CN105293944A - Glass film containing rare-earth-ion-doped Cs2LiLuCl6 microcrystalline and preparation method thereof - Google Patents
Glass film containing rare-earth-ion-doped Cs2LiLuCl6 microcrystalline and preparation method thereof Download PDFInfo
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- CN105293944A CN105293944A CN201510783208.XA CN201510783208A CN105293944A CN 105293944 A CN105293944 A CN 105293944A CN 201510783208 A CN201510783208 A CN 201510783208A CN 105293944 A CN105293944 A CN 105293944A
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Abstract
A disclosed glass film containing rare-earth-ion-doped Cs2LiLuCl6 microcrystalline is characterized in that the glass film comprises the following compositions in percent by mole: 71 mol% of silicon dioxide, 8-12 mol% of boric oxide, 5-8 mol% of niobium pentoxide, 8-12 mol% of Cs2LiLuCl6, and 1-4 mol% of a rare-earth chloride, wherein the rare-earth chloride is one of cerium chloride, europium chloride and terbium chloride. The advantages comprise that a sol-gel technology is a low-temperature wet-chemical-process glass preparation technology, the glass is obtained through hydrolysis of a precursor raw material and a polymerization chemical reaction process, the film material can be prepared under a certain liquid viscosity condition, and the low-temperature synthesis condition is capable of effectively preventing the chloride raw material from being decomposed and volatilized; and because of volatilization and decomposition of the solvent, certain micropores are generated in the glass prepared through the sol-gel method, and the micropores provide good environment for generation of nanometer chloride microcrystalline, and thus crystallized-particle nonuniformity and glass devitrification caused by incomplete uniformity of melt-glass chemical compositions and crystallization processing temperature are overcome to a certain degree.
Description
Technical field
The present invention relates to the technology of preparing containing a kind of rare earth ion doped devitrified glass film, be specifically related to a kind of be used as scintillation material containing rare earth ion doped Cs
2liLuCl
6glass 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.
Rare-earth-ion-doped Cs
2liLuCl
6crystal is a kind of material with excellent scintillation properties, due to Lu
3+with other rare earth ion, there is analogous ionic radius size and identical ionic valence condition, other multiple luminescence rare earth ion that can adulterate relatively large.Such as, Ce
3+the Cs of doping
2liLuCl
6it is high that crystal has light output, decays soon, good energy resolution, temporal resolution and linear response, has than rare earth ion doped crystal of fluoride and the higher luminous efficiency of oxide crystal, scintillation detectors efficiency can be made to increase substantially.Eu
3+, Tb
3+the Cs of doping
2liLuCl
6the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But Cs
2liLuCl
6matrix chloride crystals is because of defects such as poor, the easy cleavage of mechanical property and very easily deliquescence, and large-size crystals growth difficulty and its practical application of disadvantages affect such as expensive.
Notification number is the patent of invention of CN103951245A, then disclosing and use high temperature melting legal system for phosphorus germanate system glass, then by being incubated near glass transition temperature, separating out rare earth ion doped Cs
2liLuCl
6crystallite, is prepared into the rare earth ion doped Cs of collection glass and single crystal performance
2liLuCl
6devitrified glass.But there is following defect in the method, first: because at high temperature melting obtains, therefore easily cause the decomposition of muriate 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 Cs difficult to get access
2liLuCl
6lattice 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 thin-film material 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 Cs
2liLuCl
6glass film of crystallite and preparation method thereof, this glass film has that physical and chemical performance is stable, preparation method has that equipment is simple, production cost is lower, easy to operate, combined coefficient is high, and 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 Cs
2liLuCl
6the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 8-12mol%, Niobium Pentxoxide: 5-8mol%, Cs
2liLuCl
6: 8-12mol%, rare earth chloride: 1-4mol%, wherein rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride.
Described contains rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 12mol%, Niobium Pentxoxide: 8mol%, Cs
2liLuCl
6: 8mol%, Cerium II Chloride: 1mol%.
Described contains rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 8mol%, Niobium Pentxoxide: 5mol%, Cs
2liLuCl
6: 12mol%, Europium trichloride: 4mol%.
Described contains rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 10mol%, Niobium Pentxoxide: 7mol%, Cs
2liLuCl
6: 10mol%, terbium chloride: 2mol%.
Described contains rare earth ion doped Cs
2liLuCl
6the 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: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: rare earth chloride=71: 16-24: 10-16: 16-24: 8-12: 8-12: 1-4, and cesium chloride: lithium chloride: the mol ratio of lutecium chloride is 2: 1: 1, rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride, take analytically pure each raw materials respectively, stand-by;
The preparation of gel:
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2: 1, add methyl ethyl diketone fast, the volume ratio of tri-n-butyl borate and methyl ethyl diketone is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol niobium: the ethanol niobium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol niobium is 2: 1, add methyl ethyl diketone fast, the volume ratio of ethanol niobium and methyl ethyl diketone is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol niobium is 0.6: 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 distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, tri-n-butyl borate, ethanol niobium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured cesium chloride of scale, lithium chloride, lutecium chloride and rare earth chloride 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-temp chlorination hydrogen process 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 670-690 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen chloride 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 chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Cerium II Chloride=71: 24: 16: 16: 8: 8: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Europium trichloride=71: 16: 10: 24: 12: 12: 4.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: terbium chloride=71: 20: 14: 20: 10: 10: 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 muriate 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 muriate 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 Lu of glass network modifier
3+ion, most one is in together in micropore gap, and therefore along with the carrying out of high-temp chlorination hydrogen process, rare earth luminous ion easily enters Cs
2liLuCl
6lattice position in, obtain the rare earth ion doped and illumination effect of high density;
5, the hydrogenchloride drying treatment of high temperature impels the oxychloride in gel glass, oxyhydroxide and oxide compound etc. to convert muriate to, can carry out the dehydration reaction of muriate raw material, and effectively promotes and control Cs
2liLuCl
6the generation of crystallite.
Because this film glass matrix is SiO
2-B
2o
3-Nb
2o
5, therefore high in the transmitance of ultraviolet band, containing rare earth ion doped Cs
2liLuCl
6microcrystal silicon boron niobate glass material, therefore can according to actual needs due to three phase composites, and regulate its optics and physical and chemical performance by changing chemical composition, this system glass film has superior scintillation properties, physical strength, thermal stability characteristics, overcomes Cs
2liLuCl
6the 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 Cs
2liLuCl
6crystalline phase, obtained rare earth ion doped Cs
2liLuCl
6devitrified 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 embodiment one high-temp chlorination hydrogen thermal treatment rear film sample;
Fig. 2 be embodiment one excitation of X-rays containing Ce
3+ion doping Cs
2liLuCl
6the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu
3+ion doping Cs
2liLuCl
6the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb
3+ion doping Cs
2liLuCl
6the 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 Cs
2liLuCl
6the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Cerium II Chloride=71: 24: 16: 16: 8: 8: 1, take analytically pure each raw materials that total amount is 30 grams, stand-by;
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2: 1, add methyl ethyl diketone fast, the volume ratio of trimethyl phosphite 99 and methyl ethyl diketone is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol niobium: the ethanol niobium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol niobium is 2: 1, add methyl ethyl diketone fast, the volume ratio of ethanol niobium and methyl ethyl diketone is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol niobium is 0.6: 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 distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, tri-n-butyl borate, ethanol niobium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured cesium chloride of scale, lithium chloride, lutecium chloride and Cerium II Chloride 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 (dip-coating) 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 670 DEG C, and reaction treatment 5 hours at such a temperature, reaction treatment terminates, close hydrogen chloride 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 chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped Cs
2liLuCl
6the 71SiO of crystallite
2-12B
2o
3-8Nb
2o
5-8Cs
2liLuCl
6-1CeCl
3system glass film.
Ce is contained to what prepare
3+ion doping Cs
2liLuCl
6the 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 Cs of the sample obtained
2liLuCl
6the main diffraction peak of the standard x RD figure of crystalline phase all conforms to, and what therefore obtain is containing Cs
2liLuCl
6the glass film of crystallite.The Ce of excitation of X-rays
3+ion doping Cs
2liLuCl
6as shown in Figure 2, with compared with hydrogenchloride Crystallizing treatment, fluorescence peak intensity significantly strengthens the fluorescence spectrum of devitrified glass film.Fluorescence decay time is 35ns.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Europium trichloride=71: 16: 10: 24: 12: 12: 4, takes 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 690 DEG C, and reaction treatment 2 hours at such a temperature, finally obtain containing rare earth ion doped Cs
2liLuCl
6the 71SiO of crystallite
2-8B
2o
3-5Nb
2o
5-12Cs
2liLuCl
6-4EuCl
3system glass film.
Eu is contained to what prepare
3+ion doping Cs
2liLuCl
6the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrochlorination is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing Cs
2liLuCl
6the glass film of crystallite.The Eu of excitation of X-rays
3+ion doping Cs
2liLuCl
6as shown in Figure 3, fluorescence intensity is strong for the fluorescence spectrum of the silicon boron niobate glass film of crystallite.
Embodiment three
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: terbium chloride=71: 20: 14: 20: 10: 10: 2, takes each raw materials 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 680 DEG C, and reaction treatment 3 hours at such a temperature, finally obtain containing rare earth ion doped Cs
2liLuCl
6the 71SiO of crystallite
2-10B
2o
3-7Nb
2o
5-10Cs
2liLuCl
6-2TbCl
3system glass film.
Tb is contained to what prepare
3+ion doping Cs
2liLuCl
6the glass film of crystallite carries out performance test, and the XRD figure of glass film after hydrochlorination is substantially identical with Fig. 1, and just intensity is different, and what therefore obtain is containing Cs
2liLuCl
6the glass film of crystallite.The Tb of excitation of X-rays
3+ion doping Cs
2liLuCl
6as shown in Figure 4, luminous intensity is strong for the fluorescence spectrum of the silicon boron niobate glass film of crystallite.
Claims (8)
1. containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 8-12mol%, Niobium Pentxoxide: 5-8mol%, Cs
2liLuCl
6: 8-12mol%, rare earth chloride: 1-4mol%, wherein rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride.
2. as claimed in claim 1 containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 12mol%, Niobium Pentxoxide: 8mol%, Cs
2liLuCl
6: 8mol%, Cerium II Chloride: 1mol%.
3. as claimed in claim 1 containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 8mol%, Niobium Pentxoxide: 5mol%, Cs
2liLuCl
6: 12mol%, Europium trichloride: 4mol%.
4. as claimed in claim 1 containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: silicon-dioxide: 71mol%, boron trioxide: 10mol%, Niobium Pentxoxide: 7mol%, Cs
2liLuCl
6: 10mol%, terbium chloride: 2mol%.
5. as claimed in claim 1 containing rare earth ion doped Cs
2liLuCl
6the preparation method of the glass film of crystallite, is characterized in that comprising following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: rare earth chloride=71: 16-24: 10-16: 16-24: 8-12: 8-12: 1-4, and cesium chloride: lithium chloride: the mol ratio of lutecium chloride is 2: 1: 1, rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride, take analytically pure each raw materials respectively, stand-by;
(2), the hydrolysis of tri-n-butyl borate: the tri-n-butyl borate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tri-n-butyl borate is 2: 1, add methyl ethyl diketone fast, the volume ratio of tri-n-butyl borate and methyl ethyl diketone is 0.7: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tri-n-butyl borate is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of ethanol niobium: the ethanol niobium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and ethanol niobium is 2: 1, add methyl ethyl diketone fast, the volume ratio of ethanol niobium and methyl ethyl diketone is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and ethanol niobium is 0.6: 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 distilled water again, carry out secondary hydrolysis reaction, the mol ratio of distilled water and tetraethoxy, tri-n-butyl borate, ethanol niobium three summation is 0.6: 1, mixed hydrolysis makes solution D after reacting 0.5 hour;
(6), in solution D, add the measured cesium chloride of scale, lithium chloride, lutecium chloride and rare earth chloride 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 hydrogenchloride cylinder valve is opened, pass into dry hydrogen chloride gas, with the speed of 50 DEG C per hour, progressively intensification stove is to 670-690 DEG C, and reaction treatment 2-5 hour at such a temperature, reaction treatment terminates, close hydrogen chloride 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 chloride gas residual in nitrogen purge pipeline, all remaining hydrogen chloride gas through pipeline tail end are reclaimed by sodium hydroxide solution, finally obtain containing rare earth ion doped Cs
2liLuCl
6the glass film of crystallite.
6. as claimed in claim 5 containing rare earth ion doped Cs
2liLuCl
6the 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: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Cerium II Chloride=71: 24: 16: 16: 8: 8: 1.
7. as claimed in claim 5 containing rare earth ion doped Cs
2liLuCl
6the 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: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: Europium trichloride=71: 16: 10: 24: 12: 12: 4.
8. as claimed in claim 5 containing rare earth ion doped Cs
2liLuCl
6the 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: tri-n-butyl borate: ethanol niobium: cesium chloride: lithium chloride: lutecium chloride: terbium chloride=71: 20: 14: 20: 10: 10: 2.
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| CN201510783208.XA Withdrawn CN105293944A (en) | 2015-11-16 | 2015-11-16 | Glass film containing rare-earth-ion-doped Cs2LiLuCl6 microcrystalline and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860747A (en) * | 2021-09-10 | 2021-12-31 | 华南理工大学 | Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof |
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|---|---|---|---|---|
| CN103011589A (en) * | 2012-06-27 | 2013-04-03 | 温州大学 | Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof |
| CN103951245A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiLuCl6 microcrystalline glass and preparation method thereof |
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- 2015-11-16 CN CN201510783208.XA patent/CN105293944A/en not_active Withdrawn
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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 |
| CN103951245A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiLuCl6 microcrystalline glass and preparation method thereof |
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| 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》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860747A (en) * | 2021-09-10 | 2021-12-31 | 华南理工大学 | Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof |
| CN113860747B (en) * | 2021-09-10 | 2022-06-14 | 华南理工大学 | Chloride crystal and glass composite transparent optical functional material and preparation method and application thereof |
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Application publication date: 20160203 |