CN101560679A - Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof - Google Patents
Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof Download PDFInfo
- Publication number
- CN101560679A CN101560679A CNA2009100980028A CN200910098002A CN101560679A CN 101560679 A CN101560679 A CN 101560679A CN A2009100980028 A CNA2009100980028 A CN A2009100980028A CN 200910098002 A CN200910098002 A CN 200910098002A CN 101560679 A CN101560679 A CN 101560679A
- Authority
- CN
- China
- Prior art keywords
- cerium
- film
- green light
- gadolinium
- electrode
- 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
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a cerium-doped gadolinium oxide green light luminescent film and a preparation method thereof. A layer of cerium-doped gadolinium oxide green light luminescent film is deposited on a platinum substrate. The preparation method comprises the following steps: selecting a soluble gadolinium salt solution and a soluble cerium salt as raw materials; carrying out thin film deposition on the platinum substrate by an electrochemical method; inserting a three-electrode into an evenly-mixed solution of a gadolinium salt and the cerium salt, and depositing the mixture in a constant temperature water bath at a temperature of between 50 and 80 DEG C, wherein regulation voltage is between -0.90 and -1.2V (vs SCE saturation calomel reference electrode); and the deposition time is 15 to 60 minutes; washing and drying the obtained film; and then carrying out rapid annealing on the film for 2 to 5 minutes at a temperature of between 600 and 1,200 DEG C. The prepared luminescent film is even and compact and has no cracking; the film material has a broadband green light emission spectrum at 480 to 550 nanometers; the luminescent film has the advantages of simple technique, easily-obtained raw materials, low cost, low energy consumption and no toxicity; and the formed film is even and compact and has no cracking.
Description
Technical field
The present invention relates to a kind of cerium-doped gadolinium oxide green light luminescent film and preparation method thereof.
Background technology
The rare earth ion optical transition occurs in unsaturated intratomic shell, and good electricity and calorifics shield effectiveness are arranged between the energy state, and spectral line is very narrow, and temperature factor is very little, so be a class ideal luminescence center.Though rare earth element has good fluorescence and laser characteristics, and aspect the glaze of stained glass and pottery application potential arranged, but ree content is limited, for the performance that makes rare earth element obtains better application, [Zhou Jianguo, Li Zhenquan are reported in the research that has recently begun to occur relevant rare earth ion doped nano luminescent material ten or twenty year, Zhao Fengying, Xia Shuping, Gao Shiyang, nanometer Y
2O
3: Eu
3+The Review Study of luminescent material, chemical industry progress, 6 (2003): 573-577].
A kind of as in the rare earth element of cerium, Ce
3+Has 4f
1Electronic configuration, ground state has 2F
5/2And 2F
7/2Two reconfiguration, its radiative transition are 5d-4f eelctric dipole allowed transitions.And Ce
3+Being important activator, is again good sensitizing agent, therefore enjoys investigator's concern, is widely used in various luminescent materials [Zhu Guoxian, Lian Hongzhou, Mo Fengshan, stone Chun-shan Mountain, BaLiF
3: Ce
3+The preparation of nanoparticle and spectral response curve thereof, SCI, 27 (2006): 215-217].
Cerium-doped gadolinium oxide is as the fluorescent material of excellent property, and it is widely used in the glaze etc. of colour television set picture tube, three-color fluorescent lamp and stained glass, pottery.[Zhang Hanmou, Ma Shuyi, Zhang Guoheng, the pattern of cerium doping porous silicon and photoluminescence research, functional materials 38 (2007): 596-598].The gadolinium sesquioxide film that the electrochemical filming method prepares doped with cerium is a kind of brand-new preparation method, and can prepare the film of excellent property.By the adjusting of reaction parameter, can evenly grow on substrate material gadolinium sesquioxide and cerium oxide codeposition film both can reduce the reaction materials, saved follow-up coated technique again, reduced production costs greatly.In addition, the electrochemical method film forming is even, and deposit thickness is controlled, equipment and simple to operate, reaction conditions is gentle, environmental pollution is little, mixes the concentration height and be a kind of brand-new, clean, gentle, eco-friendly method.
Summary of the invention
The objective of the invention is to propose a kind of cerium-doped gadolinium oxide green light luminescent film and preparation method thereof, with solubility gadolinium salt and cerium solution is raw material, on the platinum substrate, deposit the cerium-doped gadolinium oxide film by electrochemical method, obtain cerium-doped gadolinium oxide green light luminescent film through high temperature rapid thermal annealing.
The technical solution used in the present invention step is as follows:
One, a kind of cerium-doped gadolinium oxide green light luminescent film:
On face of platinum substrate, deposit the green light-emitting film of one deck gadolinium sesquioxide and cerium oxide.
The chemical formula of the green light-emitting film of described gadolinium sesquioxide and cerium oxide (1) is Gd
2O
3: Ce
3+, there is the broadband green optical emission spectroscopy in this thin-film material between 560～640 nanometers.
Two, a kind of preparation method of cerium-doped gadolinium oxide green light luminescent film, the step of this method is as follows:
1) respectively with solubility gadolinium salt and cerium salt, is dissolved in the deionized water, stirs, all be made into gadolinium salts solution and the cerium solution of volumetric molar concentration 0.02～0.2mol/L;
2) get above-mentioned gadolinium salt and cerium solution and form the solution that mixes, control solution temperature at 50 ℃～80 ℃ by water bath with thermostatic control;
3) utilize the three-electrode electro Chemical pond of forming by working electrode, counter electrode and reference electrode to carry out thin film deposition on the platinum substrate, three electrodes are inserted in the mixing solutions of gadolinium salt and cerium solution composition, regulate between working electrode and SCE saturated calomel reference electrode voltage-0.9V～-1.2V between, depositing time was controlled at 15 minutes～60 minutes;
4) will deposit good film, use washed with de-ionized water, and drying, subsequently, with film 700 ℃～1200 ℃ following short annealings 2 minutes～5 minutes.
In the described three-electrode electro Chemical pond, working electrode is the platinum substrate, and counter electrode is platinum electrode, gold electrode or Graphite Electrodes, and reference electrode is the SCE saturated calomel reference electrode.
Described solubility gadolinium salt and cerium salt are nitrate.
The chemical formula of the green light-emitting film of described gadolinium sesquioxide and cerium oxide is Gd
2O
3: Ce
3+, this forming thin film even compact does not have cracking, has the broadband green optical emission spectroscopy in 480～550 nanometers.
The beneficial effect that the present invention has is:
The present invention makes a kind of novel cerium-doped gadolinium oxide green light luminescent film by simple electrochemical deposition method and follow-up high temperature rapid thermal annealing process, and this thin-film material even compact does not have cracking, has the broadband green optical emission spectroscopy in 480～550 nanometers.Processing method of the present invention is simple, raw material is easy to get, cost is low, and energy consumption is low, and is nontoxic, and the film forming even compact does not have cracking.
Description of drawings
Fig. 1 is a cerium-doped gadolinium oxide green light luminescent film structural representation on the platinum substrate
Among Fig. 1: 1, cerium-doped gadolinium oxide green light luminescent film, 2, the platinum substrate.
Fig. 2 is the energy spectrogram of embodiment 1 products therefrom.
Fig. 3 is the XRD spectra of embodiment 1 products therefrom.
Fig. 4 is electromicroscopic photograph (low power) figure of embodiment 1 products therefrom.
Fig. 5 is electromicroscopic photograph (high power) figure of embodiment 1 products therefrom.
Fig. 6 is the photoluminescence emmission spectrum of embodiment 1 products therefrom.
Embodiment
As shown in Figure 1, the present invention deposits one deck cerium-doped gadolinium oxide green light luminescent film 1 on platinum substrate 2.The chemical formula of described this light-emitting film is Gd
2O
3: Ce
3+, there is the broadband green optical emission spectroscopy in this thin-film material in 480～550 nanometers.
Embodiment 1:
Cerium-doped gadolinium oxide green light luminescent film and synthetic is dissolved in 4.342g six nitric hydrate ceriums in the 100mL deionized water, stirs, and is made into the cerium solution of volumetric molar concentration 0.1mol/L; 4.513g six nitric hydrate gadoliniums are dissolved in the 100mL deionized water, stir, be made into the gadolinium salts solution of volumetric molar concentration 0.1mol/L.
Get the example mixing according to a certain volume of above-mentioned cerium salt and gadolinium salt, mixing solutions is 12mL altogether, controls solution temperature at 50 ℃ by water bath with thermostatic control.Utilize the three-electrode electro Chemical pond to carry out the cerium-doped gadolinium oxide depositing of thin film.Working electrode is the platinum substrate.Counter electrode is highly purified platinum electrode.Reference electrode is the SCE saturated calomel reference electrode.Three electrodes are inserted gadolinium salt and cerium mixed salt solution.Regulating voltage is at-1.0V (vs SCE saturated calomel reference electrode), and depositing time was controlled at 30 minutes.The film that deposition is good is used washed with de-ionized water, and dry.Subsequently, with film 800 ℃ of following short annealings 3 minutes.Fig. 2 is the EDS collection of illustrative plates of this film product, shows on the collection of illustrative plates mainly to have oxygen, gadolinium and three kinds of elements of cerium.The atomic quantity ratio of gadolinium and cerium is about 15.8: 1, illustrates that the film that obtains is a cerium-doped gadolinium oxide.Fig. 3 is the XRD spectra of film, and the standard card (JCPDS#43-1014) of this spectrogram and cubic phase oxygen gadolinium fits like a glove.Fig. 4 is the low power electromicroscopic photograph of this routine products therefrom.As can be seen from the figure film particles is even, the fine and close nothing cracking of film.Fig. 5 is the high power electromicroscopic photograph of this routine products therefrom.This routine product has stronger photoluminescence emmission spectrum as seen from Figure 6, has the broadband green optical emission spectroscopy in 480～550 nanometers.
Embodiment 2:
Cerium-doped gadolinium oxide green light luminescent film and synthetic is dissolved in 0.8684g six nitric hydrate ceriums in the 100mL deionized water, stirs, and is made into the cerium solution of volumetric molar concentration 0.1mol/L; 0.9026g six nitric hydrate gadoliniums are dissolved in the 100mL deionized water, stir, be made into the gadolinium salts solution of volumetric molar concentration 0.1mol/L.
Get above-mentioned cerium salt and gadolinium salt certain volume mixed, mixing solutions is 12mL altogether, controls solution temperature at 70 ℃ by water bath with thermostatic control.Utilize the three-electrode electro Chemical pond to carry out the cerium-doped gadolinium oxide depositing of thin film.Working electrode is the platinum substrate.Counter electrode is highly purified platinum electrode.Reference electrode is the SCE saturated calomel reference electrode.Three electrodes are inserted gadolinium salt and cerium mixed salt solution.Regulating voltage is at-1.20V (vs SCE saturated calomel reference electrode), and depositing time was controlled at 60 minutes.The film that deposition is good is used washed with de-ionized water, and dry.Subsequently, with film 1200 ℃ of following short annealings 3 minutes.The concrete test result of prepared cerium-doped gadolinium oxide film is similar to the test effect of embodiment 1.
Embodiment 3:
Cerium-doped gadolinium oxide green light luminescent film and synthetic is dissolved in 8.684g six nitric hydrate ceriums in the 100mL deionized water, stirs, and is made into the cerium solution of volumetric molar concentration 0.2mol/L; 9.026g six nitric hydrate gadoliniums are dissolved in the 100mL deionized water, stir, be made into the gadolinium salts solution of volumetric molar concentration 0.2mol/L.
Get above-mentioned cerium salt and gadolinium salt certain volume mixed, mixing solutions is 12mL altogether, controls solution temperature at 50 ℃ by water bath with thermostatic control.Utilize the three-electrode electro Chemical pond to carry out the cerium-doped gadolinium oxide depositing of thin film.Working electrode is the platinum substrate.Counter electrode is highly purified platinum electrode.Reference electrode is the SCE saturated calomel reference electrode.Three electrodes are inserted gadolinium salt and cerium mixed salt solution.Regulating voltage is at-0.7V (vs SCE saturated calomel reference electrode), and depositing time was controlled at 60 minutes.The film that deposition is good is used washed with de-ionized water, and dry.Subsequently, with film 700 ℃ of following short annealings 5 minutes.The concrete test result of prepared cerium-doped gadolinium oxide film is similar to the test effect of embodiment 1.
Claims (6)
1, a kind of cerium-doped gadolinium oxide green light luminescent film is characterized in that: the green light-emitting film (1) that deposits one deck gadolinium sesquioxide and cerium oxide on (2) faces of platinum substrate.
2, a kind of cerium-doped gadolinium oxide green light luminescent film according to claim 1 is characterized in that: the chemical formula of the green light-emitting film of described gadolinium sesquioxide and cerium oxide (1) is Gd
2O
3: Ce
3+, there is the broadband green optical emission spectroscopy in this thin-film material between 560～640 nanometers.
3, a kind of preparation method of cerium-doped gadolinium oxide green light luminescent film is characterized in that the step of this method is as follows:
1) respectively with solubility gadolinium salt and cerium salt, is dissolved in the deionized water, stirs, all be made into gadolinium salts solution and the cerium solution of volumetric molar concentration 0.02～0.2mol/L;
2) get above-mentioned gadolinium salt and cerium solution and form the solution that mixes, control solution temperature at 50 ℃～80 ℃ by water bath with thermostatic control;
3) utilize the three-electrode electro Chemical pond of forming by working electrode, counter electrode and reference electrode to carry out thin film deposition on the platinum substrate, three electrodes are inserted in the mixing solutions of gadolinium salt and cerium solution composition, regulate between working electrode and SCE saturated calomel reference electrode voltage-0.9V～-1.2V between, depositing time was controlled at 15 minutes～60 minutes;
4) will deposit good film, use washed with de-ionized water, and drying, subsequently, with film 700 ℃～1200 ℃ following short annealings 2 minutes～5 minutes.
4, the preparation method of a kind of cerium-doped gadolinium oxide green light luminescent film according to claim 3, it is characterized in that: in the described three-electrode electro Chemical pond, working electrode is the platinum substrate, counter electrode is platinum electrode, gold electrode or Graphite Electrodes, and reference electrode is the SCE saturated calomel reference electrode.
5, the preparation method of a kind of cerium-doped gadolinium oxide green light luminescent film according to claim 3 is characterized in that: described solubility gadolinium salt and cerium salt are nitrate.
6, the preparation method of a kind of cerium-doped gadolinium oxide green light luminescent film according to claim 3 is characterized in that: the chemical formula of the green light-emitting film of described gadolinium sesquioxide and cerium oxide is Gd
2O
3: Ce
3+, this forming thin film even compact does not have cracking, has the broadband green optical emission spectroscopy in 480～550 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100980028A CN101560679A (en) | 2009-04-23 | 2009-04-23 | Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100980028A CN101560679A (en) | 2009-04-23 | 2009-04-23 | Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101560679A true CN101560679A (en) | 2009-10-21 |
Family
ID=41219644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100980028A Pending CN101560679A (en) | 2009-04-23 | 2009-04-23 | Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101560679A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024707A (en) * | 2010-11-03 | 2011-04-20 | 南京大学 | Method for manufacturing GaAs-based metal oxide semiconductor (MOS) device |
| CN103627394A (en) * | 2013-10-24 | 2014-03-12 | 浙江大学 | Method for preparing beta-NaGdF4:Yb<3+>, Er<3+> upconversion fluorescence material through electro-deposition |
| CN104152965A (en) * | 2014-08-12 | 2014-11-19 | 浙江大学 | Preparation method of bivalent europium-doped calcium fluoride blue light emitting film |
| US9387719B2 (en) | 2013-10-28 | 2016-07-12 | Honeywell International Inc. | Cold-worked metal articles including luminescent phosphor particles, methods of forming the same, and methods of authenticating the same |
| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
-
2009
- 2009-04-23 CN CNA2009100980028A patent/CN101560679A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024707A (en) * | 2010-11-03 | 2011-04-20 | 南京大学 | Method for manufacturing GaAs-based metal oxide semiconductor (MOS) device |
| CN103627394A (en) * | 2013-10-24 | 2014-03-12 | 浙江大学 | Method for preparing beta-NaGdF4:Yb<3+>, Er<3+> upconversion fluorescence material through electro-deposition |
| CN103627394B (en) * | 2013-10-24 | 2015-11-04 | 浙江大学 | β-NaGdF4:Yb3+ is prepared in galvanic deposit, the method for Er3+ upconverting fluorescent material |
| US9387719B2 (en) | 2013-10-28 | 2016-07-12 | Honeywell International Inc. | Cold-worked metal articles including luminescent phosphor particles, methods of forming the same, and methods of authenticating the same |
| CN104152965A (en) * | 2014-08-12 | 2014-11-19 | 浙江大学 | Preparation method of bivalent europium-doped calcium fluoride blue light emitting film |
| CN104152965B (en) * | 2014-08-12 | 2016-08-17 | 浙江大学 | A kind of preparation method of divalent europium doping calcium fluoride blue light luminescent film |
| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Patterning of red, green, and blue luminescent films based on CaWO4: Eu3+, CaWO4: Tb3+, and CaWO4 phosphors via microcontact printing route | |
| Armelao et al. | Structure− luminescence correlations in europium-doped sol− gel ZnO nanopowders | |
| Dhanaraj et al. | Photoluminescence characteristics of Y2O3: Eu3+ nanophosphors prepared using sol− gel thermolysis | |
| CN101560679A (en) | Cerium-doped gadolinium oxide green light luminescent film and preparation method thereof | |
| Braziulis et al. | Sol-gel derived europium doped CaMoO4: Eu3+ with complex microstructural and optical properties | |
| Kumar et al. | Synthesis, characterization and upconversion luminescence of core-shell nanocomposites NaYF4: Er/Yb@ SiO2@ Ag/Au | |
| Fang et al. | Photoluminescence characteristics of ZnO doped with Eu3+ powders | |
| Dimitrov et al. | High intensity orange-red emission of chemically deposited Sm3+-doped ZrO2 thin films-Beneficial effects of host and dopant | |
| Zhao et al. | Hydrothermal synthesis and photoluminescence properties of In3+ co-doped YVO4: Eu3+ phosphors | |
| Zhang et al. | Synthesis and luminescent property of Sr2CeO4 phosphor via EDTA-complexing process | |
| CN101462834A (en) | Terbium doped yttrium oxide green light-emitting film and preparation thereof | |
| CN102690655A (en) | Europium-doped yttrium borate red light emitting film and preparation method thereof | |
| Freeda et al. | Photoluminescence investigations of Ytterbium doped Calcium Aluminate nanophosphor synthesized by sol-gel technique (CaAl2O4: Yb) | |
| CN1185306C (en) | Process for preparing doped nm powder of zine sulfide | |
| Zhang et al. | Synthesis, characterization and luminescence of Eu3+-doped SrZrO3 nanocrystals | |
| Hou et al. | Preparation and luminescence properties of Gd2MoO6: Eu3+ nanofibers and nanobelts by electrospinning | |
| CN101560680A (en) | Terbium-doped gadolinium oxide green light luminescent film and preparation method thereof | |
| CN101560682A (en) | Praseodymium-doped gadolinium oxide orange yellow light luminescent film and preparation method thereof | |
| CN111253152B (en) | Fast-attenuation high-light-efficiency scintillation material and preparation method thereof | |
| CN100554363C (en) | A kind of manufacture method of superfine fluorescent powder | |
| CN101597141A (en) | A kind of europium-doped yttrium oxide red-light luminescent film and preparation method thereof | |
| Yan et al. | Matrix-inducing synthesis and luminescence of Zn2SiO4: xTb3+ submicrometer phosphors derived from the sol–gel assembling of different multicomponent hybrid precursors | |
| CN101560681A (en) | Samarium-doped gadolinium oxide blue light luminescent film and preparation method thereof | |
| Xiao et al. | Chemical co-precipitation synthesis and photoluminescence of Eu3+ or Dy3+ doped Zn3Nb2O8 microcrystalline phosphors from hybrid precursors | |
| Xiumei et al. | Photoluminescent properties of Ca2Gd8 (SiO4) 6O2: Dy3+ phosphor films prepared by sol-gel process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091021 |