CN105384356A - Glass film containing rare earth ion doped Ba2CsI5 microcrystal and preparation method thereof - Google Patents
Glass film containing rare earth ion doped Ba2CsI5 microcrystal and preparation method thereof Download PDFInfo
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- CN105384356A CN105384356A CN201510783193.7A CN201510783193A CN105384356A CN 105384356 A CN105384356 A CN 105384356A CN 201510783193 A CN201510783193 A CN 201510783193A CN 105384356 A CN105384356 A CN 105384356A
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Abstract
The invention discloses a chemical composition and sol-gel preparation method of a glass film containing rare earth ion doped Ba2CsI5 microcrystal. The glass film is characterized by comprising 75-78mol% of silicon dioxide, 5-10mol% of phosphorus pentoxide, 3-8mol% of gallium oxide, 6-11mol% of Ba2CsI5 and 1-3mol% of rare earth iodide, wherein rare earth iodide is cerium iodide, europium (II) iodide or terbium iodide. The glass film and the preparation method have the advantages that a sol-gel method is technology for preparing glass by low-temperature aqueous chemical synthesis and is characterized by obtaining glass through precursor raw material hydrolysis and polymerization chemical reaction processes, so that the film material can be prepared under the condition of certain liquid viscosity; the low-temperature synthesis condition can conduce to effectively preventing decomposition and volatilization of the iodide raw material.
Description
Technical field
The present invention relates to the glass film containing a kind of rare earth ion doped crystallite, be specifically related to a kind of be used as scintillation material containing rare earth ion doped Ba
2csI
5glass film of crystallite and preparation method thereof.
Background technology
Scintillation material is a kind of lower optical function material that can send visible ray of exciting at energetic ray (as x-ray, gamma-rays) or other radioactive particle, can be widely used in nuclear medicine diagnostic, safety check, anti-ly to fear, the field such as high energy physics and geological prospecting.In recent years along with the fast development in the field such as medical imaging and safety inspection, the high performance new scintillation material of demand in large quantities.Outstanding scintillation material mainly possesses following performance: luminous efficiency is high, density of material is large, fluorescence decay is fast, radiation resistance is good and the low inferior feature of production cost.
With regard to current scintillation material, primarily of single crystal and glass bi-material.Scintillating monocrystal has the advantage such as resistance to irradiation, fast decay, High Light Output usually, but it exists that technique preparation is complicated, cost value is expensive and the shortcoming such as large size single crystal body difficulty acquisition.What is more, and be doped in rare earth luminous ion in single crystal owing to there is Segregation, the distribution in crystal is very uneven, therefore seriously affects the rate of utilization of its luminescent properties and material.Scintillation glass possess rear-earth-doped evenly, the feature such as cost is low, large-size glass is easy to preparation, chemical composition easily regulates, but its aspect such as light output, multiplicity performance is inferior to single crystal usually, and therefore its application is also severely limited.
Ba
2csI
5crystal is a kind of flicker substrate material of excellence, Ce
3+the Ba of doping
2csI
5crystal has abnormal high light output, and good energy resolution, can be applicable in low energy physics and the field such as safety check, medical imaging.Eu
2+, Tb
3+the Ba of doping
2csI
5crystal also has the feature of High Light Output, fast decay, can be used for the fields such as scintillation fluor screen.But Ba
2csI
5crystal is deliquescence, poor, the easy cleavage slabbing of mechanical property, its practical application of the large-size crystals growth disadvantages affect such as difficult, expensive very easily.
Notification number is the patent of invention of CN103951223A, then disclose by high temperature melting legal system for SiO
2-NaF-BaO-Ba
2csI
5-LnI
3with SiO
2-NaF-BaO-Ba
2csI
5-LnI
2system glass, then by being incubated near glass transition temperature, separates out rare earth ion doped Ba
2csI
5crystallite, is prepared into the rare earth ion doped Ba of collection glass and single crystal performance
2csI
5devitrified glass.But there is the following major defect that cannot overcome in the method, first: because at high temperature melting obtains, therefore easily cause decomposition and the volatilization of iodide raw material; Second: its chemical composition of glass of preparation and the incomplete homogeneity of crystallization holding temperature usually, the microcrystallite size of precipitation is very uneven, very easily causes the devitrification of glass; 3rd: in Crystallization Process, rare earth luminous ion Ba difficult to get access
2csI
5lattice position in, affect the illumination effect of material.What is more, and due to high temperature melting method glass preparation technique, the glass of production is block, can not obtain the material of thin-film state.Along with extensively popularizing of civil nature, small-sized, integrated flash device is the road of the certainty of Future Development.Usual film makes the most suitable starting material of such device, and the development of therefore current scintillation material form to device from now on can produce larger restriction.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of physical and chemical performance is stable, physical strength is high, Deliquescence-resistant is strong, optical transmission is high, content of crystallite is high, have simultaneously high light output, fast decay and good energy resolution and temporal resolution characteristic containing rare earth ion doped Ba
2csI
5glass film of crystallite and preparation method thereof, this film physical and chemical performance is good, and preparation method has that equipment is simple, production cost is lower, easy to operate, combined coefficient is high, the crystallite size in the glass film of synthesis evenly, the doping content of degree of crystallinity and rare earth ion is high.
The present invention solves the problems of the technologies described above adopted technical scheme: containing rare earth ion doped Ba
2csI
5the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 75-78mol%, Vanadium Pentoxide in FLAKES: 5-10mol%, Gallium trioxide: 3-8mol%, Ba
2csI
5: 6-11mol%, rare-earth iodide: 1-3mol%, wherein rare-earth iodide is the one in cerous iodide, the sub-europium of iodate or iodate terbium.
Described contains rare earth ion doped Ba
2csI
5the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 75mol%, Vanadium Pentoxide in FLAKES: 10mol%, Gallium trioxide: 8mol%, Ba
2csI
5: 6mol%, cerous iodide: 1mol%.
Described contains rare earth ion doped Ba
2csI
5the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 78mol%, Vanadium Pentoxide in FLAKES: 5mol%, Gallium trioxide: 3mol%, Ba
2csI
5: 11mol%, sub-europium: the 3mol% of iodate.
Described contains rare earth ion doped Ba
2csI
5the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 76mol%, Vanadium Pentoxide in FLAKES: 8mol%, Gallium trioxide: 5mol%, Ba
2csI
5: 9mol%, iodate terbium: 2mol%.
Described contains rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, comprises following concrete steps:
The preparation of raw material:
(1), by raw materials in molar ratio: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: rare-earth iodide=75-78: 10-20: 6-16: 12-22: 6-11: 1-3, and barium iodide: the mol ratio of cesium iodide is 2: 1, rare-earth iodide is the one in cerous iodide, the sub-europium of iodate or iodate terbium, take analytically pure each raw materials respectively, stand-by;
The preparation of gel:
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and trimethyl phosphite 99 is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy is 1: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution A and B are slowly joined in solution C respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, trimethyl phosphite 99, ethanol gallium three summation is 0.5: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured barium iodide of scale, cesium iodide and each raw material of rare-earth iodide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
The preparation of film:
(8), solution F dip-coating method (dip-coating) is coated on clean glass substrate, the pull rate of glass substrate in solution F controls in 0.2-1 mm/second, lift 1-5 time can be repeated according to concrete thickness requirement, each lift interval time is 15 minutes, and the film after coating at room temperature dries 4 hours;
The thermal treatment of film:
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30-50 per hour DEG C to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30-50 per hour DEG C, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
The high temperature hydrogen iodide Crystallizing treatment of film:
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen iodide cylinder valve is opened, pass into dry hydrogen iodide gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 500-520 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen iodide gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen iodide gas residual in nitrogen purge pipeline, all remaining iodate hydrogen through pipeline tail end is reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped Ba
2csI
5the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: cerous iodide=75: 20: 16: 12: 6: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: sub-europium=78 of iodate: 10: 6: 22: 11: 3.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: iodate terbium=76: 16: 10: 18: 9: 2.
Compared with prior art, advantage of the present invention is:
1, sol-gel is a kind of Low Temperature Wet chemical method glass making techniques, obtains glass, therefore can be prepared into thin-film material under certain liquid viscosity by the hydrolysis of precursor raw material and polymeric chemical reaction process.
2, the synthesis condition of low temperature can prevent decomposition and the volatilization of iodide raw material effectively.
3, the glass prepared of sol-gel method is due to the volatilization of solvent and decomposition, certain micropore can be generated in the material, the environment that the generation that these micropores are nanometer iodide crystallite provides, thus the incomplete homogeneity of the chemical composition that can to a certain degree overcome due to fusion cast glass and crystallization treatment temp, cause the devitrification of the uneven of crystallization particle and glass.
4, as rare earth and the Ba of glass network modifier
2+and Cs
+ion, most one is in together in micropore gap, and therefore along with the carrying out of high temperature hydrogen iodide process, rare earth luminous ion easily enters Ba
2csI
5lattice position in, obtain the rare earth ion doped and illumination effect of high density.
5, the hydrogen iodide drying treatment of high temperature impels the oxyiodide in gel glass, oxyhydroxide and oxide compound etc. to convert iodide to, can carry out the dehydration reaction of iodide raw material, and effectively promotes and control Ba
2csI
5generation.
Because this film glass matrix is SiO
2-P
2o
5-Ga
2o
3, therefore high in the transmitance of ultraviolet band, according to the actual requirements, alterable component is equipped with and regulates its physical and chemical performance and optical property, containing rare earth ion doped Ba
2csI
5the silicon phosphorus gallate glass thin-film material of crystallite, has superior scintillation properties, physical strength, thermal stability characteristics, overcomes Ba
2csI
5the single crystal shortcoming such as very easily deliquescence, mechanical property be poor; The experiment proved that: by formula of the present invention and preparation method, separate out rare earth ion doped Ba
2csI
5crystalline phase, obtained ion doping Ba
2csI
5devitrified glass is transparent, and energy Deliquescence-resistant, good mechanical property, short wavelength's royal purple light transmission rate are higher, and have extremely strong light output, decay soon, the performances such as good energy resolution and temporal resolution, can make scintillation detectors efficiency increase substantially.This thin-film material is that the development of small-sized flash device from now on provides material base.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of glass film after the thermal treatment of embodiment one high temperature hydrogen iodide;
Fig. 2 be embodiment one excitation of X-rays containing Ce
3+ion doping Ba
2csI
5the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu
2+ion doping Ba
2csI
5the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb
3+ion doping Ba
2csI
5the fluorescence spectrum of the glass film of crystallite.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment one
Containing rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: cerous iodide=75: 20: 16: 12: 6: 1, analytically pure each raw materials that total amount is 30 grams is taken, stand-by;
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and trimethyl phosphite 99 is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and aluminium secondary butylate is 1: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution A and B are slowly joined in solution C respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, trimethyl phosphite 99, ethanol gallium three summation is 0.5: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured barium iodide of scale, cesium iodide and each raw material of cerous iodide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
(8), by solution F dip-coating method be coated on clean glass substrate, the pull rate of glass substrate in solution F controls in 0.2 mm/second, and lift 1 time, the film after coating at room temperature dries 4 hours;
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30 DEG C per hour to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30 DEG C per hour, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen iodide cylinder valve is opened, pass into dry hydrogen iodide gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 500 DEG C, and reaction treatment 5 hours at such a temperature, reaction treatment terminates, close hydrogen iodide gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen iodide gas residual in nitrogen purge pipeline, all remaining iodate hydrogen through pipeline tail end is reclaimed by sodium hydroxide solution, finally obtain containing Ce
3+ion doping Ba
2csI
5the 75SiO of crystallite
2-10P
2o
5-8Ga
2o
3-6Ba
2csI
5-1CeI
3system glass film.
Ce is contained to what prepare
3+ion doping Ba
2csI
5the glass film of crystallite carries out performance test, scrapes and collects film powder, and as shown in Figure 1, its result is as follows for the XRD figure of glass thin coating materials after hydrochlorination: through processing XRD diffraction peak and the Ba of the sample obtained
2csI
5the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and what therefore obtain is containing Ba
2csI
5the glass film of crystallite.The Ce of excitation of X-rays
3+ion doping Ba
2csI
5as shown in Figure 2, with compared with hydrogen iodide Crystallizing treatment, fluorescence intensity significantly strengthens the fluorescence spectrum of devitrified glass film.Fluorescence decay time is 41ns.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: sub-europium=78 of iodate: 10: 6: 22: 11: 3, take each raw materials respectively; In step (8), the pull rate of glass substrate in gelating soln controls in 1 mm/second, repeats lift 5 times, and lift interval time is 15 minutes at every turn; In step (9), with the ramp of 50 DEG C per hour to 100 DEG C, then heat up stove again to 340 DEG C with the speed of 50 DEG C per hour; In step (10), progressively intensification stove is to 520 DEG C, and reaction treatment 2 hours at such a temperature, finally obtain containing rare earth ion doped Ba
2csI
5the 78SiO of crystallite
2-5P
2o
5-3Ga
2o
3-11Ba
2csI
5-3EuI
2system glass film.
Eu is contained to what prepare
2+ion doping Ba
2csI
5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrogen iodide process is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing Ba
2csI
5the glass film of crystallite.The Eu of excitation of X-rays
2+ion doping Ba
2csI
5the SiO of crystallite
2-P
2o
5-Ga
2o
3as shown in Figure 3, with compared with hydrogen iodide Crystallizing treatment, fluorescence intensity significantly strengthens the fluorescence spectrum of glass film.
Embodiment three
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: iodate terbium=76: 16: 10: 18: 9: 2, takes each raw material respectively; In step (8), the pull rate of glass substrate in gelating soln controls in 0.6 mm/second, repeats lift 3 times, and lift interval time is 15 minutes at every turn; In step (9), with the ramp of 40 DEG C per hour to 100 DEG C, then heat up stove again to 340 DEG C with the speed of 40 DEG C per hour; In step (10), progressively intensification stove is to 510 DEG C, and reaction treatment 3 hours at such a temperature, finally obtain containing rare earth ion doped Ba
2csI
5the 76SiO of crystallite
2-8P
2o
5-5Ga
2o
3-9Ba
2csI
5-2TbI
3system glass film.
Tb is contained to what prepare
3+ion doping Ba
2csI
5the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrogen iodide process is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing Ba
2csI
5the glass film of crystallite.The Tb of excitation of X-rays
3+ion doping Ba
2csI
5the SiO of crystallite
2-P
2o
5-Ga
2o
3as shown in Figure 4, with the sample ratio without hydrogen iodide Crystallizing treatment, its luminous intensity significantly strengthens the fluorescence spectrum of glass film.
Claims (8)
1. containing rare earth ion doped Ba
2csI
5the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 75-78mol%, Vanadium Pentoxide in FLAKES: 5-10mol%, Gallium trioxide: 3-8mol%, Ba
2csI
5: 6-11mol%, rare-earth iodide: 1-3mol%, wherein rare-earth iodide is the one in cerous iodide, the sub-europium of iodate or iodate terbium.
2. as claimed in claim 1 containing rare earth ion doped Ba
2csI
5the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 75mol%, Vanadium Pentoxide in FLAKES: 10mol%, Gallium trioxide: 8mol%, Ba
2csI
5: 6mol%, cerous iodide: 1mol%.
3. as claimed in claim 1 containing rare earth ion doped Ba
2csI
5the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 78mol%, Vanadium Pentoxide in FLAKES: 5mol%, Gallium trioxide: 3mol%, Ba
2csI
5: 11mol%, sub-europium: the 3mol% of iodate.
4. as claimed in claim 1 containing rare earth ion doped Ba
2csI
5the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 76mol%, Vanadium Pentoxide in FLAKES: 8mol%, Gallium trioxide: 5mol%, Ba
2csI
5: 9mol%, iodate terbium: 2mol%.
5. as claimed in claim 1 containing rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, is characterized in that comprising following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: rare-earth iodide=75-78: 10-20: 6-16: 12-22: 6-11: 1-3, and barium iodide: the mol ratio of cesium iodide is 2: 1, rare-earth iodide is the one in cerous iodide, the sub-europium of iodate or iodate terbium, take analytically pure each raw materials respectively, stand-by;
(2), tripotassium phosphate ester hydrolysis: the trimethyl phosphite 99 of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and trimethyl phosphite 99 is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and trimethyl phosphite 99 is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and trimethyl phosphite 99 is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol gallium: the ethanol gallium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol gallium is 2.5: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and ethanol gallium is 0.8: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol gallium is 0.5: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), the hydrolysis of tetraethoxy: the tetraethoxy of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy is 2.5: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy is 1: 1, and be 4-5 by the pH value of concentrated nitric acid regulator solution, be hydrolyzed under room temperature reaction 1 hour, makes solution C;
(5), solution A and B are slowly joined in solution C respectively, after abundant mix and blend, drip a certain amount of distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, trimethyl phosphite 99, ethanol gallium three summation is 0.5: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured barium iodide of scale, cesium iodide and each raw material of rare-earth iodide in step (1), under vigorous stirring, hydrolysis reaction, after 2 hours, makes solution E;
(7), by after solution E sealing leave standstill 1 day, obtain the solution F of certain viscosity;
(8), solution F dip-coating method is coated on clean glass substrate, the pull rate of glass substrate in solution F controls in 0.2-1 mm/second, lift 1-5 time can be repeated according to concrete thickness requirement, each lift interval time is 15 minutes, and the film after coating at room temperature dries 4 hours;
(9), the film that step (8) is obtained is placed in stove, with the ramp of 30-50 per hour DEG C to 100 DEG C, be incubated 1 hour, to remove remaining water and ethanol, then heat up stove again to 340 DEG C with the speed of 30-50 per hour DEG C, be incubated 20 minutes, to remove organism remaining in film, thermal treatment terminates, and with 50 DEG C of rate of temperature fall per hour, Slow cooling stove is to room temperature;
(10), the film that step (9) obtains is put into the quartz pipe of tube type resistance furnace, first the air in quartz pipe is got rid of with nitrogen, then hydrogen iodide cylinder valve is opened, pass into dry hydrogen iodide gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 500-520 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen iodide gas, and with 50 DEG C of rate of temperature fall per hour, Slow cooling tube type resistance furnace is to room temperature, with hydrogen iodide gas residual in nitrogen purge pipeline, all remaining iodate hydrogen through pipeline tail end is reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped Ba
2csI
5the glass film of crystallite.
6. as claimed in claim 5 containing rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: cerous iodide=75: 20: 16: 12: 6: 1.
7. as claimed in claim 5 containing rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: sub-europium=78 of iodate: 10: 6: 22: 11: 3.
8. as claimed in claim 5 containing rare earth ion doped Ba
2csI
5the preparation method of the glass film of crystallite, it is characterized in that in described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: trimethyl phosphite 99: ethanol gallium: barium iodide: cesium iodide: iodate terbium=76: 16: 10: 18: 9: 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011589A (en) * | 2012-06-27 | 2013-04-03 | 温州大学 | Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof |
| CN103951223A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Ba2CsI5 microcrystalline glass and preparation method thereof |
-
2015
- 2015-11-16 CN CN201510783193.7A patent/CN105384356A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011589A (en) * | 2012-06-27 | 2013-04-03 | 温州大学 | Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof |
| CN103951223A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Ba2CsI5 microcrystalline glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈红兵等: "CuI微晶掺杂硅凝胶玻璃及其薄膜的制备与光谱性质", 《材料研究学报》 * |
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