CN103320861A - Indium, ytterbium and thulium triple-doped lithium niobate crystal and preparation method thereof - Google Patents

Indium, ytterbium and thulium triple-doped lithium niobate crystal and preparation method thereof Download PDF

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CN103320861A
CN103320861A CN2013102529320A CN201310252932A CN103320861A CN 103320861 A CN103320861 A CN 103320861A CN 2013102529320 A CN2013102529320 A CN 2013102529320A CN 201310252932 A CN201310252932 A CN 201310252932A CN 103320861 A CN103320861 A CN 103320861A
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indium
lithium niobate
substance
lico
crystal
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代丽
焦珊珊
钱钊
李大勇
林家齐
王喜明
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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Abstract

The invention relates to an indium, ytterbium and thulium triple-doped lithium niobate crystal and a preparation method thereof and aims at solving the problem that an existing ytterbium and thulium doped lithium niobate crystal has lower light damage resistant capacity. The indium, ytterbium and thulium triple-doped lithium niobate crystal is prepared from Nb2O5, LiCO3, In2O3, Yb2O3 and Tm2O3. The preparation method of the indium, ytterbium and thulium triple-doped lithium niobate crystal comprises the following steps of: firstly, mixing; secondly, growing the crystal by adopting a pulling method; and thirdly, carrying out polarization, thus the indium, ytterbium and thulium triple-doped lithium niobate crystal is obtained. The prepared indium, ytterbium and thulium triple-doped lithium niobate crystal is high in brightness and uniform in composition, is flawless and produces no growth striation or crack, and the original excellent performances of the ytterbium and thulium doped lithium niobate crystal are maintained while light damage resistant capacity is obviously improved; and the preparation method of the indium, ytterbium and thulium triple-doped lithium niobate crystal is simple and easy to operate, and crystal growth speed is high. The preparation method can be used for preparing the indium, ytterbium and thulium triple-doped lithium niobate crystal.

Description

A kind of indium ytterbium thulium three-doping lithium niobate crystal and preparation method thereof
Technical field
The present invention relates to a kind of doped lithium columbate crystal and preparation method thereof.
Background technology
In recent years, investigators expected always and can well with non-linear compound with laser activity, obtain the crystalline material of complex function.Reach although this requirement looks not so difficult, but because laser crystals and nonlinear crystal have respectively the different requirements that realize himself function, the crystal that often has a good laser activity does not have non-linear, and good non-linear optic crystal can not provide the case that can produce laser operation for active ions.Lithium niobate crystals is a kind of non-linear optical crystal material of excellent property, has very large nonlinear factor.Tm 3+The level structure that is easy to occur conversion is arranged, be commonly used for the active ions of laser crystals.Mix the thulium lithium niobate crystals with the non-linear and Tm of lithium niobate crystals 3+Upper conversion characteristic combine sensitizing agent Yb 3+Ion can strengthen 980nm pump absorption efficient, and the lithium niobate crystals that the ytterbium thulium mixes so we consider to grow is studied the up-conversion luminescence performance of its crystal, but in the experimentation, and we find that the lithium niobate crystals photo-damage resistance that the ytterbium thulium mixes is lower.
Summary of the invention
The present invention will solve the lower problem of lithium niobate crystals photo-damage resistance that existing ytterbium thulium mixes, and a kind of indium ytterbium thulium three-doping lithium niobate crystal and preparation method thereof is provided.
A kind of indium ytterbium of the present invention thulium three-doping lithium niobate crystal is by Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Make; Wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1; Described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance; Described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance; Described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance.
The preparation method of above-mentioned indium ytterbium thulium three-doping lithium niobate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Then five kinds of raw materials fully mix five kinds of raw materials, obtain compound, wherein, and described LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1; Described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance; Described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance; Described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 0.5mm/h～1.5mm/h, and axial-temperature gradient is 35 ℃/cm～45 ℃/cm, speed of rotation is 13r/min～18r/min, obtains crystal;
Three, polarization: it is that 1150 ℃～1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30 ± 3min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
Advantage of the present invention: one, high, the uniform component of the indium ytterbium thulium three-doping lithium niobate crystal silver dollar degree of the present invention preparation, indefectible, produce without striation and flawless, photo-damage resistance significantly improves when having guaranteed the original premium properties of lithium niobate crystals that the ytterbium thulium mixes; Two, the preparation method of indium ytterbium thulium three-doping lithium niobate crystal of the present invention is simple, convenient operation, and crystalline growth velocity is fast; Three, the indium ytterbium thulium three-doping lithium niobate crystal of the present invention preparation can have a extensive future in preparation compact type, laser diode-pumped, all solid state tunable laser, and is also significant to panchromatic demonstration, high-density storage, infrared acquisition, preparation integrated optical device in addition.
Description of drawings
Fig. 1 is the indium ytterbium thulium three-doping lithium niobate crystal infrared absorpting light spectra of different I n doping content, ☆ among Fig. 1 is the not infrared absorpting light spectra of the ytterbium thulium doped lithium columbate crystal standardized component of doped indium of simultaneous test, among Fig. 1 zero is the infrared absorpting light spectra of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one, among Fig. 1 ▲ be the infrared absorpting light spectra of test two indium ytterbium thulium three-doping lithium niobate crystal standardized component, among Fig. 1 ● for testing the infrared absorpting light spectra of three indium ytterbium thulium three-doping lithium niobate crystal standardized component;
Fig. 2 is the not conversion fluorescence spectrogram of the ytterbium thulium doped lithium columbate wafer of doped indium of simultaneous test;
Fig. 3 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one;
Fig. 4 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two;
Fig. 5 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test three.
Embodiment
Embodiment one: a kind of indium ytterbium of present embodiment thulium three-doping lithium niobate crystal is by Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Make; Wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1, described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance, described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance, described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance.
The described indium ytterbium of present embodiment thulium three-doping lithium niobate crystal silver dollar degree is high, uniform component, indefectible, produce without striation and flawless, photo-damage resistance significantly improves when having guaranteed the original premium properties of lithium niobate crystals that the ytterbium thulium mixes.
The described indium ytterbium of present embodiment thulium three-doping lithium niobate crystal can have a extensive future in preparation compact type, laser diode-pumped, all solid state tunable laser, and is also significant to panchromatic demonstration, high-density storage, infrared acquisition, preparation integrated optical device in addition.
Embodiment two: what present embodiment and embodiment one were different is: described Nb 2O 5Quality purity be 99.99%; Described LiCO 3Quality purity be 99.99%; Described In 2O 3Quality purity be 99.99%; Described Yb 2O 3Quality purity be 99.99%; Described Tm 2O 3Quality purity be 99.99%.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 31% of total amount of substance.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 32% of total amount of substance.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 34% of total amount of substance.Other is identical with one of embodiment one to four.
Embodiment six: the preparation method of a kind of indium ytterbium of present embodiment thulium three-doping lithium niobate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Then five kinds of raw materials fully mix five kinds of raw materials, obtain compound, wherein, and described LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1; Described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance; Described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance; Described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 0.5mm/h～1.5mm/h, and axial-temperature gradient is 35 ℃/cm～45 ℃/cm, speed of rotation is 13r/min～18r/min, obtains crystal;
Three, polarization: it is that 1150 ℃～1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30 ± 3min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
The described crystal pulling method specific operation process of present embodiment step 2 is as follows: (1) prepares seed crystal: adopt concentration to prepare first seed crystal; (2) shove charge: whether all parts of monitoring device are normal,, simultaneously the position of crucible, after-heater, seed crystal and ruhmkorff coil adjusted with the formation temperature gradient by stay-warm case, guarantee that the concentricity between them meets the requirements; (3) melt: the opening device power supply, adjustment programme rising intermediate frequency output rating, temperature is raised to 1240 ℃, has reached the fusing point of Lithium niobium trioxide, and after raw material melted fully, constant temperature 2 hours guaranteed that melt fully mixes; (4) seeding: first in the situation that 50 ℃ of melt overheats " rinsing seed crystal " stretch into seed crystal fast in the melt, and mention rapidly, eliminate the machining damage of seed crystal lower end and possible pollutent before the lower seed crystal; (5) shouldering: begin to enter the shouldering stage after the seeding success, adopt oblique shouldering mode; (6) isodiametric growth: the degree of isodiametric growth directly determines the stability of growth conditions, when receiving the shoulder end, adjusts furnace temperature crystal diameter is being remained unchanged; (7) pull: after the crystal growth is complete, adopt the method that pulls that heats up gradually that it is pulled from liquid level; (8) cooling annealing: crystal adopts the automatically mode of the control cooling annealing of lowering the temperature of Continental Europe table when the position of 5 millimeters～6 millimeters of distance melt liquid levels.
Present embodiment is to overcome the lower problem of ytterbium thulium doped lithium columbate crystal photo-damage resistance, adds photodamage resistant element, and at present according to the literature, the photodamage resistant ion of comparative maturity has Mg 2+, Zn 2+, In 3+, Sc 3+, Hf 4+, Zr 4+Deng, and the threshold concentration of these photodamage resistant ions minimum be In 3+, only be 1.5mol%.Therefore select doping In 3+Improve the photodamage resistant performance of ytterbium thulium doped lithium columbate crystal.
The indium ytterbium thulium three-doping lithium niobate crystal silver dollar degree of present embodiment preparation is high, uniform component, indefectible, produce without striation and flawless, photo-damage resistance significantly improves when having guaranteed the original premium properties of lithium niobate crystals that the ytterbium thulium mixes.
The preparation method of present embodiment indium ytterbium thulium three-doping lithium niobate crystal is simple, convenient operation, and crystalline growth velocity is fast.
The indium ytterbium thulium three-doping lithium niobate crystal of present embodiment preparation can have a extensive future in preparation compact type, laser diode-pumped, all solid state tunable laser, and is also significant to panchromatic demonstration, high-density storage, infrared acquisition, preparation integrated optical device in addition.
Embodiment seven: what present embodiment and embodiment six were different is: the Nb described in the step 1 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; In described in the step 1 2O 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.Other is identical with embodiment six.
Embodiment eight: what present embodiment was different from embodiment six or seven is: the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 31% of total amount of substance.Other is identical with embodiment six or seven.
Embodiment nine: what present embodiment was different from one of embodiment six to eight is: the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 32% of total amount of substance.Other is identical with one of embodiment six to eight.
Embodiment ten: what present embodiment was different from one of embodiment six to nine is: the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 34% of total amount of substance.Other is identical with one of embodiment six to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of indium ytterbium thulium three-doping lithium niobate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Five kinds of raw materials, gross weight are 200g, then five kinds of raw materials are fully mixed, and obtain compound, wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1, described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 31% of total amount of substance, described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance, described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 1mm/h, axial-temperature gradient is 40 ℃/cm, speed of rotation is 15r/min, the crystal diameter 30mm that obtains growing, striation, the flawless high quality crystal of height 20mm;
Three, polarization: it is that 1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
Nb described in this testing sequence one 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; In described in the step 1 2O 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.
This testing sequence two described crystal pulling method specific operation process are as follows: (1) prepares seed crystal: adopt concentration to prepare first seed crystal; (2) shove charge: whether all parts of monitoring device are normal,, simultaneously the position of crucible, after-heater, seed crystal and ruhmkorff coil adjusted with the formation temperature gradient by stay-warm case, guarantee that the concentricity between them meets the requirements; (3) melt: the opening device power supply, adjustment programme rising intermediate frequency output rating, temperature is raised to 1240 ℃, has reached the fusing point of Lithium niobium trioxide, and after raw material melted fully, constant temperature 2 hours guaranteed that melt fully mixes; (4) seeding: first in the situation that 50 ℃ of melt overheats " rinsing seed crystal " stretch into seed crystal fast in the melt, and mention rapidly, eliminate the machining damage of seed crystal lower end and possible pollutent before the lower seed crystal; (5) shouldering: begin to enter the shouldering stage after the seeding success, adopt oblique shouldering mode; (6) isodiametric growth: the degree of isodiametric growth directly determines the stability of growth conditions, when receiving the shoulder end, adjusts furnace temperature crystal diameter is being remained unchanged; (7) pull: after the crystal growth is complete, adopt the method that pulls that heats up gradually that it is pulled from liquid level; (8) cooling annealing: crystal is at the distance melt liquid level approximately during 5 millimeters position, adopts the automatically mode of the control cooling annealing of lowering the temperature of Continental Europe table.
Test two: a kind of preparation method of indium ytterbium thulium three-doping lithium niobate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Five kinds of raw materials, gross weight are 200g, then five kinds of raw materials are fully mixed, and obtain compound, wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1, described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 32% of total amount of substance, described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance, described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 1mm/h, axial-temperature gradient is 40 ℃/cm, speed of rotation is 15r/min, the crystal diameter 30mm that obtains growing, striation, the flawless high quality crystal of height 20mm;
Three, polarization: it is that 1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
Nb described in this testing sequence one 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; In described in the step 1 2O 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.
This testing sequence two described crystal pulling method specific operation process are as follows: (1) prepares seed crystal: adopt concentration to prepare first seed crystal; (2) shove charge: whether all parts of monitoring device are normal,, simultaneously the position of crucible, after-heater, seed crystal and ruhmkorff coil adjusted with the formation temperature gradient by stay-warm case, guarantee that the concentricity between them meets the requirements; (3) melt: the opening device power supply, adjustment programme rising intermediate frequency output rating, temperature is raised to 1240 ℃, has reached the fusing point of Lithium niobium trioxide, and after raw material melted fully, constant temperature 2 hours guaranteed that melt fully mixes; (4) seeding: first in the situation that 50 ℃ of melt overheats " rinsing seed crystal " stretch into seed crystal fast in the melt, and mention rapidly, eliminate the machining damage of seed crystal lower end and possible pollutent before the lower seed crystal; (5) shouldering: begin to enter the shouldering stage after the seeding success, adopt oblique shouldering mode; (6) isodiametric growth: the degree of isodiametric growth directly determines the stability of growth conditions, when receiving the shoulder end, adjusts furnace temperature crystal diameter is being remained unchanged; (7) pull: after the crystal growth is complete, adopt the method that pulls that heats up gradually that it is pulled from liquid level; (8) cooling annealing: crystal is at the distance melt liquid level approximately during 5 millimeters position, adopts the automatically mode of the control cooling annealing of lowering the temperature of Continental Europe table.
Test three: a kind of preparation method of indium ytterbium thulium three-doping lithium niobate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Five kinds of raw materials, gross weight are 200g, then five kinds of raw materials are fully mixed, and obtain compound, wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1, described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 34% of total amount of substance, described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance, described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 1mm/h, axial-temperature gradient is 40 ℃/cm, speed of rotation is 15r/min, the crystal diameter 30mm that obtains growing, striation, the flawless high quality crystal of height 20mm;
Three, polarization: it is that 1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
Nb described in this testing sequence one 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; In described in the step 1 2O 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.
This testing sequence two described crystal pulling method specific operation process are as follows: (1) prepares seed crystal: adopt concentration to prepare first seed crystal; (2) shove charge: whether all parts of monitoring device are normal,, simultaneously the position of crucible, after-heater, seed crystal and ruhmkorff coil adjusted with the formation temperature gradient by stay-warm case, guarantee that the concentricity between them meets the requirements; (3) melt: the opening device power supply, adjustment programme rising intermediate frequency output rating, temperature is raised to 1240 ℃, has reached the fusing point of Lithium niobium trioxide, and after raw material melted fully, constant temperature 2 hours guaranteed that melt fully mixes; (4) seeding: first in the situation that 50 ℃ of melt overheats " rinsing seed crystal " stretch into seed crystal fast in the melt, and mention rapidly, eliminate the machining damage of seed crystal lower end and possible pollutent before the lower seed crystal; (5) shouldering: begin to enter the shouldering stage after the seeding success, adopt oblique shouldering mode; (6) isodiametric growth: the degree of isodiametric growth directly determines the stability of growth conditions, when receiving the shoulder end, adjusts furnace temperature crystal diameter is being remained unchanged; (7) pull: after the crystal growth is complete, adopt the method that pulls that heats up gradually that it is pulled from liquid level; (8) cooling annealing: crystal is at the distance melt liquid level approximately during 5 millimeters position, adopts the automatically mode of the control cooling annealing of lowering the temperature of Continental Europe table.
Simultaneous test: a kind of preparation method of ytterbium thulium doped lithium columbate crystal, carry out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, Yb 2O 3And Tm 2O 3Four kinds of raw materials, gross weight are 200g, then four kinds of raw materials are fully mixed, and obtain compound, wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1, described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance, described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 1mm/h, axial-temperature gradient is 40 ℃/cm, speed of rotation is 15r/min, the crystal diameter 30mm that obtains growing, striation, the flawless high quality crystal of height 20mm;
Three, polarization: it is that 1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30min that polarizes, namely obtain ytterbium thulium doped lithium columbate crystal.
Nb described in this testing sequence one 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.
This testing sequence two described crystal pulling method specific operation process are as follows: (1) prepares seed crystal: adopt concentration to prepare first seed crystal; (2) shove charge: whether all parts of monitoring device are normal,, simultaneously the position of crucible, after-heater, seed crystal and ruhmkorff coil adjusted with the formation temperature gradient by stay-warm case, guarantee that the concentricity between them meets the requirements; (3) melt: the opening device power supply, adjustment programme rising intermediate frequency output rating, temperature is raised to 1240 ℃, has reached the fusing point of Lithium niobium trioxide, and after raw material melted fully, constant temperature 2 hours guaranteed that melt fully mixes; (4) seeding: first in the situation that 50 ℃ of melt overheats " rinsing seed crystal " stretch into seed crystal fast in the melt, and mention rapidly, eliminate the machining damage of seed crystal lower end and possible pollutent before the lower seed crystal; (5) shouldering: begin to enter the shouldering stage after the seeding success, adopt oblique shouldering mode; (6) isodiametric growth: the degree of isodiametric growth directly determines the stability of growth conditions, when receiving the shoulder end, adjusts furnace temperature crystal diameter is being remained unchanged; (7) pull: after the crystal growth is complete, adopt the method that pulls that heats up gradually that it is pulled from liquid level; (8) cooling annealing: crystal is at the distance melt liquid level approximately during 5 millimeters position, adopts the automatically mode of the control cooling annealing of lowering the temperature of Continental Europe table.
To test respectively the indium ytterbium thulium three-doping lithium niobate crystal of a preparation, the indium ytterbium thulium three-doping lithium niobate crystal of test two preparations, the indium ytterbium thulium three-doping lithium niobate crystals of test three preparations and simultaneous test not the ytterbium thulium doped lithium columbate crystal of doped indium accurately directed (Z * X * Y) is cut into used crystal chip according to 10mm * 10mm * 2.5mm, and the optical quality level is carried out on its surface polish, obtain testing one indium ytterbium thulium three-doping lithium niobate crystal standardized component, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test three and simultaneous test be the ytterbium thulium doped lithium columbate crystal standardized component of doped indium not.
Adopt TDL-J50A type laser crystal growth furnace to detect the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test three and simultaneous test be the ytterbium thulium doped lithium columbate crystal standardized component of doped indium not, the result as shown in Figure 1, Fig. 1 is the indium ytterbium thulium three-doping lithium niobate crystal infrared absorpting light spectra of different I n doping content, ☆ among Fig. 1 is the not infrared absorpting light spectra of the ytterbium thulium doped lithium columbate crystal standardized component of doped indium of simultaneous test, among Fig. 1 zero is the infrared absorpting light spectra of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one, among Fig. 1 ▲ be the infrared absorpting light spectra of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, among Fig. 1 ● for testing the infrared absorpting light spectra of three indium ytterbium thulium three-doping lithium niobate crystal standardized component, as seen from Figure 1, be 0 and during 1mol% in the In doping content, absorption peak is at 3482cm -1Near, be 2mol% and 4mol% and work as the In doping content, absorption peak is at 3507cm -1Near, illustrate that at this moment the In doping content has surpassed its threshold concentration.
Take 980nm continuous wave output laser apparatus as excitation light source, output rating is 100mW, for so that the test light emission intensity comparability is arranged, test process and device are consistent, flashlight is captured in 400nm～700nm scope, detect the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test three and simultaneous test be the ytterbium thulium doped lithium columbate crystal standardized component of doped indium not, result such as Fig. 2 of test, Fig. 3, Fig. 4 and shown in Figure 5, Fig. 2 is the not conversion fluorescence spectrogram of the ytterbium thulium doped lithium columbate wafer of doped indium of simultaneous test, Fig. 3 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test one, Fig. 4 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, Fig. 5 is the conversion fluorescence spectrogram of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test three, by Fig. 2, Fig. 3, Fig. 4 and Fig. 5 contrast are as can be known, indium ytterbium thulium three-doping lithium niobate crystal has obtained strong photo-damage resistance and good up-conversion luminescence performance, and this crystal has the application potential of very advantageous at optical waveguide laser and amplifier.
The indium ytterbium thulium three-doping lithium niobate crystal standardized component of the indium ytterbium thulium three-doping lithium niobate crystal standardized component of employing scattering of light threshold energy stream method testing experiment one, the indium ytterbium thulium three-doping lithium niobate crystal standardized component of test two, test three and simultaneous test be the photo-damage resistance of the ytterbium thulium doped lithium columbate crystal standardized component of doped indium not, and concrete outcome is as shown in table 1:
The light scattering exposure energy flow threshold value of table 1 indium ytterbium thulium three-doping lithium niobate crystal
Figure BDA00003397975300091
As can be seen from Table 1, the photic light scattering exposure energy flow threshold value of crystal is along with mixing In 3+The increase of concentration and improving, namely photo-damage resistance strengthens, and works as In 2O 3Doping when reaching 2.0mol%, the photo-damage resistance of crystal obviously strengthens.

Claims (10)

1. an indium ytterbium thulium three-doping lithium niobate crystal is characterized in that indium ytterbium thulium three-doping lithium niobate crystal is by Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Make; Wherein said LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1; Described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance; Described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance; Described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance.
2. a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 1 is characterized in that described Nb 2O 5Quality purity be 99.99%; Described LiCO 3Quality purity be 99.99%; Described In 2O 3Quality purity be 99.99%; Described Yb 2O 3Quality purity be 99.99%; Described Tm 2O 3Quality purity be 99.99%.
3. a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 1 is characterized in that described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 31% of total amount of substance.
4. a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 1 is characterized in that described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 32% of total amount of substance.
5. a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 1 is characterized in that described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 34% of total amount of substance.
6. the preparation method of a kind of indium ytterbium thulium three-doping lithium niobate crystal as claimed in claim 1 is characterized in that the preparation method of indium ytterbium thulium three-doping lithium niobate crystal carries out according to the following steps:
One, mixes: take by weighing Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 3Then five kinds of raw materials fully mix five kinds of raw materials, obtain compound, wherein, and described LiCO 3In Li and Nb 2O 5In the mol ratio of Nb be 0.946: 1; Described In 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5%～4% of total amount of substance; Described Yb 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance; Described Tm 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 30.5% of total amount of substance;
Two, adopt Czochralski grown crystal: the compound that step 1 obtains is put into the Pt crucible, adopt crystal pulling method to carry out the crystal growth, the control pull rate is 0.5mm/h～1.5mm/h, and axial-temperature gradient is 35 ℃/cm～45 ℃/cm, speed of rotation is 13r/min～18r/min, obtains crystal;
Three, polarization: it is that 1150 ℃～1200 ℃ and current density are 5mA/cm that the crystal that step 2 is obtained places temperature 2Condition under the 30 ± 3min that polarizes, namely obtain indium ytterbium thulium three-doping lithium niobate crystal.
7. the preparation method of a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 6 is characterized in that the Nb described in the step 1 2O 5Quality purity be 99.99%; LiCO described in the step 1 3Quality purity be 99.99%; In described in the step 1 2O 3Quality purity be 99.99%; Yb described in the step 1 2O 3Quality purity be 99.99%; Tm described in the step 1 2O 3Quality purity be 99.99%.
8. the preparation method of a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 6 is characterized in that the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 31% of total amount of substance.
9. the preparation method of a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 6 is characterized in that the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 32% of total amount of substance.
10. the preparation method of a kind of indium ytterbium thulium three-doping lithium niobate crystal according to claim 6 is characterized in that the In described in the step 1 2O 3Amount of substance account for Nb 2O 5, LiCO 3, In 2O 3, Yb 2O 3And Tm 2O 34% of total amount of substance.
CN2013102529320A 2013-06-24 2013-06-24 Indium, ytterbium and thulium triple-doped lithium niobate crystal and preparation method thereof Pending CN103320861A (en)

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