CN107620101B - One kind (La1-xLnx)2(MoO4)3The direct preparation method of film - Google Patents
One kind (La1-xLnx)2(MoO4)3The direct preparation method of film Download PDFInfo
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Abstract
The invention discloses one kind (La1‑xLnx)2(MoO4)3The direct preparation method of film.By La (NO3)3·6H2O or La (NO3)3·6H2O and Ln (NO3)3·6H2O is dissolved in the solution for being configured to that rare earth ion total concentration is 0.005 ~ 1mol/L in deionized water, and EDTA or citric acid, NaOH solution, Na are added wherein2MoO4·2H2O, KCl and HNO3, electric depositing solution is obtained after mixing, is placed in water-bath, its temperature is made to reach required temperature；Three-electrode system is inserted into electric depositing solution, thin film is being deposited on electro-conductive glass by electrodeposit reaction, film is used respectively deionized water, dehydrated alcohol rinse, it is subsequently placed in air dry oven dry, dried electrodeposited film is placed in tube furnace again to be heat-treated, (La is made1‑xLnx)2(MoO4)3Film.Operation of the present invention is simple, compared to the conventional method to form a film after powder is first done, greatly simplifies method for manufacturing thin film, while avoiding influence of the powder morphology to quality of forming film；And method provided by the invention is easy to operate, and time-consuming short, film quality is good.
Description
Technical field
The invention belongs to materialogy technical fields, and in particular to one kind (La1-xLnx)2(MoO4)3The directly preparation side of film
Method.
Background technique
The rare earth luminescent material of molybdic acid salt system is because it is with good chemical stability and higher fluorescence quantum efficiency
The advantages that by the fluorescent material as fields such as solid state lighting, FPD, lasers, and fluorescent material is prepared into accordingly
Film is an important premise of luminescent material device.There are many rare earth molybdic acids that method can prepare different-shape at present
Salt material, such as sol-gel method, hydro-thermal method, solid phase method, microwave method etc..The principle of sol-gal process is alkoxide or esters
It closes object dissolution in organic solvent, by hydrolysis, forms activated monomer, monomer polymerize in turn forms colloidal sol, enables colloidal sol poly-
The gel for being formed and there is certain space structure is closed, drying and heat treatment remove organic matter therein, and sintering curing is formed
The nano material of required nano material, the molybdic acid salt system of this method preparation is mostly the inhomogenous nanometer rods in surface, and is easy
Reunite, the material of such pattern is not suitable for being made into film；Hydro-thermal method is to create the environment of a high temperature and pressure, keeps those big
Insoluble or indissoluble substance dissolution under the conditions of gas, or reaction generate the lysate of the substance, by molten in control autoclave
The temperature difference of liquid makes reactant generation convection current that growth crystal be precipitated to form hypersaturated state, the molybdic acid salt system of this method preparation
Nano material more be rendered as flower shape, each flower is made of multiple nanometer sheets, and these nanometer sheets are sufficiently stable, no
Easily dispersion, thus such pattern is also not suitable for being made into film；Solid phase method refers generally to participate in using solid matter and by the variation of phase
Manufacture a kind of method of powder, the powder granularity that this method is prepared is not thin enough, and inhomogenous, thus can not be prepared
The ideal pattern of high-quality thin film；Heating speed is fast, reaction rate is big, heating is equal because its technical characterstic has for microwave process for synthesizing
Even, product purity is high and reactant can selectively adjust the synthesis that the advantages that heating is widely used in nano material
Cheng Zhong, but the pattern of the product of microwave method preparation is easy to appear agglomeration, therefore the product obtained is not still to prepare height
The ideal chose of quality thin film.
To sum up, above method synthesis condition is relatively high, show that synthesis temperature is high and the requirement to reaction vessel also compared with
High two aspects；In addition to microwave method, the synthesis process of other methods is taken a long time；Most importantly received using obtained by the above method
The pattern of rice material is not suitable for preparing high quality light-emitting film, this makes its application receive great limitation.
(La1-xLnx)2(MoO4)3With good chemical stability and higher fluorescence quantum efficiency.The present invention uses three
Electrode electro Chemical sedimentation directly prepares respective films on the glass substrate for be coated with conductive film, this device for material
It is of great significance.
Summary of the invention
In view of the above-mentioned problems of the prior art, the object of the present invention is to provide one kind (La1-xLnx)2(MoO4)3Film
Direct preparation method, this method obtains one layer using three-electrode electro Chemical deposition technique directly on the glass for be coated with conductive layer
Film, process is simple, time-consuming shorter, and gained film is smooth and fine and close.
Specific steps are as follows:
(1) by La (NO3)3·6H2O or La (NO3)3·6H2O and Ln (NO3)3·6H2O, which is dissolved in deionized water, to be matched
The rare-earth ion solution that rare earth ion total concentration is 0.005 ~ 1mol/L is made, then by EDTA or citric acid according to rare earth
The molar ratio of total ion concentration is that the ratio of 1 ~ 5:1 is added in above-mentioned rare-earth ion solution, then the NaOH of 0.1 ~ 1mol/L is added dropwise
Solution reaches 12 ~ 13 up to the pH value of mixed solution, finally adds Na2MoO4·2H2O, KCl and HNO3, wherein Na2MoO4·
2H2The additional amount of O and the molar ratio of rare earth ion total amount are 1 ~ 5:1, and the molar ratio of the additional amount and rare earth ion total amount of KCl is
1 ~ 50:1, HNO3Additional amount be used for adjust mixed solution pH value be 4 ~ 6, obtain electric depositing solution after mixing.
(2) electric depositing solution made from step (1) is placed in water-bath, stirring make the temperature of electric depositing solution reach 30 ~
80 DEG C, obtain spare electric depositing solution.
(3) glass of transparency conducting layer is coated with using surface as working electrode i.e. anode, Pt net is used as to electrode, that is, cathode,
Ag/AgCl/Cl-Electrode forms three-electrode system as reference electrode.
(4) in the spare electric depositing solution for obtaining the three-electrode system inserting step (2) of step (3) composition, setting is heavy
Product voltage is 1.3 ~ 3V, and sedimentation time is 15min ~ 3h, deposits one layer of electrodeposited film over transparent conductive layer.
(5) it uses deionized water, dehydrated alcohol to rinse respectively electrodeposited film made from step (4), is subsequently placed in 30 ~ 80
DEG C air dry oven in dry 5min ~ for 24 hours.
(6) the dried electrodeposited film of step (5) is placed in the tube furnace for be connected with nitrogen and is heat-treated, setting rises
Warm rate is 1 ~ 10 DEG C/min, is warming up to 300 ~ 700 DEG C of 0.5 ~ 10h of heat preservation, obtains (La1-xLnx)2(MoO4)3Film, wherein
0≤x<1。
The Ln is any one in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
The transparency conducting layer is ITO, FTO or AZO.
Compared with prior art, the features of the present invention and beneficial effect are:
Operation of the present invention is simple, is directly prepared on the glass substrate for be coated with conductive layer using electrochemical deposition method
(La1-xLnx)2(MoO4)3Film greatly simplifies method for manufacturing thin film, together compared to the conventional method to form a film after powder is first done
When avoid influence of the powder morphology to quality of forming film；And method provided by the invention is easy to operate, time-consuming short, film quality
It is good.
Detailed description of the invention
Fig. 1 is La prepared by the embodiment of the present invention 12(MoO4)3The XRD spectrum of film.
Fig. 2 is La prepared by the embodiment of the present invention 12(MoO4)3The pictorial diagram of film.
Fig. 3 is La prepared by the embodiment of the present invention 12(MoO4)3The SEM spectrum of film.
Fig. 4 is (La prepared by the embodiment of the present invention 20.95Eu0.05)2(MoO4)3The XRD spectrum of film.
Fig. 5 is (La prepared by the embodiment of the present invention 30.97Tb0.03)2(MoO4)3The SEM spectrum of film.
Specific embodiment
Embodiment 1:
The nitrate compound of lanthanum (La), the nitrate compound of rare earth element (Ln), ethylenediamine tetrem of the present embodiment use
Acid (EDTA), NaOH, Na2MoO4·2H2O、KCl、HNO3 It is commercially available analysis pure chemistry reagent.
Specific preparation process is as follows:
(1) by La (NO3)3·6H2It is the dilute of 0.01mol/L that O, which is dissolved in and is configured to rare earth ion total concentration in deionized water,
Then native solion ethylenediamine tetra-acetic acid (EDTA) is added according to the molar ratio of rare earth ion total amount for the ratio of 3:1
Into above-mentioned rare-earth ion solution, then the NaOH solution of 0.5mol/L is added dropwise until the pH value of mixed solution reaches 12.5, finally
Add Na2MoO4·2H2O, KCl and HNO3, wherein Na2MoO4·2H2The additional amount of O and the molar ratio of rare earth ion total amount are
The molar ratio of 2:1, KCl and rare earth ion total amount is 25:1, HNO3Additional amount be used for adjust mixed solution pH value be 6, mix
Electric depositing solution is obtained after closing uniformly.
(2) electric depositing solution made from step (1) is placed in water-bath, stirring makes the temperature of electric depositing solution reach 80
DEG C, obtain spare electric depositing solution.
(3) glass of transparency conducting layer ITO is coated with using surface as working electrode i.e. anode, it is yin that Pt net, which is used as to electrode,
Pole, Ag/AgCl/Cl-Electrode forms three-electrode system as reference electrode.
(4) in the spare electric depositing solution for obtaining the three-electrode system inserting step (2) of step (3) composition, setting is heavy
Product voltage is 1.8V, sedimentation time 1h, deposits one layer of electrodeposited film over transparent conductive layer.
(5) it uses deionized water, dehydrated alcohol to rinse respectively electrodeposited film made from step (4), is subsequently placed in 40 DEG C
Air dry oven in dry 15min.
(6) the dried electrodeposited film of step (5) is placed in the tube furnace for be connected with nitrogen and is heat-treated, setting rises
Warm rate is 5 DEG C/min, is warming up to 400 DEG C of heat preservation 3h, obtains La2(MoO4)3Film.
La made from the embodiment of the present invention2(MoO4)3Film carries out XRD material phase analysis using X-ray diffractometer, uses
Field emission scanning electron microscope carries out morphology observation and analysis, is specifically shown in Figure of description 1,2 and 3.
Embodiment 2:
The nitrate compound of lanthanum (La), the nitrate compound of rare earth element (Ln), ethylenediamine tetrem of the present embodiment use
Acid (EDTA), NaOH, Na2MoO4·2H2O、KCl、HNO3 It is commercially available analysis pure chemistry reagent.
Specific preparation process is as follows:
(1) by La (NO3)3·6H2O and Eu (NO3)3·6H2O is dissolved according to the ratio that molar ratio is La/Eu=19/1
Be configured in ionized water rare earth ion total concentration be 0.05mol/L rare-earth ion solution, then by ethylenediamine tetra-acetic acid according to
The ratio that molar ratio with rare earth ion total amount is 1:1 is added in above-mentioned rare-earth ion solution, then the NaOH of 1mol/L is added dropwise
Solution reaches 12.5 up to the pH value of mixed solution, finally adds Na2MoO4·2H2O, KCl and HNO3, wherein Na2MoO4·
2H2The molar ratio of the additional amount of O and rare earth ion total amount is 3:1, and the molar ratio of KCl and rare earth ion total amount is 10:1, HNO3's
The pH value that additional amount is used to adjust mixed solution is 5.5, obtains electric depositing solution after mixing.
(2) electric depositing solution made from step (1) is placed in water-bath, stirring makes the temperature of electric depositing solution reach 70
DEG C, obtain spare electric depositing solution.
(3) glass of transparency conducting layer ITO is coated with using surface as working electrode i.e. anode, it is yin that Pt net, which is used as to electrode,
Pole, Ag/AgCl/Cl-Electrode forms three-electrode system as reference electrode.
(4) in the spare electric depositing solution for obtaining the three-electrode system inserting step (2) of step (3) composition, setting is heavy
Product voltage is 1.95V, sedimentation time 2h, deposits one layer of electrodeposited film over transparent conductive layer.
(5) it uses deionized water, dehydrated alcohol to rinse respectively electrodeposited film made from step (4), is subsequently placed in 50 DEG C
Air dry oven in dry 15min.
(6) the dried electrodeposited film of step (5) is placed in the tube furnace for be connected with nitrogen and is heat-treated, setting rises
Warm rate is 2 DEG C/min, is warming up to 500 DEG C of heat preservation 1h, obtains (La0.95Eu0.05)2(MoO4)3Film.
(La made from the embodiment of the present invention0.95Eu0.05)2(MoO4)3Film carries out XRD object phase point using X-ray diffractometer
Analysis carries out morphology observation and analysis using field emission scanning electron microscope, is specifically shown in Figure of description 4.
Embodiment 3:
The present embodiment use the nitrate compound of lanthanum (La), the nitrate compound of rare earth element (Ln), citric acid,
NaOH、Na2MoO4·2H2O、KCl、HNO3 It is commercially available analysis pure chemistry reagent.
Specific preparation process is as follows:
(1) by La (NO3)3·6H2O and Tb (NO3)3·6H2O is dissolved according to the ratio that molar ratio is La/Tb=97/3
Be configured in ionized water rare earth ion total concentration be 0.5mol/L rare-earth ion solution, then by citric acid according to rare earth from
The molar ratio of sub- total amount be 1:1 ratio be added in above-mentioned rare-earth ion solution, then be added dropwise 1mol/L NaOH solution until
The pH value of mixed solution reaches 12.7, finally adds Na2MoO4·2H2O, KCl and HNO3, wherein Na2MoO4·2H2O's adds
Enter the molar ratio of amount and rare earth ion total amount for 1:1, the molar ratio of KCl and rare earth ion total amount is 10:1, HNO3Additional amount
PH value for adjusting mixed solution is 4, obtains electric depositing solution after mixing.
(2) electric depositing solution made from step (1) is placed in water-bath, stirring makes the temperature of electric depositing solution reach 80
DEG C, obtain spare electric depositing solution.
(3) glass of transparency conducting layer ITO is coated with using surface as working electrode i.e. anode, it is yin that Pt net, which is used as to electrode,
Pole, Ag/AgCl/Cl-Electrode forms three-electrode system as reference electrode.
(4) in the spare electric depositing solution for obtaining the three-electrode system inserting step (2) of step (3) composition, setting is heavy
Product voltage is 2.00V, sedimentation time 0.5h, deposits one layer of electrodeposited film over transparent conductive layer.
(5) it uses deionized water, dehydrated alcohol to rinse respectively electrodeposited film made from step (4), is subsequently placed in 30 DEG C
Air dry oven in dry 1h.
(6) the dried electrodeposited film of step (5) is placed in the tube furnace for be connected with nitrogen and is heat-treated, setting rises
Warm rate is 2 DEG C/min, is warming up to 600 DEG C of heat preservation 1h, obtains (La0.97Tb0.03)2(MoO4)3Film.
(La made from the embodiment of the present invention0.97Tb0.03)2(MoO4)3Film carries out XRD object phase point using X-ray diffractometer
Analysis carries out morphology observation and analysis using field emission scanning electron microscope, is specifically shown in Figure of description 5.
Claims (1)
1. one kind (La1-xLnx)2(MoO4)3The direct preparation method of film, it is characterised in that specific steps are as follows:
(1) by La (NO3)3·6H2O or La (NO3)3·6H2O and Ln (NO3)3·6H2O is dissolved in deionized water and is configured to
Rare earth ion total concentration is the rare-earth ion solution of 0.005 ~ 1mol/L, then by EDTA or citric acid according to rare earth ion
The molar ratio of total amount is that the ratio of 1 ~ 5:1 is added in above-mentioned rare-earth ion solution, then the NaOH solution of 0.1 ~ 1mol/L is added dropwise
Until the pH value of mixed solution reaches 12 ~ 13, Na is finally added2MoO4·2H2O, KCl and HNO3, wherein Na2MoO4·2H2O
Additional amount and the molar ratio of rare earth ion total amount be 1 ~ 5:1, the molar ratio of the additional amount of KCl and rare earth ion total amount is 1 ~
50:1, HNO3Additional amount be used for adjust mixed solution pH value be 4 ~ 6, obtain electric depositing solution after mixing；
(2) electric depositing solution made from step (1) being placed in water-bath, stirring makes the temperature of electric depositing solution reach 30 ~ 80 DEG C,
Obtain spare electric depositing solution；
(3) glass of transparency conducting layer is coated with using surface as working electrode i.e. anode, Pt net is used as to electrode, that is, cathode, Ag/
AgCl/Cl-Electrode forms three-electrode system as reference electrode；
(4) in the spare electric depositing solution for obtaining the three-electrode system inserting step (2) of step (3) composition, setting deposition electricity
Pressure is 2.0 ~ 3V, and sedimentation time is 15min ~ 3h, deposits one layer of electrodeposited film over transparent conductive layer；
(5) it uses deionized water, dehydrated alcohol to rinse respectively electrodeposited film made from step (4), is subsequently placed in 30 ~ 80 DEG C
Dry 5min in air dry oven ~ for 24 hours；
(6) the dried electrodeposited film of step (5) is placed in the tube furnace for be connected with nitrogen and is heat-treated, setting heating speed
Rate is 1 ~ 10 DEG C/min, is warming up to 600 ~ 700 DEG C of 0.5 ~ 10h of heat preservation, obtains (La1-xLnx)2(MoO4)3Film, wherein 0≤x
< 1；
The Ln is any one in Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm；
The transparency conducting layer is ITO, FTO or AZO.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962805A (en) * | 2010-10-15 | 2011-02-02 | 浙江大学 | Electrochemical preparation method of lanthanum phosphate or rare earth doped lanthanum phosphate film |
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2017
- 2017-07-24 CN CN201710608241.8A patent/CN107620101B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962805A (en) * | 2010-10-15 | 2011-02-02 | 浙江大学 | Electrochemical preparation method of lanthanum phosphate or rare earth doped lanthanum phosphate film |
Non-Patent Citations (1)
| Title |
|---|
| "Metathesis synthesis,characterization,spectral and photoactivity studies of Ln2/3MoO4 (Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Er and Y)";Radha Velchuri等;《JOURNAL OF RARE EARTHS》;20150831;第33卷(第8期);第837-838页 |
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Application publication date: 20180123 Assignee: Guilin long hair Xiao Zhai Biotechnology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000417 Denomination of invention: A direct preparation method of (La1-xLnx)2(MoO4)3films Granted publication date: 20190723 License type: Common License Record date: 20221227 |
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