CN102674690A - 3 mu m rare earth ion doped bismuth-germinate laser glass and preparation method thereof - Google Patents

Abstract

The invention discloses 3 mu m rare earth ion doped bismuth-germinate laser glass and a preparation method thereof. The glass comprises 32-41mol% of Bi2O3, 40-55mol% of GeO2, 9.25-15.5mol% of R12O (R1 refers to one alkali metal of Li, Na and K) and 3-6mol% of R2F3 (R2 refers to one kind or two kinds of rare earth ions such as Er, Pr, Tm, Nd and Yb). The glass prepared by a melt-quenching method is brilliant yellow in color and uniform in physicochemical property. The glass is stable in thermodynamic property, high in crystallization resistant ability and high in transmissivity at a wave band of 3 mu m. The glass has high 3 mu m fluorescence under a laser diode pump with the wavelength of 980nm and is applicable to preparation and application of optical fiber materials of the 3 mu m rare earth ion doped bismuth-germinate laser glass.

Description

Rare-earth-ion-doped bi germanate laser glass of 3 μ m and preparation method thereof

Technical field

The present invention relates to laser glass, rare-earth-ion-doped bi germanate laser glass of particularly a kind of 3 μ m and preparation method thereof.

Background technology

3 mu m wavebands are corresponding to the characteristic spectral line of many important molecule, and are important atmospheric windows transparent relatively in the air, thereby aspect military and civilian, have a wide range of applications.It comprises laser guidance, infrared distance measurement and laser aiming etc. in application of military field.Application aspect civilian comprises the detection (for example obnoxious flavoures such as nitrogen protoxide, carbon monoxide, formaldehyde, hydrogen sulfide, hydrogen bromide) of deleterious trace gas in remote sensing, the air.Therefore 3 μ m mid-infrared laser light sources have obtained extensive studies in recent years.

1980, the Bagdasarov reported first from erbium doped yttrium aluminum garnet crystal (YAG), obtained the 3 μ m laser output of 100mJ.But it is not high that laser crystals is limited to doping content, and process of growth is slow, is difficult to obtain unfavorable factors such as large-sized sample, fettered its further development.Laser glass then can overcome these shortcomings, and can process various shapes according to needs of people.1988, Pollack reported the adulterated ZBLAN fluoride fiber of Er, and centre wavelength is at 2.78 μ m, and the output energy is 75J.Although fluoride glass phonon ability is low, bad mechanical property, poor heat stability, and certain pollution is arranged for environment.General oxide glass then phonon ability is too high, is difficult to obtain effective 3 μ m output.

Bismuth-germanate glass is a kind of suitable material, and it not only has with the close phonon energy of fluorochemical, and it is even to combine the oxide glass physicochemical property again, and physical strength is high, advantages such as good rigidity.And it has also had the specific refractory power advantages of higher of heavy metal oxide glass concurrently, is infrared substrate material in a kind of ideal.But rare both at home and abroad report about bismuth-germanate glass 3 μ m output.

Summary of the invention

The technical problem that the present invention will solve is to provide rare-earth-ion-doped bi germanate laser glass of a kind of 3 μ m and preparation method thereof; This glass has good thermostability; Middle preferably infrared transmission performance can obtain 3 very strong μ m fluorescence down the laser diode-pumped of 980nm wavelength.

Technical solution of the present invention is following:

The rare-earth ion-doped bi germanate laser glass of a kind of 3 μ m, its characteristics are that the molar percentage of this glass consists of:

Wherein: R is basic metal Li, Na or K.

The preparation method of the rare-earth-ion-doped bi germanate laser glass of above-mentioned 3 μ m comprises the following steps:

1. the composition and the molar percentage of selected said glass calculate and weigh the quality that each raw material is formed, and fully grind, and mix;

2. ground compound being put into corundum crucible, to place temperature be that 1050 ~ 1100 ℃ of globars electric furnaces are founded; Aerating oxygen provides oxidizing atmosphere in the process of founding; Fusing time is 40min, treats to be cast on the mould of preheating after the complete fusion clarification of raw material;

3. treat after the glass hardening that rapidly it is moved into temperature is near the retort furnace the glass transformation temperature and anneals, near transition temperature, be incubated 3 ~ 4 hours, be cooled to room temperature with 10 ℃/hour speed then, treat to cool off fully the back and take out sample;

Technique effect of the present invention is following:

The present invention is through carrying out Er ³⁺/ Tm ³⁺/ Pr ³⁺/ Nd ³⁺/ Yb ³⁺Multiple rare earth ion doped, obtained 3 mu m luminous bismuth-germanate glasses of a series of concentration proportionings.Glass is glassy yellow, and is transparent, no crystallization, and physicochemical property are even, thermally-stabilised parameter Δ T >=150 ℃, the infrared permeation ability is good.At laser diode-pumped time of the 980nm wavelength, obtained the output of 3 μ m fluorescence.

Description of drawings

The differential thermal curve of the rare-earth ion-doped bi germanate laser glass of 3 μ m that Fig. 1 is obtained for embodiment 1#.

The rare-earth ion-doped bi germanate laser glass of the 3 μ m infrared permeation spectrum that Fig. 2 is obtained for embodiment 1#.

The fluorescence spectrum of the rare-earth ion-doped bi germanate laser glass of 3 μ m that Fig. 3 is obtained for embodiment 1# under 980nm wavelength laser diode-pumped.

Embodiment

The glass ingredient of 10 specific embodiments of the rare-earth ion-doped bi germanate laser glass of the present invention 3 μ m is as shown in table 1:

Table 1: the glass formula of concrete 10 embodiment

Embodiment 1#:

Composition is shown in 1# in the table 1, and it is following specifically to prepare process:

According to the molar percentage that 1# glass in the table 1 is formed, calculate and weigh corresponding each weight of forming, take by weighing each raw material and mix; Compound is put into corundum crucible melt in 1050 ℃ ~ 1100 ℃ globars electric furnace, the clarification of fusing back is 15 minutes fully, the fused glass metal is cast on the mould of preheating; To move into temperature rapidly be in 400 ℃ the retort furnace, be incubated 3 hours cooling back slightly, reduces to room temperature with 10 ℃/hour speed again, fully cooling back taking-up glass sample.

Test result to this glass is following:

Get a little sample after the annealing, wear into fine powdered, carry out the DTA test with agate mortar.The differential thermal curve of the rare-earth ion-doped bi germanate laser glass of the present invention 3 μ m is as shown in Figure 1.

The sheet glass that is processed into 10 * 20 * 1.0 millimeters to the sample after the annealing also polishes, and tests its infrared permeation spectrum, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.The infrared permeation spectrum of the rare-earth ion-doped bi germanate laser glass of the present invention 3 μ m is as shown in Figure 2.The fluorescence spectrum of the rare-earth ion-doped bi germanate laser glass of the present invention 3 μ m under 980nm wavelength laser diode-pumped is as shown in Figure 3.Experiment shows that it is transparent that glass is glassy yellow, no crystallization, excellent in physical and chemical performance, stability parameter Δ T >=150 ℃.Can obtain 3 very strong μ m fluorescence down the laser diode-pumped of 980nm wavelength.

Embodiment 2#:

Composition is shown in 2# in the table 1, and it is following specifically to prepare process:

According to the molar percentage that 2# glass in the table 1 is formed, calculate and weigh corresponding each weight of forming, it is even to take by weighing each raw materials mix; Compound is put into corundum crucible melt in 1050 ℃ ~ 1100 ℃ globars electric furnace, the clarification of fusing back is 15 minutes fully, glass metal is cast on the mould of preheating; To move into temperature rapidly be in 400 ℃ the retort furnace, be incubated 3 hours cooling back slightly, reduces to room temperature with 10 ℃/hour speed again, fully cooling back taking-up glass sample.

Test result to this glass is following:

Get a little sample after the annealing, wear into fine powdered, carry out the DTA test with agate mortar.

The sheet glass that is processed into 10 * 20 * 1.0 millimeters to the sample after the annealing also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.

Embodiment 3#:

Composition is shown in 3# in the table 1, and it is following specifically to prepare process:

According to the molar percentage that 3# glass in the table 1 is formed, calculate and weigh corresponding each weight of forming, it is even to take by weighing each raw materials mix; Compound is put into corundum crucible melt in 1050 ℃ ~ 1100 ℃ globars electric furnace, the clarification of fusing back is 15 minutes fully, glass metal is cast on the mould of preheating; To move into temperature rapidly be in 400 ℃ the retort furnace, be incubated 3 hours cooling back slightly, reduces to room temperature with 10 ℃/hour speed again, fully cooling back taking-up glass sample.

Test result to this glass is following:

Get a little sample after the annealing, wear into fine powdered, carry out the DTA test with agate mortar.

The sheet glass that is processed into 10 * 20 * 1.0 millimeters to the sample after the annealing also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.

Embodiment 4#:

Composition is shown in 4# in the table 1, and it is following specifically to prepare process:

According to the molar percentage that 4# glass in the table 1 is formed, calculate and weigh corresponding each weight of forming, it is even to take by weighing each raw materials mix; Compound is put into corundum crucible melt in 1050 ℃ ~ 1100 ℃ globars electric furnace, the clarification of fusing back is 15 minutes fully, glass metal is cast on the mould of preheating; To move into temperature rapidly be in 400 ℃ the retort furnace, be incubated 3 hours cooling back slightly, reduces to room temperature with 10 ℃/hour speed again, fully cooling back taking-up glass sample.

Test result to this glass is following:

Get a little sample after the annealing, wear into fine powdered, carry out the DTA test with agate mortar.

The sheet glass that is processed into 10 * 20 * 1.0 millimeters to the sample after the annealing also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.

Embodiment 5# is to 10#:

Composition to shown in the 10#, specifically prepares process such as embodiment 1# like 5# in the table 1.

Following to 5# to the test result of 10# glass:

Get a little sample after the annealing, wear into fine powdered, carry out the DTA test with agate mortar.

The sheet glass that is processed into 10 * 20 * 1.0 millimeters to the sample after the annealing also polishes, at laser diode-pumped its fluorescence spectrum of test down of 980nm wavelength.

The foregoing description test shows all has the similar results of Fig. 1, Fig. 2 of the rare-earth ion-doped bi germanate laser glass of 3 μ m that embodiment 1 obtained, differential thermal curve shown in Figure 3, infrared permeation spectrum and the fluorescence spectrum under 980nm wavelength laser diode-pumped.It is multiple rare earth ion doped that experiment shows that the present invention passes through, and can obtain the rare-earth ion-doped bi germanate laser glass of 3 μ m, and it is transparent that glass is glassy yellow, no crystallization, and excellent in physical and chemical performance, stability parameter Δ T >=150 ℃, it is good to pass through infrared property.3 very strong μ m fluorescence be can obtain down the laser diode-pumped of 980nm wavelength, the preparation and the application of rare-earth ion-doped laser glass of 3 μ m and fiber optic materials are applicable to.

Claims (3)

1. rare-earth ion-doped bi germanate laser glass of μ m is characterized in that the molar percentage of this glass consists of:

Wherein: R is basic metal Li, Na or K.

2. the rare-earth ion-doped bi germanate laser glass of 3 μ m according to claim 1 is characterized in that described rare earth ion doped mode has: Er ³⁺Singly mix, Er ³⁺-Tm ³⁺Twoly mix, Er ³⁺-Pr ³⁺Twoly mix, Er ³⁺-Nd ³⁺Twoly mix, Er ³⁺-Yb ³⁺Two mixing.

3. the preparation method of the rare-earth ion-doped bi germanate laser glass of the described 3 μ m of claim 1 is characterized in that may further comprise the steps:

1. the composition and the molar percentage of the selected said glass of claim 1 calculate and weigh the quality that each raw material is formed, and fully grind, and mix;

2. ground compound being put into corundum crucible, to place temperature be that 1050 ~ 1100 ℃ of globars electric furnaces are founded; Aerating oxygen provides oxidizing atmosphere in the process of founding; Fusing time is 40min, treats to be cast on the mould of preheating after the complete fusion clarification of raw material;

3. treat after the glass hardening rapidly it is sent near the retort furnace that has risen in advance this glass transformation temperature and anneal, near transition temperature, be incubated 3 ~ 4 hours, be cooled to room temperature with 10 ℃/hour speed then, take out sample.

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