CN105384348A - Glass film containing rare earth ion-doped Cs2LiYCl6 microcrystalline and preparation method of glass film - Google Patents
Glass film containing rare earth ion-doped Cs2LiYCl6 microcrystalline and preparation method of glass film Download PDFInfo
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- CN105384348A CN105384348A CN201510783238.0A CN201510783238A CN105384348A CN 105384348 A CN105384348 A CN 105384348A CN 201510783238 A CN201510783238 A CN 201510783238A CN 105384348 A CN105384348 A CN 105384348A
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Abstract
The invention discloses a chemical constitution of a glass film containing rare earth ion-doped Cs2LiYCl6 microcrystalline and a sol-gel preparation method of the glass film. The glass film is characterized by comprising the following components by mol percent: 71mol%-75mol% of germanium dioxide, 5mol%-10mol% of aluminum sesquioxide, 5mol%-10mol% of phosphorus pentoxide, 8mol%-12mol% of Cs2LiYCl6 and 1mol%-3mol% of rare-earth chloride, wherein rare-earth chloride is one of cerium chloride, europium chloride or terbium chloride. The sol-gel preparation method has the advantages that sol-gel is a low-temperature wet chemical method glass preparation technique, and glass is prepared by virtue of hydrolysis and chemical polymerization reaction of precursor raw materials, and a film material can be prepared under certain liquid viscosity; by virtue of low temperature synthesis conditions, the decomposition and the volatilization of the chloride raw material can be effectively prevented.
Description
Technical field
The present invention relates to 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
2liYCl
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
2liYCl
6crystal is a kind of material with excellent scintillation properties, due to Y
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
2liYCl
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
2liYCl
6the scintillation properties of crystal is also more excellent, can be used for the field such as safety check, blinking screen.But Cs
2liYCl
6the defects such as poor, the easy cleavage of matrix chloride crystals mechanical property and very easily deliquescence, and large-size crystals grows its practical applications of disadvantages affect such as difficult and expensive.
Notification number is the patent of invention of CN103951243A, then disclose by high temperature melting legal system for GeO
2-BaF
2-NaF-Y
2o
3-Cs
2liY
(1-x)ln
xcl
6system glass, then by being incubated near glass transition temperature, separates out rare earth ion doped Cs
2liYCl
6crystallite, is prepared into the rare earth ion doped Cs of collection glass and single crystal performance
2liYCl
6devitrified glass.But there is following defect in the method, first: because at high temperature melting obtains, therefore easily cause decomposition and the volatilization 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
2liYCl
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 ion doping Cs
2liYCl
6devitrified glass film 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
2liYCl
6the glass film of crystallite, its Mole percent consists of: germanium dioxide: 71-75mol%, aluminium sesquioxide: 5-10mol%, Vanadium Pentoxide in FLAKES: 5-10mol%, Cs
2liYCl
6: 8-12mol%, rare earth chloride: 1-3mol%, wherein rare earth chloride is the one in Cerium II Chloride, Europium trichloride or terbium chloride.
Described contains rare earth ion doped Cs
2liYCl
6the glass film of crystallite, its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: Cerium II Chloride=71: 10: 10: 8: 1.
Described contains rare earth ion doped Cs
2liYCl
6the glass film of crystallite, its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: Europium trichloride=75: 5: 5: 12: 3.
Described contains rare earth ion doped Cs
2liYCl
6the glass film of crystallite, its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: terbium chloride=73: 8: 7: 10: 2.
Described contains rare earth ion doped Cs
2liYCl
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 germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: rare earth chloride=71-75: 10-20: 10-20: 16-24: 8-12: 8-12: 1-3, and cesium chloride: lithium chloride: the mol ratio of Yttrium trichloride 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 tetraethoxy germanium: the tetraethoxy germanium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy germanium is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and tetraethoxy germanium is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy germanium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.6: 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 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), 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 0.5: 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 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 total tetraethoxy germanium, aluminium secondary butylate, trimethyl phosphite 99 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, Yttrium trichloride and each raw material of 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 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 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 630-650 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
2liYCl
6the glass film of crystallite.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Cerium II Chloride=71: 20: 20: 16: 8: 8: 1.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Europium trichloride=75: 10: 10: 24: 12: 12: 3.
In described step (1), raw materials is made up of according to following mol ratio following substances: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: terbium chloride=73: 16: 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 Y 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
2liYCl
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
2liYCl
6the generation of crystallite.
Because this film glass matrix is GeO
2-Al
2o
3-P
2o
5three-phase system, therefore according to actual needs, can regulate its optics and physical and chemical performance by changing chemical composition.This glass film is high in the transmitance of ultraviolet band, has superior scintillation properties, physical strength, thermal stability characteristics, overcomes Cs
2liYCl
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
2liYCl
6crystalline phase, obtained rare earth ion doped Cs
2liYCl
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 glass film after the thermal treatment of embodiment one high-temp chlorination hydrogen;
Fig. 2 be embodiment one excitation of X-rays containing Ce
3+ion doping Cs
2liYCl
6the fluorescence spectrum of the glass film of crystallite;
Fig. 3 be embodiment two excitation of X-rays containing Eu
3+ion doping Cs
2liYCl
6the fluorescence spectrum of the glass film of crystallite;
Fig. 4 be embodiment three excitation of X-rays containing Tb
3+ion doping Cs
2liYCl
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
2liYCl
6the preparation method of the glass film of crystallite, comprises following concrete steps:
(1), by raw materials in molar ratio: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Cerium II Chloride=71: 20: 20: 16: 8: 8: 1, take each raw materials of analytical pure that total amount is 30 grams, stand-by;
(2), the hydrolysis of tetraethoxy germanium: the tetraethoxy germanium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy germanium is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and tetraethoxy germanium is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy germanium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.6: 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 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), 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 0.5: 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 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 tetraethoxy germanium, aluminium secondary butylate, trimethyl phosphite 99 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, Yttrium trichloride and each raw material of 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 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-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 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 630 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
2liYCl
6the 71GeO of crystallite
2-10Al
2o
3-10P
2o
5-8Cs
2liYCl
6-1CeCl
3system glass film.
Ce is contained to what prepare
3+ion doping Cs
2liYCl
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
2liYCl
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
2liYCl
6as shown in Figure 2, with compared with hydrogenchloride Crystallizing treatment, the powerful amplitude of fluorescence peak intensity strengthens the fluorescence spectrum of devitrified glass film.Fluorescence decay time is 38ns.
Embodiment two
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Europium trichloride=75: 10: 10: 24: 12: 12: 3, takes each raw material 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 650 DEG C, and reaction treatment 2 hours at such a temperature, finally obtain containing Eu
3+ion doping Cs
2liYCl
6the 75GeO of crystallite
2-5Al
2o
3-5P
2o
5-12Cs
2liYCl
6-3EuCl
3system glass film
Eu is contained to what prepare
3+ion doping Cs
2liYCl
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
2liYCl
6the glass film of crystallite.The Eu of excitation of X-rays
3+ion doping Cs
2liYCl
6as shown in Figure 3, with compared with hydrogenchloride Crystallizing treatment, the powerful amplitude of fluorescence peak intensity strengthens the fluorescence spectrum of devitrified glass film.
Embodiment three
Substantially identical with embodiment one, difference is in step (1), raw materials is according to following mol ratio: tetraethoxy germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: terbium chloride=73: 16: 14: 20: 10: 10: 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 640 DEG C, and reaction treatment 3 hours at such a temperature.Finally obtain containing Tb
3+ion doping Cs
2liYCl
6the 73GeO of crystallite
2-8Al
2o
3-7P
2o
5-10Cs
2liYCl
6-2TbCl
3system glass film
Tb is contained to what prepare
3+ion doping Cs
2liYCl
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
2liYCl
6the glass film of crystallite.Excitation of X-rays containing Tb
3+ion doping Cs
2liYCl
6as shown in Figure 4, with compared with hydrogenchloride Crystallizing treatment, the powerful amplitude of fluorescence peak intensity strengthens the fluorescence spectrum of the film of crystallite.
Claims (8)
1. containing rare earth ion doped Cs
2liYCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: germanium dioxide: 71-75mol%, aluminium sesquioxide: 5-10mol%, Vanadium Pentoxide in FLAKES: 5-10mol%, Cs
2liYCl
6: 8-12mol%, rare earth chloride: 1-3mol%, 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
2liYCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: Cerium II Chloride=71: 10: 10: 8: 1.
3. as claimed in claim 1 containing rare earth ion doped Cs
2liYCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: Europium trichloride=75: 5: 5: 12: 3.
4. as claimed in claim 1 containing rare earth ion doped Cs
2liYCl
6the glass film of crystallite, is characterized in that its Mole percent consists of: germanium dioxide: aluminium sesquioxide: Vanadium Pentoxide in FLAKES: Cs
2liYCl
6: terbium chloride=73: 8: 7: 10: 2.
5. as claimed in claim 1 containing rare earth ion doped Cs
2liYCl
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 germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: rare earth chloride=71-75: 10-20: 10-20: 16-24: 8-12: 8-12: 1-3, and cesium chloride: lithium chloride: the mol ratio of Yttrium trichloride 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 tetraethoxy germanium: the tetraethoxy germanium of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and tetraethoxy germanium is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and tetraethoxy germanium is 0.6: 1, and carry out the stirring of strong magnetic power, progressively instill distilled water, the mol ratio of distilled water and tetraethoxy germanium is 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution A;
(3), the hydrolysis of aluminium secondary butylate: the aluminium secondary butylate of weighing in step (1) is dissolved in dehydrated alcohol, the mol ratio of dehydrated alcohol and aluminium secondary butylate is 2: 1, add methyl ethyl diketone fast, the volume ratio of methyl ethyl diketone and aluminium secondary butylate is 0.6: 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 0.6: 1, be hydrolyzed under room temperature reaction 1 hour, makes solution B;
(4), 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 0.5: 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 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 germanium, aluminium secondary butylate, trimethyl phosphite 99 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, Yttrium trichloride and each raw material of 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 630-650 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
2liYCl
6the glass film of crystallite.
6. as claimed in claim 5 containing rare earth ion doped Cs
2liYCl
6the 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 germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Cerium II Chloride=71: 20: 20: 16: 8: 8: 1.
7. as claimed in claim 5 containing rare earth ion doped Cs
2liYCl
6the 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 germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: Europium trichloride=75: 10: 10: 24: 12: 12: 3.
8. as claimed in claim 5 containing rare earth ion doped Cs
2liYCl
6the 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 germanium: aluminium secondary butylate: trimethyl phosphite 99: cesium chloride: lithium chloride: Yttrium trichloride: terbium chloride=73: 16: 14: 20: 10: 10: 2.
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|---|---|---|---|
| CN201510783238.0A CN105384348A (en) | 2015-11-16 | 2015-11-16 | Glass film containing rare earth ion-doped Cs2LiYCl6 microcrystalline and preparation method of glass film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN107794566A (en) * | 2017-10-31 | 2018-03-13 | 山东大学 | A kind of Ce detected for gamma-rays, neutron pair:Cs2LiYCl6The fast preparation method of crystal |
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| JPH05246727A (en) * | 1992-02-12 | 1993-09-24 | Hitachi Cable Ltd | Production of glass waveguide |
| CN103011589A (en) * | 2012-06-27 | 2013-04-03 | 温州大学 | Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof |
| CN103951243A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiYCl6 microcrystalline glass and preparation method thereof |
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| JPH05246727A (en) * | 1992-02-12 | 1993-09-24 | Hitachi Cable Ltd | Production of glass waveguide |
| CN103011589A (en) * | 2012-06-27 | 2013-04-03 | 温州大学 | Sodium borosilicate glass doped with In2S3 quantum dots and preparation method thereof |
| CN103951243A (en) * | 2014-05-08 | 2014-07-30 | 宁波大学 | Rare-earth-ion-doped Cs2LiYCl6 microcrystalline glass and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107366018A (en) * | 2017-07-12 | 2017-11-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN107366018B (en) * | 2017-07-12 | 2019-05-21 | 宁波大学 | A kind of rare earth halide mixing scintillation crystal and preparation method thereof |
| CN107794566A (en) * | 2017-10-31 | 2018-03-13 | 山东大学 | A kind of Ce detected for gamma-rays, neutron pair:Cs2LiYCl6The fast preparation method of crystal |
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