CN105753315A - Er<3+>/Ce<3+>/Yb<3+> tri-doped tellurate glass containing silver nano particles and preparation method thereof - Google Patents

Er<3+>/Ce<3+>/Yb<3+> tri-doped tellurate glass containing silver nano particles and preparation method thereof Download PDF

Info

Publication number
CN105753315A
CN105753315A CN201610116463.3A CN201610116463A CN105753315A CN 105753315 A CN105753315 A CN 105753315A CN 201610116463 A CN201610116463 A CN 201610116463A CN 105753315 A CN105753315 A CN 105753315A
Authority
CN
China
Prior art keywords
glass
tellurate glass
muffle furnace
temperature control
tellurate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610116463.3A
Other languages
Chinese (zh)
Other versions
CN105753315B (en
Inventor
周亚训
吴立波
杨风景
黄波
周自忠
程盼
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo University
Original Assignee
Ningbo University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo University filed Critical Ningbo University
Priority to CN201610116463.3A priority Critical patent/CN105753315B/en
Publication of CN105753315A publication Critical patent/CN105753315A/en
Application granted granted Critical
Publication of CN105753315B publication Critical patent/CN105753315B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses Er<3+>/Ce<3+>/Yb<3+> tri-doped tellurate glass containing silver nano particles and a preparation method thereof. The glass consists of the following components in percentage by mole: 65-75mol% of TeO2, 5-10mol% of Bi2O3, 10-20mol% of ZnO, 5-10mol% of Na2O, 0.1-1.0mol% of Er2O3, 0.1-1.0mol% of Ce2O3, 0.4-2.0mol% of Yb2O3 and 0.1-1.0mol% of AgNO3. The tellurate glass has the following advantages that by adopting tellurium oxide as a main component and adding bismuth oxide, zinc oxide and sodium oxide, the forming ability and physical-chemical stability of the glass are improved; due to the tri-doping way of rare earth Er<3+>, Ce<3+> and Yb<3+> ions, the sensitization among the rare earth ions is sufficiently utilized to improve the luminous efficiency of the rare earth Er<3+> ions under a commercial 980nm-wavelength semiconductor laser diode pump; and the fluorescence emission intensity of the doping Er<3+> ions in the 1.55mu m near infrared waveband is enhanced by the local field enhancement effect of the silver nano particles.

Description

A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass mixed and preparation method thereof
Technical field
The present invention relates to a kind of glass for fiber amplifier and technology of preparing thereof, especially relate to the Er of the silver-containing nanoparticles of a kind of near infrared band Fluorescence Increasing3+/Ce3+/Yb3+Three tellurate glass mixed and preparation method thereof.
Background technology
Er-doped (Er3+) fiber amplifier (EDFA, Erbium-dopedOpticalFiberAmplifier) it is optical signal amplification device indispensable in current dense wave division multipurpose (DWDM, DenseWavelengthDivisionMultiplexing) system and following High Speed System, all-optical network.Along with the extensive use of the generation information technology that big data, cloud computing, Internet of Things, mobile Internet are representative, in the urgent need to development, there is high signal gain and can operate at the broadband optical fiber amplifier of optical-fibre communications window (1.2～1.7 μm).
Rare earth Er3+Ion doping tellurate glass has caused the extensive concern of people as the gain medium of the 3rd communication window (～1.55 μm).Relative to conventional quartz glass, the maximum of tellurate glass is characterized in that doping Er3+Ion has bigger stimulated emission cross section at 1.55 mu m waveband places, and to rare earth Er3+Ion has better dissolubility, is highly suitable as C+L wave band (1530～1610nm) broadband, compact mixes Er3+The host material of fiber amplifier.
It is co-doped with mode, it is possible to effectively strengthen doping Er in tellurate glass by rare earth ion3+The fluorescent emission intensity of ion 1.55 mu m waveband.2003, Yang Jianhu et al. proposed Er3+/Ce3+It is co-doped with scheme, experiments show that: introduce the Ce of 0.5mol% and 1mol% content3+After ion, Er3+The fluorescent emission intensity of ion 1.55 mu m waveband obtains and strengthens to some extent.2006, Li Jiacheng et al. proposed Er3+/Ce3+/Yb3+Three mix scheme, experiments show that: work as Er3+/Ce3+/Yb3+Three to mix ion concentration proportioning be 3.23 × 1020/6.63×1020/2.07×1020(cm-3) time, Er3+The fluorescent emission intensity of ion 1.55 mu m waveband improves 1.34 times.2011, Jiang Huipeng et al. proposed Yb3+/Er3+Ion is co-doped with scheme, experiments show that: along with Yb3+Ion concentration is increased to 2mol%, Er by 0.5mol%3+The fluorescent emission intensity of ion 1.55 mu m waveband strengthens accordingly.In recent years, research found, at rare earth Er3+Ion doping tellurate glass introduces metal nanoparticle, it is possible to improve doping Er further3+The fluorescent emission intensity of ion.2012, V.P.P.deCampos et al. was mixing Er3+Tellurate glass introduces silver nano-grain, experiments show that: Er3+Ion 527nm, 550nm and 660nm visible waveband fluorescent emission intensity improve nearly 8 times.2015, S.K.Ghoshal et al. was mixing Er3+Tellurate glass introduces gold nano grain, experiments show that: Er3+Ion 503nm, 546nm and 637nm visible waveband fluorescent emission intensity improve nearly 4 times.But, but seldom it is related to metal nanoparticle for mixing Er both at home and abroad at present3+The report of 1.55 μm of near infrared band fluorescence raising aspects of tellurate glass.
Summary of the invention
The technical problem to be solved is to provide the Er of a kind of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass mixed and preparation method thereof, this tellurate glass is effectively improved Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.
This invention address that the technical scheme that above-mentioned technical problem adopts is: the Er of a kind of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass mixed, it is characterised in that the molar percentage composition of this tellurate glass is:
Described TeO2, described Er2O3With described Yb2O3Mass percent purity be 99.99%, described Bi2O3, described ZnO and described AgNO3Mass percent purity be 99.9%.
Described Ce2O3By Ce2(CO3)3It is converted to, described Na2O is by Na2CO3It is converted to.
Described Ce2(CO3)3Mass percent purity be 99.99%, described 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 comprise the following steps:
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material；
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 850～1000 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 4～8 minutes；Stop after stirring 18～25 minutes, be further continued for founding at the temperature of 850～1000 DEG C 4～8 minutes, found, with clarification, the glass melts obtained；This, front and back melting time and mixing time and need to reach 30 minutes or more than；
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould；
4. being moved in warmed up accurate temperature control Muffle furnace at 315～325 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared；
5. preliminary tellurate glass sample step 4. prepared is processed into double glazed glass sample；
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 355～365 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
The process of described step 4. middle annealing is: is first moved to by the copper coin mould being cast with glass melts in warmed up accurate temperature control Muffle furnace at 315～325 DEG C and is incubated 2 hours, then makes the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
The process of described step 6. middle annealing is: is first moved to by double glazed glass sample in warmed up accurate temperature control Muffle furnace at 355～365 DEG C and is incubated 24 hours, then makes the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Described TeO2, described Er2O3With described Yb2O3Mass percent purity be 99.99%, described Bi2O3, described ZnO and described AgNO3Mass percent purity be 99.9%.
Described Ce2O3By Ce2(CO3)3It is converted to, described Na2O is by Na2CO3It is converted to.
Described Ce2(CO3)3Mass percent purity be 99.99%, described Na2CO3Mass percent purity be 99.9%.
Compared with prior art, it is an advantage of the current invention that:
1) with tellurium oxide (TeO that rare earth ion dissolubility is big in the tellurate glass of the present invention2) for the key component of tellurate glass, it is simultaneously introduced a certain amount of bismuth oxide (Bi2O3) component, zinc oxide (ZnO) component and sodium oxide (Na2O) component, to improve Forming ability and the physicochemical stability of tellurate glass.
2) tellurate glass of the present invention adopts rare earth Er3+Ion, Rare-Earth Ce3+Ion and Rare Earth Y b3+Ion three mixes mode, makes full use of the sensibilization between rare earth ion, to improve the commercial laser diode-pumped lower rare earth Er of 980nm wavelength semiconductor3+The luminous efficiency of ion；It is simultaneously introduced appropriate argent nano-particle, utilizes the Localized field enhancement effect of silver nano-grain, improve doping Er with further3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.
3) present invention prepares and adopts common siliconit electric furnace to found in the process of tellurate glass and accurate temperature control Muffle furnace annealing, and the equipment adopted in manufacturing process is few and cost is low, is very suitable for the application in actual production.
Accompanying drawing explanation
Fig. 1 is Er in embodiment one, embodiment two, embodiment three, the tellurate glass sample of embodiment four and the tellurate glass sample of not silver-containing nanoparticles3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
Embodiment one:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
By the above-mentioned final tellurate glass sample preparing and being of a size of 10mm × 10mm × 1.5mm, at the fluorescence emission spectrum of laser diode-pumped its 1.55 μm of near infrared bands of lower test of 980nm wavelength semiconductor, fluorescence emission spectrum is as shown in Figure 1.Experiments show that, the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment two:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
By the above-mentioned final tellurate glass sample preparing and being of a size of 10mm × 10mm × 1.5mm, at the fluorescence emission spectrum of laser diode-pumped its 1.55 μm of near infrared bands of lower test of 980nm wavelength semiconductor, fluorescence emission spectrum is as shown in Figure 1.Experiments show that, the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment three:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
By the above-mentioned final tellurate glass sample preparing and being of a size of 10mm × 10mm × 1.5mm, at the fluorescence emission spectrum of laser diode-pumped its 1.55 μm of near infrared bands of lower test of 980nm wavelength semiconductor, fluorescence emission spectrum is as shown in Figure 1.Experiments show that, the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment four:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
By the above-mentioned final tellurate glass sample preparing and being of a size of 10mm × 10mm × 1.5mm, at the fluorescence emission spectrum of laser diode-pumped its 1.55 μm of near infrared bands of lower test of 980nm wavelength semiconductor, fluorescence emission spectrum is as shown in Figure 1.Experiments show that, the physical and chemical performance of the final tellurate glass sample of preparation is excellent.
Embodiment five:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment six:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 1000 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 4 minutes；Stop after stirring 22 minutes, be further continued for founding at the temperature of 1000 DEG C 6 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 325 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 325 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 355 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 355 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment seven:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 850 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 8 minutes；Stop after stirring 18 minutes, be further continued for founding at the temperature of 850 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 315 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 315 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 365 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 365 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment eight:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 6 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 8 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 315 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 315 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 355 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 355 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment nine:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 950 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 8 minutes；Stop after stirring 18 minutes, be further continued for founding at the temperature of 950 DEG C 6 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment ten:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
Embodiment 11:
The Er of a kind of silver-containing nanoparticles that the present embodiment proposes3+/Ce3+/Yb3+Three tellurate glass mixed, its molar percentage composition is:
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+Specifically comprising the following steps that of the preparation method of three tellurate glass mixed
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material.
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 900 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 5 minutes；Stop after stirring 20 minutes, be further continued for founding at the temperature of 900 DEG C 5 minutes, found, with clarification, the glass melts obtained.
In actual melting process, front and back melting time and mixing time and need to reach 30 minutes or more than, so can obtain founding uniform glass melts.
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould.
At this, the temperature of preheated copper coin mould is substantially at about 250 DEG C.
4. being moved in warmed up accurate temperature control Muffle furnace at 320 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared.
Step 4. in the process of annealing be: first the copper coin mould being cast with glass melts is moved to warmed up to 320 DEG C at accurate temperature control Muffle furnace in insulation 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
5. preliminary tellurate glass sample step 4. prepared is processed into the double glazed glass sample being of a size of 10mm × 10mm × 1.5mm.
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 360 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
Step 6. in the process of annealing be: first double glazed glass sample is moved to warmed up to 360 DEG C at accurate temperature control Muffle furnace in insulation 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
The step preparation utilizing embodiment one identical does not introduce argent nano-particle, and changes TeO2The tellurate glass of molar percentage, namely the molar percentage of each raw material is:
By the above-mentioned final tellurate glass sample (not silver-containing nanoparticles) preparing and being of a size of 10mm × 10mm × 1.5mm, at the fluorescence emission spectrum of laser diode-pumped its 1.55 μm of near infrared bands of lower test of 980nm wavelength semiconductor, fluorescence emission spectrum is as shown in Figure 1.
Fig. 1 gives Er in embodiment one, embodiment two, embodiment three, the tellurate glass sample of embodiment four and the tellurate glass sample of not silver-containing nanoparticles3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.Analysis chart 1 finds: introduce the silver nano-grain of 0.25mol% content in the tellurate glass sample of embodiment one, compared to the tellurate glass sample of not silver-containing nanoparticles, 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 coverage；The tellurate glass sample of embodiment two introduces the silver nano-grain of 0.5mol% content, 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 further raising, and spectrum covers 1450～1650nm wave-length coverage；The tellurate glass sample of embodiment three introduces the silver nano-grain of 0.75mol% content, compared to the tellurate glass sample of embodiment two, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion slightly improves, and spectrum covers 1450～1650nm wave-length coverage；The tellurate glass sample of embodiment four introduces the silver nano-grain of 1mol% content, compared to the tellurate glass sample of embodiment three, Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion weakens, but still is significantly stronger than the tellurate glass sample of not silver-containing nanoparticles, and spectrum covers 1450～1650nm wave-length coverage.The above analysis, at Er3+/Ce3+/Yb3+Three mix and introduce a certain amount of silver nano-grain, Er in tellurate glass3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion is obtained for enhancing in various degree, and in tellurate glass, silver nano-grain optimum doping content is at about 0.75mol%.
The respective tellurate glass sample of embodiment five to embodiment 11 changes doping content and the matrix components proportioning of rare earth ion.The tellurate glass sample that embodiment five to embodiment 11 is each prepared is equally at laser diode-pumped its Er of lower test of 980nm wavelength semiconductor3+The fluorescence emission spectrum of 1.55 μm of near infrared bands of ion.Experiments show that, relative to the tellurate glass sample of not silver-containing nanoparticles, the Er after the silver nano-grain 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 a degree of enhancing.
Experimental tests show that, the Er of the silver-containing nanoparticles that the present invention proposes3+/Ce3+/Yb3+Three tellurate glass mixed have characteristics that
1) present invention uses the heavy metal oxidation tellurium (TeO that rare earth ion dissolubility is big2) for glass key component, it is simultaneously introduced a certain amount of bismuth oxide (Bi2O3) component, zinc oxide (ZnO) component and sodium oxide (Na2O) component, improves Forming ability and the physicochemical stability of glass.
2) present invention adopts rare earth Er3+Ion, Rare-Earth Ce3+Ion and Rare Earth Y b3+Ion three mixes mode, makes full use of the sensibilization between rare earth ion, to improve the commercial laser diode-pumped lower rare earth Er of 980nm wavelength semiconductor3+The luminous efficiency of ion.Wherein, Yb is introduced3+Ion can fully absorb the 980nm wavelength pump light of semiconductor laser diode, again through Yb3+Ion is to Er3+The sensibilization of ion and energy transmission, improve Er indirectly3+The 980nm wavelength pumping efficiency of ion.And introduce Ce3+Ion can produce Er3+Ion is to Ce3+The sensibilization of ion, improves Er3+Ion is from pumping level to the radiationless transition speed of fluorescence energy level.Both can improve Er at combined effect3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.
3) present invention is at Er3+/Ce3+/Yb3+Three mix and introduce appropriate argent nano-particle in tellurate glass, make use of the crystalline field enhancement effect that the local surface plasma resonance effect of field local effect that silver nano-grain and host glass dielectric function mismatch cause and silver nano-grain causes, by strengthening Er3+Local fields around ion improves its rate of irradiation, thus further increasing doping Er3+The fluorescent emission intensity of 1.55 μm of near infrared bands of ion.

Claims (10)

1. the Er of a silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass mixed, it is characterised in that the molar percentage composition of this tellurate glass is:
。
2. the Er of a kind of silver-containing nanoparticles according to claim 13+/Ce3+/Yb3+Three tellurate glass mixed, it is characterised in that described TeO2, described Er2O3With described Yb2O3Mass percent purity be 99.99%, described Bi2O3, described ZnO and described AgNO3Mass percent purity be 99.9%.
3. the Er of a kind of silver-containing nanoparticles according to claim 1 and 23+/Ce3+/Yb3+Three tellurate glass mixed, it is characterised in that described Ce2O3By Ce2(CO3)3It is converted to, described Na2O is by Na2CO3It is converted to.
4. the Er of a kind of silver-containing nanoparticles according to claim 33+/Ce3+/Yb3+Three tellurate glass mixed, it is characterised in that described Ce2(CO3)3Mass percent purity be 99.99%, described Na2CO3Mass percent purity be 99.9%.
5. the Er of a silver-containing nanoparticles3+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that comprise the following steps:
1. according to the selected composition of raw materials of the molar percentage composition of following tellurate glass, then calculate the percentage by weight of each raw material according to the total amount of the tellurate glass of required preparation, and weigh each raw material；
2. by weighed highly purified TeO2、Bi2O3、ZnO、Na2O、Er2O3、Ce2O3、Yb2O3And AgNO3After dusty raw materials Homogeneous phase mixing, pour in corundum crucible；Then the corundum crucible being loaded with raw mixture is placed in the siliconit electric furnace that temperature is 850～1000 DEG C, raw mixture is founded；After raw mixture is completely melt, then carry out uniform stirring after founding 4～8 minutes；Stop after stirring 18～25 minutes, be further continued for founding at the temperature of 850～1000 DEG C 4～8 minutes, found, with clarification, the glass melts obtained；
3. take out and 2. found, through step, the glass melts obtained, then glass melts is cast on preheated copper coin mould；
4. being moved in warmed up accurate temperature control Muffle furnace at 315～325 DEG C by the copper coin mould being cast with glass melts rapidly and be annealed, accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the preliminary tellurate glass sample prepared；
5. preliminary tellurate glass sample step 4. prepared is processed into double glazed glass sample；
6. double glazed glass sample step being 5. processed into moves to and carries out double annealing in warmed up accurate temperature control Muffle furnace at 355～365 DEG C, and accurate temperature control Muffle furnace is closed in annealing after terminating, further take out the final tellurate glass sample prepared.
6. the Er of a kind of silver-containing nanoparticles according to claim 53+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterized in that during described step is 4., the process of annealing is: first moved to by the copper coin mould being cast with glass melts in warmed up accurate temperature control Muffle furnace at 315～325 DEG C and be incubated 2 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
7. the Er of a kind of silver-containing nanoparticles according to claim 5 or 63+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterized in that during described step is 6., the process of annealing is: first moved to by double glazed glass sample in warmed up accurate temperature control Muffle furnace at 355～365 DEG C and be incubated 24 hours, then make the temperature in accurate temperature control Muffle furnace drop to room temperature with the speed of 10 DEG C/h.
8. the Er of a kind of silver-containing nanoparticles according to claim 53+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that described TeO2, described Er2O3With described Yb2O3Mass percent purity be 99.99%, described Bi2O3, described ZnO and described AgNO3Mass percent purity be 99.9%.
9. the Er of a kind of silver-containing nanoparticles according to claim 5 or 83+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that described Ce2O3By Ce2(CO3)3It is converted to, described Na2O is by Na2CO3It is converted to.
10. the Er of a kind of silver-containing nanoparticles according to claim 93+/Ce3+/Yb3+The preparation method of three tellurate glass mixed, it is characterised in that described Ce2(CO3)3Mass percent purity be 99.99%, described Na2CO3Mass percent purity be 99.9%.
CN201610116463.3A 2016-03-02 2016-03-02 A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed Active CN105753315B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610116463.3A CN105753315B (en) 2016-03-02 2016-03-02 A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610116463.3A CN105753315B (en) 2016-03-02 2016-03-02 A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed

Publications (2)

Publication Number Publication Date
CN105753315A true CN105753315A (en) 2016-07-13
CN105753315B CN105753315B (en) 2018-11-09

Family

ID=56332307

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610116463.3A Active CN105753315B (en) 2016-03-02 2016-03-02 A kind of Er of silver-containing nanoparticles3+/Ce3+/Yb3+Three tellurate glass and preparation method thereof mixed

Country Status (1)

Country Link
CN (1) CN105753315B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083637A (en) * 2017-12-13 2018-05-29 上海应用技术大学 A kind of fiber amplifier brilliant enhancing er-doped bismuthates laser glass of silver nanoparticle and preparation method thereof
CN109384394A (en) * 2018-12-12 2019-02-26 内蒙古科技大学 A kind of high non-linearity low-loss bismuth tellurite glasses and optical fiber and preparation method thereof
WO2019071324A1 (en) * 2017-10-13 2019-04-18 The University Of Adelaide Method for controlling the formation of metallic nanoparticles in glass and products thereof
CN110304831A (en) * 2019-07-22 2019-10-08 中国科学院上海光学精密机械研究所 Dy-Ag is co-doped with silicate Anti-splash glass sheet and preparation method thereof
CN110759639A (en) * 2019-10-28 2020-02-07 宁波大学 Near-infrared dual-band ultra-wideband emission rare earth doped glass and preparation method thereof
CN112110648A (en) * 2020-09-23 2020-12-22 中国计量大学 Holmium-ytterbium co-doped oxyhalide system mid-infrared glass and preparation method thereof
CN114195383A (en) * 2021-12-27 2022-03-18 苏州广辰光学科技有限公司 Preparation process of blue glass for infrared cut-off filter
CN116375343A (en) * 2023-03-28 2023-07-04 华南理工大学 Silver-containing nanoparticle tellurate photo-functional glass ceramic material with photoinduced resistance enhancement characteristic, and preparation method and application thereof
CN116589183A (en) * 2023-05-19 2023-08-15 东北大学 Tellurate glass based on fluorescence intensity ratio, temperature sensing system and manufacturing method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271730A (en) * 2015-10-20 2016-01-27 宁波大学 Multicolor-emitting tellurium bismuth titanium glass and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105271730A (en) * 2015-10-20 2016-01-27 宁波大学 Multicolor-emitting tellurium bismuth titanium glass and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
SHENGXI PENG ET AL.: "Multicolor upconversion emission and energy transfer mechanism in Er3+/Tm3+/Yb3+ codoped tellurite glasses", 《JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER》 *
周亚训等: "Er3+/Yb3+/Ce3+共掺碲酸盐玻璃光谱特性及能量传递机理", 《硅酸盐学报》 *
沈亮标等: "纳米颗粒与铒共掺光放大用材料的研究进展", 《材料导报:综述篇》 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019071324A1 (en) * 2017-10-13 2019-04-18 The University Of Adelaide Method for controlling the formation of metallic nanoparticles in glass and products thereof
CN108083637A (en) * 2017-12-13 2018-05-29 上海应用技术大学 A kind of fiber amplifier brilliant enhancing er-doped bismuthates laser glass of silver nanoparticle and preparation method thereof
CN109384394A (en) * 2018-12-12 2019-02-26 内蒙古科技大学 A kind of high non-linearity low-loss bismuth tellurite glasses and optical fiber and preparation method thereof
CN110304831A (en) * 2019-07-22 2019-10-08 中国科学院上海光学精密机械研究所 Dy-Ag is co-doped with silicate Anti-splash glass sheet and preparation method thereof
CN110304831B (en) * 2019-07-22 2021-11-30 中国科学院上海光学精密机械研究所 Dy-Ag co-doped silicate anti-sputtering plate glass and preparation method thereof
CN110759639B (en) * 2019-10-28 2021-11-30 宁波大学 Near-infrared dual-band ultra-wideband emission rare earth doped glass and preparation method thereof
CN110759639A (en) * 2019-10-28 2020-02-07 宁波大学 Near-infrared dual-band ultra-wideband emission rare earth doped glass and preparation method thereof
CN112110648A (en) * 2020-09-23 2020-12-22 中国计量大学 Holmium-ytterbium co-doped oxyhalide system mid-infrared glass and preparation method thereof
CN112110648B (en) * 2020-09-23 2022-12-30 中国计量大学 Holmium-ytterbium co-doped oxyhalide system mid-infrared glass and preparation method thereof
CN114195383A (en) * 2021-12-27 2022-03-18 苏州广辰光学科技有限公司 Preparation process of blue glass for infrared cut-off filter
CN116375343A (en) * 2023-03-28 2023-07-04 华南理工大学 Silver-containing nanoparticle tellurate photo-functional glass ceramic material with photoinduced resistance enhancement characteristic, and preparation method and application thereof
CN116375343B (en) * 2023-03-28 2024-09-03 华南理工大学 Silver-containing nanoparticle tellurate photo-functional glass ceramic material with photoinduced resistance enhancement characteristic, and preparation method and application thereof
CN116589183A (en) * 2023-05-19 2023-08-15 东北大学 Tellurate glass based on fluorescence intensity ratio, temperature sensing system and manufacturing method thereof
CN116589183B (en) * 2023-05-19 2024-04-26 东北大学 Tellurate glass based on fluorescence intensity ratio, temperature sensing system and manufacturing method thereof

Also Published As

Publication number Publication date
CN105753315B (en) 2018-11-09

Similar Documents

Publication Publication Date Title
CN105753315A (en) Er&lt;3+&gt;/Ce&lt;3+&gt;/Yb&lt;3+&gt; tri-doped tellurate glass containing silver nano particles and preparation method thereof
Chai et al. 2.7 μm emission from transparent Er3+, Tm3+ codoped yttrium aluminum garnet (Y3Al5O12) nanocrystals–tellurate glass composites by novel comelting technology
Sołtys et al. Electrical and optical properties of glasses and glass-ceramics
Serqueira et al. Judd Ofelt calculation of quantum efficiencies and branching ratios of Nd3+ doped glasses
CN101531459B (en) Rare earth thulium-doped aluminate fluorescent glass and preparation method thereof
CN102659313B (en) Near-infrared broadband luminescence erbium and thulium-co-doped bismuthate laser glass and preparation method thereof
CN103241948B (en) Method for preparing oxygen fluorine chlorine tellurate glass with intermediate infrared fluorescence output at 4 mu m
CN101812299A (en) Nanocrystal reinforced rare earth doped tellurate luminous film material and preparation method thereof
Wang et al. Glass‐forming regions and enhanced 2.7 μm emission by Er3+ heavily doping in TeO2–Ga2O3–R2O (or MO) glasses
Du et al. Silver nanoparticles enhanced multichannel transition luminescence of Pr3+ in heavy metal germanium tellurite glasses
CN1807310A (en) Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses
CN113087397A (en) Double-phase transparent glass ceramic with ultra-wideband fluorescence emission characteristic and preparation method thereof
CN105906205A (en) Luminescent glass used for controllable precipitation of ML-Ag cluster and Ag nanocrystals through rare earth compound codoping, and preparation method thereof
CN101121574B (en) Thulium adulterated germanate laser glass and preparation method thereof
Zhang et al. The effect of Nd3+ concentration on fabrication, microstructure, and luminescent properties of anisotropic S‐FAP ceramics
Wu et al. Enhanced 1.53 μm band fluorescence in Er3+/Ce3+ codoped tellurite glasses containing Ag NPs
CN116119925A (en) Thulium-doped fluorine tellurate glass, preparation method and application thereof
CN100395380C (en) Process for preparing barium tungstate single crystal with improved doping concentration of rare earth ion
CN112110648B (en) Holmium-ytterbium co-doped oxyhalide system mid-infrared glass and preparation method thereof
Rao et al. Upconversion luminescence in Er3+/Yb3+ codoped lead bismuth indium borate glasses
Ravangvong et al. Comparative study of Al2O3-MO-BaO-P2O5 glasses doped with Sm3+ (MO= Na2O and ZnO)
CN116253512A (en) Germanate glass capable of inhibiting darkening of gamma ray irradiation and preparation method thereof
CN102515513A (en) Er&lt;3+&gt; and Ce&lt;3+&gt; codoped bismuth titanium tellurite glass and its preparation method
Koçyiğit et al. The impact of heat treatment on the luminescence properties of Dy/Ag co-doped sodium alumina borate glasses
CN1278970C (en) Method for manufacturing bismuth-doped high-silica near-infrared broadband luminescent glass

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant