CN106929917B - A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature - Google Patents

A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature Download PDF

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Publication number
CN106929917B
CN106929917B CN201710280810.0A CN201710280810A CN106929917B CN 106929917 B CN106929917 B CN 106929917B CN 201710280810 A CN201710280810 A CN 201710280810A CN 106929917 B CN106929917 B CN 106929917B
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lithium niobate
double
crystal
doped lithium
phase
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CN106929917A (en
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孔勇发
孔腾飞
刘士国
刘宏德
陈绍林
郑大怀
葛新宇
徐培明
卞志勇
许京军
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Nankai University
Taishan Sports Industry Group Co Ltd
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Taishan Sports Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/30—Niobates; Vanadates; Tantalates
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Lasers (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The present invention relates to nonlinear optical crystal fields, more particularly to a kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature.The double-doped lithium niobate crystal is by Li2CO3、Nb2O5、ZrO2It is made with MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.88~0.94: 1, ZrO2Incorporation by mole being calculated as 1.1~1.9mol%, the incorporation of MgO is by mole being calculated as 3.0~6.0mol%.The present invention solves the problems, such as existing magnesium-doped lithium niobate crystal, and there are 90 ° of high phase-matching temperatures (being greater than 100 DEG C) and narrow matching temperature half widths (less than 0.5 DEG C).90 ° of phase-matching temperatures of double-doped lithium niobate crystal provided by the invention are down to 25.1 DEG C, matching temperature half width reaches 1.2 DEG C, it does not need using heating furnace and precision temperature control component, 90 ° of phase matcheds can be realized at room temperature, there is anti-photorefraction ability outstanding simultaneously, 2 orders of magnitude are improved than congruent magnesium (5.0mol%) lithium columbate crystal of mixing, can be applied to the fields such as laser freuqency doubling, optical parametric oscillation, Q-switch and optical waveguide.

Description

A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature
Technical field
The present invention relates to nonlinear optical crystal fields, more particularly to a kind of double-doped niobic acid of 90 ° of phase matcheds of room temperature Crystalline lithium.
Background technique
Lithium columbate crystal is one of most important frequency-doubling crystal in nonlinear optics.Since it is in visible and near infrared spectrum Area has big negative index, biggish nonlinear optical coefficients and higher frequency-doubling conversion efficiency and is easy to reach phase matched Etc. excellent characteristics, have important application it in nonlinear optics.But the photorefractive effect of lithium columbate crystal limits Its laser freuqency doubling, optical parametric oscillation, Q-switch and in terms of application.Doping is modifies one of lithium niobate crystal Kind effective means, such as mix magnesium, zinc, scandium or zirconium and its anti-photorefraction ability can be improved.In order to guarantee good anti-photorefraction energy Power is most widely used with mixing the congruent lithium columbate crystal of magnesium 5.0mol%.
Usual magnesium-doped lithium niobate crystal uses 90 ° of phase matched (also referred to as temperature mainly as Nd:YAG laser frequency-doubling device Phase matched) mode works.When magnesium-doped lithium niobate crystal is as the 90 ° of frequency doubling device work of Nd:YAG laser, high phase Make the frequency doubling device that must use heating furnace with temperature (being greater than 100 DEG C) and narrow matching temperature half width (less than 0.5 DEG C) With precision temperature control component, and this will lead to laser aid structural compactness reduce and short service life.Currently, also not See and is not only able to achieve 90 ° of phase matcheds of room temperature but also the relevant report of the lithium columbate crystal with anti-photorefraction ability outstanding.Therefore, Exploration introduces new doping in magnesium-doped lithium niobate crystal, to optimize improvement crystal property, realizes 90 ° of phase matcheds of room temperature, right Magnesium-doped lithium niobate crystal is all solid state in easy to use, compact-sized simple high power as 90 ° of frequency doubling devices of Nd:YAG laser Functionization in long wavelength laser is very important, and has huge application prospect.
Summary of the invention
The purpose of the present invention: solving existing magnesium-doped lithium niobate crystal, there are 90 ° of high phase-matching temperatures and narrow matchings The problem of temperature half width, provides one kind and had not only been able to achieve 90 ° of phase matcheds of room temperature but also had had anti-photorefraction ability outstanding Double-doped lithium niobate crystal.
The technical scheme adopted by the invention is that:
A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature, by Li2CO3、Nb2O5、ZrO2It is made with MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.88~0.94: 1, ZrO2Incorporation by mole being calculated as 1.1~1.9mol%, The incorporation of MgO is by mole being calculated as 3.0~6.0mol%；(incorporation means expression ZrO by mole meter2 Or the percentage of the amount of the substance of the amount of the substance of MgO and mixture entirety, i.e. ZrO2Molar percentage in the mixture is The molar percentage of 1.1~1.9mol%, MgO in the mixture is 3.0~6.0mol%.)
A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature is made of Czochralski czochralski method.
Advantages of the present invention and effect: the present invention provides a kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature: (1) Using 90 ° of phase matched modes, using electro-optical Q-switch Nd:YAG laser as fundamental frequency light source, the phase-matching temperatures of the crystal Down to 25.1 DEG C, matching temperature half width reaches 1.2 DEG C, and solving existing magnesium-doped lithium niobate crystal, there are 90 ° of high phases With temperature (be greater than 100 DEG C) and the problem of narrow matching temperature half width (less than 0.5 DEG C), do not need using heating furnace and precision 90 ° of phase matcheds can be realized in temperature control unit at room temperature；(2) under the irradiation of 532nm continuous laser, the crystal Anti-photorefraction ability reach 6.5MW/cm2, 2 orders of magnitude are improved than congruent magnesium (5.0mol%) lithium columbate crystal of mixing. Therefore, a kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature can be used for optical parametric oscillation, Q-switch, optical waveguide And it is directly used in easy to use, compact-sized simple high power at room temperature as 90 ° of frequency doubling devices of Nd:YAG laser All solid state long wavelength laser has huge application prospect.
Specific embodiment
Principles and features of the present invention are described with reference to embodiments, the given examples are served only to explain the present invention, It is not intended to limit the scope of the present invention.
Embodiment 1
(1) Li is weighed2CO3、Nb2O5、ZrO2Ingredient is carried out with MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.88: 1, ZrO2Molar percentage in the mixture is 1.9mol%, and the molar percentage of MgO in the mixture is 6.0mol%.? Powder was dried in constant temperature 2 hours at 300 DEG C, then with 300r/min ground and mixed 24 hours on planetary ball mill, 800 DEG C constant temperature 4 hours, make Li2CO3It sufficiently decomposes, is calcined 12 hours at 1100 DEG C, can be prepared by zirconium magnesium double-doped lithium niobate powder；
(2) powder obtained in (1) is compacted, is put in platinum crucible, heated with Medium frequency induction crucible method, used Czochralski Czochralski grown, dip direction according to seeding, draw neck, shouldering, isometrical, ending program to grow, i.e., along C axis Obtain zirconium magnesium double-doped lithium niobate crystal.Technological parameter are as follows: pulling rate 0.8mm/h, revolving speed 7r/min, 20 DEG C of gas-liquid temperature difference, in melt 1.5 DEG C/mm of temperature gradient above 1.0 DEG C/mm of temperature gradient, melt；
(3) crystal after growing is in 1200 DEG C, current density 5mA/cm2Under conditions of poling, it is oriented, cutting, mill Process is thrown, that is, can be made into experiment zirconium magnesium double-doped lithium niobate crystal.
In frequency multiplication experiment, using 90 ° of phase matched modes, using electro-optical Q-switch Nd:YAG laser as fundamental frequency light source, The phase-matching temperatures for measuring crystal are 26.1 DEG C, and matching temperature half width is 1.2 DEG C.Using 532nm continuous wave laser, pass through Hot spot distortion method observe crystal light intensity be 6.5MW/cm2Strong illumination under there is no light injury；And pass through holographic note Record obtains crystal under high power laser light irradiation, and the variation of crystal refractive index is only 3.86 × 10-6.Therefore, the double-doped niobium Sour crystalline lithium can be applied to optical parametric oscillation, Q-switch, optical waveguide and as 90 ° of frequency doubling devices of Nd:YAG laser in room temperature item It is directly used under part, does not need heating furnace and precision temperature control component.
Embodiment 2
(1) Li is weighed2CO3、Nb2O5、ZrO2Ingredient is carried out with MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.92: 1, ZrO2Molar percentage in the mixture is 1.5mol%, and the molar percentage of MgO in the mixture is 3.0mol%.? Powder was dried in constant temperature 2 hours at 300 DEG C, then with 300r/min ground and mixed 24 hours on planetary ball mill, 800 DEG C constant temperature 4 hours, make Li2CO3It sufficiently decomposes, is calcined 12 hours at 1100 DEG C, can be prepared by zirconium magnesium double-doped lithium niobate powder；
(2) powder obtained in (1) is compacted, is put in platinum crucible, heated with Medium frequency induction crucible method, used Czochralski Czochralski grown, dip direction according to seeding, draw neck, shouldering, isometrical, ending program to grow, i.e., along C axis Obtain zirconium magnesium double-doped lithium niobate crystal.Technological parameter are as follows: pulling rate 0.8mm/h, revolving speed 7r/min, 20 DEG C of gas-liquid temperature difference, in melt 1.5 DEG C/mm of temperature gradient above 1.0 DEG C/mm of temperature gradient, melt；
(3) crystal after growing is in 1200 DEG C, current density 5mA/cm2Under conditions of poling, it is oriented, cutting, mill Process is thrown, that is, can be made into experiment zirconium magnesium double-doped lithium niobate crystal.
In frequency multiplication experiment, using 90 ° of phase matched modes, using electro-optical Q-switch Nd:YAG laser as fundamental frequency light source, The phase-matching temperatures for measuring crystal are 25.6 DEG C, and matching temperature half width is 1.2 DEG C.Using 532nm continuous wave laser, pass through Hot spot distortion method observe crystal light intensity be 6.5MW/cm2Strong illumination under there is no light injury；And pass through holographic note Record obtains crystal under high power laser light irradiation, and the variation of crystal refractive index is only 3.93 × 10-6.Therefore, the double-doped niobium Sour crystalline lithium can be applied to optical parametric oscillation, Q-switch, optical waveguide and as 90 ° of frequency doubling devices of Nd:YAG laser in room temperature item It is directly used under part, does not need heating furnace and precision temperature control component.
Embodiment 3
(1) Li is weighed2CO3、Nb2O5、ZrO2Ingredient is carried out with MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.94: 1, ZrO2Molar percentage in the mixture is 1.1mol%, and the molar percentage of MgO in the mixture is 4.6mol%.? Powder was dried in constant temperature 2 hours at 300 DEG C, then with 300r/min ground and mixed 24 hours on planetary ball mill, 800 DEG C constant temperature 4 hours, make Li2CO3It sufficiently decomposes, is calcined 12 hours at 1100 DEG C, can be prepared by zirconium magnesium double-doped lithium niobate powder；
(2) powder obtained in (1) is compacted, is put in platinum crucible, heated with Medium frequency induction crucible method, used Czochralski Czochralski grown, dip direction along C axis, according to seeding, draw neck, shouldering, isometrical, epilogue growth to get To zirconium magnesium double-doped lithium niobate crystal.Technological parameter are as follows: pulling rate 0.8mm/h, revolving speed 7r/min, 20 DEG C of gas-liquid temperature difference, temperature in melt Spend 1.0 DEG C/mm of gradient, melt top 1.5 DEG C/mm of temperature gradient；
(3) crystal after growing is in 1200 DEG C, current density 5mA/cm2Under conditions of poling, it is oriented, cutting, mill Process is thrown, that is, can be made into experiment zirconium magnesium double-doped lithium niobate crystal.
In frequency multiplication experiment, using 90 ° of phase matched modes, using electro-optical Q-switch Nd:YAG laser as fundamental frequency light source, The phase-matching temperatures for measuring crystal are 25.1 DEG C, and matching temperature half width is 1.2 DEG C.Using 532nm continuous wave laser, pass through Hot spot distortion method observe crystal light intensity be 6.5MW/cm2Strong illumination under there is no light injury；And pass through holographic note Record obtains crystal under high power laser light irradiation, and the variation of crystal refractive index is only 3.91 × 10-6.Therefore, the double-doped niobium Sour crystalline lithium can be applied to optical parametric oscillation, Q-switch, optical waveguide and as 90 ° of frequency doubling devices of Nd:YAG laser in room temperature item It is directly used under part, does not need heating furnace and precision temperature control component.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Made any modifications, equivalent replacements, and improvements etc., is all included in the scope of protection of the present invention within principle.

Claims (2)

1. a kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature, it is characterised in that: the double-doped lithium niobate crystal be by Li2CO3、Nb2O5、ZrO2It is made with the mixture of MgO, wherein Li2CO3And Nb2O5Molar ratio be 0.88~0.94: 1, ZrO2 Molar percentage in the mixture be 1.1~1.9mol%, the molar percentage of MgO in the mixture be 3.0~ 6.0mol%.
2. a kind of application of the double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature according to claim 1, feature exist In: at room temperature, it can directly be used the double-doped lithium niobate crystal as 90 ° of frequency doubling devices of Nd:YAG laser, It does not need using heating furnace and precision temperature control component.
CN201710280810.0A 2017-04-25 2017-04-25 A kind of double-doped lithium niobate crystal of 90 ° of phase matcheds of room temperature Expired - Fee Related CN106929917B (en)

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