CN101956236A - Big-size doped lithium niobate crystal and preparation method thereof - Google Patents
Big-size doped lithium niobate crystal and preparation method thereof Download PDFInfo
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- CN101956236A CN101956236A CN 201010514569 CN201010514569A CN101956236A CN 101956236 A CN101956236 A CN 101956236A CN 201010514569 CN201010514569 CN 201010514569 CN 201010514569 A CN201010514569 A CN 201010514569A CN 101956236 A CN101956236 A CN 101956236A
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Abstract
The invention provides a big-size doped lithium niobate crystal and a preparation method thereof. The preparation method comprises the following steps of: fully and evenly mixing various raw materials and a dopant, keeping the constant temperature for two hours at 650-700 DEG C, heating to 1100-1200 DEG C and then holding the temperature for 3 hours so as to synthesize an LiNbO3 (lithium niobate) polycrystalline material; heating the synthesized LiNbO3 polycrystalline material to grow big-size doped lithium niobate crystals by a crystal pulling method according to the processes of seeding, shouldering, growing with a constant diameter, pulling and annealing; and polarizing the grown LiNbO3 crystals to obtain monodomain big-size doped LiNbO3 crystals.
Description
Technical field
What the present invention relates to is a kind of optical crystal, particularly a kind of large size doped lithium columbate crystal (LiNbO
3).The invention still further relates to a kind of preparation method of large size doped lithium columbate crystal.
Background technology
LiNbO
3Be a kind of integrate piezoelectricity, thermoelectricity, ferroelectric, electric light, acousto-optic, photoelastic, non-linear, light is sold off and the artificial lens of multiple effect such as laser activity, implementing can present various properties after different the doping, is the crystal that the photon performance is maximum, overall target is best that people found so far.The LN crystal has very wide market application prospect, it is used widely in the engineering field, and the device of making of it has surface acoustic wave device, high frequency high energy transverter, infrared eye, laser modulator, laser frequency multiplier, optical parametric oscillator, wireless high freguency bandpass filter, retarding line, image intensifer, photoswitch, optical memory and fiber waveguide device etc.
As everyone knows, the crystalline size is big more, and the electronic devices and components integrated level of preparation is also high more, so the lithium niobate crystals of growing large-size has very strong engineering using value.But simultaneously, because LiNbO
3Be at high temperature to prepare by molten-salt growth method, crystalline size is big more, and residual thermal stress is also big with regard to the phase strain, causes crystal cleavage easily.The not doped lithium columbate crystal size of report has reached 200mm at present.In practical application area, in order to satisfy demand to specific function, must be to LiNbO
3Carry out doping vario-property, as mix iron, manganese, copper, cerium plasma energy and improve its photorefractive property, mix zinc, magnesium, indium, scandium plasma energy and improve its anti-photic scattering property, mix rare earth element such as erbium, ytterbium, praseodymium etc. and can obtain laser crystals.Dopant ion can significantly improve some performance of crystalline on the one hand, but causes that so crystal produces very big structural aberration, also causes crystal cleavage, easily large size Li doped NbO simultaneously again in process of growth
3Preparation just become very difficult.
Summary of the invention
The object of the present invention is to provide a kind of crystal diameter big, do not have obvious macroscopic defects, optical homogeneity is the large size doped lithium columbate crystal preferably.The present invention also aims to provide a kind of preparation method of large size doped lithium columbate crystal.
The object of the present invention is achieved like this:
Large size doped lithium columbate crystal of the present invention is by Li
2CO
3With Nb
2O
5High-purity powder and doping agent prepare from fused salt by crystal pulling method.
Described Li
2CO
3With Nb
2O
5The high-purity powder raw material adopts same proportioning components, i.e. [Li
2CO
3]/[Nb
2O
5]=48.6/51.4.
Described doping agent add-on is respectively: photorefractive media Fe, Mn, Cu or Ce incorporation are 0.01-0.1wt.%; Anti-photic scattering medium MgO incorporation 1-6mol%, ZnO incorporation 1-7mol%, In
2O
3Incorporation 0.5-3mol% or Sc
2O
3Incorporation 0.5-3mol%; Er, Yb or Pr rare earth element incorporation 0.1-1wt.%.
The preparation method of large size doped lithium columbate crystal of the present invention is:
1, according to Li
2CO
3/ Nb
2O
5=48.6/51.4; The doping agent add-on is respectively: photorefractive media Fe, Mn, Cu or Ce incorporation are 0.01-0.1wt.%, anti-photic scattering medium MgO incorporation 1-6mol%, ZnO incorporation 1-7mol%, In
2O
3Incorporation 0.5-3mol% or Sc
2O
3Incorporation 0.5-3mol%, Er, Yb or Pr rare earth element incorporation 0.1-1wt.%; Thorough mixing is placed in the platinum crucible after evenly, at first 650-700 ℃ of following constant temperature 2 hours, makes CO
2From Li
2CO
3In slowly divide and take off;
2, next be warmed up to 1100-1200 ℃, constant temperature 3 hours makes Nb
2O
5With Li
2O fully carries out solid state reaction, synthesizes LiNbO
3Polycrystal;
3, utilize heating in medium frequency synthetic LiNbO
3Polycrystal utilizes crystal pulling method, by seeding, shouldering, isodiametric growth, pull and annealing process growing large-size doped lithium columbate crystal, thermograde 5-10 ℃/cm, pull rate 1-1.5mm/ hour, speed of rotation 2-4rpm/min;
4, the LiNbO to growing
3The processing that polarizes, 1200 ℃ of polarization temperature, polarizing current is 5mA/cm
2, 30 minutes conduction time, annealing obtains poling large size Li doped NbO then
3Crystal.
Because the growing large-size crystal, crystal mass is bigger, so the seed rod that adopts among the present invention good platinum rhodium bar that is hot strength; The seed crystal that adopts is also bigger, is of a size of 5mm * 5mm * 15mm.Want the growing large-size crystal, must reduce thermograde, the present invention adopts heating in medium frequency stove growing crystal, has adopted the mullite of the good heat insulating brick of preserving moisture to process stay-warm case, makes thermograde reach 5-10 ℃/cm, has reached the requirement of growing large-size crystalline.In addition, the pull rate that adopts in the process of the present invention is 1-1.5mm/ hour, and speed of rotation is 2-4rpm/min.For the crystal that prevents to grow ftractures owing to static, on seed rod, connected the lead of ground connection, to eliminate the static that produces.In order to reduce the thermal stresses that produces in the crystal growing process, adopt the method that slowly is annealed to room temperature, annealing speed is 20-40 ℃/hour.
Description of drawings
Fig. 1 mixes zinc niobate crystalline lithium photo for three inches;
Five inches doped iron lithium niobate crystal photos of Fig. 2.
Embodiment
The preparation method of large size doped lithium columbate crystal of the present invention specifically comprises the steps:
1, various raw materials of weighing and doping agent on electronic balance, and thorough mixing is even, the raw material that mixes is placed in the platinum crucible, and at first 650-700 ℃ of following constant temperature 2 hours, purpose was the thorough roasting raw material, makes CO
2From Li
2CO
3In slowly divide and take off, avoid CO in process of growth
2The quick volatilization of gas is taken away component and has been destroyed crystal growth condition.
2, next be warmed up to 1100-1200 ℃, constant temperature 3 hours, purpose is to make Nb
2O
5With Li
2O fully carries out solid state reaction, synthesizes LiNbO
3Polycrystal, the sintered material that at this moment obtains just can be used as the raw material of growing crystal.
3, utilize heating in medium frequency synthetic LiNbO
3Polycrystal utilizes crystal pulling method, by seeding, shouldering, isodiametric growth, pull and annealing process growing large-size doped lithium columbate crystal, and thermograde 5-10 ℃/cm, pull rate 1～1.5mm/ hour, speed of rotation 2～4rpm/min.
4, the LiNbO to growing
3The processing that polarizes, 1200 ℃ of polarization temperature, polarizing current is 5mA/cm
2, 30 minutes conduction time, annealing obtains poling large size Li doped NbO then
3Crystal.
Below enumerate two specific exampless:
1, by [Li
2CO
3]/[Nb
2O
5]=48.6/51.4 ratio takes by weighing raw material, takes by weighing the ZnO of 7mol% again by the Zn incorporation, and the platinum crucible of packing into behind the thorough mixing 700 ℃ of following roastings 2 hours, is warmed up to 1100 ℃, is incubated 3 hours.Then carry out heating in medium frequency, make material melting, by seeding, shouldering, isodiametric growth, pull and annealing process growing large-size doped lithium columbate crystal 6 ℃/cm of thermograde, pull rate 2mm/ hour, speed of rotation 4rpm/min.Obtain 1 inch and mix the zinc niobate crystalline lithium as shown in Figure 2.
2, by [Li
2CO
3]/[Nb
2O
5]=48.6/51.4 ratio takes by weighing raw material, takes by weighing the Fe of 0.03wt.% again by the Fe incorporation
2O
3, the platinum crucible of packing into behind the thorough mixing 650 ℃ of following roastings 2 hours, is warmed up to 1100 ℃, is incubated 3 hours.Then carry out heating in medium frequency, make material melting, by seeding, shouldering, isodiametric growth, pull and annealing process growing large-size doped lithium columbate crystal 5 ℃/cm of thermograde, pull rate 1mm/ hour, speed of rotation 3rpm/min.Obtain 5 inches doped iron lithium niobate crystals as shown in Figure 2.
Claims (4)
1. a large size doped lithium columbate crystal is characterized in that by Li
2CO
3With Nb
2O
5High-purity powder and doping agent prepare from fused salt by crystal pulling method.
2. large size doped lithium columbate crystal according to claim 1 is characterized in that: described Li
2CO
3With Nb
2O
5The high-purity powder raw material adopts same proportioning components, i.e. [Li
2CO
3]/[Nb
2O
5]=48.6/51.4.
3. large size doped lithium columbate crystal according to claim 1 and 2 is characterized in that: described doping agent add-on is respectively: photorefractive media Fe, Mn, Cu or Ce incorporation are 0.01-0.1wt.%; Anti-photic scattering medium MgO incorporation 1-6mol%, ZnO incorporation 1-7mol%, In
2O
3Incorporation 0.5-3mol% or Sc
2O
3Incorporation 0.5-3mol%; Er, Yb or Pr rare earth element incorporation 0.1-1wt.%.
4. the preparation method of a large size doped lithium columbate crystal is characterized in that:
(1), according to Li
2CO
3/ Nb
2O
5=48.6/51.4; The doping agent add-on is respectively: photorefractive media Fe, Mn, Cu or Ce incorporation are 0.01-0.1wt.%, anti-photic scattering medium MgO incorporation 1-6mol%, ZnO incorporation 1-7mol%, In
2O
3Incorporation 0.5-3mol% or Sc
2O
3Incorporation 0.5-3mol%, Er, Yb or Pr rare earth element incorporation 0.1-1wt.%; Thorough mixing is placed in the platinum crucible after evenly, at first 650-700 ℃ of following constant temperature 2 hours, makes CO
2From Li
2CO
3In slowly divide and take off;
(2), next be warmed up to 1100-1200 ℃, constant temperature 3 hours makes Nb
2O
5With Li
2O fully carries out solid state reaction, synthesizes LiNbO
3Polycrystal;
(3), utilize heating in medium frequency synthetic LiNbO
3Polycrystal utilizes crystal pulling method, by seeding, shouldering, isodiametric growth, pull and annealing process growing large-size doped lithium columbate crystal, thermograde 5-10 ℃/cm, pull rate 1-1.5mm/ hour, speed of rotation 2-4rpm/min;
(4), the LiNbO to growing
3The processing that polarizes, 1200 ℃ of polarization temperature, polarizing current is 5mA/cm
2, 30 minutes conduction time, annealing obtains poling large size Li doped NbO then
3Crystal.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732965A (en) * | 2012-07-04 | 2012-10-17 | 杭州士兰明芯科技有限公司 | Lithium niobate substrate and manufacturing method thereof |
| CN102797038A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院上海光学精密机械研究所 | Mg-Yb-Er doped lithium niobate laser crystals and preparation method thereof |
| CN106012019A (en) * | 2016-06-12 | 2016-10-12 | 哈尔滨理工大学 | Hafnium and dysprosium double-doped lithium niobate crystal and preparation method thereof |
| CN107108263A (en) * | 2014-11-03 | 2017-08-29 | 谢珀德颜色公司 | Based on LiSbO3And LiNbO3The pigment of dependency structure |
| CN107925399A (en) * | 2016-07-11 | 2018-04-17 | 株式会社山寿瑟拉密克斯 | Acoustic surface wave element substrate and its manufacture method |
| CN109763171A (en) * | 2019-03-27 | 2019-05-17 | 焦作科尔光电科技有限公司 | One kind mixing praseodymium lithium columbate crystal and preparation method thereof |
| JP2019202915A (en) * | 2018-05-24 | 2019-11-28 | 住友金属鉱山株式会社 | Heat treatment method for oxide single crystal |
| JP2020147459A (en) * | 2019-03-12 | 2020-09-17 | 住友金属鉱山株式会社 | Method for growing lithium niobate single crystal |
| CN113529170A (en) * | 2021-07-07 | 2021-10-22 | 济南大学 | Method for growing oversized lithium niobate single crystal |
| CN113862774A (en) * | 2021-09-29 | 2021-12-31 | 福州大学 | Praseodymium lithium niobate scandate magneto-optical crystal and preparation method thereof |
| WO2022047822A1 (en) * | 2020-09-03 | 2022-03-10 | 天通控股股份有限公司 | Method for preparing large-size lithium tantalate crystals |
| CN117604640A (en) * | 2023-11-23 | 2024-02-27 | 哈尔滨理工大学 | Scandium cerium iron doped lithium niobate crystal and preparation method and application thereof |
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|---|---|---|---|---|
| CN1052516A (en) * | 1991-01-03 | 1991-06-26 | 天津大学 | The preparation of lithium niobate monocrystal by erbium and magnesium doping |
| CN1362545A (en) * | 2001-12-17 | 2002-08-07 | 南开大学 | Lithium niobate crysal with near stoichiometric ratio and its growth process |
-
2010
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Patent Citations (2)
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|---|---|---|---|---|
| CN1052516A (en) * | 1991-01-03 | 1991-06-26 | 天津大学 | The preparation of lithium niobate monocrystal by erbium and magnesium doping |
| CN1362545A (en) * | 2001-12-17 | 2002-08-07 | 南开大学 | Lithium niobate crysal with near stoichiometric ratio and its growth process |
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| 《Materials Chemistry and Physics》 20041231 Tao Zhang等 Optical homogeneity and second harmonic generation in Li-rich Mg-doped LiNbO3 crystals 第97-101页 第88卷, 2 * |
Cited By (17)
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|---|---|---|---|---|
| CN102732965B (en) * | 2012-07-04 | 2015-07-15 | 杭州士兰明芯科技有限公司 | Lithium niobate substrate and manufacturing method thereof |
| CN102732965A (en) * | 2012-07-04 | 2012-10-17 | 杭州士兰明芯科技有限公司 | Lithium niobate substrate and manufacturing method thereof |
| CN102797038A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院上海光学精密机械研究所 | Mg-Yb-Er doped lithium niobate laser crystals and preparation method thereof |
| CN107108263B (en) * | 2014-11-03 | 2019-09-17 | 谢珀德颜色公司 | Based on LiSbO3And LiNbO3The pigment of dependency structure |
| CN107108263A (en) * | 2014-11-03 | 2017-08-29 | 谢珀德颜色公司 | Based on LiSbO3And LiNbO3The pigment of dependency structure |
| CN106012019A (en) * | 2016-06-12 | 2016-10-12 | 哈尔滨理工大学 | Hafnium and dysprosium double-doped lithium niobate crystal and preparation method thereof |
| CN107925399A (en) * | 2016-07-11 | 2018-04-17 | 株式会社山寿瑟拉密克斯 | Acoustic surface wave element substrate and its manufacture method |
| JP2019202915A (en) * | 2018-05-24 | 2019-11-28 | 住友金属鉱山株式会社 | Heat treatment method for oxide single crystal |
| JP7095403B2 (en) | 2018-05-24 | 2022-07-05 | 住友金属鉱山株式会社 | Heat treatment method for oxide single crystal |
| JP2020147459A (en) * | 2019-03-12 | 2020-09-17 | 住友金属鉱山株式会社 | Method for growing lithium niobate single crystal |
| JP7275674B2 (en) | 2019-03-12 | 2023-05-18 | 住友金属鉱山株式会社 | Method for growing lithium niobate single crystal |
| CN109763171A (en) * | 2019-03-27 | 2019-05-17 | 焦作科尔光电科技有限公司 | One kind mixing praseodymium lithium columbate crystal and preparation method thereof |
| WO2022047822A1 (en) * | 2020-09-03 | 2022-03-10 | 天通控股股份有限公司 | Method for preparing large-size lithium tantalate crystals |
| CN113529170A (en) * | 2021-07-07 | 2021-10-22 | 济南大学 | Method for growing oversized lithium niobate single crystal |
| CN113862774A (en) * | 2021-09-29 | 2021-12-31 | 福州大学 | Praseodymium lithium niobate scandate magneto-optical crystal and preparation method thereof |
| CN113862774B (en) * | 2021-09-29 | 2023-10-27 | 福州大学 | Praseodymium lithium niobate scandium acid magneto-optical crystal and preparation method thereof |
| CN117604640A (en) * | 2023-11-23 | 2024-02-27 | 哈尔滨理工大学 | Scandium cerium iron doped lithium niobate crystal and preparation method and application thereof |
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Application publication date: 20110126 |