CN105753315B - A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed - Google Patents

A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed Download PDF

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CN105753315B
CN105753315B CN201610116463.3A CN201610116463A CN105753315B CN 105753315 B CN105753315 B CN 105753315B CN 201610116463 A CN201610116463 A CN 201610116463A CN 105753315 B CN105753315 B CN 105753315B
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glass
temperature control
tellurate
muffle furnace
melted
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CN105753315A (en
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周亚训
吴立波
杨风景
黄波
周自忠
程盼
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Ningbo University
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

Abstract

The invention discloses a kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed, the molar percentage composition of the glass are：The TeO of 65~75mol%2, 5~10mol% Bi2O3, the ZnO of 10~20mol%, 5~10mol% Na2O, the Er of 0.1~1.0mol%2O3, 0.1~1.0mol% Ce2O3, 0.4~2.0mol% Yb2O3, 0.1~1.0mol% AgNO3；Advantage is that bismuth oxide, zinc oxide and sodium oxide molybdena is added, improves the Forming ability and physicochemical stability of glass using tellurium oxide as key component；Using rare earth Er3+、Ce3+And Yb3+Ion three mixes mode, and the sensibilization between rare earth ion is made full use of to improve the laser diode-pumped lower rare earth Er of commercialization 980nm wavelength semiconductors3+The luminous efficiency of ion；Doping Er is improved using the Localized field enhancement effect of silver nano-grain3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.

Description

A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass mixed and its system Preparation Method
Technical field
The present invention relates to a kind of glass and its technology of preparing for fiber amplifier, more particularly, to a kind of near-infrared wave The Er of the silver-containing nanoparticles of section Fluorescence Increasing3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed.
Background technology
Er-doped (Er3+) fiber amplifier (EDFA, Erbium-doped Optical Fiber Amplifier) is current Dense wave division multipurpose (DWDM, Dense Wavelength Division Multiplexing) system and the following High Speed System, Indispensable optical signal amplification device in all-optical network.As big data, cloud computing, Internet of Things, mobile Internet are representative Generation information technology extensive use, there is an urgent need to develop to can operate at optical-fibre communications window with high RST gain The broadband optical fiber amplifier of (1.2~1.7 μm).
Rare earth Er3+Ion doping tellurate glass has drawn as the laser gain medium of third communication window (~1.55 μm) Play the extensive concern of people.Relative to conventional quartz glass, the maximum feature of tellurate glass is to adulterate Er3+Ion exists Stimulated emission cross section with bigger at 1.55 mu m wavebands, and to rare earth Er3+Ion has better dissolubility, is very suitable for Er is mixed as the broadband C+L wave bands (1530~1610nm), compact3+The host material of fiber amplifier.
It is co-doped with mode by rare earth ion, can effectively enhance and adulterate Er in tellurate glass3+1.55 mu m waveband of ion Fluorescent emission intensity.2003, Yang Jianhu et al. proposed Er3+/Ce3+It is co-doped with scheme, experiment shows：Introduce 0.5mol% and The Ce of 1mol% contents3+After ion, Er3+The fluorescent emission intensity of 1.55 mu m waveband of ion has obtained enhancing to some extent. 2006, Li Jiacheng et al. proposed Er3+/Ce3+/Yb3+Three mix scheme, and experiment shows：Work as Er3+/Ce3+/Yb3+Three to mix ion dense Degree proportioning is 3.23 × 1020/6.63×1020/2.07×1020(cm-3) when, Er3+The fluorescent emission of 1.55 mu m waveband of ion is strong Degree improves 1.34 times.2011, Jiang Huipeng et al. proposed Yb3+/Er3+Ion is co-doped with scheme, and experiment shows：With Yb3+From Sub- content increases to 2mol%, Er by 0.5mol%3+The fluorescent emission intensity of 1.55 mu m waveband of ion accordingly enhances.In recent years Come, the study found that in rare earth Er3+Metal nanoparticle is introduced in ion doping tellurate glass, doping can be further increased Er3+The fluorescent emission intensity of ion.2012, V.P.P.de Campos et al. were mixing Er3+Silver is introduced in tellurate glass to receive Rice grain, experiment show：Er3+The fluorescent emission intensity of ion 527nm, 550nm and 660nm visible waveband improves nearly 8 times. 2015, S.K.Ghoshal et al. was mixing Er3+Gold nano grain is introduced in tellurate glass, experiment shows：Er3+Ion The fluorescent emission intensity of 503nm, 546nm and 637nm visible waveband improves nearly 4 times.However, but seldom related both at home and abroad at present In metal nanoparticle for mixing Er3+Report in terms of 1.55 μm of near infrared band fluorescence raisings of tellurate glass.
Invention content
Technical problem to be solved by the invention is to provide a kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three telluriums mixed Silicate glass and preparation method thereof, the tellurate glass are effectively improved Er3+The fluorescence of 1.55 μm of near infrared bands of ion is sent out Penetrate intensity.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of Er of silver-containing nanoparticles3+/Ce3+/ Yb3+Three tellurate glass mixed, it is characterised in that the molar percentage composition of the tellurate glass is：
The TeO2, described Er2O3With the Yb2O3Mass percent purity be 99.99%, it is described Bi2O3, the ZnO and the AgNO3Mass percent purity be 99.9%.
The Ce2O3By Ce2(CO3)3It is converted to, the Na2O is by Na2CO3It is converted to.
The Ce2(CO3)3Mass percent purity be 99.99%, the Na2CO3Mass percent purity be 99.9%.
A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that packet Include following steps：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material；
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then by the corundum crucible for being loaded with raw mixture be placed in temperature be 850~ In 1000 DEG C of Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted 4~8 points Uniform stirring is carried out after clock；Stirring stops after 18~25 minutes, is further continued for that 4~8 points are melted at a temperature of 850~1000 DEG C Clock, to clarify the glass melts for being melted and obtaining；Here, front and back melting time and mixing time and need to reach 30 minutes or more；
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool；
4. the copper coin mold for being cast with glass melts to be moved to rapidly the accurate temperature control horse having warmed up at 315~325 DEG C It not anneals in stove, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass being prepared Sample；
5. 4. preliminary tellurate glass sample that step is prepared is processed into double glazed glass sample；
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control having warmed up at 355~365 DEG C Double annealing is carried out in Muffle furnace, and accurate temperature control Muffle furnace is closed after annealing, further takes out the final telluric acid being prepared Salt glass sample.
4. the middle process annealed is the step：First the copper coin mold for being cast with glass melts is moved to have warmed up to 2 hours are kept the temperature in accurate temperature control Muffle furnace at 315~325 DEG C, accurate temperature control Muffle furnace is then made with 10 DEG C/h of rate In temperature under be down to room temperature.
6. the middle process annealed is the step：First double glazed glass sample is moved to and is had warmed up to 355~365 DEG C Under accurate temperature control Muffle furnace in keep the temperature 24 hours, the temperature in accurate temperature control Muffle furnace is then made with 10 DEG C/h of rate Drop to room temperature.
The TeO2, described Er2O3With the Yb2O3Mass percent purity be 99.99%, it is described Bi2O3, the ZnO and the AgNO3Mass percent purity be 99.9%.
The Ce2O3By Ce2(CO3)3It is converted to, the Na2O is by Na2CO3It is converted to.
The Ce2(CO3)3Mass percent purity be 99.99%, the Na2CO3Mass percent purity be 99.9%.
Compared with the prior art, the advantages of the present invention are as follows：
1) with the big tellurium oxide (TeO of rare earth ion solubility in tellurate glass of the invention2) it is tellurate glass Key component, while a certain amount of bismuth oxide (Bi is added2O3) component, zinc oxide (ZnO) component and sodium oxide molybdena (Na2O) group Point, to improve the Forming ability and physicochemical stability of tellurate glass.
2) rare earth Er is used in tellurate glass of the invention3+Ion, Rare-Earth Ce3+Ion and Rare Earth Y b3+Ion three is mixed Mode makes full use of the sensibilization between rare earth ion, with improve commercialization 980nm wavelength semiconductors it is laser diode-pumped under it is dilute Native Er3+The luminous efficiency of ion；Appropriate metal silver nano-grain is introduced simultaneously, is imitated using the Localized field enhancement of silver nano-grain It answers, to further increase doping Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.
3) present invention is melted and accurate temperature control Muffle during preparing tellurate glass using common Elema electric furnace Furnace annealing, the equipment employed in manufacturing process is few and at low cost, the application being very suitable in actual production.
Description of the drawings
Fig. 1 be embodiment one, embodiment two, embodiment three, example IV tellurate glass sample and be free of silver nanoparticle Er in the tellurate glass sample of particle3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail.
Embodiment one：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
By the final tellurate glass sample that the above-mentioned size being prepared is 10mm × 10mm × 1.5mm, in 980nm The laser diode-pumped lower fluorescence emission spectrum for testing its 1.55 μm of near infrared bands of wavelength semiconductor, fluorescence emission spectrum is such as Shown in Fig. 1.Experiment shows that the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment two：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
By the final tellurate glass sample that the above-mentioned size being prepared is 10mm × 10mm × 1.5mm, in 980nm The laser diode-pumped lower fluorescence emission spectrum for testing its 1.55 μm of near infrared bands of wavelength semiconductor, fluorescence emission spectrum is such as Shown in Fig. 1.Experiment shows that the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment three：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
By the final tellurate glass sample that the above-mentioned size being prepared is 10mm × 10mm × 1.5mm, in 980nm The laser diode-pumped lower fluorescence emission spectrum for testing its 1.55 μm of near infrared bands of wavelength semiconductor, fluorescence emission spectrum is such as Shown in Fig. 1.Experiment shows that the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Example IV：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
By the final tellurate glass sample that the above-mentioned size being prepared is 10mm × 10mm × 1.5mm, in 980nm The laser diode-pumped lower fluorescence emission spectrum for testing its 1.55 μm of near infrared bands of wavelength semiconductor, fluorescence emission spectrum is such as Shown in Fig. 1.Experiment shows that the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment five：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment six：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 1000 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature Elema electric furnace in, raw mixture is melted；After raw mixture is completely melt, then carried out after being melted 4 minutes Uniform stirring；Stirring stops after 22 minutes, is further continued for being melted 6 minutes at a temperature of 1000 DEG C, to clarify the glass for being melted and obtaining Glass melt.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 325 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 325 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 355 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 355 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment seven：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 850 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；It is carried out after raw mixture is completely melt, then after being melted 8 minutes equal Even stirring；Stirring stops after 18 minutes, is further continued for being melted 5 minutes at a temperature of 850 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 315 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 315 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 365 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 365 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment eight：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；It is carried out after raw mixture is completely melt, then after being melted 6 minutes equal Even stirring；Stirring stops after twenty minutes, is further continued for being melted 8 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 315 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 315 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 355 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 355 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment nine：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 950 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；It is carried out after raw mixture is completely melt, then after being melted 8 minutes equal Even stirring；Stirring stops after 18 minutes, is further continued for being melted 6 minutes at a temperature of 950 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment ten：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Embodiment 11：
A kind of Er for silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, moles hundred Divide and is divided into than group：
In this particular embodiment, TeO2、Er2O3And Yb2O3Mass percent purity be 99.99%, Bi2O3、 ZnO and AgNO3Mass percent purity be 99.9%.
In this particular embodiment, Ce2O3By Ce2(CO3)3It is converted to, Ce2(CO3)3Mass percent purity be 99.99%；Na2O is by Na2CO3It is converted to, Na2CO3Mass percent purity be 99.9%.
The Er of above-mentioned silver-containing nanoparticles3+/Ce3+/Yb3+The specific steps of the preparation method of three tellurate glass mixed It is as follows：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to required preparation The total amount of tellurate glass calculates the weight percent of each raw material, and weighs each raw material.
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Powdered original Material after evenly mixing, pours into corundum crucible；Then it is 900 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature In Elema electric furnace, raw mixture is melted；After raw mixture is completely melt, then it is melted and carries out after five minutes Even stirring；Stirring stops after twenty minutes, is further continued for being melted 5 minutes at a temperature of 900 DEG C, is melted with clarifying the glass for being melted and obtaining Liquid.
It in practical melting process, front and back melting time and mixing time and need to reach 30 minutes or more, in this way can It obtains that uniform glass melts are melted.
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mould On tool.
Here, the temperature of preheated copper coin mold is substantially at 250 DEG C or so.
4. the copper coin mold for being cast with glass melts is moved to rapidly in the accurate temperature control Muffle furnace having warmed up at 320 DEG C It anneals, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared.
In step, 4. the middle process annealed is：First the copper coin mold for being cast with glass melts is moved to and is had warmed up to 320 DEG C Under accurate temperature control Muffle furnace in keep the temperature 2 hours, then made with 10 DEG C/h of rate at the temperature in accurate temperature control Muffle furnace It is down to room temperature.
5. it is 10mm × 10mm × 1.5mm that 4. preliminary tellurate glass sample that step is prepared, which is processed into size, Double glazed glass sample.
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle furnace having warmed up at 360 DEG C Middle carry out double annealing closes accurate temperature control Muffle furnace, further takes out the final tellurate glass being prepared after annealing Sample.
In step, 6. the middle process annealed is：Double glazed glass sample is first moved to the precision having warmed up at 360 DEG C 24 hours are kept the temperature in temperature control Muffle furnace, then makes to be down to room at the temperature in accurate temperature control Muffle furnace with 10 DEG C/h of rate Temperature.
Metal silver nano-grain is not introduced using the identical step preparation of embodiment one, and changes TeO2Molar percentage Tellurate glass, i.e., the molar percentage of each raw material is：
By final tellurate glass sample (the not argentiferous that the above-mentioned size being prepared is 10mm × 10mm × 1.5mm Nano particle), in the laser diode-pumped lower fluorescence emission for testing its 1.55 μm of near infrared bands of 980nm wavelength semiconductors Spectrum, fluorescence emission spectrum are as shown in Figure 1.
Fig. 1 gives embodiment one, embodiment two, embodiment three, the tellurate glass sample of example IV and not argentiferous Er in the tellurate glass sample of nano particle3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.Analysis chart 1 is found： The silver nano-grain that 0.25mol% contents are introduced in the tellurate glass sample of embodiment one, compared to without silver nanoparticle The tellurate glass sample of grain, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion is significantly improved, and spectrum covers 1450~1650nm wave-length coverages are covered；The Yin Na of 0.5mol% contents is introduced in the tellurate glass sample of embodiment two Rice grain, compared to the tellurate glass sample of embodiment one, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion obtains To further increasing, spectrum covers 1450~1650nm wave-length coverages；It is introduced in the tellurate glass sample of embodiment three The silver nano-grain of 0.75mol% contents, compared to the tellurate glass sample of embodiment two, Er3+1.55 μm of ion is close red The fluorescent emission intensity of wave section slightly improves, and spectrum covers 1450~1650nm wave-length coverages；The tellurate of example IV The silver nano-grain that 1mol% contents are introduced in glass sample, compared to the tellurate glass sample of embodiment three, Er3+Ion The fluorescent emission intensity of 1.55 μm of near infrared bands weakens, but still is significantly stronger than the tellurate glass of not silver-containing nanoparticles Sample, spectrum cover 1450~1650nm wave-length coverages.The above analysis, in Er3+/Ce3+/Yb3+Three mix tellurate glass It is middle to introduce a certain amount of silver nano-grain, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion is obtained for different journeys The enhancing of degree, silver nano-grain optimum doping content is in 0.75mol% or so in tellurate glass.
Embodiment five changes the doping concentration and base of rare earth ion to 11 respective tellurate glass sample of embodiment Matter component proportion.The tellurate glass sample that embodiment five to embodiment 11 is respectively prepared is equally in 980nm wavelength Its Er is tested under semiconductor laser diode pumping3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.Experiment shows phase For the tellurate glass sample of not silver-containing nanoparticles, the Er after the silver nano-grain for introducing the given content of the present invention3+/ Ce3+/Yb3+Three mix tellurate glass sample, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion can obtain centainly The enhancing of degree.
Experimental tests show that the Er of silver-containing nanoparticles proposed by the present invention3+/Ce3+/Yb3+Three tellurate glass mixed With following characteristic：
1) present invention uses the big heavy metal oxidation tellurium (TeO of rare earth ion solubility2) it is glass key component, add simultaneously Enter a certain amount of bismuth oxide (Bi2O3) component, zinc oxide (ZnO) component and sodium oxide molybdena (Na2O) component improves the shape of glass At ability and physicochemical stability.
2) present invention uses rare earth Er3+Ion, Rare-Earth Ce3+Ion and Rare Earth Y b3+Ion three mixes mode, makes full use of Sensibilization between rare earth ion, to improve the laser diode-pumped lower rare earth Er of commercialization 980nm wavelength semiconductors3+The hair of ion Light efficiency.Wherein, Yb is introduced3+Ion can fully absorb the 980nm wavelength pump lights of semiconductor laser diode, then pass through Yb3+Ion is to Er3+Sensibilization, that is, energy transmission of ion, improves Er indirectly3+The 980nm wavelength pumping efficiencies of ion. And introduce Ce3+Ion can generate Er3+Ion is to Ce3+The sensibilization of ion, improves Er3+Ion is from pumping level to glimmering The radiationless transition rate of optical power level.The two collective effect can improve Er3+The fluorescent emission of 1.55 μm of near infrared bands of ion Intensity.
3) present invention is in Er3+/Ce3+/Yb3+Three mix and introduce appropriate metal silver nano-grain in tellurate glass, and silver is utilized Local surface of field local effect and silver nano-grain caused by nano particle and host glass dielectric function mismatch etc. from Crystalline field enhancement effect caused by daughter resonance effects, by enhancing Er3+Local fields around ion improve its rate of irradiation, from And further improve doping Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.

Claims (6)

1. a kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that including Following steps：
1. the molar percentage composition according to following tellurate glass selectes composition of raw materials, then according to the telluric acid of required preparation The total amount of salt glass calculates the weight percent of each raw material, and weighs each raw material；
2. by the TeO of weighed high-purity2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3Dusty raw materials are equal After even mixing, pour into corundum crucible；Then it is 850~1000 DEG C the corundum crucible for being loaded with raw mixture to be placed in temperature Elema electric furnace in, raw mixture is melted；After raw mixture is completely melt, then melted 4~8 minutes laggard Row uniform stirring；Stirring stops after 18~25 minutes, is further continued for being melted 4~8 minutes at a temperature of 850~1000 DEG C, with clear It is clear that obtained glass melts are melted；
Obtained glass melts are 2. melted by step 3. taking out, then glass melts are cast in preheated copper coin mold On；
4. the copper coin mold for being cast with glass melts to be moved to rapidly the accurate temperature control Muffle furnace having warmed up at 315~325 DEG C In anneal, accurate temperature control Muffle furnace is closed after annealing, further takes out the preliminary tellurate glass sample being prepared；
5. 4. preliminary tellurate glass sample that step is prepared is processed into double glazed glass sample；
6. 5. double glazed glass sample that step is processed into be moved to the accurate temperature control Muffle having warmed up at 355~365 DEG C Double annealing is carried out in stove, and accurate temperature control Muffle furnace is closed after annealing, further takes out the final tellurate glass being prepared Glass sample.
2. a kind of Er of silver-containing nanoparticles according to claim 13+/Ce3+/Yb3+The preparation of three tellurate glass mixed Method, it is characterised in that 4. the middle process annealed is the step：First the copper coin mold for being cast with glass melts is moved to It is warming up in the accurate temperature control Muffle furnace at 315~325 DEG C and keeps the temperature 2 hours, accurate temperature control is then made with 10 DEG C/h of rate It is down to room temperature at temperature in Muffle furnace.
3. a kind of Er of silver-containing nanoparticles according to claim 1 or 23+/Ce3+/Yb3+Three tellurate glass mixed Preparation method, it is characterised in that 6. the middle process annealed is the step：First double glazed glass sample is moved to and is had warmed up 24 hours are kept the temperature in accurate temperature control Muffle furnace to 355~365 DEG C, accurate temperature control horse is then made with 10 DEG C/h of rate Not room temperature is down at the temperature in stove.
4. a kind of Er of silver-containing nanoparticles according to claim 13+/Ce3+/Yb3+The preparation of three tellurate glass mixed Method, it is characterised in that the TeO2, described Er2O3With the Yb2O3Mass percent purity be 99.99%, The Bi2O3, the ZnO and the AgNO3Mass percent purity be 99.9%.
5. a kind of Er of silver-containing nanoparticles according to claim 1 or 43+/Ce3+/Yb3+Three tellurate glass mixed Preparation method, it is characterised in that the Ce2O3By Ce2(CO3)3It is converted to, the Na2O is by Na2CO3It is converted to.
6. a kind of Er of silver-containing nanoparticles according to claim 53+/Ce3+/Yb3+The preparation of three tellurate glass mixed Method, it is characterised in that the Ce2(CO3)3Mass percent purity be 99.99%, the Na2CO3Quality percentage It is 99.9% than purity.
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Multicolor upconversion emission and energy transfer mechanism in Er3+/Tm3+/Yb3+ codoped tellurite glasses;Shengxi Peng et al.;《Journal of Quantitative Spectroscopy & Radiative Transfer》;20140604;2.1.Glass preparation *
纳米颗粒与铒共掺光放大用材料的研究进展;沈亮标等;《材料导报:综述篇》;20090930;第23卷(第9期);第1.2节 *

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