CN103397302B - Preparation method of up-conversion luminescence Er / Yb co-doped TiO2 thin film - Google Patents
Preparation method of up-conversion luminescence Er / Yb co-doped TiO2 thin film Download PDFInfo
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- CN103397302B CN103397302B CN201310271374.2A CN201310271374A CN103397302B CN 103397302 B CN103397302 B CN 103397302B CN 201310271374 A CN201310271374 A CN 201310271374A CN 103397302 B CN103397302 B CN 103397302B
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Abstract
The invention belongs to the technical fields of solar energy and laser, and specifically provides a preparation method of an up-conversion luminescence Er / Yb co-doped TiO2 thin film. The method provided by the invention employs radio frequency magnetron sputtering technology, and employs a TiO2 ceramic target inlaid with an Er film and an Yb film as a target material, and quartz or a silicon wafer as a substrate. Radio frequency magnetron sputtering is employed to prepare the up-conversion luminescence rare earth element Er / Yb co-doped TiO2 film, and the content of Er and Yb in the target is controlled to control the amount of doping, so as to obtain the up-conversion luminescence Er / Yb co-doped TiO2 thin film with good compactness, high degree of uniformity, and excellent mechanical and optical properties.
Description
Technical field
The invention belongs to sun power and laser technology field, be specifically related to the preparation method based on rear-earth-doped up-conversion luminescence film.
Background technology
Up-conversion luminescence sends the anti-Stokes luminescence that the shorter photon of wavelength realizes.The electronic configuration of rare earth element makes it become the first-selection of up-conversion luminescent material.China is the country that rare earth resources enriches, more and more paid close attention to based on the laserable material of rare earth and luminescent material, the rare earth doped research realizing up-conversion luminescence is utilized also extensively to be carried out at present, it is mainly used in opticfiber communication, data store, the optics of the aspects such as laser apparatus
[1], also can be applicable to solar cell.Based on Er in up-conversion luminescent material
3+the existing many reports of up-conversion luminescent material of doping.Er
3+energy level highly beneficial for the up-conversion luminescence of the mono-pump light source of 980 nm, simultaneously as Er
3+sensitized ions Yb
3+980 nm there is larger absorption cross section and can effectively by transmission ofenergy to Er
3+, can strengthen further absorbing, improve up-conversion luminescence efficiency.The generation of up-conversion luminescence be unable to do without suitable substrate material, but the phonon energy of different substrates material is different, and it is very large on up-conversion luminescence efficiency impact.The substrate material being applied to rear-earth-doped up-conversion luminescence at present is mainly divided into three kinds: fluorochemical, oxide compound and muriate.But the very low mechanical property of fluorochemical phonon energy is poor, muriate mechanical property very well but phonon energy is very large, oxide compound has relatively low phonon energy and excellent mechanical property and is widely used.TiO in oxide compound
2possess lower phonon energy and be used as the substrate material of up-conversion luminescence, and TiO
2as a kind of important semiconductor material, there is excellent optics, electrology characteristic, in addition fast light corrosive power strong, chemistry, stable mechanical property, cheap and to advantages such as human non-toxic's property.There is bibliographical information Er doped Ti O in recent years
2the preparation of powder body material
[2], but due to powder body material limitation in actual applications, Er/Yb codoped TiO
2thin-film material starts to obtain attention.Thin-film material is conducive to making optical waveguide device
[3], also can be applicable to solar cell
[4] [5].At present about preparation Er/Yb codoped TiO
2thin-film material mainly adopts sol-gel (sol-gel) method
[6], and have no the report of magnetron sputtering technology of preparing.The film thickness that sol-gel method prepares is difficult to accurate control, and film compactness is poor, and degree of uniformity is low, machinery and optical property poor.Magnetron sputtering method is adopted to prepare Er/Yb codoped TiO
2film effectively can overcome the shortcoming of sol-gel method.
The present invention utilizes magnetron sputtering technique to prepare Er/Yb codoped TiO
2film, target is the TiO of embedded with metal Er sheet and Yb sheet
2ceramic target.According to metal Er and Yb and TiO
2sputtering yield, by adjustment Er, Yb and TiO
2target is at the doping content of the area control Er/Yb in ise district.Film-forming process once completes in a vacuum chamber, and doping content, film thickness can accurately control, method simple and effective.By the Er/Yb codoped TiO prepared
2film is placed in resistance furnace and anneals, thus obtains the film with up-conversion luminescence performance.By changing film thickness, the processing parameter such as doping content and heat-treat condition, can obtain the Er/Yb codoped TiO with best up-conversion luminescence performance
2film.
Reference
[1] San-Yuan Chen, Chu-Chi Ting, Wen-Feng Hsieh. Comparison of visible fluorescence properties between sol-gel derived Er
3+-Yb
3+and Er
3+-Y
3+co-doped TiO
2films. Thin Solid Films. 2003,434:171-177
[2] reach the clouds in vain, Su Xianyun, Lei Mingkai. complexing action to sol-gol legal system for Er
3+doped Ti O
2powder photoluminescence property affects. Journal of Inorganic Materials. and 2006,21 (5): 1085-1091
[3] A Bahtat, M Bouderbala, M Bahtat, M Bouazaoui, J Mugnier, M Druetta. Structural characterisation of Er
3+doped sol–gel TiO
2planar optical waveguides Original Research Article. Thin Solid Films. 1998,22(1-2):59-62
[4] Jun Zheng, Yeliao Tao, Wei Wang, Zhihua Ma, Yuhua Zuo, Buwen Cheng, Qiming Wang. Intense 974 nm emission from Er
xYb
2?xSi
2O
7films through efficient energy transfer up-conversion from Er
3+to Yb
3+for Si solar cell. Journal of Luminescence. 2012,132(9):2341-2344
[5] A Shalav, B.S. Richards, M.A. Green. Luminescent layers for enhanced silicon solar cell performance: Up-conversion. Solar Energy Materials and Solar Cells. 2007,91(9):829-842
[6] Zhengwen Yang, Kan Zhu, Zhiguo Song, Dacheng Zhou, Zhaoyi Yin, Jianbei Qiu. Preparation and upconversion emission properties of TiO
2:Yb, Er inverse opals. Solid State Communications. 2011,151(5):364-367。
Summary of the invention
The object of this invention is to provide a kind of preparation method based on rear-earth-doped up-conversion luminescence film, so that it is good to obtain compactness, degree of uniformity is high, the up-conversion luminescence film of machinery and excellent optical performance.
The preparation method provided based on rear-earth-doped up-conversion luminescence film of the present invention, adopts radiofrequency magnetron sputtering technology, and target uses the TiO of embedded with metal Er sheet and Yb sheet
2ceramic target, substrate is quartz or silicon chip; Rf magnetron sputtering is prepared into the rare earth element er/Yb codoped TiO of up-conversion luminescence
2film, and carry out controlled doping amount by the content controlling Er and Yb in target, thus it is good to obtain compactness, degree of uniformity is high, the up-conversion luminescence film of machinery and excellent optical performance.
Concrete preparation condition is as follows:
Preparing time substrate temperature is room temperature to 300 DEG C;
Sputtering room, initial vacuum background pressure is 2.0 × 10
-3pa, use oxygen argon mixture gas during rf magnetron sputtering, total gas pressure is 0.1 ~ 1.0 Pa, wherein O
2point covering total gas pressure ratio is 0.5 ~ 10.0%; Sputtering power density is 17.7 ~ 177 kW/m
2(target diameter 60 mm, corresponding sputtering power 50 ~ 500 W);
The film sample prepared can be annealed under air, also can anneal under nitrogen, protection of inert gas, and annealing temperature is 500 ~ 1200 DEG C, and annealing time is 0.5 ~ 5 hour.
In the present invention, target used is the TiO of embedded with metal Er sheet and Yb sheet
2ceramic target, purity is 99%; The molar concentration rate of Er/Ti is the molar concentration rate of 0.1 ~ 5 %, Yb/Ti is 0.5 ~ 30 %, by the ise district on target, and Er sheet, Yb sheet and TiO
2area ratio and the product of sputtering raste ratio control.The spacing of target and substrate is 50 ~ 75 mm.
The Er/Yb codoped TiO that the inventive method is obtained
2overall film thickness is 100 ~ 1000 nm, adjusts thickness by controlling sputtering time.
Concrete operation step is as follows:
(1) substrate adopts polishing silica glass or silicon chip, is fixed on frame substrate after deionized water, acetone, alcohol ultrasonic cleaning;
(2) sputtering room, initial vacuum background pressure is 2.0 × 10
-3pa, passes into oxygen argon mixture gas as sputter gas to 0.1 ~ 1.0 Pa, under certain substrate temperature, adopts radiofrequency magnetron sputtering technology to deposit, and radio-frequency sputtering power density is 17 ~ 177 kW/m
2;
(3) length controlling sputtering time under above-mentioned condition can obtain the film of thickness 100 ~ 1000 nm.
(4) anneal sputtering the film obtained, annealing temperature is 500 ~ 1200 DEG C, and time controling was at 0.5 ~ 5 hour.
Experimental result shows, the Er/Yb codoped TiO prepared in this way
2film has excellent up-conversion luminescence performance under 980nm pumping source excites.The inventive method technology stability is good, has IP prospecting, is that one prepares rare earth element er/Yb codoped TiO
2the novel method of film.
Accompanying drawing explanation
Fig. 1 is the TiO of embedded with metal Er sheet and Yb sheet
2ceramic target schematic diagram.
Fig. 2 is Er
3+doped Ti O
2the luminous intensity of film sample under 980nm pumping source excites.Wherein, (a) 0.2 mol% Er
3+; (b) 1.8 mol% Er
3+.
Fig. 3 is Er
3+/ Yb
3+codoped TiO
2the luminous intensity of film sample under 980nm pumping source excites.Wherein, (a) 1.0 mol% Er
3+/ 1.0 mol% Yb
3+; (b) 1.0 mol% Er
3+/ 25.0 mol% Yb
3+.
Fig. 4 is Er
3+/ Yb
3+codoped TiO
2the luminous intensity of film sample under 980nm pumping source excites.Wherein, (a) annealing temperature 600 DEG C; (b) annealing temperature 1100 DEG C.
Embodiment
Embodiment 1:
In fig. 2, substrate temperature is room temperature, and in sputter gas, oxygen partial pressure accounts for total gas pressure ratio is 2.5%, and sputtering pressure 0.5 Pa, Sputtering power density is 106 kW/m
2, film thickness about 500 nm.900 DEG C of annealing 150 min in an atmosphere.
Measure luminous pumping source and adopt 980 nm semiconductor lasers, power 2000 mW, 45° angle incides film surface.
Under pumping source excites, Er
3+doped Ti O
2the upper conversion light intensity of film sample is as shown in Fig. 2 (a), (b).(a) 0.2 mol% Er
3+；(b) 1.8 mol% Er
3+。
Embodiment 2:
In figure 3, prepare other conditions of film with embodiment one, changing the content of Yb in mosaic target is (a) 1.0 mol% Er
3+/ 1.0 mol% Yb
3+; (b) 1.0 mol% Er
3+/ 25.0 mol% Yb
3+.900 DEG C of annealing 200min in an atmosphere.
Under pumping source excites, Er
3+/ Yb
3+codoped TiO
2film sample is at different Yb
3+upper conversion light intensity under doping content is as shown in Fig. 3 (a), (b).
Embodiment 3:
In the diagram, other conditions of film are prepared with embodiment one, Er
3+/ Yb
3+volumetric molar concentration is 1.0 mol% Er
3+/ 10 mol% Yb
3+.Changing annealing temperature is (a) 600 DEG C; (b) 1100 DEG C.
Under pumping source excites, Er
3+/ Yb
3+codoped TiO
2the upper conversion light intensity of film sample under different annealing temperature is as shown in Fig. 4 (a), (b).
Claims (3)
1. the Er/Yb codoped TiO of a up-conversion luminescence
2the preparation method of film, is characterized in that, adopts radiofrequency magnetron sputtering technology, and target uses the TiO of embedded with metal Er sheet and Yb sheet
2ceramic target, substrate adopts quartz or silicon chip, and rf magnetron sputtering is prepared into the rare earth element er/Yb codoped TiO of up-conversion luminescence
2film, carrys out controlled doping amount by the content controlling Er and Yb in target; The actual conditions of preparation is as follows:
Substrate temperature is room temperature to 300 DEG C;
Sputtering room, initial vacuum background pressure is 2.0 × 10
-3pa, use oxygen argon mixture gas during rf magnetron sputtering, total gas pressure is 0.1 ~ 1.0 Pa, wherein, O
2point covering total gas pressure ratio is 0.5 ~ 10.0%; Sputtering power density is 17.7 ~ 177 kW/m
2;
The film sample prepared is annealed under air, or anneals under nitrogen, protection of inert gas, and annealing temperature is 500 ~ 1200 DEG C, and annealing time is 0.5 ~ 5 hour.
2. preparation method according to claim 1, is characterized in that, target purity used is 99%, and wherein, the molar concentration rate of Er/Ti is the molar concentration rate of 0.1 ~ 5 %, Yb/Ti is 0.5 ~ 30 %, by the ise district on target, and Er sheet, Yb sheet and TiO
2area ratio and the product of sputtering raste ratio control; The spacing of target and substrate is 50 ~ 75 mm.
3. preparation method according to claim 1, is characterized in that, obtained Er/Yb codoped TiO
2overall film thickness is 100 ~ 1000 nm, and film thickness adjusts by controlling sputtering time.
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| CN104195520B (en) * | 2014-07-02 | 2016-08-24 | 贵州民族大学 | One two-step method prepares carbon dope TiO2the method of thin film |
| CN105112861A (en) * | 2015-09-29 | 2015-12-02 | 哈尔滨工业大学 | Preparation method of erbium-single-doped vanadium dioxide polycrystalline film |
| CN108192607B (en) * | 2018-01-09 | 2021-07-30 | 南京大学 | Up-conversion strong red light emission TiO2Preparation and application of nano material |
| CN109713561B (en) * | 2019-02-12 | 2020-05-08 | 暨南大学 | Cobalt-erbium double-doped laser crystal facing 2.6-4.0 micron mid-infrared all-solid-state laser |
| CN113980679A (en) * | 2021-09-03 | 2022-01-28 | 昆明理工大学 | TiO 22Preparation and application of Yb, Er up-conversion luminescence anti-counterfeiting fluorescent powder |
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| CN1826424A (en) * | 2003-05-23 | 2006-08-30 | 希莫菲克斯公司 | Energy conversion and storage films and devices by physical vapor deposition of titanium and titanium oxides and sub-oxides |
| CN101591769A (en) * | 2009-07-02 | 2009-12-02 | 复旦大学 | A kind of C, the co-doped nano TiO that N content is adjustable 2The preparation method of film |
| CN102295929A (en) * | 2011-06-13 | 2011-12-28 | 浙江东晶光电科技有限公司 | Preparation method of core-shell structured TiO2-based nanocrystalline up-converting phosphor |
| CN102836704A (en) * | 2012-09-20 | 2012-12-26 | 复旦大学 | Molybdenum-doped TiO2 photocatalytic film with three-layer structure and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826424A (en) * | 2003-05-23 | 2006-08-30 | 希莫菲克斯公司 | Energy conversion and storage films and devices by physical vapor deposition of titanium and titanium oxides and sub-oxides |
| CN101591769A (en) * | 2009-07-02 | 2009-12-02 | 复旦大学 | A kind of C, the co-doped nano TiO that N content is adjustable 2The preparation method of film |
| CN102295929A (en) * | 2011-06-13 | 2011-12-28 | 浙江东晶光电科技有限公司 | Preparation method of core-shell structured TiO2-based nanocrystalline up-converting phosphor |
| CN102836704A (en) * | 2012-09-20 | 2012-12-26 | 复旦大学 | Molybdenum-doped TiO2 photocatalytic film with three-layer structure and preparation method thereof |
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