CN104926114B - phosphate laser neodymium glass - Google Patents
phosphate laser neodymium glass Download PDFInfo
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- CN104926114B CN104926114B CN201510340333.3A CN201510340333A CN104926114B CN 104926114 B CN104926114 B CN 104926114B CN 201510340333 A CN201510340333 A CN 201510340333A CN 104926114 B CN104926114 B CN 104926114B
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Abstract
A kind of stimulated emission cross section of present invention offer is high, thermo-optical coeffecient is small, phosphate laser neodymium glass suitable for device of high power laser, and its molar percentage composition includes：P2O550 70mol%；Al2O31 15mol%；One or more in MO 5 25mol%, M Ba, Mg, Zn；R2One or more in O 10 20mol%, R Li, Na, K；R2O3One or more in 0.5 5mol%, R Y, La, Nd；Nb2O50.5 5mol%.The present invention is by reasonable disposition each component, the nonlinear refractive index n of obtained phosphate laser neodymium glass2For 1.16~1.24 (10‑13Esu), stimulated emission cross section σ is 4.0~4.8 (10‑20cm2), (20 60 DEG C) of thermo-optical coeffecient ds/dT is 1~2 (10‑7/K)。
Description
Technical field
The present invention relates to a kind of phosphate laser neodymium glass, more particularly to a kind of stimulated emission cross section height, thermo-optical coeffecient
Laser glass that is low, being suitable for device of high power laser.
Background technology
Because neodymium glass fluorescence lifetime is long, stimulated emission cross section is big, block piece is big and can manufacture, thus in laser system
It is used widely in system.Neodymium glass also has good energy storage effect, turns into the first choice of high power laser system amplifying device
Operation material, such as the God Light device in U.S. LLNL igniter and China, all it is to be used as amplification medium by the use of neodymium glass.Neodymium
The spectral quality of glass directly affects device of high power laser design, therefore studies the spectral quality of neodymium glass to high power laser light
Device design is particularly important.The spectral quality of neodymium glass includes absorption coefficient, transmitting transition probability, metastable state fluorescence lifetime, spoke
Penetrate quantum efficiency, stimulated emission cross section and Excited-state Absorption dipole moment etc..Wherein, stimulated emission cross section is to weigh laser work thing
One most basic physical quantity of matter optical quality, it is one of most important parameters for designing device of high power laser.
Spectroscopy is conventional to be absorbed with emission cross section to represent absorption and emission probability.Section has the dimension of area, its with
The ratio of beam area represents an absorption or launching centre (atom or molecule) absorbs or the probability of transmitting light radiation.Emission cross section
It is the threshold value of assessment material and the important spectrum parameter of slope efficiency.The size of emission cross section directly influences the gain of neodymium glass
Efficiency, therefore, it plays the effect of key in laser system design.
Phosphate laser neodymium glass is primarily used to the operation material of laser amplifier in device of high power laser.One side
Face, in order to realize high-gain, it is desirable to which the stimulated emission cross section of neodymium glass is as big as possible, and fluorescence lifetime is as long as possible.In addition, in order to
Bigger output energy is obtained, using the neodymium glass of high concentration as amplification material.But with Concentration of Neodymium Ion in Czochralski in neodymium glass
Increase, stimulated emission cross section will reduce therewith.Therefore, suitable material composition how is designed, there is high neodymium keeping glass
While ion concentration, its stimulated emission cross section is further improved, is the weight of neodymium glass research to realize higher laser gain
Want problem.
Existing phosphate laser neodymium glass domestic at present, as N31 glass (N31 laser neodymium glass acceptance reports, 1998 12
Month), its stimulated emission cross section is not high by (3.9 × 10-20cm2), its thermo-optical coeffecient (dS/dT=14 × 10-7/ K) it is larger, it is impossible to it is full
Requirement of the following device of high power laser of foot to laser glass low-heat luminous effect；Thermo-optical coeffecient (dS/ disclosed in CN 1765795A
DT=0.3 × 10-7/ K) it is smaller, but its stimulated emission cross section is not also high by (3.9 × 10-20cm2)。
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of stimulated emission cross section is high, thermo-optical coeffecient is small, suitable for height
The phosphate laser neodymium glass of power laser device.
Solution is used by the present invention solves technical problem：Phosphate laser neodymium glass, its constituent are rubbed
You include percentage composition：P2O550-70mol%；Al2O31-15mol%；MO 5-25mol%, wherein, M Ba, Mg, Zn
In one or more；R2O 10-20mol%, wherein, the one or more in R Li, Na, K；R2O30.5-5mol%, its
In, the one or more in R Y, La, Nd；Nb2O50.5-5mol%.
Further, wherein, BaO 5-20mol% and/or ZnO 1-5mol% and/or MgO 0-5mol%.
Further, wherein, MO 10-20mol%.
Further, wherein, Y2O30-3mol% and/or La2O30-3mol% and/or Nd2O30-3mol%.
Further, wherein, Al2O32-10mol%.
Further, wherein, BaO 10-18mol%.
Further, the scope of the fluorescence lifetime of the glass is 315-325 μ s.
Further, the nonlinear refractive index n of the glass2For 1.16~1.24 (10-13esu)。
Further, the stimulated emission cross section σ of the glass is 4.0~4.8 (10-20cm2)。
Further, (20-60 DEG C) of the thermo-optical coeffecient ds/dT of the glass is 1~2 (10-7/K)。
The beneficial effects of the invention are as follows：The present invention is by reasonable disposition each component and its content, obtained phosphate laser
The nonlinear refractive index n of neodymium glass2For 1.16~1.24 (10-13Esu), stimulated emission cross section σ is 4.0~4.8 (10-20cm2),
(20-60 DEG C) of thermo-optical coeffecient ds/dT is 1~2 (10-7/ K), suitable for device of high power laser.
Brief description of the drawings
Fig. 1 is the absorption spectrum of the glass of the embodiment of the present invention 6.
Fig. 2 is the fluorescence spectrum of the glass of the embodiment of the present invention 6.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, but the protection model of the present invention should not be limited with this
Enclose.
The technology of the present invention route is in unobvious increase neodymium glass nonlinear refractive index n2With thermo-optical coeffecient ds/dT premise
Under, the weaker oxide of a certain amount of cation electric field is introduced, to increase Nd3+Surrounding is coordinated normal asymmetry, so as to carry
The transmitting transition probability A of high neodymium glassrad.Stimulated emission cross section σ and the relation for launching transition probability are as follows：
In formula (1)：λPIt is the peak wavelength of neodymium glass emission spectrum；C is the light velocity in vacuum；N is wavelength XPRefraction
Rate；Δ λ eff are the effective line width of glass fluorescence emission spectrum.
Specifically, introduce the small monovalence alkali metal oxide Li of refractive index in the glass formula of the present invention2O、Na2O、K2O
In one or more, and one or more in small divalent alkaline-earth metal oxide M gO, ZnO, the BaO of refractive index, with drop
The refractive index of hypophosphate laser neodymium glass and dispersion, reaching reduces nonlinear refractive index n2Purpose；Meanwhile in not clear development
On the premise of ringing glass stimulated emission cross section, A1 is suitably introduced into2O3The chemical stability of glass can be not only improved, can also be dropped
The thermo-optical coeffecient dS/dT of low glass, i.e. temperature change caused by light laser will not cause the change of light path.
The transmitting transition probability A of phosphate laser neodymium glassradThe reason for big is Nd3+The asymmetry in ligand field.Silicate
The cation electric field of glass is stronger, the deformation of network structure and Nd3+The asymmetry in ligand field is bigger；In contrast, due to phosphorus
The cation sites of silicate glass are to carry out chain link, therefore cation electric field is weaker, and the arrangement of chain link shape is more irregular,
Nd3+The asymmetry in the ligand field of surrounding is also just bigger.Therefore, nonlinear refractive index n is improved in unobvious2On the premise of, draw
Enter the weak Y of a certain amount of cation electric field2O3、La2O3Deng oxide, the transmitting transition probability of neodymium glass can be significantly improved
Arad, so as to improve the stimulated emission cross section of neodymium glass.
The preparation method of the phosphate laser neodymium glass of the present invention, may comprise steps of：
1) glass formula is selected, weighs each raw material；
2) raw material is sufficiently mixed uniformly, forms compound；
3) carborundum smelting furnace is warming up to 1300-1400 DEG C, divides 20-25Kg/h to be homogeneously added into described compound
In silicification hopper in carborundum smelting furnace；
4) it is passed through O in described silicification hopper2+CC14Gaseous mixture, throughput are 1-2L/ minutes；
5) after stopping ventilation, glass metal is injected into platinum crucible, at 1350-1450 DEG C is clarified to glass metal 3-4 hours；
6) at 1250-1350 DEG C is carried out to glass metal mechanical agitation 6-10 hours；
7) obtained glass metal is poured into graphite jig and shaped, annealing cooling.
The method of testing of the indices of glass of the present invention is as follows：
1) nonlinear refractive index n2Method of testing
The second nonlinear refractive index n of glass2Expressed with following formula：
In formula (2)：ndFor refractive index of the glass at 587.6nm wavelength；υ is the Abbe number of glass, and calculation formula is：
In formula (3)：nF、nCRespectively refractive index of the glass at 486.1nm and 656.3nm wavelength.nd、nF、nCBy
GMR-1D precision goniometers are tested to obtain.
By test, the nonlinear refractive index n of glass of the present invention2For 1.16~1.24 (10-13esu)。
2) the stimulated emission cross section σ of glass method of testing
Absorption coefficient integration ∫ k (λ) the d λ of electronics dipole and the strength relationship of absorption line are as follows：
In formula (4)：K (λ) is the absorption coefficient of wavelength X；N0It is neodymium ion (Nd3+) concentration；It is being averaged for absorption band
Wavelength；J is ground state angular momentum summation；N is refractive index；E is electricity electricity；C is the light velocity in vacuum；H is Planck's constant.
According to Judd-Ofelt models, initial level J | (S, L) J>To final state energy level J ' | (S ', L ') J '>Electronics dipole jumps
The intensity of spectral line moved is：
In formula (5)：It is the matrix element of Judd-Ofelt models；<||U(t)||>It is Nd3+Inhale
Transition matrix element is received, the digital solution of unit tensor is calculated by Carnall et al..
Glass sample is processed into 1cm thickness, the two light pass surface depth of parallelisms are measured within 1 ' with Hitachi's U-4100 spectrophotometrics
The absorption line of test agent, measurement range are 350~1100nm, and be absorbed spectrum.
According to formula (4), (5) and the absorption line of various concentration samples and the transition matrix element of neodymium ion, using minimum
Square law is fitted to absorption line, obtains the Ω of various concentrationt(t=2,4,6).Pass through ΩtBeginning energy level can be obtained | (S ',
L′)J′>To energy levelRadiative transistion probability be：
The effective line width Δ λ eff of test sample.Sample is processed into 1mm thickness, then measures sample with XRF
Fluorescence spectrum.Fluorescent belt at 1053nm is integrated, obtained integrated intensity divided by 1053nm fluorescence intensity, is exactly 1053nm
Effective line width, i.e.,：
Formula (6), (7) result of calculation are brought into formula (1), that is, calculate the stimulated emission cross section of sample.
By test, the stimulated emission cross section σ of glass of the present invention is 4.0~4.8 (10-20cm2)。
3) thermo-optical coeffecient ds/dT method of testing
Thermo-optical coeffecient ds/dT test is obtained by following expression measuring and calculation：
In formula (8)：N is the refractive index of glass；Dn/dT is the thermal refractive index coefficient of glass, is surveyed by GMR-1D is accurate
Angle instrument is tested to obtain；α is the thermal coefficient of expansion of glass, is tested using DIL-402C thermal dilatometers.
By test, (20-60 DEG C) of the thermo-optical coeffecient ds/dT of glass of the present invention is 1~2 (10-7/K)。
4) method of testing of fluorescence lifetime
Sample is processed into 1mm thickness, transient state spectrum test is carried out with XRF, calculating is fitted to transient state spectrum
Obtain fluorescence lifetime.
By test, the scope of fluorescence lifetime of the invention is 315-325 μ s.
The specific embodiment (1-10) of the present invention is shown in Table 1.Given in table 1 glass composition (molar percentage),
Fluorescence life τ (μ s), nonlinear refractive index n2(10-13Esu), the stimulated emission cross section σ (10 of glass-20cm2) and thermo-optical coeffecient
ds/dT。
Table 1
By the glass processing of above-described embodiment 6 into sample thick 1cm, its absorption spectrum is tested with spectrophotometer, is obtained
Absorption spectrum curve needed for its stimulated emission cross section measuring and calculation, as shown in Figure 1.
By the glass processing of above-described embodiment 6 into sample thick 1mm, its fluorescence spectrum is measured with XRF, is obtained
Fluorescent spectrum curve needed for its stimulated emission cross section measuring and calculation, as shown in Figure 2.
Claims (10)
1. phosphate laser neodymium glass, it is characterised in that the molar percentage composition of its constituent includes：P2O5 50-
70mol%；Al2O31-15mol%；MO 5-25mol%, wherein, the one or more in M Ba, Mg, Zn；R2O 10-
17mol%, wherein, the one or more in R Li, Na, K；R2O30.5-5mol%, wherein, one kind in R Y, La, Nd
It is or a variety of；Nb2O50.5-5mol%.
2. phosphate laser neodymium glass as claimed in claim 1, it is characterised in that wherein, BaO 5-20mol% and/or ZnO
1-5mol% and/or MgO 0-5mol%.
3. phosphate laser neodymium glass as claimed in claim 1, it is characterised in that wherein, MO 10-20mol%.
4. phosphate laser neodymium glass as claimed in claim 1, it is characterised in that wherein, Y2O30-3mol% and/or La2O3
0-3mol% and/or Nd2O30-3mol%.
5. phosphate laser neodymium glass as claimed in claim 1, it is characterised in that wherein, Al2O32-10mol%.
6. phosphate laser neodymium glass as claimed in claim 1, it is characterised in that wherein, BaO 10-18mol%.
7. phosphate laser neodymium glass as claimed in claim 1 or 2, it is characterised in that the model of the fluorescence lifetime of the glass
It is 315-325 μ s to enclose.
8. phosphate laser neodymium glass as claimed in claim 1 or 2, it is characterised in that the nonlinear refractive index n of the glass2
For 1.16~1.24 (10-13esu)。
9. phosphate laser neodymium glass as claimed in claim 1 or 2, it is characterised in that the stimulated emission cross section σ of the glass
For 4.0~4.8 (10-20cm2)。
10. phosphate laser neodymium glass as claimed in claim 1 or 2, it is characterised in that the thermo-optical coeffecient ds/ of the glass
(20-60 DEG C) of dT is 1~2 (10-7/K)。
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| CN201510340333.3A CN104926114B (en) | 2015-06-18 | 2015-06-18 | phosphate laser neodymium glass |
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| CN201510340333.3A CN104926114B (en) | 2015-06-18 | 2015-06-18 | phosphate laser neodymium glass |
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| CN104926114B true CN104926114B (en) | 2018-02-16 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347674B (en) * | 2015-11-19 | 2018-07-13 | 成都光明光电有限责任公司 | High heat conductance Nd-doped phosphate glass |
| CN113461328B (en) * | 2021-06-28 | 2022-04-15 | 成都光明光电有限责任公司 | Phosphate laser neodymium glass and preparation method thereof |
| CN114644456A (en) * | 2022-03-09 | 2022-06-21 | 中国科学院上海光学精密机械研究所 | Phosphate laser glass |
| CN114634310B (en) * | 2022-03-09 | 2023-07-18 | 中国科学院上海光学精密机械研究所 | Phosphate laser neodymium glass and preparation method thereof |
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| CN1765795A (en) * | 2005-08-24 | 2006-05-03 | 中国科学院上海光学精密机械研究所 | Phosphate laser neodymium glass |
| CN102173584A (en) * | 2009-11-20 | 2011-09-07 | 长春理工大学 | Phosphate glass containing 5% to 20% of aluminum oxide and 2% to 15% of yttrium oxide |
| US9006120B2 (en) * | 2012-11-28 | 2015-04-14 | Schott Corporation | Ultra-broad bandwidth laser glasses for short-pulse and high peak power lasers |
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