CN102162133A - Zirconium, erbium and ytterbium-doped lithium niobate crystal and preparation method thereof - Google Patents
Zirconium, erbium and ytterbium-doped lithium niobate crystal and preparation method thereof Download PDFInfo
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- CN102162133A CN102162133A CN 201110074197 CN201110074197A CN102162133A CN 102162133 A CN102162133 A CN 102162133A CN 201110074197 CN201110074197 CN 201110074197 CN 201110074197 A CN201110074197 A CN 201110074197A CN 102162133 A CN102162133 A CN 102162133A
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Abstract
The invention discloses zirconium, erbium and ytterbium-doped lithium niobate crystal and a preparation method thereof, and relates to three-doped LiNbO3 crystal and a preparation method thereof. The problems of low luminous intensity and short lifetime of the conventional erbium-doped lithium niobate crystal are solved. The zirconium, erbium and ytterbium-doped lithium niobate crystal is prepared from five raw materials, namely zirconium oxide, erbium oxide, ytterbium oxide, niobium pentaoxide and lithium carbonate. The method comprises the following steps of: weighing the raw materials, melting the raw materials to obtain a melt, performing crystal growth by adopting a pulling method, annealing, and performing polarization treatment. Compared with an un-doped sample, the emission intensity of the crystal under 1,550nm band light is improved by about 3 times. The 4I13/2 energy level life tau of Er<3+> ions of the crystal reaches 4.23ms, is prolonged by 8.18 percent compared with the erbium and ytterbium-doped lithium niobate crystal, and is prolonged by nearly two times compared with the life (2.3ms) of the single Er (1mol%)-doped LiNbO3 crystal. The crystal has good application prospect on the aspects of optical waveguide laser devices and amplifiers.
Description
Technical field
The present invention relates to a kind of three and mix LiNbO
3Crystal and preparation method thereof.
Background technology
Along with the Internet access, the surge requirement of telecommunication and broadband service, the researchist is devoted to study the light wave emission, though the institute of light wave emission inherent performance own is better than electronic technology, can not satisfy the demand that system increases fast at once.In order to satisfy this requirement, the research of more and more tight miniaturization optical elements necessitates.The success of existing technology develop a peacekeeping two-dimension optical structure, yet the three-dimensional optical structure still be not developed, this is still to be difficult under the current technology obtain because three-dimensional waveguide is recorded in.Therefore, the development of pluralistic function integrated circuit block will effectively obtain great progress aspect integrated improving and improve.In fact, the development of the multiple function integration of whole integrated morphology can reduce commercial cost, increases its compactness, raises the efficiency.Therefore, people extensively begin to pay close attention to the gain of light, the research and development of type materials such as photoconduction and photoswitch.Along this line, simultaneously applied integrated one of the research topic that present people are most interested in that becomes of multiple character.Multi-functional lithium niobate crystals (LiNbO
3) be expected to its piezoelectricity, ferroelectric, photoelectricity, character such as acoustic-electric and second-order optical nonlinearity combine, so lithium niobate crystals becomes integrated optics one of material of researching value is arranged most.In fact, because these character, being applied to of lithium niobate crystals success (as photomodulator, acousto-optic modulator, pul restrain this element etc.) in the integrating device, and lithium niobate crystals has also become the substrate of light emission and light amplification.LiNbO
3Crystalline character has more outstanding application prospect compared to traditional laser crystals, the LiNbO of doping with rare-earth ions
3Crystal makes to have integrated laser device and Q-switch, and locked mode etc. develop into possibility at following coml.And trivalent Er
3+The induced transition of ionic internal layer 4f electronics from the metastable level to the ground state level can provide the light amplification of optical communication window wavelength 1.54 μ m.Because this special level structure of erbium makes it become the optimal selection of optical communication with the amplifier gain medium.But only the adulterated lithium niobate crystals of erbium is still needing raising aspect luminous intensity and life-span.
Summary of the invention
The objective of the invention is to the invention provides a kind of zirconium erbium ytterbium three-doped lithium niobate crystal and preparation method thereof in order to solve the existing adulterated lithium niobate crystals of erbium in bad problem aspect luminous intensity and life-span.
Zirconium erbium ytterbium three-doped lithium niobate crystal of the present invention is by zirconium white (ZrO
2), Erbium trioxide (Er
2O
3), ytterbium oxide (Yb
2O
3), Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard make, wherein, the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities.Wherein the quality purity of zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard is 99.99%.
The preparation method of zirconium erbium ytterbium three-doped lithium niobate crystal of the present invention realizes by following steps: one, take by weighing zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard, then five kinds of raw materials are mixed compound, wherein the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities; Two, the compound of step 1 is put into platinum crucible, be warming up to 750 ℃～800 ℃, be incubated 2h～4h then, be warming up to 1100 ℃～1200 ℃ again, and be incubated 2～5h, get polycrystal powder; Three, the platinum crucible of the polycrystal raw material that doped lithium columbate is housed of step 2 is put into monocrystal growing furnace, is warming up to 1200～1300 ℃, be incubated 30～60min then, liquation; Four, adopt crystal pulling method to carry out crystal growth and get crystal, wherein controlling axial-temperature gradient is 40～50 ℃/cm, and isodiametric growth stage control pull rate is 0.3～1.8mm/h, speed of rotation 15～25rpm, and cooling rate is 0.5～1.5 ℃/h; Five, step 4 being obtained crystal is that 1150～1200 ℃, current density are 4～6mA/cm in temperature
2Condition under polarize, the polarization time is 20～40min, zirconium erbium ytterbium three-doped lithium niobate crystal, finish the preparation of zirconium erbium ytterbium three-doped lithium niobate crystal.
The quality purity of five kinds of raw materials is 99.99% in the step 1 of the present invention.
Be warming up to 750 ℃～800 ℃ in the step 2 of the present invention, the purpose that is incubated 2h～4h then is to make Li
2CO
3Fully decompose, and make CO
2All volatilizations.Be warming up to 1100～1200 ℃ again, and the purpose that is incubated 2～5h is with two kinds of compound L i in the raw material
2O and Nb
2O
5Solid building-up reactions: Li takes place
2O (s)+Nb
2O
5(s) → 2LiNbO
3(s), the final LiNbO that obtains
3Polycrystal powder.
The concrete operations of crystal pulling method are in the step 4 of the present invention:
(1) chooses seed crystal, hang then and get seed crystal, again seed crystal is dropped to apart from liquation liquid level 1～2mm place, with 15～25rpm (rev/min) rotation time constant temperature 10～30min, then seed crystal is dropped to about 0.5～2mm below the liquation liquid level and carry out necking down, contracting seed crystal thin gradually is 1～2mm to diameter, lowers the temperature 0.1～0.5 ℃ again; (2) tiltedly shouldering growth: in cooling rate is 0.5～1.5 ℃/h, and pull rate is under 0.1～1mm/h, carries out oblique shouldering growth; (3) receive shoulder: after crystal diameter reaches the requirement size, heat up 2～10 ℃, receive shoulder; (4) isodiametric growth: after receiving shoulder, adopt at the uniform velocity cooling realization isodiametric growth, the control pull rate is 0.3～1.8mm/h, speed of rotation 15～25rpm, and cooling rate is 0.5～1.5 ℃/h; (5) pull: stop to lift the back and heat up 0.1～2 ℃, be incubated 1～10min again after, crystal is lifted out the about 5～10mm of liquation liquid level, and then, reduces to room temperature with the speed annealing of 20～80 ℃/h.
The optic test result of zirconium erbium ytterbium three-doped lithium niobate crystal of the present invention shows that behind the doping Zr ion, crystal 1550nm band of light emissive porwer ratio not doped samples has improved about about 3 times.The Er of zirconium erbium ytterbium three-doped lithium niobate crystal of the present invention
3+Ionic
4I
13/2The life time of the level, τ reached 4.23ms, with Zr ionic erbium ytterbium two erbium-doped lithium niobate crystals that do not mix (τ=3.91ms) compares and has prolonged 8.18%, such result with singly mix Er (1mol%): LiNbO
3Crystalline life-span τ=2.3ms compares and has improved near about twice.The present invention has obtained the life-span of the 1550nm of the near infrared 1550nm luminous intensity of obvious raising and significant prolongation, and illustrating effectively mixes makes zirconium erbium ytterbium three-doped lithium niobate crystal have good application prospects aspect optical waveguide laser and the amplifier.
Preparation technology of the present invention is simple, zirconium is added in raw material with zirconic form, and in conjunction with the crystal pulling method processing parameter of concrete optimization of the present invention, obtain the zirconium erbium ytterbium three-doped lithium niobate crystal with good luminous intensity and life-span of the present invention.
In the step 4 of the present invention crystal pulling method utilize conventional means carry out seed crystal choose and hang get seed crystal after, by after seeding, the crystalline substance that contracts, tiltedly shouldering growth, receiving shoulder, isodiametric growth, pull and anneal, promptly finish successively.
The crystal that step 4 of the present invention grows is a lightpink, and diameter is approximately 30mm, and highly about 20mm is the high quality crystal of macroscopic defectss such as no wrap, no striped, flawless.
Integrated use of the present invention is at Er:LiNbO
3Photodamage resistant ion Zr simultaneously mixes in (the adulterated lithium niobate crystals of erbium)
4+With sensitized ions Yb
3+, adopt Czochralski grown crystal, realize Er:LiNbO
3The increase and the life-time dilatation of crystal 1.54 mu m luminous intensity.To Er:LiNbO
3Pushing effect has been played in the application of crystal in integrated optics.
Description of drawings
Fig. 1 is the emissive porwer test result figure of lithium niobate crystals on the 1400-1700nm emission spectrum, and wherein curve 1 is the zirconium erbium ytterbium three-doped lithium niobate crystal of embodiment 20, and curve 2 is erbium ytterbium two erbium-doped lithium niobate crystals of embodiment 21; Fig. 2 is Er in the zirconium erbium ytterbium three-doped lithium niobate crystal of embodiment 20
3+Ionic
4I
13/2Matched curve life time of the level figure; Fig. 3 is Er in erbium ytterbium two erbium-doped lithium niobate crystals of embodiment 21
3+Ionic
4I
13/2Matched curve life time of the level figure.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is a zirconium erbium ytterbium three-doped lithium niobate crystal, and zirconium erbium ytterbium three-doped lithium niobate crystal is by zirconium white (ZrO
2), Erbium trioxide (Er
2O
3), ytterbium oxide (Yb
2O
3), Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard make, wherein, the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities.
The zirconium erbium ytterbium three-doped lithium niobate crystal of present embodiment has good luminous intensity and life-span, and optic test is the result show, behind the doping Zr ion, crystal 1550nm band of light emissive porwer ratio not doped samples has improved about about 3 times.The Er of zirconium erbium ytterbium three-doped lithium niobate crystal of the present invention
3+Ionic
4I
13/2The life time of the level, τ reached 4.23ms, with Zr ionic erbium ytterbium two erbium-doped lithium niobate crystals that do not mix (τ=3.91ms) compares and has prolonged 8.18%, such result with singly mix Er (1mol%): LiNbO
3Crystalline life-span τ=2.3ms compares and has improved near about twice.The present invention has obtained the life-span of the 1550nm of the near infrared 1550nm luminous intensity of obvious raising and significant prolongation, and illustrating effectively mixes makes zirconium erbium ytterbium three-doped lithium niobate crystal have good application prospects aspect optical waveguide laser and the amplifier.
Present embodiment is at Er:LiNbO
3Photodamage resistant ion Zr simultaneously mixes in (the adulterated lithium niobate crystals of erbium)
4+With sensitized ions Yb
3+, adopt Czochralski grown crystal, realize Er:LiNbO
3The increase and the life-time dilatation of crystal 1.54 mu m luminous intensity.To Er:LiNbO
3Pushing effect has been played in the application of crystal in integrated optics.
Embodiment two: present embodiment and embodiment one are different is that the quality purity of zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard is 99.99%.Other parameter is identical with embodiment one.
Embodiment three: present embodiment is different with embodiment one or two be the zirconium white molar weight account for five kinds of raw material integral molar quantities 2%.Other parameter is identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one, two or three are different be the Erbium trioxide molar weight account for five kinds of raw material integral molar quantities 1%.Other parameter is identical with embodiment one, two or three.
Embodiment five: present embodiment is different with one of embodiment one to four be the ytterbium oxide molar weight account for five kinds of raw material integral molar quantities 1%.Other parameter is identical with one of embodiment one to four.
Embodiment six: present embodiment is the concrete preparation method who implements a described zirconium erbium ytterbium three-doped lithium niobate crystal, it is realized by following steps: one, take by weighing zirconium white, Erbium trioxide, ytterbium oxide, five kinds of raw materials of Niobium Pentxoxide and Quilonum Retard, then five kinds of raw materials are mixed compound, wherein the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities; Two, the compound of step 1 is put into platinum crucible, be warming up to 750 ℃～800 ℃, be incubated 2h～4h then, be warming up to 1100 ℃～1200 ℃ again, and be incubated 2～5h, get polycrystal powder; Three, the platinum crucible of the polycrystal raw material that doped lithium columbate is housed of step 2 is put into monocrystal growing furnace, is warming up to 1200～1300 ℃, be incubated 30～60min then, liquation; Four, adopt crystal pulling method to carry out crystal growth and get crystal, wherein controlling axial-temperature gradient is 40～50 ℃/cm, and isodiametric growth stage control pull rate is 0.3～1.8mm/h, speed of rotation 15～25rpm, and cooling rate is 0.5～1.5 ℃/h; Five, step 4 being obtained crystal is that 1150～1200 ℃, current density are 4～6mA/cm in temperature
2Condition under polarize, the polarization time is 20～40min, zirconium erbium ytterbium three-doped lithium niobate crystal, finish the preparation of zirconium erbium ytterbium three-doped lithium niobate crystal.
The preparation technology of present embodiment is simple, zirconium is added in raw material with zirconic form, and in conjunction with the crystal pulling method processing parameter of concrete optimization of the present invention, obtain the zirconium erbium ytterbium three-doped lithium niobate crystal with good luminous intensity and life-span of the present invention.
Embodiment seven: present embodiment and embodiment six are different is that the quality purity of five kinds of raw materials in the step 1 is 99.99%.Other step and parameter are identical with embodiment six.
Embodiment eight: present embodiment is different with embodiment six or seven be that the zirconium white molar weight accounts for five kinds of raw material integral molar quantities in the step 1 2%.Other parameter is identical with embodiment six or seven.
Embodiment nine: what present embodiment and embodiment six, seven or eight were different is that step 1 Erbium trioxide molar weight accounts for 1% of five kinds of raw material integral molar quantities.Other parameter is identical with embodiment six, seven or eight.
Embodiment ten: what present embodiment was different with one of embodiment six to nine is that step 1 ytterbium oxide molar weight accounts for 1% of five kinds of raw material integral molar quantities.Other parameter is identical with one of embodiment six to nine.
Embodiment 11: what present embodiment was different with one of embodiment six to ten is to be warming up to 750 ℃ in the step 2, is incubated 3h then.Other step and parameter are identical with one of embodiment six to ten.
Embodiment 12: what present embodiment was different with one of embodiment six to 11 is to be warming up to 1150 ℃ in the step 2 again, and insulation 4h.Other step and parameter are identical with one of embodiment six to 11.
Embodiment 13: what present embodiment was different with one of embodiment six to 12 is to be warming up to 1250 ℃ in the step 3, is incubated 50min then.Other step and parameter are identical with one of embodiment six to 12.
Embodiment 14: what present embodiment was different with one of embodiment six to 13 is that isometrical growth phase control pull rate is 0.5～1.5mm/h in the step 4, speed of rotation 18～23rpm, and cooling rate is 0.8～12 ℃/h.Other step and parameter are identical with one of embodiment six to 13.
Embodiment 15: what present embodiment was different with one of embodiment six to 13 is that isometrical growth phase control pull rate is 1.0mm/h in the step 4, speed of rotation 20rpm, and cooling rate is 1.0 ℃/h.Other step and parameter are identical with one of embodiment six to 13.
Embodiment 16: present embodiment is different with one of embodiment six to 15 is that the concrete operations of crystal pulling method in the step 4 are:
(1) chooses seed crystal, hang then and get seed crystal, again seed crystal is dropped to apart from liquation liquid level 1～2mm place, with 15～25rpm (rev/min) rotation time constant temperature 10～30min, then seed crystal is dropped to about 0.5～2mm below the liquation liquid level and carry out necking down, contracting seed crystal thin gradually is 1～2mm to diameter, lowers the temperature 0.1～0.5 ℃ again;
(2) tiltedly shouldering growth: in cooling rate is 0.5～1.5 ℃/h, and pull rate is under 0.1～1mm/h, carries out oblique shouldering growth;
(3) receive shoulder: after crystal diameter reaches the requirement size, heat up 2～10 ℃ and receive shoulder;
(4) isodiametric growth: after receiving shoulder, adopt at the uniform velocity cooling realization isodiametric growth, the control pull rate is 0.3～1.8mm/h, speed of rotation 15～25rpm, and cooling rate is 0.5～1.5 ℃/h;
(5) pull: stop to lift the back and heat up 0.1～2 ℃, be incubated 1～10min again after, crystal is lifted out the about 5～10mm of liquation liquid level, and then, reduces to room temperature with the speed annealing of 20～80 ℃/h.
Other step and parameter are identical with one of embodiment six to 15.
Choose seed crystal in the step of present embodiment (1) and hang and get seed crystal and all adopt those skilled in the art's routine operation to carry out.
Embodiment 17: present embodiment is different with one of embodiment six to 16 is that in the step 5 step 4 to be obtained crystal be that 1180 ℃, current density are 5mA/cm in temperature
2Condition under polarize.Other step and parameter are identical with one of embodiment six to 16.
Embodiment 18: present embodiment is different with one of embodiment six to 17 be in the step 5 polarization time be 30min.Other step and parameter are identical with one of embodiment six to 17.
Embodiment 19: present embodiment is different with one of embodiment six to 18 be in the step 3 control to be warming up to 1200～1300 ℃ of required times be 2～3h.Other step and parameter are identical with one of embodiment six to 18.
In the present embodiment, it is general in actual temperature-rise period that to be raised to 1200～1300 ℃ temperature in 2 to 3 hours just passable, in the stage that is warming up to 700～800 ℃, it is faster that temperature rise rate can be controlled, the back is warming up to 1200～1300 ℃ of can control slower, is beneficial to observe the variation of melt.Temperature rise rate is just passable so long as not the tolerance range that is rapidly heated suddenly above instrument.
Embodiment 20: present embodiment is a zirconium erbium ytterbium three-doped lithium niobate crystal, zirconium erbium ytterbium three-doped lithium niobate crystal is made by zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard, wherein, the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 2% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 1% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 1% of five kinds of raw material integral molar quantities.
The quality purity of five kinds of raw materials is 99.99% in the present embodiment.
The luminous intensity and the life-span of the zirconium erbium ytterbium three-doped lithium niobate crystal of present embodiment all increase.
The zirconium erbium ytterbium three-doped lithium niobate crystal of present embodiment is processed into 20mm * 10mm * 2mm, and (wafer of the size of Z * X * Y), and carry out high-precision optical grade polishing thinks that optic test is used.
Adopt Ti-sapphire lasers excites source, in excitation wavelength is 980nm, exciting power is 100mW, step-length maintains under the test condition of 0.25nm, the emissive porwer of zirconium erbium ytterbium three-doped lithium niobate crystal on the 1400-1700nm emission spectrum of test present embodiment, test result is shown in curve among Fig. 11 (long and short dash line).
Ti-sapphire laser apparatus with 980nm is an incident light source, and the zirconium erbium ytterbium three-doped lithium niobate crystal of test present embodiment is at the temporal resolution emission spectrum at 1.54 μ m places, Er
3+Ionic
4I
13/2The life time of the level fitting result as shown in Figure 2, as seen, τ=4.23ms.
Embodiment 21: present embodiment is the contrast experiment: erbium ytterbium two erbium-doped lithium niobate crystals, zirconium erbium ytterbium three-doped lithium niobate crystal is made by Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and four kinds of raw materials of Quilonum Retard, wherein, the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the Erbium trioxide molar weight accounts for 1% of four kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 1% of four kinds of raw material integral molar quantities.
The preparation method of erbium ytterbium two erbium-doped lithium niobate crystals of present embodiment and the difference of embodiment 22 are to take by weighing in the step 1 Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and four kinds of raw materials of Quilonum Retard, then four kinds of raw materials are mixed compound, wherein the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the Erbium trioxide molar weight accounts for 1% of four kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 1% of four kinds of raw material integral molar quantities
The erbium ytterbium three-doped lithium niobate crystal of present embodiment is processed into 20mm * 10mm * 2mm, and (wafer of the size of Z * X * Y), and carry out high-precision optical grade polishing thinks that optic test is used.Adopt and with the described identical testing method of embodiment 20 erbium ytterbium two erbium-doped lithium niobate crystals to be carried out emissive porwer respectively and in the test of the temporal resolution emission spectrum at 1.54 μ m places, test result is respectively as curve among Fig. 12 and shown in Figure 3.As shown in Figure 3, τ=3.91ms.
As seen from Figure 1, the emissive porwer of the zirconium erbium ytterbium three-doped lithium niobate crystal of embodiment 20 is stronger, at the 1550nm place the strongest luminous intensity is arranged, behind the doping Zr ion, zirconium erbium ytterbium three-doped lithium niobate crystal 1550nm band of light emissive porwer has improved about about 3 times than the erbium ytterbium two erbium-doped lithium niobate crystal samples of the Zr that do not mix.
Comparison diagram 2 and Fig. 3, zirconium erbium ytterbium three-doped lithium niobate crystal Er
3+Ionic
4I
13/2The life time of the level, τ reached 4.23ms, compare with the Zr ionic erbium ytterbium two erbium-doped lithium niobate crystal samples that do not mix to have prolonged 8.18%, such result with singly mix Er (1mol%): LiNbO
3Crystalline life-span τ=2.3ms compares and has improved near about twice.
Embodiment 22: present embodiment is the preparation method of embodiment 20 described zirconium erbium ytterbium three-doped lithium niobate crystals, it is realized by following steps: one, take by weighing zirconium white, Erbium trioxide, ytterbium oxide, five kinds of raw materials of Niobium Pentxoxide and Quilonum Retard, then five kinds of raw materials are mixed compound, wherein the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 2% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 1% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 1% of five kinds of raw material integral molar quantities; Two, the compound of step 1 is put into platinum crucible, be warming up to 750 ℃, be incubated 3h then, be warming up to 1150 ℃ again, and insulation 4h, polycrystal powder got; Three, the platinum crucible of the polycrystal raw material that doped lithium columbate is housed of step 2 is put into monocrystal growing furnace, is warming up to 1250 ℃, be incubated 50min then, liquation; Four, adopt crystal pulling method to carry out crystal growth and get crystal, wherein controlling axial-temperature gradient is 40 ℃/cm, and isodiametric growth stage control pull rate is 1.0mm/h, speed of rotation 20rpm, and cooling rate is 1.0 ℃/h; Five, step 4 being obtained crystal is that 1180 ℃, current density are 5mA/cm in temperature
2Condition under polarize, the polarization time is 30min, zirconium erbium ytterbium three-doped lithium niobate crystal, finish the preparation of zirconium erbium ytterbium three-doped lithium niobate crystal.
The quality purity of five kinds of raw materials is 99.99% in the present embodiment step 1.
The concrete processing parameter of the crystal pulling method described in the present embodiment step 4, except the isodiametric growth processing parameter of step (4) was different, other step and parameter were identical with embodiment 16,
Adopt the method for present embodiment can access zirconium erbium ytterbium three-doped lithium niobate crystal with good emissive porwer and life-span.
Claims (10)
1. zirconium erbium ytterbium three-doped lithium niobate crystal, it is characterized in that zirconium erbium ytterbium three-doped lithium niobate crystal made by zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard, wherein, the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities.
2. a kind of zirconium erbium ytterbium three-doped lithium niobate crystal according to claim 1 is characterized in that the quality purity of zirconium white, Erbium trioxide, ytterbium oxide, Niobium Pentxoxide and five kinds of raw materials of Quilonum Retard is 99.99%.
3. a kind of zirconium erbium ytterbium three-doped lithium niobate crystal according to claim 1 and 2 is characterized in that the zirconium white molar weight accounts for 2% of five kinds of raw material integral molar quantities.
4. a kind of zirconium erbium ytterbium three-doped lithium niobate crystal according to claim 1 and 2 is characterized in that the Erbium trioxide molar weight accounts for 1% of five kinds of raw material integral molar quantities.
5. a kind of zirconium erbium ytterbium three-doped lithium niobate crystal according to claim 1 and 2 is characterized in that the ytterbium oxide molar weight accounts for 1% of five kinds of raw material integral molar quantities.
6. the preparation method of zirconium erbium ytterbium three-doped lithium niobate crystal as claimed in claim 1, the preparation method who it is characterized in that zirconium erbium ytterbium three-doped lithium niobate crystal realizes by following steps: one, take by weighing zirconium white, Erbium trioxide, ytterbium oxide, five kinds of raw materials of Niobium Pentxoxide and Quilonum Retard, then five kinds of raw materials are mixed compound, wherein the mol ratio of Quilonum Retard and Niobium Pentxoxide is 0.946: 1, the zirconium white molar weight accounts for 1%～5% of five kinds of raw material integral molar quantities, the Erbium trioxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities, and the ytterbium oxide molar weight accounts for 0.5%～3% of five kinds of raw material integral molar quantities; Two, the compound of step 1 is put into platinum crucible, be warming up to 750 ℃～800 ℃, be incubated 2h～4h then, be warming up to 1100 ℃～1200 ℃ again, and be incubated 2～5h, get polycrystal powder; Three, the platinum crucible of the polycrystal raw material that doped lithium columbate is housed of step 2 is put into monocrystal growing furnace, is warming up to 1200～1300 ℃, be incubated 30～60min then, liquation; Four, adopt crystal pulling method to carry out crystal growth and get crystal, wherein controlling axial-temperature gradient is 40～50 ℃/cm, and isodiametric growth stage control pull rate is 0.3～1.8mm/h, speed of rotation 15～25rpm, and cooling rate is 0.5～1.5 ℃/h; Five, step 4 being obtained crystal is that 1150～1200 ℃, current density are 4～6mA/cm in temperature
2Condition under polarize, the polarization time is 20～40min, zirconium erbium ytterbium three-doped lithium niobate crystal, finish the preparation of zirconium erbium ytterbium three-doped lithium niobate crystal.
7. the preparation method of zirconium erbium ytterbium three-doped lithium niobate crystal according to claim 6 is characterized in that the quality purity of five kinds of raw materials in the step 1 is 99.99%.
8. according to the preparation method of claim 6 or 7 described zirconium erbium ytterbium three-doped lithium niobate crystals, it is characterized in that the zirconium white molar weight accounts for 2% of five kinds of raw material integral molar quantities in the step 1.
9. according to the preparation method of claim 6 or 7 described zirconium erbium ytterbium three-doped lithium niobate crystals, it is characterized in that the Erbium trioxide molar weight accounts for 1% of five kinds of raw material integral molar quantities in the step 1.
10. according to the preparation method of claim 6 or 7 described zirconium erbium ytterbium three-doped lithium niobate crystals, it is characterized in that the ytterbium oxide molar weight accounts for 1% of five kinds of raw material integral molar quantities in the step 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676167A (en) * | 2012-05-25 | 2012-09-19 | 哈尔滨理工大学 | Zirconium-ytterbium-holmium tri-doped lithium niobate crystal high-upconversion luminescent material and method for preparing same |
| CN105839178A (en) * | 2016-04-12 | 2016-08-10 | 盐城市振弘电子材料厂 | Preparation method of lithium niobate single crystal |
| CN109097044A (en) * | 2018-09-14 | 2018-12-28 | 广东工业大学 | A kind of small size erbium and ytterbium double doping lithium niobate fluorescent powder and its preparation method and application |
| CN112899781A (en) * | 2021-01-20 | 2021-06-04 | 南开大学 | Bismuth-zinc double-doped lithium niobate crystal and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024901A (en) * | 2007-01-15 | 2007-08-29 | 哈尔滨工业大学 | Zr:LiNbO3 crystal and its preparing method |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101024901A (en) * | 2007-01-15 | 2007-08-29 | 哈尔滨工业大学 | Zr:LiNbO3 crystal and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Luminescence》 20050603 Xihe Zhen等 Spectroscopic characterizations and optical damage resistance of Zn:Yb:Er:LiNbO3 crystals 288-292 第114卷, * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676167A (en) * | 2012-05-25 | 2012-09-19 | 哈尔滨理工大学 | Zirconium-ytterbium-holmium tri-doped lithium niobate crystal high-upconversion luminescent material and method for preparing same |
| CN105839178A (en) * | 2016-04-12 | 2016-08-10 | 盐城市振弘电子材料厂 | Preparation method of lithium niobate single crystal |
| CN105839178B (en) * | 2016-04-12 | 2019-01-04 | 盐城市振弘电子材料厂 | A kind of preparation method of lithium niobate monocrystal |
| CN109097044A (en) * | 2018-09-14 | 2018-12-28 | 广东工业大学 | A kind of small size erbium and ytterbium double doping lithium niobate fluorescent powder and its preparation method and application |
| CN112899781A (en) * | 2021-01-20 | 2021-06-04 | 南开大学 | Bismuth-zinc double-doped lithium niobate crystal and preparation method and application thereof |
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