CN108840564B - Phosphate laser neodymium glass without thermal effect - Google Patents
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Abstract
The invention provides phosphate laser neodymium glass with a non-thermal-luminous effect, which comprises the following components in percentage by mol: p2O5 50‑70mol％；Al2O3 3‑25mol％；MO 5‑25mol％、R2O 10‑20mol％；R2O30.5-5mol%, wherein MO is one or more of BaO, MgO and ZnO; r2O is Li2O、Na2O、K2One or more of O; r2O3Is B2O3、Sb2O3、Nd2O3One or more of (a). The invention realizes that the thermo-optic coefficient ds/dT is close to 0 and reduces the nonlinear refractive index n by reasonably selecting each component and the content thereof2The requirement of a high-power laser device can be met by increasing the stimulated emission cross section of the neodymium glass.
Description
The application is a divisional application of an invention patent application with the name of 'phosphate laser neodymium glass without thermal effect' with the application number of 201410781664.6 and the application date of 2014, 12 and 16.
Technical Field
The invention relates to phosphate laser neodymium glass, in particular to laser glass suitable for a high-power laser device, which has high stimulated emission cross section, low second-order nonlinear refractive index and no optical effect.
Background
The elimination of thermo-optic distortion is one of the major issues in the development of high energy laser glass. The athermal glass is glass with an optical path length which does not change along with temperature, namely the thermo-optic coefficient ds/dT is close to 0. Generally, when optical pumping is repeated to oscillate laser light, the temperature of glass increases, and the optical path length changes. Because the glass is heated and the temperature is not uniformly distributed, the optical path length change of the gradient is formed, and the wavefront deformation, namely the photo-thermal distortion, is caused. With the continuous enlargement of the scale of high-power laser devices, the laser output energy is continuously improved, and after the laser energy density of a unit surface area reaches a certain magnitude, the thermo-optic effect of laser glass must be emphasized.
The smaller the change in optical path length due to temperature change, i.e., the smaller ds/dT, the less likely photothermal distortion will occur. Phosphate laser neodymium glass is mainly used as a working substance of a laser amplifier in a high-power laser device, and in order to realize high gain, the stimulated emission cross section of the neodymium glass is required to be as large as possible, and the nonlinear refractive index n2As low as possible, but at the same time the effect of the thermo-optic effect of the glass cannot be neglected. Therefore, the reasonable formulation is needed, and the thermo-optic effect of the neodymium glass is reduced or eliminated as much as possible while the large stimulated emission section, the low second-order nonlinear refractive index and the high gain are obtained.
At present, phosphate laser neodymium glass such as N31 glass (N31 laser neodymium glass acceptance report, 12 months 1998) is in domestic use, although the stimulated emission cross section is higher (3.9 multiplied by 10)-20cm2) However, the thermo-optic coefficient (dS/dT ═ 14X 10)-7the/K) is large, and the requirement of a future high-power laser device on the low thermo-optic effect of the laser glass cannot be met.
US 4108673, US 5526369 and US5032315 disclose a phosphate laser neodymium glass respectively, but the phosphate laser neodymium glass does not belong to phosphate laser neodymium glass with high receiving and emitting cross section, low second-order nonlinear refractive index and no optical effect.
Disclosure of Invention
The invention aims to provide phosphate laser neodymium glass with a non-thermal effect, which can meet the requirements of high-power laser devices.
The technical problem to be solved by the invention is as follows: the phosphate laser neodymium glass without the thermoluminescent effect comprises the following components in percentage by mol: p2O5 50-70mol％；Al2O3 3-25mol％；MO 5-25mol％、R2O 10-20mol％；R2O3 0.5-5mol％，Wherein, MO is one or more of BaO, MgO and ZnO; r2O is Li2O、Na2O、K2One or more of O; r2O3Is B2O3、Sb2O3、Nd2O3One or more of (a).
Further, the method also comprises the following steps: nb2O5 0-0.5mol％；Sb2O3 0-1mol％。
Further, wherein, BaO 5-20 mol%; 0-5 mol% of MgO.
Further, wherein B2O3 0-2mol％。
Further, wherein Al2O3 5-15mol％。
Further, MO is 10-20 mol%.
Further, wherein, BaO 9-17 mol%.
Further, the second order nonlinear refractive index n of the glass21.05 to 1.14 (10)-13esu)。
Further, the stimulated emission cross section sigma of the glass is 3.9-4.4 (10)-20cm2)。
Further, the glass has a thermo-optic coefficient ds/dT (20-60 ℃) of 0.1 to 3 (10)-7/K)。
The invention has the beneficial effects that: the invention realizes that the thermo-optic coefficient ds/dT is close to 0 by reasonably selecting the components and the contents of the phosphate glass with small refractive index temperature coefficient and large expansion coefficient; the nonlinear refractive index n is reduced by reducing the linear refractive index and the dispersion of the phosphate laser neodymium glass2The object of (a); by increasing a plurality of components capable of improving the emission section of the neodymium ions and increasing the stimulated emission section of the neodymium glass, the comprehensive performance of the material is optimal, and the requirement of a high-power laser device can be met.
Drawings
FIG. 1 is a fluorescence spectrum curve of a glass of example 6 of the present invention.
Detailed Description
The technical route of the invention is through the counter refractionPhosphate glass with small specific temperature coefficient and large expansion coefficient is selected to realize ds/dT close to 0; simultaneously, the nonlinear refractive index n is reduced by reducing the linear refractive index and the dispersion of the phosphate laser neodymium glass2The object of (a); by increasing a plurality of components which are commonly used and can improve the emission cross section of the neodymium ions, the stimulated emission cross section of the neodymium glass is increased, so that the comprehensive performance of the material is optimal.
The temperature coefficient of the optical path length is:
in the formula (1), (n-1) and the coefficient of expansion α are positive numbers, and the refractive index of a general glass material increases as the temperature increases. As can be seen from the expression (1), in order to make ds/dT close to 0, it is necessary to make dn/dT negative, which is a problem of the relationship between the temperature coefficient of refractive index and the expansion coefficient, and the thermo-optic effect of the glass, that is, the thermo-optic coefficient ds/dT is reduced to close to 0, by adjusting the temperature coefficient of refractive index and the expansion coefficient of the phosphate glass so that the negative value of the temperature coefficient of refractive index cancels the increase in the optical path length of the glass due to thermal expansion, thereby eliminating the thermo-optic effect of the glass.
The phosphate laser neodymium glass without the thermoluminescent effect comprises the following components in percentage by mol: p2O550-70mol％；Al2O3 3-25mol％；MO 5-25mol％、R2O 10-20mol％；R2O3 0.5-5mol％。
Wherein, the MO is one or more of BaO, MgO and ZnO; r2O is Li2O、Na2O、K2One or more of O; r2O3Is B2O3、Sb2O3、Nd2O3One or more of (a).
Wherein, BaO 5-20 mol%; 0-5 mol% of MgO; nb2O5 0-0.5mol％；B2O3 0-2mol％；Sb2O3 0-1mol％。
Preferably, Al2O3 5-15mol％；MO 10-20mol％、BaO 9-17mol％。
In the above composition, a monovalent alkali metal oxide Li2O、Na2O、K2O and MgO in the alkaline earth metal oxide can reduce the refractive index and dispersion of the phosphate laser neodymium glass, thereby achieving the purpose of reducing the nonlinear refractive index n2The purpose of (1). In addition, the inventors found through research that in the phosphate glass, the order of increasing the stimulated emission cross section of the neodymium glass from small to large of the alkali metal oxide and the alkaline earth metal oxide is respectively Li2O→Na2O→K2O, MgO → CaO → SrO → BaO, and the proportion of each oxide is properly adjusted according to the rule, so as not to obviously increase the nonlinear refractive index n2Under the premise of properly increasing K2The content proportion of the O component and the more BaO content are introduced to improve the stimulated emission section of the neodymium glass.
The formula of the invention introduces Al with proper content2O3Thus, the glass has better processing characteristics. At the same time, Al2O3The introduction of (a) increases the expansion coefficient alpha of the glass to a certain extent. By Al2O3And the adjustment of BaO content, so that the glass expansion coefficient alpha is matched with the temperature coefficient of the refractive index, thereby achieving the purpose of reducing the thermo-optic coefficient.
The preparation method of the phosphate laser neodymium glass without the thermoluminescent effect comprises the following steps:
firstly, selecting a glass formula and weighing raw materials;
secondly, the raw materials are fully and uniformly mixed to form a mixture;
thirdly, heating the silicon carbide melting furnace to 1300-1400 ℃, and uniformly adding the mixture into a quartz melting tank in the silicon carbide melting furnace by 20-25 Kg/h;
fourthly, O is introduced into the quartz material groove2+SOC12Mixing gas, wherein the gas flow is 1-2L/min;
after stopping ventilation, injecting the glass liquid into a platinum crucible, and clarifying the glass liquid for 3-4 hours at 1350-;
sixthly, mechanically stirring the glass liquid for 6 to 10 hours at 1250-1350 ℃;
and seventhly, pouring the prepared glass liquid into a graphite mold for shaping, annealing and cooling to obtain the phosphate laser neodymium glass with the thermo-optical effect.
The test method of each index of the glass comprises the following steps:
1) non-linear refractive index n2Test method (2)
Second order nonlinear refractive index n of glass2Expressed by the following formula:
in the formula, ndThe refractive index of the glass at a wavelength of 587.6nm is shown, upsilon is the Abbe number of the glass, and the calculation formula is as follows:
nF、nCthe refractive indices of the glass at wavelengths of 486.1nm and 656.3nm, respectively. n isd、nF、nCAll obtained by testing with a GMR-1D precision goniometer.
The nonlinear refractive index n of the glass of the invention is tested21.05 to 1.14 (10)-13esu)。
2) Method for testing stimulated emission cross section sigma of glass
The stimulated emission cross section of the glass is calculated by a Judd-Ofelt model. In Judd-Ofelt theory, the stimulated emission cross section σ and the radiative transition probability A [ (4F3/2)；(4F11/2)]The relationship of (1) is:
wherein λ ispIs the peak wavelength of fluorescence, λeffIs the effective line width of the peak wavelength of fluorescence, i.e.
λeff＝∫I(λ)dλ/I1053
Through tests, the stimulated emission cross section sigma of the glass is 3.9-4.4 (10)-20cm2)。
3) Method for testing thermo-optic coefficient ds/dT
The test for the thermo-optic coefficient ds/dT is calculated by the following expression test:
in the formula, n is the refractive index of the glass, and dn/dT is the temperature coefficient of the refractive index of the glass, which are obtained by testing a GMR-1D precise angle meter.
Alpha is the coefficient of thermal expansion of the glass and is measured using a DIL-402C thermal expansion instrument.
Through tests, the thermo-optic coefficient ds/dT (20-60 ℃) of the glass is 0.1-3 (10)-7/K)。
10 examples of the present invention are shown in Table 1. The molar percentage composition, the nonlinear refractive index n, of the glass is given in Table 12(10-13esu), stimulated emission cross section σ (10) of the glass-20cm2) And a thermo-optic coefficient ds/dT.
TABLE 1
FIG. 1 is a graph showing the fluorescence spectrum curve calculated by the stimulated emission cross section test of the glass of example 6 obtained by processing the glass of example 6 into a sample with a thickness of 1mm and then measuring the fluorescence spectrum by a fluorescence spectrometer.
Claims (9)
1. The phosphate laser neodymium glass without the thermoluminescent effect is characterized by comprising the following components in percentage by mole: p2O5 50-70mol%；Al2O3 11-25 mol%；MO 5-25 mol%、R2O 10-20 mol%；R2O30.5-5mol%, wherein MO is one or more of BaO, MgO and ZnOA plurality of types; r2O is Li2O、Na2O、K2One or more of O; r2O3Is B2O3、Sb2O3、Nd2O3Wherein K is2O content greater than Li2O content, Na2The content of O; the BaO content is larger than the MgO content, and the stimulated emission cross section sigma of the glass is 3.9-4.4 multiplied by 10-20cm2。
2. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, further comprising: nb2O5 0-0.5 mol%；Sb2O3 0-1 mol%。
3. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, wherein BaO 5 to 20 mol%; 0-5 mol% of MgO.
4. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, wherein B is2O3 0-2 mol%。
5. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, wherein Al is2O3 11-15 mol%。
6. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, wherein MO is 10-20 mol%.
7. The non-pyroelectric effect phosphate laser neodymium glass of claim 1, wherein BaO 9-17 mol%.
8. The non-thermo-optic effect phosphate laser neodymium glass according to claim 1, wherein the second-order nonlinear refractive index n of the glass21.05 to 1.14X 10-13esu。
9. The non-pyroelectric effect phosphate laser neodymium glass as claimed in claim 1, wherein the glass has a thermo-optic coefficient ds/dT of 0.1-3 x 10 at 20-60 ℃-7/K。
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| CN201811022539.1A CN108840564B (en) | 2014-12-16 | 2014-12-16 | Phosphate laser neodymium glass without thermal effect |
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| CN201811022539.1A CN108840564B (en) | 2014-12-16 | 2014-12-16 | Phosphate laser neodymium glass without thermal effect |
| CN201410781664.6A CN105753316B (en) | 2014-12-16 | 2014-12-16 | The phosphate laser neodymium glass of luminescence effect |
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| CN109081579B (en) * | 2018-09-17 | 2021-07-27 | 成都光明光电有限责任公司 | Phosphate laser neodymium glass |
| CN110423002A (en) * | 2019-06-17 | 2019-11-08 | 苏州艾斯康光电智能科技有限公司 | A kind of rear-earth-doped glass and preparation method thereof |
| CN110530549B (en) * | 2019-08-12 | 2021-09-21 | 华南理工大学 | Preparation method of temperature-insensitive fiber Bragg grating sensor |
| US20220298060A1 (en) * | 2019-08-21 | 2022-09-22 | National Institute Of Advanced Industrial Science And Technology | Phosphate glass and light-emitting device using same |
| CN113277731B (en) * | 2021-05-28 | 2022-04-15 | 成都光明光电有限责任公司 | Silver-containing nanoparticle laser glass and method for producing same |
| CN113636755B (en) * | 2021-06-28 | 2022-06-03 | 成都光明光电有限责任公司 | Phosphate laser glass and preparation method thereof |
| 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 |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| US5053165A (en) * | 1989-07-26 | 1991-10-01 | Hoya Optics, Inc. | Glass of improved thermal shock resistance for high average power solid state laser system |
| US5322820A (en) * | 1992-12-08 | 1994-06-21 | Kigre, Inc. | Athermal laser glass compositions with high thermal loading capacity |
| 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 |
| CN101880127A (en) * | 2010-05-26 | 2010-11-10 | 中国科学院上海光学精密机械研究所 | Phosphate laser neodymium glass with enhanced surface ion modification and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2717916C3 (en) * | 1977-04-22 | 1980-06-12 | Jenaer Glaswerk Schott & Gen., 6500 Mainz | Glasses with a small non-linear refractive index, especially for laser technology |
| JPS5443220A (en) * | 1977-09-09 | 1979-04-05 | Hoya Glass Works Ltd | Laser glass having optical length with little or no temperature dependency |
| JPS60191029A (en) * | 1984-03-13 | 1985-09-28 | Hoya Corp | Laser glass |
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- 2014-12-16 CN CN201410781664.6A patent/CN105753316B/en active Active
- 2014-12-16 CN CN201811022539.1A patent/CN108840564B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239645A (en) * | 1975-03-18 | 1980-12-16 | Hoya Glass Works, Ltd. | Phosphate base laser glasses |
| US5053165A (en) * | 1989-07-26 | 1991-10-01 | Hoya Optics, Inc. | Glass of improved thermal shock resistance for high average power solid state laser system |
| US5322820A (en) * | 1992-12-08 | 1994-06-21 | Kigre, Inc. | Athermal laser glass compositions with high thermal loading capacity |
| US5322820C1 (en) * | 1992-12-08 | 2001-04-24 | Kigre Inc | Athermal laser glass compositions with high thermal loading capacity |
| 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 |
| CN101880127A (en) * | 2010-05-26 | 2010-11-10 | 中国科学院上海光学精密机械研究所 | Phosphate laser neodymium glass with enhanced surface ion modification and preparation method thereof |
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| CN108840564A (en) | 2018-11-20 |
| CN105753316B (en) | 2019-02-26 |
| CN105753316A (en) | 2016-07-13 |
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