CN101871114B - Method for preparing calcium fluoride or rare earth doping calcium fluoride film by adopting electrodeposition - Google Patents
Method for preparing calcium fluoride or rare earth doping calcium fluoride film by adopting electrodeposition Download PDFInfo
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- CN101871114B CN101871114B CN2010101887438A CN201010188743A CN101871114B CN 101871114 B CN101871114 B CN 101871114B CN 2010101887438 A CN2010101887438 A CN 2010101887438A CN 201010188743 A CN201010188743 A CN 201010188743A CN 101871114 B CN101871114 B CN 101871114B
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Abstract
The present invention discloses a method for preparing calcium fluoride or rare earth doping calcium fluoride film by adopting electrodeposition, comprising the following steps of: (1) cleaning ITO (indium tin oxide) conducting glass 2-3 times with acetone, then placing the ITO conducting glass into an ultrasonic cleaner to be cleaned with deionized water for 10-30 minutes, then placing the ITO conducting glass into a 10% salpeter solution to be activated for 10-30 seconds, and finally cleaning with the deionized water for standby; (2) adding sodium ascorbate to a compound solution of 0.01-1 mol/L of ethylene diamine tetraacetic acid and calcium ions, then adding an ammonium fluoride solution, and regulating a pH value to 6-9 to obtain electrolyte for later use; and (3) placing the ITO conducting glass used as a working electrode, a platinum electrode used as a counter electrode and a calomel electrode used as a reference electrode into the electrolyte for the electrodeposition so as to obtain the calcium fluoride film, wherein the deposition potential of an anode relative to the calomel electrode is 0.8-1.4 V. The method for preparing calcium fluoride or rare earth doping calcium fluoride film by adopting electrodeposition provided by the present invention has the advantages of simple equipment, low cost, ordinary pressure and low temperature, is not only suitable for scientific research, but also expected to realize the large-scale industrialized production.
Description
Technical field
The present invention relates to the preparation of film, relate in particular to a kind of method that adopts electrodip process to prepare Calcium Fluoride (Fluorspan) or rear-earth-doped calcium-fluoride thin film.
Background technology
Alkaline earth fluoride is widely used in photoelectricity, microelectronic device, and Calcium Fluoride (Fluorspan) is a kind of typical alkaline earth fluoride, has face-centred cubic structure.The Calcium Fluoride (Fluorspan) good stability, non-hygroscopic and have a good optical transmission, can (see through light in 0.3～8mm) scope, thereby be suitable as fluorescence matrix at the wavelength of broad.When in the Calcium Fluoride (Fluorspan) during doping proper amount of rare-earth element, show the luminescent properties of feature, be good laserable material.Compare with semiconductor-quantum-point with organic dye, the rare earth element fluorescence emission peak is sharp-pointed, the quantum yield height, and the life-span is long, and the light stability height is expected to substitute them as novel organism fluorescence labeling material.
Up to the present, developed the preparation method of some Calcium Fluoride (Fluorspan) and rear-earth-doped calcium fluoride crystal, as hydrothermal method, sol-gel method, reverse micelle method, chemical precipitation method, flame synthesis method etc.Yet these methods require high temperature, high vacuum, and complex apparatus and strict experimental arrangement have greatly hindered their widespread usage.In this invention, adopt electrochemical deposition method to prepare Calcium Fluoride (Fluorspan) and the rear-earth-doped calcium-fluoride thin film with certain orientation, equipment is simple, easy to operate, can carry out under the low-temperature atmosphere-pressure.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of employing electrodip process of simple and effective to prepare the method for calcium-fluoride thin film or rear-earth-doped calcium-fluoride thin film.
The method that adopts electrodip process to prepare calcium-fluoride thin film comprises the steps:
1) cleans the ITO conductive glass 2～3 times with acetone, with deionized water the ITO conductive glass is placed on again and cleans 10～30 minutes in the ultrasonic cleaner, then the ITO conductive glass is placed in 10% the salpeter solution and activates 10～30 seconds, use washed with de-ionized water at last, stand-by;
2) in the disodium ethylene diamine tetraacetate of 0.01～1 mol and the calcium ion complexes solution, add 0.02～2 mol sodium ascorbate, add the ammonium fluoride solution of 0.04～4 mol again, the pH value of regulator solution is 6～9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V～1.4V, and depositing temperature is 25～80 ℃, obtains calcium-fluoride thin film.
The method that adopts electrodip process to prepare rear-earth-doped calcium-fluoride thin film comprises the steps:
1) cleans the ITO conductive glass 2～3 times with acetone, with deionized water the ITO conductive glass is placed on again and cleans 10～30 minutes in the ultrasonic cleaner, then the ITO conductive glass is placed in 10% the salpeter solution and activates 10～30 seconds, use washed with de-ionized water at last, stand-by;
2) add the europium nitrate or the Terbium trinitrate of 0.0001～0.5 mol in the calcium chloride solution of 0.01～1 mol, the disodium ethylene diamine tetraacetate that adds 0.0101～1.5 mol, form complex solution, the sodium ascorbate that adds 0.02～3 mol, the ammonium fluoride solution that adds 0.04～6 mol again, the regulator solution pH value is 6～9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V～1.4V, depositing temperature is 25～80 ℃, obtains rear-earth-doped calcium-fluoride thin film.
The present invention has the advantages that equipment is simple, cost is low, sedimentation rate is fast, the material growth temperature is low, can operate at normal temperatures and pressures, is expected to carry out suitability for industrialized production.The calcium-fluoride thin film of electrodip process preparation is even, and pattern is a spheroidal, good crystallinity,＜111〉orientation has certain advantage.Rare earth elements europium, terbium are doped in calcium-fluoride thin film equably, have strong fluorescence emission peak, can be used as laserable material and organism fluorescence labeling material.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure of calcium-fluoride thin film;
Fig. 2 is the X-ray diffractogram of calcium-fluoride thin film;
Fig. 3 is a fluorescence emission spectrogram of mixing the europium calcium-fluoride thin film;
Fig. 4 is a fluorescence emission spectrogram of mixing the terbium calcium-fluoride thin film.
Embodiment
Embodiment 1
1) clean the ITO conductive glass 2 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 10 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 10 seconds, use washed with de-ionized water at last, stand-by;
2) in the disodium ethylene diamine tetraacetate of 0.01 mol and the calcium ion complexes solution, add 0.02 mol sodium ascorbate, add the ammonium fluoride solution of 0.04 mol again, the pH value of regulator solution is 6, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V, and depositing temperature is 25 ℃, obtains calcium-fluoride thin film.
1) clean the ITO conductive glass 3 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 30 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 30 seconds, use washed with de-ionized water at last, stand-by;
2) in the disodium ethylene diamine tetraacetate of 1 mol and the calcium ion complexes solution, add 2 mol sodium ascorbates, add the ammonium fluoride solution of 4 mol again, the pH value of regulator solution is 9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 1.4V, and depositing temperature is 80 ℃, obtains calcium-fluoride thin film.
Embodiment 3
1) clean the ITO conductive glass 2 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 15 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 15 seconds, use washed with de-ionized water at last, stand-by;
2) in the disodium ethylene diamine tetraacetate of 0.02 mol and the calcium ion complexes solution, add 0.04 mol sodium ascorbate, add the ammonium fluoride solution of 0.08 mol again, the pH value of regulator solution is 7, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 1.1V, and depositing temperature is 25 ℃, obtains calcium-fluoride thin film.
Through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc., the structure of the calcium-fluoride thin film of galvanic deposit on the ITO conductive glass is characterized.Scanning electron microscope Fig. 1 shows that calcium-fluoride thin film is smoothly fine and close, is spheroidal; X-ray diffraction Fig. 2 shows＜111〉orientation certain advantage is arranged.
Embodiment 4
1) clean the ITO conductive glass 2 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 10 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 10 seconds, use washed with de-ionized water at last, stand-by;
2) europium nitrate or the Terbium trinitrate of adding 0.0001 mol in the calcium chloride solution of 0.01 mol, the disodium ethylene diamine tetraacetate that adds 0.0101 mol, form complex solution, the sodium ascorbate that adds 0.02 mol, the ammonium fluoride solution that adds 0.04 mol again, the regulator solution pH value is 6, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V, and depositing temperature is 25 ℃, obtains rear-earth-doped calcium-fluoride thin film.
Embodiment 5
1) clean the ITO conductive glass 3 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 30 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 30 seconds, use washed with de-ionized water at last, stand-by;
2) europium nitrate or the Terbium trinitrate of adding 0.5 mol in the calcium chloride solution of 1 mol, the disodium ethylene diamine tetraacetate that adds 1.5 mol, form complex solution, the sodium ascorbate that adds 3 mol, the ammonium fluoride solution that adds 6 mol again, the regulator solution pH value is 9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 1.4V, and depositing temperature is 80 ℃, obtains rear-earth-doped calcium-fluoride thin film.
Embodiment 6
1) clean the ITO conductive glass 2 times with acetone, with deionized water the ITO conductive glass is placed in the ultrasonic cleaner again and cleaned 15 minutes, then the ITO conductive glass was placed in 10% the salpeter solution activation 15 seconds, use washed with de-ionized water at last, stand-by;
2) europium nitrate or the Terbium trinitrate of adding 0.0025 mol in the calcium chloride solution of 0.05 mol, the disodium ethylene diamine tetraacetate that adds 0.0525 mol, form complex solution, the sodium ascorbate that adds 0.105 mol, the ammonium fluoride solution that adds 0.2 mol again, the regulator solution pH value is 7, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 1.1V, and depositing temperature is 50 ℃, obtains rear-earth-doped calcium-fluoride thin film.
Through fluorescence emission spectrum (PL), the rear-earth-doped calcium-fluoride thin film of galvanic deposit on the ITO conductive glass characterized.Fig. 3 is a fluorescence emission spectrum of mixing the europium calcium-fluoride thin film, shows the feature emission peak of europium, and excitation wavelength is 397nm; Fig. 4 is a fluorescence emission spectrum of mixing the terbium calcium-fluoride thin film, shows the feature emission peak of terbium, and excitation wavelength is 378nm.
Claims (2)
1. a method that adopts the prepared by electrodeposition calcium-fluoride thin film is characterized in that comprising the steps:
1) cleans the ITO conductive glass 2～3 times with acetone, with deionized water the ITO conductive glass is placed on again and cleans 10～30 minutes in the ultrasonic cleaner, then the ITO conductive glass is placed in 10% the salpeter solution and activates 10～30 seconds, use washed with de-ionized water at last, stand-by;
2) in the disodium ethylene diamine tetraacetate of 0.01～1 mol and the calcium ion complexes solution, add the sodium ascorbate of 0.02～2 mol, add the ammonium fluoride solution of 0.04～4 mol again, regulator solution pH value is 6～9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, and mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V～1.4V, and depositing temperature is 25～80 ℃, obtains calcium-fluoride thin film.
2. a method that adopts the rear-earth-doped calcium-fluoride thin film of prepared by electrodeposition is characterized in that comprising the steps:
1) cleans the ITO conductive glass 2～3 times with acetone, with deionized water the ITO conductive glass is placed on again and cleans 10～30 minutes in the ultrasonic cleaner, then the ITO conductive glass is placed in 10% the salpeter solution and activates 10～30 seconds, use washed with de-ionized water at last, stand-by;
2) add the europium nitrate or the Terbium trinitrate of 0.0001～0.5 mol in the calcium chloride solution of 0.01～1 mol, the disodium ethylene diamine tetraacetate that adds 0.0101～1.5 mol, form complex solution, the sodium ascorbate that adds 0.02～3 mol, the ammonium fluoride solution that adds 0.04～6 mol again, regulator solution pH value is 6～9, obtains electrolytic solution, and is stand-by;
3) be working electrode with the ITO conductive glass, platinum electrode is a counter electrode, mercurous chloride electrode is that reference electrode is formed three-electrode system, place electrolytic solution to carry out galvanic deposit, anodically deposit current potential with respect to mercurous chloride electrode is 0.8V～1.4V, depositing temperature is 25～80 ℃, obtains rear-earth-doped calcium-fluoride thin film.
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| CN102140662B (en) * | 2011-01-18 | 2012-04-25 | 浙江大学 | Method for preparing NaYF4: yb, er up-conversion fluorescent material by electrodeposition |
| CN103774198B (en) * | 2014-01-15 | 2016-01-20 | 浙江大学 | Help electrodip process on titania nanotube, prepare rare earth Eu doping CaF by light 2the method of 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 |
| CN107686131B (en) * | 2017-07-24 | 2019-07-23 | 桂林理工大学 | A kind of Sm2(MoO4)3The direct preparation method of film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD299742A7 (en) * | 1973-01-04 | 1992-05-07 | Rft Messelektronik Dresden Veb | Process for the electrophoretic deposition of a CaF ind2 -LiF mixture |
| US5301204A (en) * | 1992-09-15 | 1994-04-05 | Texas Instruments Incorporated | Porous silicon as a light source for rare earth-doped CaF2 laser |
| CN101333672A (en) * | 2008-08-05 | 2008-12-31 | 浙江大学 | Electrochemical method for preparing high oriented cuprous bromide semiconductor film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD299742A7 (en) * | 1973-01-04 | 1992-05-07 | Rft Messelektronik Dresden Veb | Process for the electrophoretic deposition of a CaF ind2 -LiF mixture |
| US5301204A (en) * | 1992-09-15 | 1994-04-05 | Texas Instruments Incorporated | Porous silicon as a light source for rare earth-doped CaF2 laser |
| CN101333672A (en) * | 2008-08-05 | 2008-12-31 | 浙江大学 | Electrochemical method for preparing high oriented cuprous bromide semiconductor film |
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