CN1190530C - Process for preparing chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure - Google Patents
Process for preparing chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure Download PDFInfo
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- CN1190530C CN1190530C CNB021006237A CN02100623A CN1190530C CN 1190530 C CN1190530 C CN 1190530C CN B021006237 A CNB021006237 A CN B021006237A CN 02100623 A CN02100623 A CN 02100623A CN 1190530 C CN1190530 C CN 1190530C
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Abstract
The present invention relates to a technology for preparing chemical-specific magnesium doped lithium niobate crystals with periodic polarization micro structures, which belongs to the technical field of nonlinear optical crystal materials. Congruent lithium niobate crystals which are grown under usual conditions have the defects of low light and damage resistant performance, high crystal constituent fluctuation, poor uniformity, poor uniformity and the like, and do not meet requirements of integrated optics; particularly, an extremely high electric field is needed to be additionally added during the preparation of crystals with periodical polarization full optical micro structure, which brings many difficulties and limits the crystal usage. Therefore, the present invention provides the technology for preparing chemical-specific magnesium doped lithium niobate crystals with periodic polarization micro structure to solve the technical problems; the present invention has the technical scheme that powder lot of magnesium doped lithium niobate is used; a Czochralski crystal growth method is used for preparing lithium niobate crystals; then, a vapor phase balance diffusion transport technique is used for enhancing the uniformity of crystal components; the lithium niobate crystals are polarized at room temperatures and in low pressure so that the crystal has a periodic structure. The crystal can be widely used in frequency conversion techniques of frequency multiplication, difference frequency, sum frequency, optical parametric oscillation, etc.
Description
Technical field
The present invention is a kind of technology for preparing chemical-specific Mg-doped lithium niobate periodic polarizing microstructure wafer, belongs to the non-linear optical crystal material technical field.
Background technology
As everyone knows, in nonlinear optical technology field, lithium niobate crystals is the non-linear optic crystal of integrated performance index the best, and it is very general that lithium niobate crystals uses, and the full light microstructure of Lithium niobium trioxide crystal is the preferred material that realizes quasi-phase matching at present.Should say that integrated optics is to the requirement of lithium niobate substrate and not second to the requirement to silicon chip of unicircuit.It has big nonlinear factor, wide logical optical range, a series of characteristics such as preparation technology is simple, and is with low cost.Realize the nonlinear crystal of laser freuqency doubling or laser parameter process,, also must on this matching direction, have bigger nonlinear optical coefficients as far as possible except satisfying the phase-matching condition.But, do not meet the requirement of high-quality optics because the fast light damage performance that the intrinsic lithium niobate crystals that grows out under the usual conditions exists light to sell off to be caused is low, crystal composition fluctuates characteristics such as big and lack of homogeneity; It is high particularly to prepare the required extra electric field of full light microstructure, and this will bring many side effects: sample easily punctures, crystal thickness is little, periodic polarizing microstructure is inhomogeneous and imperfect etc.All these have all limited the practicability of lithium niobate crystals periodic polarizing microstructure.How can reduce the light of lithium niobate crystals and sell off its fast light damage performance of raising, can increase lithium niobate crystals periodic polarizing microstructure thickness again, become the focus of countries nowadays scientific worker research.
Recently, we studies confirm that, stoichiometric lithium niobate crystal ([Li]/[Nb] ≈ 1) is compared with congruent lithium niobate crystals ([Li]/[Nb]=48.5: 51.5), not only has bigger photoelectric coefficient, and can greatly reduce crystal polarization reversal electric field.Low polarized electric field not only helps increasing crystal polarization thickness, improves the efficiency of conversion of accurate phase matched light wave conversion, and is easy to produce the even perfection of polarization structure, the full optical device of the accurate phase matched of meticulous fine.
As mentioned above, stoichiometric lithium niobate crystal has excellent electro-optical properties and low polarized electric field, but its photo-damage resistance is lower.Recently, people such as Furukawa utilization is mixed the magnesium growth method and is grown the magnesium-doped near stoichiometric lithium niobate crystal, and it is studied, and studies show that the magnesium that only need mix 0.78mol% in stoichiometric lithium niobate crystal, and crystal does not have the light injury phenomenon and occurs.From their report, [Li]/[Nb] is more inhomogeneous than very in the crystal, and there is a large amount of striations, the crystalline ununiformity can directly influence the performance of device, the existence of a large amount of striations directly influences the intensity of material and the diffusion and the precipitation of impurity, and the existence of striation brings such or such problem and influence usually for the performance of material.
Therefore, this crystal (mix the magnesium growth method and grow the magnesium-doped near stoichiometric lithium niobate crystal) is desirable not enough.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of more satisfactory lithium niobate crystals-chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure, all more superior by the lithium niobate crystals of this prepared than above-mentioned intrinsic lithium niobate crystals, stoichiometric lithium niobate crystal and magnesium-doped near stoichiometric lithium niobate crystal performance.
Technical scheme of the present invention is: pack in the platinum crucible with the mg-doped lithium niobate powder, prepare lithium niobate crystals with the Czochralski crystal pulling method, obtain the chemical-specific Mg-doped lithium niobate crystal through vapour phase balance diffusion technique, obtain the chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure through high voltage polarization again.
Chemical-specific Mg-doped lithium niobate crystal of the present invention has even, the strong fast light damage strength of component height, big nonlinear factor and low coercive field, period polarized strength of electric field only is 1.2KV/mm, be 1/20 of the required polarized electric field of polarization intrinsic lithium niobate crystals, promptly polarized electric field has reduced most magnitudes; Strong fast light damage ability is promptly shone and is not almost had the light injury phenomenon for the～superpower Argon ion laser of 500nm with wavelength; Carry out the frequency doubled light test with this crystal fabrication cycle polarizing microstructure crystal, can obtain frequency-doubling conversion efficiency up to 40%; Make the integrated optics optical waveguides with this crystal, its waveguide mode and polarizability are very stable.
Embodiment
The implementation step that the present invention is concrete:
(1) takes by weighing the Li that metallic element is formed in metering
2CO
3, Nb
2O
5, and MgO, with the powder oven dry, thorough mixing 24 hours on mixer then 850 ℃ of constant temperature 2 hours, made abundant decomposition, becomes the mg-doped lithium niobate powder in 2 hours 1100 ℃ of calcinings 150 ℃ of following constant temperature 2 hours.(2) with this powder compacting, put into platinum crucible, heat with intermediate frequency furnace, the Czochralski crystal pulling method is along the c direction of principal axis, by drawing process growth magnesium-doped lithium niobate crystals such as neck, shouldering, isometrical, ending, pulling rate 1-3mm/ hour, rotating speed 15-30rpm, 1.5 ℃/mm of thermograde in 20 ℃ of the gas-liquid temperature differences, melt, melt top thermograde is 1 ℃/mm.(3) crystal after the growth through operations such as orientation, cutting, rubbing downs, can get magnesium-doped lithium niobate crystal in 1200 ℃ of polings, annealing.(4) with magnesium-doped lithium niobate crystal along Z to cutting into the wafer that thickness is 1-3mm, and then to the wafer rubbing down.(5) take by weighing the Li that metering is formed
2CO
3, and Nb
2O
5, with the powder oven dry, thorough mixing 24 hours on the powder machine after the powder compacting, was placed in the platinum crucible then, becomes rich lithium Lithium niobium trioxide source crucible in 2 hours 1050 ℃ of calcinings 150 ℃ of following constant temperature 2 hours.(6) wafer is hung vertically in source crucible top, with the platinum lid that crucible is airtight, to put into the intermediate frequency furnace heating and carry out the diffusion of vapour phase balance and transport, heating gradient is 10 ℃/min, 1100 ℃ of constant temperature 120～360 hours, naturally cools to room temperature then.(7) wafer after diffusion transports to the vapour phase balance carries out the processing of rubbing down optics, can get the chemical-specific Mg-doped lithium niobate crystal.(8) certain thickness Z being cut the chemical-specific Mg-doped lithium niobate wafer cleans, utilize sophisticated semiconductor technology wafer+carry out photoetching on the Z surface, etch fan-shaped metal A 1 grid electrode, on electrode, evenly smear one deck glue against corrosion then by designed mask plate structure.(9) at room temperature, with wafer+Z links to each other with liquid electrode respectively with-Z face, receives high-voltage pulse power source, the square electricimpulse that wafer is applied certain pulse height, width and number polarizes.(10) wafer after will polarizing is immersed in and removes glue against corrosion and metal A l mask in the organic solution, then wafer is cleaned, and at last logical light end face is carried out optics processing (can plate anti-reflection film), obtains the full light microstructure of chemical-specific Mg-doped lithium niobate crystal.
Embodiment
(1) takes by weighing metering and form [Li
2CO
3]/Nb
2O
5]=0.94 and 2mol%MgO, with the powder oven dry, thorough mixing 24 hours on mixer then 850 ℃ of constant temperature 2 hours, made abundant decomposition, becomes the mg-doped lithium niobate powder in 2 hours 1100 ℃ of calcinings 150 ℃ of following constant temperature 2 hours.(2) with this powder compacting, put into platinum crucible, heat with intermediate frequency furnace, the Czochralski crystal pulling method along the c direction of principal axis by drawing process growth magnesium-doped lithium niobate crystals such as neck, shouldering, isometrical, ending, pulling rate 3mm/ hour, rotating speed 27rpm, 20 ℃ of gas-liquid temperature differences, 1.5 ℃/mm of thermograde in the melt, melt top thermograde is 1 ℃/mn.(3) crystal after the growth through operations such as orientation, cutting, rubbing downs, can get the mg-doped lithium niobate wafer in 1200 ℃ of polings, annealing.(4) with magnesium-doped lithium niobate crystal along Z to cutting into the wafer that thickness is 2mm, and then to the wafer rubbing down.(5) take by weighing mol ratio [Li
2CO
3]/[Nb
2O
5]=68/32, with the powder oven dry, thorough mixing 24 hours on the powder machine after the powder compacting, was placed in the platinum crucible then, becomes rich lithium Lithium niobium trioxide source crucible in 2 hours 1050 ℃ of calcinings 150 ℃ of following constant temperature 2 hours.(6) wafer is hung vertically in source crucible top, with the platinum lid that crucible is airtight, to put into the intermediate frequency furnace heating and carry out the diffusion of vapour phase balance and transport, heating gradient is 10 ℃/min, 1100 ℃ of constant temperature 240 hours, naturally cools to room temperature then.(7) wafer after diffusion transports to the vapour phase balance carries out the processing of rubbing down optics, can get the thick chemical-specific Mg-doped lithium niobate crystal of 2mm that is.(8) to one thick for 2mm, long for 15mm, widely clean for the Z of 12mm cuts the chemical-specific Mg-doped lithium niobate wafer, utilize sophisticated semiconductor technology wafer+carry out photoetching on the Z surface, etching by the designed cycle is fan-shaped metal A 1 grid electrode of 5.2-6.8 μ m, evenly smears the thick glue against corrosion of 2nm that is then on electrode.(9) at room temperature, with wafer+Z links to each other with the NaCl liquid electrode respectively with-Z face, receives high-voltage pulse power source, it is that 3KV, pulsewidth are that 10 square electricimpulses of 30ms polarize that wafer is applied amplitude.(10) wafer after will polarizing is immersed in and removes glue against corrosion and metal A l mask in the acetone soln, then wafer is cleaned, at last logical light end face is carried out optics processing (can plate anti-reflection film), incidence surface and exiting surface angle are 1 ° and obtain the thick full light microstructure of the chemical-specific Mg-doped lithium niobate crystal of 2mm that is.
Claims (7)
1. the preparation technology of a chemical-specific Mg-doped lithium niobate periodic polarizing microstructure wafer, be to utilize Czochralski crystal pulling method, microtomy to prepare wafer, it is characterized in that: mix magnesium when adopting the Czochralski Czochralski grown crystal, the magnesium amount of mixing of growing crystal is 2mol%, carry out the diffusion of vapour phase balance afterwards and transport technology, use the high voltage polarization electric field to carry out periodic polarized at last wafer.
2. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: it is that (1) takes by weighing the Li that metering is formed that the diffusion of vapour phase balance transports technology
2CO
3And Nb
2O
5, with the powder oven dry, thorough mixing 24 hours on the powder machine after the powder compacting, was placed in the platinum crucible then, becomes rich lithium Lithium niobium trioxide source crucible in 2 hours 1050 ℃ of calcinings 150 ℃ of following constant temperature 2 hours; (2) wafer is hung vertically in source crucible top, with the platinum lid that crucible is airtight, to put into the intermediate frequency furnace heating and carry out the diffusion of vapour phase balance and transport, heating gradient is 10 ℃/min, 1100 ℃ of constant temperature 120～360 hours, naturally cools to room temperature then.
3. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: using and adding that polarized electric field polarizes is at room temperature, with wafer+Z links to each other with liquid electrode respectively with-Z face, receive high-voltage pulse power source, the square electricimpulse that wafer is applied 3KV pulse height, width 30ms and 10 numbers polarizes.
4. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: the pulsed voltage of the high voltage polarization electric field of use is 3KV.
5. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: use to add that polarized electric field polarizes be at room temperature to carry out.
6. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: the electrode that adds polarized electric field is liquid electrode NaCl.
7. according to the preparation technology of the said chemical-specific Mg-doped lithium niobate periodic polarizing microstructure of claim 1 wafer, it is characterized in that: carry out photoetching before the wafer polarization, etch fan-shaped metal A l grid electrode by designed mask plate structure, on electrode, evenly smear one deck glue against corrosion then, at last wafer is polarized, can obtain having the fan-shaped chemical-specific Mg-doped lithium niobate periodic polarizing microstructure wafer of gradual period.
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| CNB021006237A CN1190530C (en) | 2002-01-25 | 2002-01-25 | Process for preparing chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure |
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| CNB021006237A CN1190530C (en) | 2002-01-25 | 2002-01-25 | Process for preparing chemical-specific Mg-doped lithium niobate crystal with periodic polarizing microstructure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332078C (en) * | 2006-05-15 | 2007-08-15 | 山东大学 | Polarization method for lithium niobate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102044833A (en) * | 2010-11-24 | 2011-05-04 | 江苏省邮电规划设计院有限责任公司 | Method for setting broadband continuously-tunable lasers and implementation device thereof |
| CN102899722B (en) * | 2012-09-12 | 2015-09-09 | 江西匀晶光电技术有限公司 | Congruent lithium niobate crystal chip of a kind of doped with magnesia and preparation method thereof |
| CN106283194B (en) * | 2016-08-29 | 2018-07-17 | 南开大学 | A kind of preparation facilities and method of the domain structure of lithium columbate crystal nanometer |
| CN108166065A (en) * | 2017-12-12 | 2018-06-15 | 南京大学 | A kind of method for preparing lithium niobate single crystal thin film domain structure |
| CN108301044A (en) * | 2018-02-11 | 2018-07-20 | 陕西师范大学 | A kind of preparation method of nonlinear optical crystal |
| CN111575791A (en) * | 2020-05-13 | 2020-08-25 | 济南大学 | Self-pumping optical parametric oscillation substrate crystal and preparation method thereof |
| CN111893560A (en) * | 2020-07-21 | 2020-11-06 | 江西匀晶光电技术有限公司 | Method and device for growing magnesium-doped lithium niobate single crystal |
| CN112965269B (en) * | 2021-03-07 | 2022-09-20 | 天津大学 | Auto-collimation spatial lithium niobate electro-optic phase modulator and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332078C (en) * | 2006-05-15 | 2007-08-15 | 山东大学 | Polarization method for lithium niobate |
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