CN1807310A - Rare earth doped gallium germanium bismuth lead luminous glass material and its preparation method and uses - Google Patents

Abstract

The invention discloses a gallium germanium bismuth lead luminescent glass material doped _with rare earth, which is made of _{Ga2O3 , Bi2O3} , _GeO2 , lead-containing compound and rare earth compound. The preparation method includes mixing the components and melting to obtain molten glass; pouring the molten glass into a mold after clarification to obtain glass, and quickly putting the glass into a muffle furnace that has been heated to the glass transition temperature Keep warm and cool down to room temperature. The material can be made into blocks, flakes, rods or fibers, and is used to prepare gain media for light-emitting devices such as all-optical switch devices, fiber lasers, waveguide lasers, large-screen color displays, or fiber amplifiers.

Description

Gallium-germanium-bismuth-lead luminescent glass material doped with rare earth and its preparation method and application

technical field

The invention relates to a luminescent glass material, in particular to a rare earth-doped gallium germanium bismuth lead luminescent glass material.

The present invention also relates to a preparation method of the above-mentioned luminescent glass material.

The present invention also relates to the application of the above-mentioned luminescent glass material.

Background technique

At present, the combination of Dense Wavelength Division Multiplexing (DWDM) technology and broadband amplifier is the development trend of optical communication. The amplification band (1530-1565nm) of the erbium-doped silica-based fiber amplifier (EDFA) currently used in wavelength division multiplexing (WDM) technology transmission systems only covers a part of the low-loss window of quartz single-mode fibers, which limits the available transmission wavelength. number of channels. Therefore, it is still the direction of people's efforts to find erbium-doped matrix glass with wide bandwidth, high gain, thermal stability and good mechanical processing performance in the 1.5 μm wave band; ~1650nm), Thulium-doped 1.47μm band fiber amplifier (TDFA) has become another target of people's attention. How to choose a suitable host material to improve the luminescence properties of 1.47μm has become a research hotspot again. Research in the above fields has huge economic and social benefits for telecom companies looking for low-loss, powerful, high-performance, and highly-integrable optical fiber amplifier matrix materials for long-distance, high-capacity communications. In addition, with the rapid development of technologies such as information processing, data storage, underwater communication, video display and surface treatment, the demand for high-efficiency, low-cost, high-performance visible wavelength laser devices is becoming more and more urgent, such as blue-green lasers This component can significantly improve the printing speed and resolution of existing laser printers. In addition, blue-green laser devices also show great commercial and military application prospects in optical communication, optical fiber sensing and laser medical treatment. In addition, the existing technology also has an urgent demand for luminescence in some special bands. For example, luminescence in the 2.0 μm band has extremely important application value in medical diagnosis.

Doping different rare earth ions in various matrix materials can achieve visible-near-infrared light emission. The matrix glass materials used in the above light-emitting device devices in the prior art include: traditional oxide glass, fluoride glass, and sulfide glass. , chloride glass, etc. Among these glasses, the host material for up-conversion luminescence and 1.47μm band light-emitting devices is usually fluoride glass. However, the biggest disadvantage of fluoride glass as a rare earth-doped optical fiber matrix material is its poor chemical stability and mechanical strength, and it is difficult to draw optical fibers due to easy devitrification, which greatly limits its application. However, the traditional oxide glass with good chemical stability and mechanical strength is difficult to obtain high-efficiency upconversion luminescence due to the high phonon energy. In addition, Tm3+ ions in the glass with high phonon energy due to the influence of multi-phonon relaxation It is difficult to observe the luminescence in the 1.47μm band. In addition, although the upconversion luminous efficiency of rare earth ions in tellurite glasses is much higher than that of traditional oxide glasses such as borate, silicate and phosphate, there is still a large gap compared with non-oxide glasses. gap; in addition, the anti-devitrification stability of tellurate glass is poor, and it is easy to produce devitrification in the process of optical fiber drawing, making it difficult to be practical [see U.S.patent 6356387, date of publication March 12, 2002, named TELLURITE GLASS, OPTICAL AMPLIFIER, AND LIGHTSOURCE].

Compared with the glass systems mentioned above, Ga ₂ O ₃ -Bi ₂ O ₃ -PbO glasses, which do not contain any conventional oxide glass formers, have attracted great interest since their discovery. The glass system contains two or more heavy metal oxides such as germanium oxide, lead oxide, bismuth oxide, and gallium oxide. It has high refractive index, good mechanical properties, good thermal stability, high chemical stability and Excellent properties such as excellent infrared transmission range (~8μm). The phonon energy of heavy metal oxide glass is low and the refractive index is high, which is conducive to improving the luminous efficiency and emission cross section of doped rare earth ions, and is suitable for use as a host material for solid-state lasers and amplifiers. Compared with fluoride glass and sulfide glass, gallium germanium bismuth lead glass system has its unique advantages due to its high mechanical strength, chemical stability, anti-devitrification ability and easy to draw optical fiber; The characteristics of traditional oxide glass phonon energy make it possible to be used as a host material doped with Er ³⁺ , Tm ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Tb ³⁺ and other rare earth ions to achieve visible-near The luminescence of multiple infrared bands has been widely used in light-emitting devices such as fiber amplifiers, optical waveguides, lasers, and up-conversion devices. In addition, due to the large nonlinear optical refractive index, fast response time and small absorption coefficient of heavy metal oxide glass, it has become one of the candidate materials for all-optical switching devices. Therefore, the unique advantages of heavy metal oxide glass in the above aspects indicate that this glass system has broad application prospects in the field of optoelectronics.

Contents of the invention

The invention overcomes the disadvantages of the prior art and provides a rare earth-doped gallium germanium bismuth lead luminous glass material, which has the characteristics of excellent physical and chemical properties, good mechanical processing performance and high luminous efficiency.

Another object of the present invention is to provide a preparation method and application of the above-mentioned material.

The rare earth-doped gallium germanium bismuth lead luminescent glass material of the present invention is made of Ga ₂ O ₃ , Bi ₂ O ₃ , GeO ₂ , lead-containing compounds, and rare earth compounds, wherein Ga ₂ O ₃ , Bi ₂ O ₃ , GeO ₂ , The sum of the molar fractions of lead-containing compounds is 100, and the molar fractions of each component are as follows:

Ga ₂ O ₃ 0～30

Bi ₂ O ₃ 15～50

GeO ₂ 0～70

Leaded compounds 0～60

Rare earth compound 0～4.

The lead-containing compound is preferably lead oxide and/or lead halide, and the mole fraction of the lead halide is 0-45.

The rare earth compound is preferably one or a mixture of oxides of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), and ytterbium (Yb).

Among them, the molar fraction of Er ₂ O ₃ and Yb ₂ O ₃ is 0-2.5, the molar fraction of Tm ₂ O ₃ is 0-1.5, and the molar fraction of Ho ₂ O ₃ , Dy ₂ O ₃ and Tb ₂ O ₃ 0 to 2.

The rare-earth-doped gallium-germanium-bismuth-lead luminescent glass material of the present invention can be prepared by a common method in the prior art, or by the preparation method of the present invention, which includes the following steps:

(1) melting each component after mixing, the melting temperature is 900-1100° C., and the melting time is 15-30 minutes to obtain molten glass;

(2) After the molten glass is clarified, pour it into a mold to obtain glass, put it into a muffle furnace that has been heated to the glass transition temperature and keep it warm for 1 hour, and then cool it down to 100°C at a rate of 5-10°C/hour , turn off the power of the muffle furnace and cool down to room temperature naturally.

The materials described in the present invention are made into blocks, flakes, rods or fibers, which can be applied to the preparation of gain media for light-emitting devices such as all-optical switch devices, fiber lasers, waveguide lasers, large-screen color displays or fiber amplifiers. Advantages of cheapness, high efficiency, integration and miniaturization.

For example, the annealed glass is made into blocks, flakes, rods or fibers, which are used to prepare gain media for light-emitting devices such as lasers and amplifiers pumped by laser diodes.

The glass material co-doped with Tm ³⁺ or Tm ³⁺ and Yb ³⁺ or Ho ³⁺ of the present invention is used as the gain medium of the blue up-conversion laser, and a strong blue color can be observed under the pumping of a 980nm laser diode Upconversion luminescence.

Using the Er ³⁺ doped or Er ³⁺ and Yb ³⁺ co-doped glass material of the present invention as the gain medium of a green up-conversion laser, strong green up-conversion luminescence can be observed under pumping of a 980nm laser diode.

When the glass material doped with Tm ³⁺ or Tm ³⁺ and Yb ³⁺ , Tb ³⁺ , Dy ³⁺ or Ho ³⁺ of the present invention is pumped by a laser diode at 800 nm, a strong 1.47 μm waveband can be observed Luminescence, the luminescence in this band can make full use of the low-loss window of 1450-1650nm of the quartz-based communication fiber, which is extremely beneficial for the realization of S-band amplifiers.

When the Er ³⁺ or Er ³⁺ and Yb ³⁺ co-doped glass material of the present invention is pumped by a 980nm laser diode, strong luminescence in the 1.53μm band can be observed, which is conducive to the realization of wide bandwidth and high gain 1.53μm band amplifier.

Compared with prior art, the present invention has following advantage:

(1) The highest phonon energy of the material of the present invention is equivalent to that of fluoride glass, but its chemical stability, mechanical strength and devitrification resistance are much higher than that of fluoride glass, and the preparation process is also quite simple.

(2) Compared with the tellurite glass, the material of the present invention has the advantages of better machinability and anti-devitrification stability.

(3) Compared with traditional oxide glasses such as silicates, borates, and phosphates, the material of the present invention has the advantages of high up-conversion efficiency and multiple emission wavelengths.

(4) The material of the present invention can realize up-conversion blue-green luminescence, luminescence in the 1.47 μm band, 1.53 μm band and 2.0 μm band.

(5) The material of the present invention can be made into blocks, flakes, rods or fibers, and is applied to light-emitting devices such as all-optical switch devices, fiber lasers, waveguide lasers, large-screen color displays or fiber amplifiers, which is beneficial to realize low-cost, Efficient, integrated and miniaturized optical and photonic devices.

Description of drawings

Fig. 1 is the differential thermal analysis curve figure of the material made in embodiment 1;

Fig. 2 is the up-conversion luminescent spectrum diagram of the material prepared in Example 1;

Fig. 3 is the up-conversion luminescent spectrum diagram of the material prepared in Example 2;

Fig. 4 is the luminescent spectrogram of the material made in embodiment 3;

Fig. 5 is the up-conversion luminescent spectrum diagram of the material prepared in Example 4;

Fig. 6 is the differential thermal analysis curve diagram of the material made in embodiment 5;

Fig. 7 is the luminescence spectrum diagram of the material prepared in Example 5.

Detailed ways

The present invention will be described in detail below in conjunction with the examples, but the present invention is not limited thereto.

Example 1

(1) Weigh 20g of the following mole percentage components, mix them evenly, put them into a covered platinum crucible and place them in a silicon carbon rod electric furnace for melting, the melting temperature is 1100°C, and the melting time is 30 minutes The molten glass is obtained, and after the molten liquid is clarified, it is poured into a preheated stainless steel mold to obtain glass;

(2) Quickly put the above glass into a muffle furnace that has been heated to the material transition temperature _Tg (344°C) for 1 hour, then cool down to 100°C at a rate of 10°C/hour, turn off the power, and automatically cool down to room temperature , the luminescent glass material of the present invention can be obtained.

Each component and its mole percentage are:

Ga ₂ O ₃ 0; GeO ₂ 70; Bi ₂ O ₃ 15; PbO 10;

PbF ₂ 5; Er ₂ O ₃ 1.5; Yb ₂ O ₃ 1.0.

A small part of the sample after annealing was ground into a fine powder of over 80 mesh with an agate mortar, and 10 mg was taken for differential thermal analysis. The differential thermal analysis curve is shown in Figure 1. The _Tg of the sample measured by differential thermal analysis is 344°C, and the _Tx is 468°C. Based on this, the parameter ΔT of the anti-devitrification stability of the sample is calculated to be 124°C, which is very beneficial for optical fiber drawing.

The rest of the samples were processed into 15mm×15mm×2mm glass sheets with two polished surfaces. The UV absorption cut-off wavelength was measured to be 413nm through spectral testing, and a 977nm LD was used as the pump light source to obtain a strong uptake at room temperature. The green light is converted, and its up-conversion luminescence spectrum is shown in Figure 2.

Example 2

(1) Weigh 20g of the following mole percentage components, mix them evenly, put them into a covered platinum crucible and place them in a silicon carbon rod electric furnace for melting, the melting temperature is 900°C, and the melting time is 30 minutes The molten glass is obtained, and after the molten liquid is clarified, it is poured into a preheated stainless steel mold to obtain glass;

(2) Quickly put the above glass into a muffle furnace heated to the material transition temperature _Tg (357°C) for 1 hour, then cool down to 100°C at a rate of 5°C/hour, turn off the power, and automatically cool down to room temperature , the luminescent glass material of the present invention can be obtained.

Each component and its molar content are:

Ga ₂ O ₃ 30; GeO ₂ 0; Bi ₂ O ₃ 20; PbO 5;

PbF ₂ 45; Tm ₂ O ₃ 1.5; Yb ₂ O ₃ 2.

Take a small part of the sample after annealing and grind it into a fine powder of over 80 mesh with an agate mortar, and take 10 mg for differential thermal analysis. The _Tg of the sample measured by differential thermal analysis is 357°C, and the _Tx is 481°C. Based on this, the parameter ΔT of the anti-devitrification stability of the sample is calculated to be 124°C, which is very beneficial for optical fiber drawing.

The rest of the samples were processed into 15mm×15mm×2mm glass sheets with two polished surfaces. The UV absorption cut-off wavelength was measured to be 424nm through spectral testing. Using 977nm LD as the pumping light source, a strong uptake can be obtained at room temperature. Convert blue light, and its up-conversion luminescence spectrum is shown in Figure 3.

Example 3

(1) Weigh 20g of the following mole percentage components, mix them evenly, put them into a covered platinum crucible and place them in a silicon carbon rod electric furnace for melting, the melting temperature is 1000°C, and the melting time is 20 minutes The molten glass is obtained, and after the molten liquid is clarified, it is poured into a preheated stainless steel mold to obtain glass;

(2) Quickly put the above glass into a muffle furnace that has been heated to the material transition temperature _Tg (357°C) for 1 hour, then cool down to 100°C at a rate of 8°C/hour, turn off the power, and automatically cool down to room temperature , the luminescent glass material of the present invention can be obtained.

Each component and its molar content are:

Ga ₂ O ₃ 15; GeO ₂ 20; Bi ₂ O ₃ 50; PbO 15;

PbF 20 ; Tm ₂ O ₃ 0.2; Ho ₂ O ₃ 2.

Take the annealed sample and process it into a 15mm×15mm×2mm glass sheet with two polished surfaces. The UV absorption cut-off wavelength is measured at 424nm through spectral testing. Using 808nm LD as the pump light source, a wide range can be obtained at room temperature. The luminescence in the 1.47μm band, the fluorescence half-maximum width of 123nm, is conducive to the preparation of broadband S-band fiber amplifiers, and its luminescence spectrum is shown in Figure 4.

Example 4

(1) Weigh 20g of the following mole percentage components, mix them evenly, put them into a covered platinum crucible and place them in a silicon carbon rod electric furnace for melting, the melting temperature is 1050°C, and the melting time is 15 minutes The molten glass is obtained, and after the molten liquid is clarified, it is poured into a preheated stainless steel mold to obtain glass;

(2) Quickly put the above glass into a muffle furnace heated to the material transition temperature T _g (412°C) for 1 hour, then cool down to 100°C at a rate of 10°C/hour, turn off the power, and automatically cool down to room temperature , the luminescent glass material of the present invention can be obtained.

Each component and its molar content are:

GeO ₂ 20; Bi ₂ O ₃ 20; PbO 30; PbF ₂ 30;

_{Er2O3 1.5} ; _{Yb2O3 0.5} .

The annealed sample was processed into a 15mm×15mm×2mm glass sheet with two polished surfaces. The UV absorption cut-off wavelength was measured to be 399nm through spectral testing. Using 977nm LD as the pump light source, a strong The up-conversion green light, and its up-conversion luminescence spectrum is shown in Figure 5.

Example 5

(1) Weigh 20g of the following components in molar percentages, mix them evenly, put them into a covered platinum crucible and place them in a silicon carbon rod electric furnace for melting, the melting temperature is 1100°C, and the melting time is 15 minutes The molten glass is obtained, and after the molten liquid is clarified, it is poured into a preheated stainless steel mold to obtain glass;

(2) Quickly put the above glass into a muffle furnace heated to the material transition temperature _Tg (437°C) for 1 hour, then cool down to 100°C at a rate of 5°C/hour, turn off the power, and automatically cool down to room temperature , the luminescent glass material of the present invention can be obtained.

Each component and its molar content are:

GeO ₂ 62; Bi ₂ O ₃ 25; PbO 13;

Er ₂ O ₃ 0.5; Yb ₂ O ₃ 0.5.

A small part of the sample after annealing was ground into a fine powder over 80 mesh with an agate mortar, and 10 mg was taken for differential thermal analysis. The differential thermal analysis curve is shown in Figure 6. The _Tg of the sample measured by differential thermal analysis is 437°C, and the _Tx is 528°C. Based on this, the parameter ΔT of the anti-devitrification stability of the sample is calculated to be 91°C, which can meet the requirements of optical fiber drawing.

The rest of the samples were processed into 15mm×15mm×2mm glass sheets with two polished surfaces. The UV absorption cut-off wavelength was measured to be 404nm through spectral testing. Using 977nm LD as the pump light source, a wide 1.53 nm wavelength can be obtained at room temperature. The luminescence in the μm band, the half-maximum width of the fluorescence reaches 60nm, which is conducive to the preparation of broadband and high-gain C-band fiber amplifiers, and its luminescence spectrum is shown in Figure 7.

Claims (10)

1. A gallium-germanium-bismuth-lead luminescent glass material doped with rare earth, characterized in that it is made of Ga ₂ O ₃ , Bi ₂ O ₃ , GeO ₂ , lead-containing compounds, and rare earth compounds, wherein Ga ₂ O ₃ , Bi ₂ The sum of the molar fractions of O ₃ , GeO ₂ , and lead-containing compounds is 100, and the molar fractions of each component are as follows: Ga ₂ O ₃ 0～30 Bi ₂ O ₃ 15～50 GeO ₂ 0～70 Leaded compounds 0～60 Rare earth compound 0～4. 2. The material according to claim 1, characterized in that the lead-containing compound is lead oxide and/or lead halide, and the mole fraction of the lead halide is 0-45. 3. The material according to claim 1 or 2, characterized in that the rare earth compound is terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) One or more mixtures of oxides. 4. The material according to claim 3, wherein the mole fraction of Er ₂ O ₃ and Yb ₂ O ₃ is 0-2.5, the mole fraction of Tm ₂ O ₃ is 0-1.5, and the mole fraction of Ho ₂ O 3 is 0-2.5. _3. The mole fraction of Dy ₂ O ₃ and Tb ₂ O ₃ is 0-2. 5. A material according to any one of claims 1-4, characterized in that its preparation method comprises the following steps: (1) melting each component after mixing, the melting temperature is 900-1100° C., and the melting time is 15-30 minutes to obtain molten glass; (2) After the molten glass is clarified, pour it into a mold to obtain glass, put it into a muffle furnace that has been heated to the glass transition temperature and keep it warm for 1 hour, and then cool it down to 100°C at a rate of 5-10°C/hour , turn off the power of the muffle furnace and cool down to room temperature naturally. 6. The use of the material according to claims 1-4 in the preparation of gain media for all-optical switch devices. 7. The use of the material according to claims 1-4 in the preparation of gain media for fiber lasers. 8. The use of the material according to claims 1-4 in the preparation of gain media for waveguide lasers. 9. The use of the material according to claims 1-4 in the preparation of gain media for large-screen color displays. 10. The use of the material according to claims 1-4 in the preparation of gain media for optical fiber amplifiers.

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