水乙醇和去离子水超声洗涤。也可以根据进一步应用选用衬底，如ITO玻璃衬底。靶材与衬底的距离优选为45 mm～95 mm。更优选地，靶材与衬底的距离为60 mm。靶材装入溅射腔体内后，用机械泵或者分子泵将腔体的真空度抽至1.0×10-3 Pa～1.0×10-5 Pa以上，优选为6.0×10-4 Pa。要得到性能优异的钛掺杂三元系硅酸盐薄膜，工艺条件设置非常重要。溅射腔内的工作气体为惰性气体和氢气的混合气体，其中，氢气体积百分比为1%～15%，优选为3%～8%。优选地，混合气体流量为20 sccm～30 sccm，工作压强为1.5 Pa～2.5 Pa，衬底温度为400oC～600oC，溅射功率为100 W～140 W。进一步，对制得的钛掺杂三元系硅酸盐薄膜进行退火处理，能够提高薄膜的性能。对上述特定工艺条件下制得的钛掺杂三元系硅酸盐薄膜进行退火处理，退火处理包括将钛掺杂三元系硅酸盐薄膜升温至退火温度并保温的过程。退火温度为500oC～800oC。优选地，退火温度为550oC～650oC退火环境可以为惰性气体，如氮气，氩气等，或者真空退火。在本发明一个优选实施例中，退火处理是在0.01 Pa的真空炉中退火。退火升温不易过快或者过慢，升温速率为1oC/min～10oC/min，优选地，升温速率为5oC/min～8oC/min。升温至退火温度后，保持1 h～3 h，优选地，保持2 h。退火提高了薄膜的结晶质量，增加薄膜，提高薄膜的发光效率。
本发明实施例还提供上述钛掺杂三元系硅酸盐薄膜在场发射器件、阴极射线管和/或电致发光器件中的应用。以电致发光器件为例，请参阅图2，示出采用上述实施例中钛掺杂三元系硅酸盐薄膜电致发光器件，其包括依次层叠设置的玻璃基层21、阳极22、发光层23、和阴极24。阳极22可采用氧化铟锡（简称为ITO），发光层23包含本发明实施例中的钛掺杂三元系硅酸盐薄膜；阴极24可以是但不限于金属Ag。因而，在一个具体实施例中，薄膜电致发光器件结构表示为：玻璃/ITO/钛掺杂三元系硅酸盐薄膜/Ag。各层可采用现有方法形成，如可以采用带有ITO层的玻璃衬底，采用磁控溅射方法溅射上述钛掺杂三元系硅酸盐薄膜，再蒸镀Ag层。
本发明实施例提供一种钛掺杂三元系硅酸盐薄膜，通过少量钛掺杂，获得结晶度高的钛掺杂三元系硅酸盐薄膜。该钛掺杂三元系硅酸盐薄膜的制备方法，采用磁控溅射法，实现了薄膜发光强度高，性能稳定，同时保持较好的使用寿命。而且，采用惰性气体和氢气的混合气体对溅射所得的钛掺杂三元系硅酸盐薄膜进行退火处理，能够提高薄膜的发光效率，较少量的掺杂就可以获得性能优异的薄膜，在蓝光区有较强的发射。
以下结合具体实施例对本发明的具体实现进行详细描述：
实施例1：
选用纯度为99.99%的CaO粉体、MgO粉体、SiO2粉体和TiO2粉体混合，混合物中各组份的摩尔比为CaO: MgO: SiO2: TiO2为1.994: 1: 2: 0.006，CaO粉体的质量为111.6 g，MgO粉体的质量为40 g，SiO2粉体的质量为120 g, TiO2粉体的质量为0.48 g。经过均匀混合后，1250oC高温烧结成Ф 50×2 mm的陶瓷靶材，并将靶材装入真空腔体内。先后用丙酮、无水乙醇和去离子水超声清洗带ITO的玻璃衬底，并对其进行氧等离子处理，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到5.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为5%（体积比百分含量），气体流量为25 sccm，压强调节为2.0 Pa，衬底温度设定为500oC，溅射功率调节为120 W，溅射得到钛掺杂三元系硅酸盐薄膜。再将所得钛掺杂三元系硅酸盐薄膜在0.01 Pa的真空炉中退火，其中，退火温度为600oC，升温速率为6oC/min，保温时间为2 h。得到的薄膜样品化学式为Ca1.994MgSi2O7: 0.006Ti4+。
实施例2：
选用纯度为99.99%的CaO粉体、MgO粉体、SiO2粉体和TiO2粉体混合，混合物中各组份的摩尔比为CaO: MgO5: SiO2: TiO2为1.9997: 1: 2: 0.0003，CaO粉体的质量为111.98g，MgO粉体的质量为40 g，SiO2粉体的质量为120 g, TiO2粉体的质量为0.024 g。经过均匀混合后，900oC高温烧结成Ф 50×2 mm的陶瓷靶材，并将靶材装入真空腔体内。先后用丙酮、无水乙醇和去离子水超声清洗蓝宝石衬底，再用去离子水冲洗，最后用高温氮气吹干，放入真空腔体。把靶材和衬底的距离设定为45 mm。用机械泵和分子泵把腔体的真空度抽到1.0×10-3 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为1%（体积比百分含量），气体流量为10 sccm，压强调节为0.2 Pa，衬底温度设定为250oC，溅射功率调节为30 W，溅射得到钛掺杂三元系硅酸盐薄膜。再将所得钛掺杂三元系硅酸盐薄膜在0.01 Pa的真空炉中退火，其中，退火温度为500oC，升温速率为10oC/min，保温时间为1 h。得到的薄膜样品化学式为Ca1.9997MgSi2O7: 0.0003Ti4+。
实施例3：
选用纯度为99.99%的CaO粉体、MgO粉体、SiO2粉体和TiO2粉体混合，混合物中各组份的摩尔比为CaO: MgO: SiO2: TiO2为1.995: 1: 2: 0.005，CaO粉体的质量为111.72g，MgO粉体的质量为40 g，SiO2粉体的质量为120 g, TiO2粉体的质量为0.4 g。经过均匀混合后，1300oC高温烧结成Ф 50×2 mm的陶瓷靶材，并将靶材装入真空腔体内。先后用丙酮、无水乙醇和去离子水超声清洗蓝宝石衬底，再用去离子水冲洗，最后用高温氮气吹干，放入真空腔体。把靶材和衬底的距离设定为95 mm。用机械泵和分子泵把腔体的真空度抽到1.0×10-5 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为1%（体积比百分含量），气体流量为35 sccm，压强调节为4.0 Pa，衬底温度设定为750oC，溅射功率调节为200 W，溅射得到钛掺杂三元系硅酸盐薄膜。再将所得钛掺杂三元系硅酸盐薄膜在0.01 Pa的真空炉中退火，其中，退火温度为800oC，升温速率为1oC/min，保温时间为3 h。得到的薄膜样品化学式为Ca1.95MgSi2O7: 0.05Ti4+。
实施例4：
选用纯度为99.99%的CaO粉体、MgO粉体、SiO2粉体和TiO2粉体混合，混合物中各组份的摩尔比为CaO: MgO: SiO2: TiO2为1.99983: 1: 2: 0.00017，CaO粉体的质量为111.99g，MgO粉体的质量为40 g，SiO2粉体的质量为120 g, TiO2粉体的质量为0.0136 g。经过均匀混合后，1200oC高温烧结成Ф 50×2 mm的陶瓷靶材，并将靶材装入真空腔体内。先后用丙酮、无水乙醇和去离子水超声清洗蓝宝石衬底，再用去离子水冲洗，最后用高温氮气吹干，放入真空腔体。把靶材和衬底的距离设定为50 mm。用机械泵和分子泵把腔体的真空度抽到8.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为3%（体积比百分含量），气体流量为15 sccm，压强调节为2.5 Pa，衬底温度设定为400oC，溅射功率调节为100 W，溅射得到钛掺杂三元系硅酸盐薄膜。再将所得钛掺杂三元系硅酸盐薄膜在氩气中退火，其中，退火温度为650oC，升温速率为4oC/min，保温时间为2.5 h。得到的薄膜样品化学式为Ca1.99983MgSi2O7: 0.00017Ti4+。
实施例5：
选用纯度为99.99%的CaO粉体、MgO粉体、SiO2粉体和TiO2粉体混合，混合物中各组份的摩尔比为CaO: MgO: SiO2: TiO2为1.9744: 1: 2: 0.0256，CaO粉体的质量为110.57 g，MgO粉体的质量为40 g，SiO2粉体的质量为120 g, TiO2粉体的质量为2.048 g。经过均匀混合后，1200oC高温烧结成Ф 50×2 mm的陶瓷靶材，并将靶材装入真空腔体内。先后用丙酮、无水乙醇和去离子水超声清洗蓝宝石衬底，再用去离子水冲洗，最后用高温氮气吹干，放入真空腔体。把靶材和衬底的距离设定为70 mm。用机械泵和分子泵把腔体的真空度抽到7.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为8%（体积比百分含量），气体流量为30 sccm，压强调节为1.5 Pa，衬底温度设定为600oC，溅射功率调节为140 W，溅射得到钛掺杂三元系硅酸盐薄膜。再将所得钛掺杂三元系硅酸盐薄膜在氩气中退火，其中，退火温度为550oC，升温速率为8oC/min，保温时间为1.5 h。得到的薄膜样品化学式为Ca1.9744MgSi2O7: 0.0256Ti4+。
图3是本发明实施例1制备的钛掺杂三元系硅酸盐薄膜的电致发光光谱图，其在480 nm处有很强的蓝光发射峰，表明钛掺杂三元系硅酸盐是一种性能良好的蓝光材料。
图4是本发明实施例1制备的钛掺杂三元系硅酸盐薄膜XRD谱图。对照标准与JCPDS 标准卡片，图中特征峰是基质硅酸盐的结晶峰，没有出现掺杂元素以及其它杂质的衍射峰。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种钛掺杂三元系硅酸盐薄膜，其特征在于，所述钛掺杂三元系硅酸盐薄膜的通式为Ca2-xMgSi2O7: xTi4+，其中，x取值为0.00017～0.0256。
  2. 如权利要求1所述的钛掺杂三元系硅酸盐薄膜， 其特征在于，所述x取值为0.001～0.008。
  3. 一种钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，所述方法包括如下步骤：
    将CaO粉体、MgO粉体、SiO2粉体和TiO2粉体按照摩尔比（2-x）: 1: 2: x混合，烧结作为靶材，其中，x取值为0.00017～0.0256；
    将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2 Pa～4 Pa，通入惰性气体和氢气的混合气体，混合气体流量为15 sccm～35 sccm，衬底温度为250 oC～750 oC，溅射功率为30 W～200 W，溅射得钛掺杂三元系硅酸盐薄膜。
  4. 权利要求3所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，对制得的钛掺杂三元系硅酸盐薄膜进一步进行退火处理。
  5. 如权利要求4所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，所述退火处理的退火温度为500oC～800oC，所述退火的保温时间为1 h～3 h。
  6. 如权利要求3所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，x取值为0.001～0.008。
  7. 如权利要求3所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，所述混合气体中氢气的体积百分含量为1%～15%。
  8. 如权利要求3所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，所述混合气体中氢气的体积百分含量为3%～8%。
  9. 如权利要求3至8择一所述的钛掺杂三元系硅酸盐薄膜的制备方法，其特征在于，所述腔体的工作压强为1.5 Pa～2.5 Pa，所述衬底温度为400oC～600oC，所述溅射功率为100 W～140 W。
  10. 如权利要求1或2所述的钛掺杂三元系硅酸盐薄膜在场发射器件、阴极射线管和/或电致发光器件中的应用。
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