Doubly doped lithium niobate crystals

Abstract

This invention relates to the field of materials of the photorefractive crystal. The composition of these crystals is Li1−xNb1+yO3: Fem, Mn, where M can be magnesium, indium, or zinc; when using q to denote the ion valence of M (q=2 when M is Mg or Zn, and q=3 when M is In), the values of x, y, m, and n are in the range of 0.05≦x≦0.13, 0.00≦y≦0.01, 5.0×10−5≦m≦7.5×10−4, and 0.02≦qn≦0.13. This invention greatly improves the photorefractive properties of LiNbO3 crystals: makes it have a high diffraction efficiency (more than 68%), a fast response speed for photorefraction (an order of magnitude faster than iron doped LiNbO3), and a high resistance to optical scattering (the light intensity threshold to photorefractive fan scattering near two orders of magnitude larger than LiNbO3: Fe). This invention is an excellent three-dimensional optical storage material and has a vast potential market.

Description

TECHNICAL FIELD

[0001] The invention relates to the field of photorefractive crystal material.

BACKGROUND ART

[0002] Three-dimensional optical storage will enter the market, but it does not mean that the product has been done very well. The main problem is no excellent three-dimensional optical storage material found. In fact, scientists in the world have been looking for satisfied three-dimensional optical storage material for a long time. Up to now, the iron doped lithium niobate is still considered as the first candidate. But there are big shortcomings for LiNbO3:Fe, such as a too long response time and a low ability to resist optic scattering (A. Hellemans, Holograms can storage terabytes, but where? Science 286 (1999) 1502). Now, improving and optimizing the properties of LiNbO3:Fe crystal (restrain the laser induced voltage effect and maintain its good photorefraction properties in the mean time) is still the most important task at present.

DISCLOSURE OF THE INVENTION

[0003] The objection of this invention is to supply a doubly doped lithium niobate crystal, which is an improvement and optimization of LiNbO3:Fe, and has an excellent photorefractive properties, and can be used as the three-dimensional holographic optical storage material.

[0004] The doubly doped lithium niobate crystal of the invention is doped with iron and a second radius-matched metal ion in the meantime. Its composition can be denoted as Li1−xNb1+yO3:Fem,Mn, where M is magnesium, indium, or zinc; when using q to denote the ion valence of M (q=2 when M is Mg or Zn, and q=3 when M is In), the values of x, y, m, and n are in the range of 0.05≦x≦0.13, 0.00≦y≦0.01, 5.0×10−5≦m≦7.5×10−4, and 0.02≦qn≦0.13, respectively.

[0005] The composition of doubly doped lithium niobate crystals can:

[0006] doped with 0.007˜0.03 wt. % Fe and 1.0˜5.0 mol. % Mg,

[0007] doped with 0.01˜0.05 wt. % Fe and 0.75˜3.0 mol. % In, or

[0008] doped with 0.02˜0.06 wt. % Fe and 1.5˜6.5 mol. % Zn,

[0009] While the congruent composition is [Li]/[Nb]=0.87˜0.95.

[0010] The implement steps of the invention are:

[0011] (1) Weigh up Li2CO3, Nb2O3, Fe2O3, and MgO, ln2O3 or ZnO powders according to the crystal composition, and dry them at 120˜150° C. for 25 hours, then thoroughly mix them at a mixer lasting for 24 hours, and keep them at 800˜850° C. for 25 hours to make Li2CO3 decompose sufficiently, and then sinter at 1050˜1150° C. for 28 hours to obtain doubly doped lithium niobate powder. (2) Put the above doped lithium niobate powder into a Pt crucible after impacted then heat the powder by a middle frequency stove. Grow the doubly doped lithium niobate crystals using the Czochralski pulling method along c or a axis via the procedures of necking, shouldering, uniform-diametering, and tailing, with the pulling rate being 1˜3 mm/h, the rotation rate being 15˜30 rpm, the temperature difference of the melt-crystal interface being 20° C., the temperature gradient in the melt volume near the surface being 1.5° C./mm, and the temperature gradient above the melt surface being 1.0° C./mm, respectively. (3) Pole and anneal the grown doped lithium niobate crystals at 1200° C. to obtain a single-domain structure.

OPTIMUM REALIZATION OF THE INVENTION

[0012] The outstandingly essential characteristics and effects of the invention can be seen from the following embodiments, but they do no limit to the scope of this invention.

[0013] Embodiment 1:

[0014] (1) Weigh up 0.01 wt. % Fe2O3 and 3 mol. % MgO, and [Li2CO3]/[Nb2O5]=0.94. and dry them at 150° C. for 2 hours, then thoroughly mix them at a mixer lasting for 24 hours, and keep them at 850° C. for 2 hours to make Li2CO3 decompose sufficiently, and then sinter at 1100° C. for 2 hours to obtain doubly doped lithium niobate powder. (2) Put the above doped lithium niobate powder into a Pt crucible after impacted then heat the powder by a middle frequency stove. Grow the doubly doped lithium niobate crystals using the Czochralski pulling method along c axis via the procedures of necking, shouldering, uniform-diametering, and tailing, with the pulling rate being 3 mm/h, the rotation rate being 27 rpm, the temperature difference of the melt-crystal interface being 20° C., the temperature gradient in the melt volume near the surface being 1.5° C./mm, and the temperature gradient above the melt surface being 1.0° C./mm, respectively. (3) Pole and anneal the grown doped lithium niobate crystals at 1200° C. to get a single-domain structure. After being orientated, cut, grinded, and polished to optical grade, the maximum diffraction efficiency of this Fe and Mg doubly lithium niobate crystal is 70%, the light intensity threshold to optic scattering is larger than 20 mW, and the average write time for holographic storage is 5 s (I˜1 W/cm2).

[0015] Embodiment 2:

[0016] (1) Weigh up 0.015 wt. % Fe2O3 and 0.5 mol. % In2O3, and [Li2CO3]/[Nb2O5]=0.945. and dry them at 150° C. for 2 hours, then thoroughly mix them at a mixer lasting for 24 hours, and keep them at 850° C. for 2 hours to make Li2CO3 decompose sufficiently, and then sinter at 1100° C. for 2 hours to obtain doubly doped lithium niobate powder. (2) Put the above doped lithium niobate powder into a Pt crucible after impacted, then heat the powder by a middle frequency stove. Grow the doubly doped lithium niobate crystals using the Czochralski pulling method along c axis via the procedures of necking, shouldering, uniform-diametering, and tailing, with the pulling rate being 2 mm/h, the rotation rate being 25 rpm, the temperature difference of the melt-crystal interface being 20° C., the temperature gradient in the melt volume near the surface being 1.5° C./mm, and the temperature gradient above the melt surface being 1.0° C./mm, respectively. (3) Pole and anneal the grown doped lithium niobate crystals at 1200° C. to get a single-domain structure. After being orientated, cut, grinded, and polished to optical grade, the maximum diffraction efficiency of this Fe and In doubly lithium niobate crystal is 72%, the light intensity threshold to optic scattering is larger than 30 mW, and the average write time for holographic storage is 3 s (I˜1 W/cm2).

[0017] Embodiment 3:

[0018] (1) Weigh up 0.025 wt. % Fe2O3 and 6 mol. % ZnO, and [Li2CO3]/[Nb2O5]=0.88. and dry them at 150° C. for 2 hours, then thoroughly mix them at a mixer lasting for 24 hours, and keep them at 850° C. for 2 hours to make Li2CO3 decompose sufficiently, and then sinter at 1100° C. for 2 hours to obtain doubly doped lithium niobate powder. (2) Put the above doped lithium niobate powder into a Pt crucible after impacted, then heat the powder by a middle frequency stove. Grow the doubly doped lithium niobate crystals using the Czochralski pulling method along c axis via the procedures of necking, shouldering, uniform-diametering, and tailing, with the pulling rate being 1.5 mm/h, the rotation rate being 20 rpm, the temperature difference of the melt-crystal interface being 20° C., the temperature gradient in the melt volume near the surface being 1.5° C./mm, and the temperature gradient above the melt surface being 1.0° C./mm, respectively. (3) Pole and anneal the grown doped lithium niobate crystals at 1200° C. to get a single-domain structure. After being orientated, cut, grinded, and polished to optical grade, the maximum diffraction efficiency of this Fe and Zn doubly lithium niobate crystal is 68%, the light intensity threshold to optic scattering is larger than 50 mW, and the average write time for holographic storage is 3 s (I˜1 W/cm2).

INDUSTRIAL APPLICABILITY

[0019] The invented doubly doped lithium niobate crystals have high diffraction efficiency for three-dimensional holographic photorefractive grating, which is more than 68%. The photorefractive response time is 3˜5 s, an order of magnitude faster than LiNbO3:Fe. They have a high resistance to optical scattering, that is the light intensity threshold for photorefractive fanning optical scattering is as almost two orders of magnitude higher than LiNbO3: Fe crystal. Comparing with the same products in the world, the response times of these doubly doped lithium niobate crystals have been improved by 1-2 orders of magnitude so as to be an excellent three-dimensional holographic optical storage material. These doubly doped lithium niobate crystals have widely potential applications in three-dimensional holographic optical disk, integration optics, military antagonizing, civil navigation, finance, stocks, etc.

Claims

1. A doubly doped lithium niobate crystal, wherein iron and a second radius-matched ion both are doped in the mean time into LiNbO3, its composition being denoted as Li1−xNb1+yO3:Fem, Mn, where M is magnesium, indium, or zinc, when using q to denote the ion valence of M (q=2 when M is Mg or Zn, and q=3 when M is In), the values of x, y, m, and n are in the range of 0.05≦x≦0.13, 0.00≦y≦0.01, 5.0×10−5≦m≦7.5×10−4, and 0.02≦qn≦0.13.

2. The doubly doped lithium niobate crystal as claimed in claim 1, wherein said composition can doped with 0.007˜0.03 wt. % Fe and 1.0˜5.0 mol. % Mg, while the congruent composition is [Li]/[Nb]=0.90˜0.95.

3. The doubly doped lithium niobate crystal as claimed in claim 1, wherein said composition can doped with 0.01˜0.05 wt. % Fe and 0.75˜3.0 mol. % In, while the congruent composition is [Li]/[Nb]=0.91˜0.95.

4. The doubly doped lithium niobate crystal as claimed in claim 1, wherein said composition can doped with 0.02˜0.06 wt. % Fe and 1.5˜6.5 mol. % Zn, while the congruent composition is [Li]/[Nb]=0.87˜0.95.

5. A process for growing doubly doped lithium niobate crystal as claimed in anyone of claim 1-4, wherein said process includes the following steps: (1) Weigh up high purity Li2CO3, Nb2O3, Fe2O3, and MgO, In2O3 or ZnO powders according to the crystal composition, and dry them at 120˜150° C., then thoroughly mix them lasting for 24 hours, and keep them at 800˜850° C. for 2˜5 hours to make Li2CO3 decompose sufficiently, and then sinter at 1050˜1150° C. for 2˜8 hours to obtain doubly doped lithium niobate powder. (2) Put the above doped lithium niobate powder into a Pt crucible after impacted, then heat the powder by a middle frequency stove; Grow the doubly doped lithium niobate crystals using the Czochralski pulling method along c or a axis via the procedures of necking, shouldering, uniform-diametering, and tailing, with the pulling rate being 1˜3 mm/h, the rotation rate being 15˜30 rpm, the temperature difference of the melt-crystal interface being 20° C., the temperature gradient in the melt volume near the surface being 1.5° C./mm, and the temperature gradient above the melt surface being 1.020 C./mm, respectively. (3) Pole and anneal the grown doped lithium niobate crystals at 1200° C. to obtain single-domained doubly doped lithium niobate crystals

6. A usage of said doubly doped lithium niobate crystals claimed in claim 1, wherein said doubly doped lithium niobate crystals can be used for a three-dimensional optical storage material.