CN101892504B - Method for preparing strontium fluoride or rare-earth doped strontium fluoride film by adopting electrolytic deposition - Google Patents
Method for preparing strontium fluoride or rare-earth doped strontium fluoride film by adopting electrolytic deposition Download PDFInfo
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- CN101892504B CN101892504B CN2010102201204A CN201010220120A CN101892504B CN 101892504 B CN101892504 B CN 101892504B CN 2010102201204 A CN2010102201204 A CN 2010102201204A CN 201010220120 A CN201010220120 A CN 201010220120A CN 101892504 B CN101892504 B CN 101892504B
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Abstract
The invention discloses a method for preparing a strontium fluoride or rare-earth doped strontium fluoride film by adopting electrolytic deposition. The method comprises the following steps of: 1) cleaning an ITO conductive glass twice or thrice by using acetone, then cleaning the ITO conductive glass in an ultrasonic cleaner for 10 to 30 minutes by using deionized water, activating the ITO conductive glass for 10 to 30 seconds in 10 percent nitric acid solution, and cleaning the ITO conductive glass by using the deionized water for later use; 2) adding sodium ascorbate and ammonium fluoride solution into compound solution of 0.01 to 0.5mol/L ethylene diamine tetraacetic acid and strontium ions, and adjusting the pH value to be between 6 and 9 to obtain electrolyte for later use; and 3) placing the ITO conductive glass serving as a working electrode, a platinum electrode serving as a counter electrode and a calomel electrode serving as a reference electrode into the electrolyte to perform electrolytic deposition so as to obtain the strontium fluoride film at an anode deposition potential of 0.8V to 1.4V relative to the calomel electrode. The method has the advantages of simple equipment, low cost and normal-pressure low temperature, is suitable for scientific research, and is expected to realize 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 strontium fluoride or rare-earth doped strontium fluoride film.
Background technology
Fluorochemical has low phonon energy, macroion, is widely used in opticinstrument as window, eyeglass, scintillation crystal.Strontium fluoride is a kind of typical alkaline earth fluoride, has stronger optical transmission, is mainly used in to make opticglass, advanced electronic components, and is good fluorescence matrix.When in the strontium fluoride during doping proper amount of rare-earth element, show the luminescent properties of feature, be good laserable material.In addition, rare-earth doped strontium fluoride has character such as light amplification, last conversion.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, some strontium fluorides and rare-earth doped strontium fluoride crystalline preparation method have been developed, as hydrothermal method, sol-gel method, chemical precipitation method, microwave 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 strontium fluoride and the rare-earth doped strontium fluoride 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 strontium fluoride film or rare-earth doped strontium fluoride film.
The method that adopts electrodip process to prepare strontium fluoride 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 0.01～0.5 mol and the strontium ion complex solution, add 0.02～1 mol sodium ascorbate, add the ammonium fluoride solution of 0.04～2 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 25～50 ℃, obtains strontium fluoride film.
The method that adopts electrodip process to prepare rare-earth doped strontium fluoride 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 0.0002～0.05 mol in the strontium chloride solution of 0.01～0.5 mol, the disodium ethylene diamine tetraacetate that adds 0.0102～0.55 mol, form complex solution, the sodium ascorbate that adds 0.02～1 mol, the ammonium fluoride solution that adds 0.04～2 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 25～50 ℃, obtains rear-earth-doped strontium fluoride 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 strontium fluoride 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 strontium fluoride 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 strontium fluoride film;
Fig. 2 is the X-ray diffractogram of strontium fluoride film;
Fig. 3 is a fluorescence emission spectrogram of mixing the europium strontium fluoride film;
Fig. 4 is a fluorescence emission spectrogram of mixing the terbium strontium fluoride 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 strontium ion complex 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 strontium fluoride film.
Embodiment 2
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 0.5 mol and the strontium ion complex solution, add 1 mol sodium ascorbate, add the ammonium fluoride solution of 2 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 50 ℃, obtains strontium fluoride 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 strontium ion complex 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 30 ℃, obtains strontium fluoride film.
Through field emission scanning electron microscope (FE-SEM) and X-ray diffraction (XRD) etc., the structure of the strontium fluoride film of galvanic deposit on the ITO conductive glass is characterized.Scanning electron microscope Fig. 1 shows that strontium fluoride 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 0.0002 mol in the strontium chloride solution of 0.01 mol, the disodium ethylene diamine tetraacetate that adds 0.0102 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 strontium fluoride 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) europium nitrate or the Terbium trinitrate of adding 0.05 mol in the strontium chloride solution of 0.5 mol, the disodium ethylene diamine tetraacetate that adds 0.55 mol, form complex solution, the sodium ascorbate that adds 1 mol, the ammonium fluoride solution that adds 2 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 50 ℃, obtains rear-earth-doped strontium fluoride 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 0.001 mol in the strontium chloride solution of 0.02 mol, the disodium ethylene diamine tetraacetate that adds 0.021 mol, form complex solution, the sodium ascorbate that adds 0.04 mol, the ammonium fluoride solution that adds 0.08 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 1.3V, and depositing temperature is 30 ℃, obtains rear-earth-doped strontium fluoride film.
Through fluorescence emission spectrum (PL), the rare-earth doped strontium fluoride film of galvanic deposit on the ITO conductive glass characterized.Fig. 3 is a fluorescence emission spectrum of mixing the europium strontium fluoride film, shows the feature emission peak of europium, and excitation wavelength is 397nm; Fig. 4 is a fluorescence emission spectrum of mixing the terbium strontium fluoride film, shows the feature emission peak of terbium, and excitation wavelength is 378nm.
Claims (2)
1. a method that adopts the prepared by electrodeposition strontium fluoride 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 0.01～0.5 mol and the strontium ion complex solution, add the sodium ascorbate of 0.02～1 mol, add the ammonium fluoride solution of 0.04～2 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 25～50 ℃, obtains strontium fluoride film.
2. a method that adopts the prepared by electrodeposition rare-earth doped strontium fluoride 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) add the europium nitrate or the Terbium trinitrate of 0.0002～0.05 mol in the strontium chloride solution of 0.01～0.5 mol, the disodium ethylene diamine tetraacetate that adds 0.0102～0.55 mol, form complex solution, the sodium ascorbate that adds 0.02～1 mol, the ammonium fluoride solution that adds 0.04～2 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 25～50 ℃, obtains rear-earth-doped strontium fluoride film.
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| JP平3-94419A 1991.04.19 |
| 康红兰.CuX（X=Br，I）的电沉积制备及形貌调控研究.《浙江大学硕士学位论文》.2008,45-50. * |
| 李赫等.在ITO导电衬底上室温电沉积高取向的CuBr薄膜.《无机化学学报》.2009,第25卷(第2期),231-235. * |
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