CN101168473B - Ytterbium-nickel codoping transparent silicate micro-crystal glass and preparation method thereof - Google Patents

Abstract

The invention relates to yttrium nickel co-doping transparent silicate microcrystalline glass used for wideband light amplification, and a process for preparation, wherein the formula of the microcrystalline glass comprises 50-70mol% SiO2, 15-30mol% Ga2O3, 10-30mol% Li2O, 0.005-1mol% NiO, and 0.005-2mol% Yb2O3. The prepared transparent microcrystalline glass can generate near-infrared communication wavelength fluorescent light stronger than nickel-doping transparent silicate microcrystalline glass, under 980nm light pump. Test proves that the near-infrared fluorescent light strength of microcrystalline glass is improved 8.5 times than microcrystalline glass with single nickel doping, and the service life of fluorescent light can be improved from 480 microseconds with single nickel doping to 920 microseconds with co-doping, with wide application in the technical fields of wideband light amplifier, high-power laser, tunable laser and the like.

Description

Ytterbium-nickel codoping transparent silicate micro-crystal glass and preparation method thereof

Technical field

The present invention relates to the optical clear devitrified glass, particularly a kind of Ytterbium-nickel codoping transparent silicate micro-crystal glass that is used for the broadband light amplification and preparation method thereof.This transparent glass-ceramics can produce the near infrared communication band fluorescence stronger than the adulterated transparent silicate glass-ceramics of single Ni under the pumping of 980nm light source, has long fluorescence lifetime, wide gain bandwidth is suitable as the gain media of wide-band optical amplifier and laser apparatus.

Background technology

In recent years, along with the develop rapidly of computer network and other new data transport service, fiber optic transmission system long haul sharply expands to the demand of message capacity.How further to improve the message capacity of existing fiber transmission system,, become the focus of optical communication field research to satisfy this demand of expansible day by day.Think extensively that at present increasing the gain bandwidth of fiber amplifier in the ferry optical transmission system and flatness is the effective means that increases the Optical Fiber Transmission capacity.Yet, practical now gain of EDFA bandwidth is difficult to be widened again, this is because the bandwidth of rare earth ion 4f-4f optical transition is narrow in essence, so by a kind of rare earth ion doped and the expansion optical amplifier bandwidth that causes is limited.Same problem also occurs in thulium, on one's body the praseodymium, rare earth ions such as samarium.Amplify in broadband in optical fiber Raman amplifier (FRAs) can be realized on a large scale, but its multiwave pumping of needs and gain efficiency are low, and broadband FRAs complex structure, needs extra heavy pump laser, and energy expenditure is big.Therefore, if can develop a kind of ultra-wideband-light amplifier that has high gain and cover whole communication window, so just might only realize that with an image intensifer optical signal of whole communication window obtains amplifying simultaneously, this will cause the progress that optical communication field is tremendous, promote that optical communication develops to all-optical communication network.

Recently, Ni ²⁺The doping transparent devitrified glass has been subjected to people's extensive concern.This Ni ²⁺The doping optical material has wide absorption band near 1050nm, cover overall optical communication window (1200～1600nm) fluorescence with laser diode-pumped can the generation of 980nm, has long fluorescence lifetime, wide gain bandwidth is expected to be applied in fields such as wide-band optical amplifier, superpower laser, tunable laser.

As everyone knows, Yb ³⁺Ion has high and wide absorption band near 980nm, this and the emission wavelength (980nm) of commercial InGaAs laser diode coupling fine at present, therefore usually as some rare earth ions (as Er ³⁺, Pr ³⁺) sensitizing agent of doping laserable material to be to improve their pumping efficiency.This is because Yb ³⁺Ion ²F _5/2→ ²F _7/2Emission and Er ³⁺Ion ⁴I _15/2→ ⁴I _11/2, Pr ³⁺Ion ³H ₄→ ¹G ₄Absorption have big spectra overlapping, cause Yb ³⁺Ion is to Er ³⁺, Pr ³⁺Ion generation useful energy shifts.

Summary of the invention

The objective of the invention is in order to improve nickel (Ni in the transparent glass-ceramics ²⁺) ion spectra character, a kind of Ytterbium-nickel codoping transparent silicate micro-crystal glass and preparation method thereof is proposed, luminosity with strongthener, improve the near-infrared fluorescent intensity and the fluorescence lifetime of devitrified glass, make it to be expected to be applied in fields such as wide-band optical amplifier, superpower laser, tunable laser.

Technical solution of the present invention is as follows:

A kind of Ytterbium-nickel codoping transparent silicate micro-crystal glass, it is as follows that it forms proportioning:

Ingredient m ol%

SiO ₂ 50～70

Ga ₂O ₃ 15～30

Li ₂O 10～30

NiO 0.005～1

Yb ₂O ₃ 0.005～2

The preparation method of above-mentioned Ytterbium-nickel codoping transparent silicate micro-crystal glass comprises the following steps:

(1) selected glass molar percentage is formed proportioning, and each raw material by the certain total amount of this proportioning weighing ground in agate mortar 10～60 minutes;

(2) ground raw material is put into Platinum crucible, melt soaking time 1～10 hour in 1500～1600 ℃;

(3) glass melt is cast on the stainless-steel sheet, and use another roller flatteningl roller levelling, change over to afterwards in the retort furnace and under 500～580 ℃, anneal soaking time 0.5～10 hour, close the retort furnace power supply then and reduce to room temperature with stove, take out and promptly get transparent glass by glass;

(4) temperature rise rate with 300 ℃/h is raised to 650～700 ℃ from room temperature, is incubated 1～20 hour, closes the retort furnace power supply then and arrives room temperature by the glass furnace cooling, and taking-up can obtain transparent glass-ceramics.

Technique effect of the present invention:

Ytterbium-nickel codoping glass and transparent glass-ceramics thereof present different colours because of NiO concentration is different: Ytterbium-nickel codoping glass presents little Huang with the increase of NiO concentration, and is yellowish, pale brown, yellowish brown and brown; The Ytterbium-nickel codoping transparent devitrified glass presents approximate colourless with the increase of NiO concentration, pale blue green, blue-greenish colour and dark green.The crystallite of transparent silicate glass-ceramics of the present invention is LiGa mutually ₅O ₈Spinel.In the Ytterbium-nickel codoping transparent devitrified glass, Ni ²⁺Ion enters LiGa ₅O ₈Occupy the position of octahedra hexa-coordinate in the nanometer crystalline phase, and Yb ³⁺Ion owing to do not match with nanocrystalline space case stays still in the glassy phase that (the rare earth class ion generally needs the dodecahedron case, and LiGa ₅O ₈Have only tetrahedron and octahedra two kinds of cases in nanocrystalline).What is interesting is that we find Ni in the devitrified glass ²⁺Ion ³A ₂( ³F) → ³T ₂( ³F) absorption and Yb ³⁺Ion ²F _5/2→ ²F _7/2Emission have big spectra overlapping, therefore as shown in Figure 1, Yb might take place ³⁺Ion is to Ni ²⁺The ionic useful energy shifts, and makes Ni in the devitrified glass ²⁺The ionic near-infrared fluorescence is greatly improved.Our result also proves Yb ³⁺Ion is to Ni ²⁺The useful energy transfer has taken place in ion, has improved Ni greatly ²⁺The near-infrared luminous character of ionic.

The present invention shifts luminosity with strongthener by ytterbium to the energy of nickel.Make by Ytterbium-nickel codoping that the near-infrared fluorescent intensity of devitrified glass is the highest to improve about 8.5 times, fluorescence lifetime can be brought up to 920 microseconds when mixing altogether from 480 microseconds of singly mixing nickel, makes the transparent glass-ceramics of this Ytterbium-nickel codoping be expected to be applied in fields such as wide-band optical amplifier, superpower laser, tunable laser.

Description of drawings

Fig. 1 is the emmission spectrum (curve 1 is that the laser diode of 980nm excites with optical maser wavelength) of comparative example's 2 devitrified glasses of the present invention and the absorption spectrum (curve 2) of comparative example's 3 devitrified glasses.

Fig. 2 is the emmission spectrum (optical maser wavelength is that the laser diode of 980nm excites) of the devitrified glass of comparative example 3 of the present invention and embodiment 4 to embodiment 7.

Embodiment

The present invention is further illustrated below in conjunction with embodiment and accompanying drawing, but should not limit protection scope of the present invention with this.

Table 1 has been listed composition and the molar percentage thereof of totally 11 embodiment of glass of the present invention, the color of the color of corresponding glass, heat treating regime, devitrified glass and devitrified glass fluorescence peak position, halfwidth, the test result in life-span under the 980nm pump light excites, wherein embodiment 2 and embodiment 3 are Comparative Examples.

Embodiment 1

The composition of this embodiment only mixed micro-NiO and Yb ₂O ₃The preparation method of present embodiment transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning weighing of embodiment 1, ground 30 minutes in agate mortar, place the inherent 1550 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 550 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass, is little yellow.The transparent glass sample is put into retort furnace be raised to 650 ℃ with the speed of 300 ℃/h from room temperature, be incubated 10 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics, is approximate colourless.This devitrified glass sample is processed into 7 * 7 * 2mm ³, the polishing back is for the usefulness of test.Because of doping content is very low, 980nm is laser diode-pumped have only down very weak from Ni ²⁺Ionic is near-infrared luminous, the about 206nm of halfwidth, and the life-span under the room temperature is about 85 microseconds.

Comparative example 2 and comparative example 3

Comparative example 2 and comparative example 3 have singly mixed Yb respectively ₂O ₃And NiO.The preparation method of transparent glass-ceramics is as follows: press the raw material of comparative example 2 and comparative example's 3 the about 50g of composition proportioning difference weighing, ground 30 minutes in agate mortar, place the inherent 1600 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 550 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass.Comparative example's 2 glass are colourless, and comparative example's 3 glass are pale brown look.The transparent glass sample is put into retort furnace be raised to 660 ℃ with the speed of 300 ℃/h from room temperature, be incubated 10 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics.Comparative example's 2 devitrified glasses are colourless, and comparative example's 3 devitrified glasses are light green.The devitrified glass sample is processed into 7 * 7 * 2mm ³, the polishing back is for the usefulness of test.Fig. 1 is emission (980nm excites) spectrum of comparative example's 2 devitrified glasses and the absorption spectrum of comparative example's 3 devitrified glasses, can see Yb in the devitrified glass ³⁺Ionic 1020nm emission and Ni ²⁺The ion center is together overlapped in the absorption of 1030nm, so Yb ³⁺Ion is to Ni ²⁺It is possible that energy of ions shifts.Fluorescence spectrum under comparative example's 3 devitrified glass 980nm pumpings as shown in Figure 2, the fluorescence peak position is at 1290nm, the fluorescence halfwidth is about 265nm, the life-span under the room temperature is about 450 microseconds.

Embodiment 4 to embodiment 7

These four embodiment's Yb of different content have mixed ₂O ₃, and the content of NiO is fixed as 0.1mol%.The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning difference weighing of four embodiment, ground 30 minutes in agate mortar, place the inherent 1600 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 550 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass, all is pale brown look.The transparent glass sample is put into retort furnace be raised to 680 ℃ with the speed of 300 ℃/h from room temperature, be incubated 10 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics, all is the pale blue green.The devitrified glass sample is processed into 7 * 7 * 2mm ³, the polishing back is for the usefulness of test.The fluorescence spectrum of devitrified glass can be seen along with Yb as shown in Figure 2 ₂O ₃The increase Ni of concentration ²⁺The ionic fluorescence intensity constantly strengthens, and at Yb ₂O ₃Fluorescence intensity began to descend when concentration surpassed 0.75mol%.Singly mix the fluorescence intensity of NiO devitrified glass with comparative example 3 and compare, embodiment 4,5, and 6 and 7 fluorescence intensity has strengthened about 5.5,6.5,8.0 and 6.0 times respectively, and the fluorescence halfwidth has improved about 10～25nm, and fluorescence lifetime has improved about 120～440 microseconds.

Embodiment 8 to embodiment 11

These four embodiment's NiO and Yb of high level have mixed ₂O ₃The preparation method of transparent glass-ceramics is as follows: press the raw material of the about 50g of composition proportioning difference weighing of these four embodiment, ground 30 minutes in agate mortar, place the inherent 1600 ℃ of fusions of Platinum crucible 2 hours then; Glass melt is cast on the stainless-steel sheet fast, and gently flattens with another block plate, changes over to afterwards in the retort furnace to anneal 2 hours down at 550 ℃, closes the retort furnace power supply then and reduces to room temperature by glass with stove, takes out and promptly gets transparent glass; The glass of embodiment 8 is yellowish brown, and its excess-three is individual to be brown.The transparent glass sample is put into retort furnace be raised to 700 ℃ with the speed of 300 ℃/h from room temperature, be incubated 10 hours, close the retort furnace power supply then and drop to room temperature by glass sample with stove, taking-up can obtain transparent glass-ceramics.The devitrified glass of embodiment 8 is blue-greenish colour, and the devitrified glass of its excess-three embodiment is dark green.The devitrified glass sample is processed into 7 * 7 * 2mm ³, the polishing back is for the usefulness of test.Because NiO and Yb ₂O ₃Doping content higher, Ni ²⁺Concentration quenching between the ion and Ni ²⁺Ion and Yb ³⁺Cross relaxation between the ion greatly reduces Ni ²⁺The ionic fluorescence intensity, fluorescence lifetime also shortens greatly simultaneously, and the fluorescence peak position is then with NiO concentration increase red shift gradually, and the fluorescence halfwidth also increases gradually with NiO concentration, sees Table 1.

Table 1

The embodiment sequence number	1	2	3	4	5
						SiO 2 Ga 2O 3 Li 2O NiO Yb 2O 3The glass colour heat treating regime (℃-h) devitrified glass color crystallite phase fluorescence peak position (nm) fluorescence halfwidth (nm) fluorescence lifetime * (μ s)	50 30 20 0.005 0.005 little yellow 650-10 are similar to colourless LiGa 5O 8 1280 206 85	The colourless LiGa of 54 15 25 01 colourless 660-10 5O 8 1020 - 650	59.9 25 15 0.1 0 pale brown 660-10 light green LiGa 5O 8 1300 265 480	62.65 the green LiGa of 25 13 0.1 0.25 pale brown 680-10 pale blue 5O 8 1300 290 710	63.623130.10.50 the green LiGa of pale brown 680-10 pale blue 5O 81300286805

Emission wavelength is the semiconductor diode pump of 980nm

Continuous table 1

6	7	8	9	10	11
						64.25 the green LiGa of 23 12 0.1 0.75 pale brown 680-10 pale blue 5O 8 1300 295 920	62.9 the green LiGa of 22 12 0.1 1 pale brown 680-10 pale blue 5O 8 1300 280 600	66.2 21 11 0.3 1.5 yellowish-brown 700-10 blue-greenish colour LiGa 5O 8 1308 295 380	The dark green LiGa of 68 20 10 0.5 1.5 brown 700-10 5O 8 1317 304 230	67.3 the dark green LiGa of 20 10 0.7 2 brown 700-10 5O 8 1328 312 140	The dark green LiGa of 67 20 10 12 brown 700-10 5O 8 1336 320 95

Claims (2)

1. Ytterbium-nickel codoping transparent silicate micro-crystal glass is characterized in that the composition proportioning of this devitrified glass is as follows:

Ingredient m ol%

SiO ₂ 50～70

Ga ₂O ₃ 15～30

Li ₂O 10～30

NiO 0.005～1

Yb ₂O ₃ 0.005～2。

2. the preparation method of the described Ytterbium-nickel codoping transparent silicate micro-crystal glass of claim 1 is characterized in that comprising the following steps:

(1) the composition proportioning of selected glass, each raw material by the certain total amount of this proportioning weighing ground in agate mortar 10～60 minutes;

(2) ground raw material is put into Platinum crucible, melt soaking time 1～10 hour in 1500～1600 ℃;

(3) glass melt is cast on the stainless-steel sheet, and use another roller flatteningl roller levelling, change over to afterwards in the retort furnace and under 500～580 ℃, anneal soaking time 0.5～10 hour, close the retort furnace power supply then and reduce to room temperature with stove, take out and promptly get transparent glass by glass;

(4) temperature rise rate with 300 ℃/h is raised to 650～700 ℃ from room temperature, is incubated 1～20 hour, closes the retort furnace power supply then and arrives room temperature by the glass furnace cooling, and taking-up can obtain transparent glass-ceramics.

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