CN109867444A - A kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics - Google Patents
A kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics Download PDFInfo
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Abstract
The invention belongs to special glass manufacturing technology fields, and in particular to a kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics.It is stirred including grinding source chemicals；It is melted in high temperature furnace and obtains glass metal, glass metal quenching is suppressed to obtain transparent presoma glass sample with copper sheet；Presoma glass sample is made annealing treatment；It carries out being heat-treated again, fluoride microcrystal is precipitated in glass sample, obtains devitrified glass.The chemical composition of source chemicals is by mole the SiO for being calculated as 55mol%2, 22.5mol% KF, 22.5mol%.Doped ions are 0.1~0.9mol%YbF of doping on the basis of glass matrix3.This method preparation process is simple, it can be achieved that mass production.The devitrified glass transparency of preparation is high, and luminous efficiency is high, and strong blue emission can be able to achieve under 980nm diode-end-pumped, with excellent chemical stability, can be used as illumination display luminous glass material, can also using with optical fiber laser field, have a extensive future.
Description
Technical field
The invention belongs to special glass manufacturing technology fields, and in particular to a kind of Yb of high transparency3+Single doping fluorine silicon
The preparation method of hydrochlorate devitrified glass.
Background technique
Transparent glass-ceramics refers to the special glass that the crystal of nano-scale is controllably precipitated in the glass of homogeneous transparent,
It is widely used as the gain material of illumination display and optical fiber laser.In research of the past about the material of up-conversion luminescence,
Most of is using rare earth ion doped crystalline material as research object.In general, the preparation of crystalline material is more difficult,
Price is more high, to limit the application of rare earth ion doped up-conversion luminescence crystalline material.It is rare earth ion doped transparent
Excellent chemical stability, mechanical strength and the high laser damage threshold of the existing general oxide glass of devitrified glass, and have height
Upper transfer efficiency, preparation be also relatively easy to, it will be a potential developing direction of up-conversion luminescent material.
Long-wave radiation is converted into shortwave radiation by multi-photon mechanism and is known as upper conversion.So-called up-conversion is exactly
It, can be with the material of the fluorescence of transmitting ratio excitation wave length when referring to by light excitation.It can be seen that the essence of up-conversion luminescence is one
Kind anti-Stokes luminescence, therefore also referred to as up-conversion luminescence is anti-Stokes luminescence.Early in nineteen fifty-nine, there have been upper conversions
Luminous report.With the infrared ray excited polycrystalline ZnS of 960nm, 525nm green emitting observed.1962, such phenomenon was again
Further confirmation is obtained in selenides, the efficiency that infra-red radiation is converted into visible light has reached quite high level.
1966, Auzel had been surprisingly found that when studying wolframic acid ytterbium soda-lime glass when mixing Yb in host material3+When ion, Er3+、Ho3+With
Tm3+Ion is when infrared ray excited, it is seen that shines and almost improves two orders of magnitude, it is confirmed that proposing " up-conversion luminescence "
Viewpoint.From there on, the relevant report of up-conversion luminescent material emerges one after another, and up-conversion gradually develops as important light
Transition material is composed, to realize the efficient conversion from infrared laser to visible light.Up to the present, up-conversion luminescent material is being shown
The fields such as illumination, biological fluorescent labelling, visible solid laser, infrared quantum counter and solar battery are shown
Great application potential.Currently, the material category due to up-conversion luminescence is various, mainly there are monocrystalline, polycrystalline and glass material.
Monocrystal material luminescent properties are excellent, but preparation process is complicated, cannot achieve mass production；The scattering of polycrystalline material grain boundaries is tight
Weight, light transmission are poor；Although glass material light transmission is good, luminous efficiency is low.Devitrified glass both has glass
Good light transmission, and there is the higher up-conversion luminescence efficiency of crystal, preparation is simple, has preferable machinability, is
A kind of excellent up-conversion luminescent material is particularly suitable for the fields such as display illumination, Solid State Laser and solar battery.
Yb is more special one of rare earth element, and ion energy level is very simple, only2F7/2With2F5/2Two energy levels,
Corresponding energy level transition is 980nm.Therefore, Yb is mixed3+Excited-state Absorption is not present in laser material, and fluorescence efficiency is high.Meanwhile
Yb3+Stimulated radiation have that pumping range is wide, fluorescence lifetime is long and can be special with InGaAs semiconductor pump light source efficient coupling etc.
Point, makes Yb3+Doped-glass is considered as very potential high power laser material.Yb in oxide glass3+Be stimulated
It penetrates and observes under cryogenic first, in the 1990s, people realize Yb:YAG Laser emission at room temperature.Mesh
Before, the laser-conversion efficiency of Yb:YAG is up to 50%, and continuous laser output power is up to 346W.Mix Yb3+Laser glass is in optical fiber
The fields such as laser, amplifier have a wide range of applications, thus are the solid state laser of matrix by people using various glass
More and more extensive concern.
Yb3+Up-conversion luminescence be a kind of very special cooperation up-conversion luminescence, from level structure, theoretically
Such ion, which does not have, generates the condition converted, because it, only there are two energy level, absorbs and the wavelength of transmitting relatively connects
Closely, substantially without Stokes shift.However, when two such ions lean on it is close when, interionic Wave function overlap,
Coupling forms ion pair, and energy level redistribution forms a virtual visible luminescent energy level E.At this point, two ions absorb simultaneously
The identical photon transfer of energy returns to G ground state level to E energy level, then by E energy level to ion pair, and generates an optical photon
Transmitting, it is seen that the energy of photon is twice or so for absorbing energy.Currently, this special up-conversion luminescence is typically only capable in height
The Yb of concentration3+It is just able to achieve inside certain special systems of ion doping, such as YbPO4Deng.Yb3+Adulterate CaF2Matrix, it is lower dense
The Yb of degree3+Doping can obtain Yb3+The cooperation up-conversion luminescence of ion, is primarily due to Yb3+Adulterate CaF2Easily assemble when matrix
Form cluster.However, above-mentioned Yb3+The up-conversion luminescence of ion is realized in crystal substrate.Crystalline material preparation process
Complex process, lower physical and chemical stability also limit it in some application demands than under relatively rugged environment.
Summary of the invention
The purpose of the present invention is to provide a kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics,
The Fluorosilicate Glass-Ceramics transparency prepared by this method is high, it is strong to be able to achieve under 980nm diode-end-pumped
Blue emission.
A kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics, specifically includes the following steps:
Source chemicals are ground stirring in the smooth agate mortar of clean surface and keep source chemicals equal in 20 minutes by step 1
Even mixing；
Mixture reagent is fitted into platinum crucible by step 2, is melted 20 minutes in 1400 DEG C of high temperature furnace, is obtained glass
Glass liquid；
Step 3, the glass metal quenching that will be melted: glass metal is poured in copper mold, and suppresses to obtain with one piece of copper sheet
Transparent presoma glass sample；
Presoma glass sample is placed in annealing furnace and makes annealing treatment by step 4, eliminates the stress in glass, after 3 hours with
Furnace is cooled to room temperature；
Glass sample after annealing is placed in Muffle furnace and is heat-treated by step 5, and fluorination is precipitated in glass sample
Object crystallite, obtains devitrified glass.
A kind of Yb of the high transparency3+List adulterates the preparation method of Fluorosilicate Glass-Ceramics, and source chemicals are pressed in step 1
Molar percent, by the SiO of 55mol%2, 22.5mol% KF, 22.5mol% ZnF2With the rare earth of 0~0.9mol%
Ion doping reagent YbF3Composition.
The beneficial effects of the present invention are:
This method preparation process is simple, it can be achieved that mass production.The devitrified glass transparency of this method preparation is high, shines
It is high-efficient, strong blue emission can be able to achieve under 980nm diode-end-pumped, and there is excellent chemical stabilization
Property.The devitrified glass of this method preparation can be used as the luminous glass material of illumination display, simultaneously because the high light transmittance of glass
With excellent machinability, also there is important application in optical fiber laser field.
Detailed description of the invention
Fig. 1 is the XRD diffracting spectrum for the glass that embodiment 3 and embodiment 7 are prepared；
Fig. 2 is the glass that is prepared of embodiment 1, embodiment 2, embodiment 3 and embodiment 4 in two pole of 980nm semiconductor
Emission spectrum under the excitation of pipe laser；
Fig. 3 is the glass that embodiment 3, embodiment 5, embodiment 6 and embodiment 7 are prepared and devitrified glass in 980nm
Emission spectrum under semiconductor diode laser excitation.
Fig. 4 is the transmission spectrogram of devitrified glass sample in the present invention.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.
A kind of preparation method of the transparent glass-ceramics under room temperature environment with strong blue up-conversion luminous characteristic, packet
Include the following contents:
1, the preparation of host glass:
On the basis of the molar percentage of glass matrix composition, 0.1~0.9mol%YbF3 is added.30g mixture is existed
It is sufficiently mixed after twenty minutes in agate grinding alms bowl, mixture is put into platinum crucible, added for 1400 degrees Celsius under air environment
Heat 20 minutes.Then melt-glass is poured on copper mold, compression moulding.In order to eliminate the stress of inside glass, immediately will
Glass is put into annealing furnace and carries out annealing 3h in 450 DEG C of temperature.
2, the preparation of devitrified glass:
Annealed glass is subjected to reheating, carries out controlled micro crystallization processing, so that size is precipitated in glass in 5-20nm
Fluoride microcrystal in range finally obtains transparent devitrified glass.
In a specific embodiment of the invention, SiO2It buys with KF in the limited public affairs of Shanghai Aladdin biochemical technology share
Department, purity is respectively 99.99% and 99.5%；ZnF2It buys in Shanghai Mike's woods biochemical technology Co., Ltd, purity 99%；
YbF3It buys in Beijing Zhong Yan Science and Technology Ltd., purity 99.99%.Glass ingredient in the present invention is by above-mentioned corresponding
Reagent introduces.The test equipment of XRD is the D8 advanced version X-ray diffractometer of Brooker,Switzerland company production, the survey of emission spectrum
Test instrument is the FLS920 type spectrometer of Edinburgh, Britain company production.
A kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics, comprising the following steps:
Raw material is fitted into the smooth agate mortar of clean surface and grinds according to parameter described in table 1 and formula by step 1
Stirring uniformly mixing in 20 minutes；
Mixture reagent is fitted into platinum crucible by step 2, close the lid 1400 DEG C glass melting temperature be melted 20 points
Clock obtains glass metal；
Obtained glass metal progress quenching will be melted in step 3 at 1400 DEG C: by glass metal to extremely copper mold, copper mill
Tool is 10*10cm square, and 1cm is thick, and surrounding prepares thickness of glass with 0.2mm hassock piece control, suppressed with another piece of copper sheet
To transparent presoma glass sample；
Presoma glass sample is placed in 450 DEG C of annealing furnace and makes annealing treatment by step 4, cools to room with the furnace after 3 hours
Temperature；
Glass sample after annealing is placed in 540 DEG C of Muffle furnace and is heat-treated by step 5, obtains crystallite glass
Glass.
Wherein, when source chemicals, the molar percentage of raw material, glass melting temperature, melting time, heat treatment temperature, heat treatment
Between as shown in table 1.
The Yb of the high transparency of 1 embodiment 1-7 of table3+Single doped microcrystalline glass ingredient molar percentage, glass melting temperature and time
And its heat treatment temperature and time
As shown in Fig. 1, the XRD diffracting spectrum of the glass and devitrified glass that are prepared for embodiment 3 and embodiment 7.
It is whole there is no crystal peak it can be seen that the glass sample that embodiment 3 obtains nearby has a non-structure cell at 30 ° from XRD diagram
Occur.In addition, the XRD spectrum of embodiment 7, which can see, there is apparent crystal peak on the basis of the XRD spectrum of embodiment 3,
And with KZnF3The peak position of (89-4110) card is coincide.Result described above illustrates the Yb of high transparency provided by the invention3+
Single doped microcrystalline glass is a kind of good devitrified glass system.
As shown in Fig. 2, the glass being prepared for embodiment 1, embodiment 2, embodiment 3 and embodiment 4 is in 980nm half
Emission spectrum under the excitation of conductor diode laser；Embodiment 1, embodiment 2, embodiment 3 and embodiment 4 are prepared
The Yb of high transparency can be obtained at the square block glass of 1*1cm size in glass-cutting after being processed by shot blasting to two sides3+Single doping
Fluorosilicate glass.Under the excitation of 980nm semiconductor laser blue emission can be obtained, launching light spectrogram is such as in the glass
Shown in attached drawing 2.
As shown in Fig. 3, the glass and crystallite glass being prepared for embodiment 3, embodiment 5, embodiment 6 and embodiment 7
Emission spectrum of the glass under the excitation of 980nm semiconductor diode laser；By embodiment 3, embodiment 5, embodiment 6 and embodiment
High transparency can be obtained after being processed by shot blasting to two sides at the square block glass of 1*1cm size in 7 glass-cuttings being prepared
Yb3+Single doping Fluorosilicate Glass-Ceramics.Blue light can be obtained under the excitation of 980nm semiconductor laser in the glass sample
Transmitting, launching light spectrogram are as shown in Fig. 3.
It as shown in Fig. 4, is the transmission spectrogram of devitrified glass sample in the present invention.The glass that embodiment is prepared
It is cut into the square block glass of 1*1cm size, the Yb of high transparency can be obtained after being processed by shot blasting to two sides3+Single doping fluorine silicon
Hydrochlorate devitrified glass.It is as shown in Fig. 4 through spectrogram.
To sum up, the present invention is to provide a kind of at room temperature with the transparent glass-ceramics of efficient up-conversion luminescence.
Including glass matrix and Doped ions, the chemical composition of prepared glass matrix is (mol%) 55SiO2-22.5ZnF2-
22.5KF.The sum of molar percentage of each compound is 100%.Doped ions be on the basis of glass matrix doping 0.1~
0.9mol%YbF3.Devitrified glass transparency prepared by the present invention is high, and luminous efficiency is high, and has excellent chemical stabilization
Property, preparation process is simple, it can be achieved that mass production.The luminous glass material that can be used as illumination display, simultaneously as glass
High light transmittance and excellent machinability, so that it is also had important application in optical fiber laser field.
Claims (2)
1. a kind of Yb of high transparency3+The preparation method of single doping Fluorosilicate Glass-Ceramics, which is characterized in that specifically include following
Step:
Source chemicals are ground stirring in the smooth agate mortar of clean surface and mix source chemicals uniformly in 20 minutes by step 1
It closes；
Mixture reagent is fitted into platinum crucible by step 2, is melted 20 minutes in 1400 DEG C of high temperature furnace, is obtained glass metal；
Step 3, glass metal quenching that will be melted: glass metal is poured in copper mold, and with one piece of copper sheet suppresses to obtain transparent
Presoma glass sample；
Presoma glass sample is placed in annealing furnace and makes annealing treatment by step 4, eliminates the stress in glass, cold with furnace after 3 hours
But to room temperature；
Glass sample after annealing is placed in Muffle furnace and is heat-treated by step 5, and it is micro- that fluoride is precipitated in glass sample
Crystalline substance obtains devitrified glass.
2. a kind of Yb of high transparency according to claim 13+The preparation method of single doping Fluorosilicate Glass-Ceramics, feature
It is, source chemicals described in step 1 are by mole meter, by the SiO of 55mol%2, 22.5mol% KF,
The ZnF of 22.5mol%2With the rare earth ion doped reagent YbF of 0~0.9mol%3Composition.
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Cited By (2)
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| CN111233321A (en) * | 2020-03-20 | 2020-06-05 | 苏州凯文堡尼光电科技有限公司 | Preparation method of fluorosilicate glass for preparing visible light waveband optical fiber |
| CN115010371A (en) * | 2022-06-07 | 2022-09-06 | 宁波大学 | High-crystallinity intermediate infrared luminescent nano glass ceramic material and preparation method thereof |
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| CN111233321A (en) * | 2020-03-20 | 2020-06-05 | 苏州凯文堡尼光电科技有限公司 | Preparation method of fluorosilicate glass for preparing visible light waveband optical fiber |
| CN115010371A (en) * | 2022-06-07 | 2022-09-06 | 宁波大学 | High-crystallinity intermediate infrared luminescent nano glass ceramic material and preparation method thereof |
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Application publication date: 20190611 |