CN1331791C - Neodymium doped borate glass with high luminous quantum efficiency and its preparing method - Google Patents

Abstract

The present invention discloses neodymium-doped borate glass with high efficiency of luminous quanta and a preparation method thereof, which relates to the field of laser glass. The present invention provides neodymium-doped borate glass with higher efficiency of luminous quanta than that of the borate glass in the prior art. The neodymium-doped borate glass of the present invention is prepared from B2O3, Bi2O3, alkalis and alkaline earth oxides (RmOn), and a luminous ion oxide (Nd2O3). The neodymium-doped borate glass prepared by the present invention can meet the requirements for any dimension, and is suitable to be used in lasers and optical fiber communication.

Description

Has neodymium doped borate glass of high luminous quantum efficiency and preparation method thereof

Technical field

The present invention relates to the laser glass field, especially relate to a kind of neodymium doped borate glass and preparation thereof.

Background technology

Compare with laser crystals, it is low that laser glass has a cost, and preparation is simple, and shape and size can change, and structure is adjusted easily, isotropy, the advantage of character uniformity on the large volume.At present, laser glass all plays an important role at aspects such as Laser emission, amplification and optical information storage transmission, and as glass optical fiber, optical waveguides and thin-film material the photonics device miniatureization and integrated aspect very application prospects is also arranged.The laser glass that has been applied at present mainly is rare-earth-ion-doped silicate, borate, phosphoric acid salt and fluoride glass.Wherein, borate glass because have low melting temperature (Tm) (with respect to silicate glass), be difficult for containing moisture (with respect to phosphate glass), toxicity little (with respect to fluoride glass), physical and chemical performance is stable and the simple advantage of experimental installation, has received special concern.But with the glassy phase ratio of other kind, its luminous quantum efficiency is lower, and up to the present, the luminous quantum efficiency of the neodymium doped borate glass of existing report is only up to about 20% in the world, and its host glass moiety is Na ₂O-Al ₂O ₃-B ₂O ₃(referring to V.Mehta, G.Aka, A.L.Dawar, and A.Mansingh, Opt.Mater., 12[1] 53-63 (1999).And luminous quantum efficiency and laser operation efficient are closely related, low luminous quantum efficiency immediate constraint the application of such glass material in laser field.

Summary of the invention

The present invention proposes a kind of borate glass component and preparation technology thereof of neodymium-doped, purpose is to prepare has high luminous quantum efficiency, and big stimulated emission cross section can be used for the neodymium doped borate glass of Laser emission and amplification.

Borate glass component of the present invention is: the neodymium doped borate glass that contains alkali and alkaline-earth oxide and heavy metal ion oxide compound.Its each moiety proportioning such as following relational expression: XNd ₂O ₃: (1-X) [YR _mO _n: ZBi ₂O ₃: (1-Y-Z) B ₂O ₃], X=0.1～1.5mol% wherein, Y=0～20mol%, Z=30～60mol%, R _mO _nBe Al ₂O ₃, or MgO, or Na ₂O.

In this glass ingredient, B ₂O ₃And Bi ₂O ₃The effect of mainly serving as glass network former, R _mO _nServe as glass network and adjust the effect of body, Nd ₂O ₃It is the light emitting ionic oxide compound.Neodymium ion has the four-level structure, when its electronics from ⁴F _3/2Energy level transition arrives ⁴I _11/2During energy level, send the laser that wavelength is about 1060nm.Because this laser channeling has higher stimulated emission cross section than other laser channeling, easier realization Laser emission, therefore for the laserable material of neodymium-doped, mainly research is the laser at 1060nm wavelength place.Use the Judd-Ofelt theory, neodymium-doped laser glass is at the stimulated emission cross section σ at 1060nm place _{JJ '}Can provide by the following relationship formula with luminous quantum efficiency η:

${\mathrm{\σ}}_{{\mathrm{JJ}}^{\′}}=\frac{{\mathrm{\λ}}_{{\mathrm{JJ}}^{\′}}^4{A}_{{\mathrm{JJ}}^{\′}}^{\mathrm{ed}}(J\→J^{\′})}{8\mathrm{\π}{\mathrm{cn}}^2\mathrm{\Δ}{\mathrm{\λ}}_{e{\mathrm{ff}}^{\′}}}$

$\mathrm{\η}=\frac{{\mathrm{\τ}}_f}{{\mathrm{\τ}}_r}$

Wherein

$A_{{\mathrm{JJ}}^{\text{'}}}^{\mathrm{ed}}(J\→J^{\text{'}})=\frac{64{\mathrm{\π}}^4{e}^2}{3h(2J+1){\mathrm{\λ}}^3}\frac{n{(n^2+2)}^2}{9}\underset{i=\mathrm{2,4,6}}{\mathrm{\Σ}}{\mathrm{\Ω}}_i\left|{\⟨}^4{F}_{3/2}\right|\left|U^{\left(t\right)}\right|{|}^4{I}_{J^{\text{'}}}\⟩{|}^2$

${\mathrm{\τ}}_r=\frac{1}{\underset{J^{\′}}{\mathrm{\Σ}}{A}_{{\mathrm{JJ}}^{\′}}^{\mathrm{ed}}}$

In the above-mentioned formula, λ _{JJ '}Be emission wavelength, A _{JJ '} ^EdBe radiative transistion probability, c is the light velocity, and n is the specific refractory power of glass, Δ λ _EffBe effective fluorescence bandwidth of fluorescence Spectra, τ _fBe fluorescence lifetime, τ _rBe radiative lifetime, e is an elementary charge, and h is a quantum of action, and J, J ' are respectively the energy level of transition initial state and final state, Ω _t(t=2,4,6) are the Judd-Ofelt intensive parameter, U ^(t)Tensor operator for the secondary reduced matrix.

The present invention adopts and to be prepared as follows technology: adopt at glass melting temperature (Tm) point distortion not occur, soften, or with metal, alloy or the corresponding crucible of oxide compound high temperature material manufacturing and the forming mould of glass ingredient and sintering atmosphere react with.The powder raw material that will have the above purity of analytical pure is placed in the loft drier dry 20-40 hour, be placed in the agate abrasive disk than accurate weighing according to certain set of dispense then and ground 20-30 minute, powder raw material after grinding is placed crucible, crucible is put into the temperature controllable heating installation and is put between above 100-200 ℃ insulation 8-15 hour in the glass melting temperature (Tm), in insulating process, the agitator arm stirred glass liquid made from high temperature material simultaneously.Then, glass metal is poured in the forming mould that is preheating between the following 50-100 of glass transition temperature point ℃, insulation is 2-5 hour in temperature controllable equipment, carries out anneal with 15-45 ℃ rate of cooling per hour then.Obtain the good laser glass sample of optical quality at last.As long as being carried out polished finish, the surface of this glass sample can in laser apparatus and optical-fibre communications, use.

Adopt above preparation technology and glass ingredient, successfully obtained emission wavelength roughly at the 1060nm place, stimulated emission cross section is approximately 4.5 * 10 ^-20Cm ², luminous quantum efficiency reaches as high as 56% neodymium-doped salt laser glass.Table 1 has been listed this component glass sample (in the table first) and other borate reported and commercial comparative result with silicate laser glass spectrum parameter.

Table 1:

Host glass	Luminous quantum efficiency η (%)	Stimulated emission cross section σ 1.06(10 -20cm 2)
			Bi 2O 3-Al 2O 3-B 2O 3	56	4.5
Na 2O-Al 2O 3-B 2O 3	20	3.1
			3699A	52	1.05
ED-2	83	2.71
			LSG-91H	78	2.45

The melting temperature (Tm) of each component glass of the present invention is lower, and not strict to the requirement of required experimental installation, preparation technology is simple, and cost is lower, can once shaped obtain as bulk, the various shapes that meet service requirements such as bar-shaped and optical fiber shape; Borate glass of the present invention owing to be the neodymium doped borate glass that contains the heavy metal ion oxide compound, is compared with the neodymium doped borate glass of prior art, and stimulated emission cross section is big, the luminous quantum efficiency height; Spectrum parameters such as stimulated emission cross section that it is relevant with laser activity and luminous quantum efficiency can be comparable to the neodymium-doped silicate laser glass of commercial usefulness, and have high optical quality, hot light stability and physical and chemical performance, so borate glass of the present invention may become a kind of novel working-laser material.

Embodiment

Example 1: adopting dried purity is analytically pure H ₃BO ₃, Bi ₂O ₃And Al ₂O ₃With purity greater than 99.99% Nd ₂O ₃Powder is pressed 0.5Nd ₂O ₃: 99.5 (40Bi ₂O ₃: 15Al ₂O ₃: 45B ₂O ₃) the accurate raw materials weighing of proportioning of (mol ratio).After raw material ground and mixed in the agate abrasive disk is even, pour in the platinum crucible, place the temperature controllable resistance furnace then 1000 ℃ of left and right sides fusions 13 hours.In melting process, the stirring fused solution that the speed that the agitator arm that uses platinum to make changes with per minute 30 is not stopped.Fused solution is poured in the brass die of the specified shape that is preheating to 500 ℃ afterwards, put into annealing furnace insulation 4 hours, with the rate of cooling about 45 ℃ per hour glass sample is carried out anneal then.The glass sample that obtains records stimulated emission cross section and is approximately 4.5 * 10 through after the polished finish ^-20Cm ², luminous quantum efficiency is 56%.

Example 2: adopting dried purity is analytically pure H ₃BO ₃, Bi ₂O ₃And Al ₂O ₃With purity greater than 99.99% Nd ₂O ₃Powder is pressed 1Nd ₂O ₃: 99 (40Bi ₂O ₃: 10Al ₂O ₃: 50B ₂O ₃) the accurate raw materials weighing of proportioning of (mol ratio).After raw material ground and mixed in the agate abrasive disk is even, pour in the platinum crucible, place the temperature controllable resistance furnace then 900 ℃ of left and right sides fusions 13 hours.In melting process, the stirring fused solution that the speed that the agitator arm that uses platinum to make changes with per minute 30 is not stopped.Fused solution is poured in the brass die of the specified shape that is preheating to 450 ℃ afterwards, put into annealing furnace insulation 4 hours, with the rate of cooling about 45 ℃ per hour glass sample is carried out anneal then.The glass sample that obtains records stimulated emission cross section and is approximately 3.9 * 10 through after the polished finish ^-20Cm ², luminous quantum efficiency is 41%.

Example 3: adopting dried purity is analytically pure H ₃BO ₃, Bi ₂O ₃And MgCO ₃With purity greater than 99.99% Nd ₂O ₃Powder is pressed 0.5Nd ₂O ₃: 99.5 (40Bi ₂O ₃: 5MgO: 55B ₂O ₃) the accurate raw materials weighing of proportioning of (mol ratio).After raw material ground and mixed in the agate abrasive disk is even, pour in the platinum crucible, place the temperature controllable resistance furnace then 950 ℃ of left and right sides fusions 10 hours.In melting process, the stirring fused solution that the speed that the agitator arm that uses platinum to make changes with per minute 40 is not stopped.Fused solution is poured in the brass die of the specified shape that is preheating to 450 ℃ afterwards, put into annealing furnace insulation 3 hours, with the rate of cooling about 30 ℃ per hour glass sample is carried out anneal then.The glass sample that obtains is through after the polished finish, and the stimulated emission cross section that records is approximately 4.4 * 10 ^-20Cm ², luminous quantum efficiency is 54%.

Example 4: adopting dried purity is analytically pure H ₃BO ₃, Bi ₂O ₃And NaCO ₃With purity greater than 99.99% Nd ₂O ₃Powder is pressed 0.5Nd ₂O ₃: 99.5 (40Bi ₂O ₃: 5Na ₂O: 55B ₂O ₃) the accurate raw materials weighing of proportioning of (mol ratio).After raw material ground and mixed in the agate abrasive disk is even, pour in the platinum crucible, place the temperature controllable resistance furnace then 800 ℃ of left and right sides fusions 10 hours.In melting process, the stirring fused solution that the speed that the agitator arm that uses platinum to make changes with per minute 20 is not stopped.Fused solution is poured in the brass die of the specified shape that is preheating to 400 ℃ afterwards, put into annealing furnace insulation 2 hours, with the rate of cooling about 20 ℃ per hour glass sample is carried out anneal then.The glass sample that obtains is through after the polished finish, and the stimulated emission cross section that records is approximately 4.6 * 10 ^-20Cm ², luminous quantum efficiency is 53%.

Example 5: adopting dried purity is analytically pure H ₃BO ₃, Bi ₂O ₃And NaCO ₃With purity greater than 99.99% Nd ₂O ₃Powder is pressed 0.5Nd ₂O ₃: 99.5 (40Bi ₂O ₃: 10Na ₂O: 50B ₂O ₃) the accurate raw materials weighing of proportioning of (mol ratio).After raw material ground and mixed in the agate abrasive disk is even, pour in the platinum crucible, place the temperature controllable resistance furnace then 800 ℃ of left and right sides fusions 8 hours.In melting process, the stirring fused solution that the speed that the agitator arm that uses platinum to make changes with per minute 20 is not stopped.Fused solution is poured in the brass die of the specified shape that is preheating to 350 ℃ afterwards, put into annealing furnace insulation 2 hours, with the rate of cooling about 20 ℃ per hour glass sample is carried out anneal then.The glass sample that obtains is through after the polished finish, and the stimulated emission cross section that records is approximately 4.4 * 10 ^-20Cm ², luminous quantum efficiency is 51%.

Claims (3)

1, a kind of neodymium doped borate glass with high luminous quantum efficiency is characterized in that: its each moiety proportioning such as following relational expression: XNd ₂O ₃: (1-X) [YR _mO _n: ZBi ₂O ₃: (1-Y-Z) B ₂O ₃], wherein, X=0.1～1.5mol%.Y=0～20mol%, Z=30～60mol%, R _mO _nBe Al ₂O ₃, or MgO, or Na ₂O.

2, a kind of preparation method of neodymium doped borate glass of claim 1, it is characterized in that: the powder raw material that will have the above purity of analytical pure is placed in the loft drier dry 20-40 hour, be placed in the agate abrasive disk than accurate weighing according to each set of dispense then and ground 20-30 minute, powder raw material after grinding is placed crucible, crucible is put into the temperature controllable heating installation and is put between above 100-200 ℃ insulation 8-15 hour in the glass melting temperature (Tm), in insulating process, the agitator arm stirred glass liquid made from high temperature material simultaneously; Then, glass metal is poured in the forming mould that is preheating between the following 50-100 of glass transition temperature point ℃, insulation is 2-5 hour in temperature controllable equipment, carries out anneal with 15-45 ℃ rate of cooling per hour then.

3, a kind of purposes of neodymium doped borate glass of claim 1, it is characterized in that: it is as working-laser material.