CN114481321B - Electro-optic crystal potassium boroniobate and application thereof - Google Patents

Electro-optic crystal potassium boroniobate and application thereof Download PDF

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CN114481321B
CN114481321B CN202011270841.6A CN202011270841A CN114481321B CN 114481321 B CN114481321 B CN 114481321B CN 202011270841 A CN202011270841 A CN 202011270841A CN 114481321 B CN114481321 B CN 114481321B
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CN114481321A (en
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龙西法
单排
王祖建
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/36—Single-crystal growth by pulling from a melt, e.g. Czochralski method characterised by the seed, e.g. its crystallographic orientation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/10—Production of homogeneous polycrystalline material with defined structure from liquids by pulling from a melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0018—Electro-optical materials
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/03—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on ceramics or electro-optical crystals, e.g. exhibiting Pockels effect or Kerr effect
    • G02F1/0305—Constructional arrangements
    • G02F1/0311—Structural association of optical elements, e.g. lenses, polarizers, phase plates, with the crystal

Abstract

The invention discloses electro-optical crystal potassium boroniobate and application thereof, which are characterized in that the chemical formula of the potassium boroniobate crystal is K 3 Nb 3 B 2 O 12 KNBO crystal in orthorhombic system at room temperature, P2 1 ma space group, unit cell parameters are:
Figure DDA0002777646210000011
Figure DDA0002777646210000012
α = β = γ =90 °; the boron potassium niobate crystal is applied to manufacturing an electro-optical device; the electro-optical devices include, but are not limited to, phase modulators, electro-optical Q-switch devices, optical intensity modulators, electro-optical deflection devices. When the size of the electro-optical device is the same, the applied voltage of the KNBO crystal electro-optical device prepared by the invention is obviously lower than that of a BBO crystal electro-optical device.

Description

Electro-optic crystal potassium boroniobate and application thereof
Technical Field
The invention belongs to the field of functional materials, and particularly relates to a novel electro-optic crystal potassium boroniobate and application thereof in the laser field, the photoelectron technical field and the communication field.
Background
The electro-optical effect is the phenomenon that the refractive index of the crystal changes along with an external electric field, the electro-optical effect of the crystal material can be used for realizing the modulation of the phase, the intensity and the propagation direction of light, practical electro-optical devices such as a high-speed electro-optical switch, an electro-optical modulator, an electro-optical deflector, an electro-optical integrated device and the like are manufactured, and the electro-optical device is widely applied to high-precision fields such as laser radar, laser ranging, biomedical micro-imaging, optical communication and the like.
The main electro-optic crystal in commercial use at present is potassium dideuterium phosphate (KD) 2 PO 4 DKDP for short), lithium niobate (LiNbO) 3 LN for short) and rubidium titanyl phosphate (RbTiOPO) 4 RTP) crystal, which has advantages, has been widely used for many years. However, with the development of laser technology and photonic integration technology, some characteristics of the laser technology and the photonic integration technology cannot meet the requirements of special applications. Such as: DKDP is a water-soluble crystal, is easy to deliquesce, needs a moisture-proof measure and a temperature control measure, has a complex structure and has hidden danger in reliability; the LN crystal can be applied to the laser field and the photon integration field, but the laser damage threshold is low and is limited by the piezoelectric ringing effect in use; high quality RTP crystals rely primarily on importation and are expensive. Another common feature of the above electro-optic crystals is that they all exhibit varying degrees of piezoelectric ringing. The piezoelectric ringing effect means that when high voltage with high frequency change is applied to two ends of the electro-optical crystal, the electro-optical crystal can deform while showing the piezoelectric effect under the action of an electric field; this deformation causes the crystal to vibrate acoustically even after the electric field is removed. And this piezoelectric ringing effect causes a reduction in the laser output performance.
Novel electro-optical crystal gallium silicate (La) newly developed by Chinese scientists 3 Ga 5 SiO 14 LGS for short) and beta-phase barium metaborate (. Beta. -BaB) 2 O 4 BBO) crystals have high laser damage thresholds and weak piezoelectric ringing. But the electro-optic coefficients of the two are small, the LGS crystal has an optical rotation effect, the application difficulty is increased, and the BBO has certain difficulty in growing the crystal with the thickness and the size capable of meeting the practical application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an application of an electro-optical material boron potassium niobate crystal in an electro-optical device.
Electro-optical crystal of boron potassium niobateThe chemical formula of the boron potassium niobate crystal is K 3 Nb 3 B 2 O 12 KNBO crystal in orthorhombic system at room temperature, P2 1 ma space group, unit cell parameters are:
Figure BDA0002777646190000021
α＝β＝γ＝90°；
the boron potassium niobate crystal is applied to manufacturing an electro-optical device; the electro-optical devices include, but are not limited to, phase modulators, electro-optical Q-switch devices, optical intensity modulators, electro-optical deflection devices.
According to the technical scheme of the invention, the KNBO crystal is a colorless transparent crystal.
According to the technical scheme of the invention, the KNBO crystal can be in but not limited to a space group at the temperature higher than 90 ℃ or lower than-70 DEG C
Figure BDA0002777646190000022
Pm, C2mm or C2mb.
According to the technical scheme of the invention, the KNBO crystal has an X-ray crystal diffraction pattern substantially as shown in fig. 2 and/or a crystal structure diagram as shown in fig. 3.
According to the technical scheme of the invention, the electro-optic coefficient of the KNBO crystal is 3.3pm/V, the electro-optic coefficient of the KNBO crystal is obtained by measuring through a half-wave voltage method, and the relationship between the electro-optic coefficient of the crystal and the half-wave voltage is shown in a formula (1):
Figure BDA0002777646190000023
wherein, λ is the laser wavelength, n is the crystal refractive index, d is the thickness between the electrodes, and L is the length of the crystal in the light passing direction.
According to the technical scheme of the invention, when an electro-optical device is manufactured, the boron potassium niobate crystal is cut into a cube, an electric field is applied along the physical Z direction of the electro-optical crystal, and the light passing direction is vertical to the Z direction.
According to the technical scheme of the invention, the voltage for preparing the electro-optical device is 0 to 9000 volts.
According to the technical scheme of the invention, the used wavelength range for preparing the electro-optical device is 300 nanometers to 5 micrometers.
According to the technical scheme of the invention, when the electro-optical device is prepared, two end faces perpendicular to the light transmission direction are polished, and an antireflection film is plated.
According to the technical scheme of the invention, the surface of the Z end of the crystal is plated with the conductive film.
According to the technical scheme of the invention, the conductive film is a gold film, a silver film or a copper film.
According to the technical scheme of the invention, the conductive film and/or the antireflection film is plated in one or more modes of ion sputtering, vacuum evaporation and coating of conductive adhesive.
The invention also provides a preparation method of the KNBO crystal, which comprises the following steps: according to K 3 Nb 3 B 2 O 12 And weighing a potassium-containing compound, a niobium-containing compound, a boron-containing compound and a fluxing agent according to a stoichiometric ratio, mixing, and preparing the KNBO crystal by adopting a high-temperature molten salt method or a top seed crystal method.
According to an embodiment of the invention, the high temperature molten salt method for preparing the KNBO crystal comprises the following steps:
according to K 3 Nb 3 B 2 O 12 And weighing a potassium-containing compound, a niobium-containing compound and a boron-containing compound according to a stoichiometric ratio, mixing the potassium-containing compound, the niobium-containing compound and the boron-containing compound with a fluxing agent, and heating, melting, preserving heat and cooling in a molten salt furnace to obtain the KNBO crystal.
According to an embodiment of the present invention, the top-seed process for producing KNBO crystals comprises the steps of:
according to K 3 Nb 3 B 2 O 12 Weighing a potassium-containing compound, a niobium-containing compound and a boron-containing compound according to a stoichiometric ratio, mixing the potassium-containing compound, the niobium-containing compound and the boron-containing compound with a fluxing agent, and obtaining the KNBO crystal after heating, melting, heat preservation, seed crystal introduction, cooling and annealing in a molten salt furnace.
According to the invention, K 3 Nb 3 B 2 O 12 Of stoichiometrically raw materials to fluxesThe molar ratio may be (1-4): 1-12, for example the molar ratio is (1.5-3): 2-6, illustratively 1:2. Wherein, K is 3 Nb 3 B 2 O 12 The stoichiometric ratio refers to K: nb: B: O =3.
According to the present invention, the fluxing agent is a mixture of a potassium-containing compound and a boron-containing compound, wherein the molar ratio of the potassium-containing compound to the boron-containing compound may be (1-8) to (1-8), for example, the molar ratio is (2-6) to (2-6), illustratively 1:1.
According to the technical scheme of the invention, the potassium-containing compound is K 2 CO 3 、K 2 At least one of O, KCl and KOH.
According to the technical scheme of the invention, the niobium-containing compound is Nb 2 O 5 。
According to the technical scheme of the invention, the boron-containing compound is B 2 O 3 、H 3 BO 3 At least one of (1).
According to the technical scheme of the invention, the temperature rise is to raise the temperature to 800-1200 ℃, for example 950-1200 ℃, such as 1000-1100 ℃. Further, the rate of temperature rise is 10 to 300 ℃/hour, for example 30 to 60 ℃/hour, such as 40 to 50 ℃/hour.
According to the technical scheme of the invention, the heat preservation time is 0.5-5 days, such as 1-3 days.
According to the technical scheme of the invention, the temperature is reduced to 15-100 ℃, such as 20-25 ℃. Further, the rate of cooling is 0.1-100 ℃/day, for example 0.1-2 ℃/day, such as 10-20 ℃/day.
According to the technical scheme of the invention, the annealing speed is 5-40 ℃/h, for example 10-40 ℃/h, such as 15-30 ℃/h.
According to the technical scheme of the invention, the growth direction of the seed crystal is the (001) or (100) or (111) direction.
As used herein, the term "room temperature" means a temperature of between 15 ℃ and 40 ℃, such as between 20 ℃ and 35 ℃, preferably 25 ℃.
According to the technical scheme of the invention, the preparation method of the electro-optical Q-switch device specifically comprises the following steps:
taking two KNBO crystals I and two KNBO crystals II with the same size to realize the natural birefringence compensation of the crystals, wherein the light passing direction is along the X direction or the Y direction of the physics of the crystals, or the other directions parallel to the X/Y plane; polishing two end faces perpendicular to the light transmission direction, and plating an antireflection film; and plating a conductive film on the Z-end surfaces of the two crystals as electrodes, and applying an electric field along the Z direction of the crystal physics to prepare the electro-optical Q-switch device.
According to the technical scheme of the invention, the preparation method of the phase modulator comprises the following specific steps: processing the KNBO crystal into a cube, applying an electric field along the Z direction of the crystal physics, pressurizing the surface of the KNBO crystal to form a metal electrode, and preparing the phase modulator along the X direction or the Y direction of the crystal physics or other directions parallel to the XY plane in the light passing direction.
According to the technical scheme of the invention, the preparation method of the light intensity modulator comprises the following specific steps:
plating metal on the KNBO crystal along the Z end face of the crystal physics, preparing electrodes, applying an electric field along the Z direction of the crystal physics, placing two polaroids or polarizing prisms on two sides of the crystal and in the light passing direction respectively along the X direction or the Y direction of the crystal physics or other directions parallel to the XY plane, and preparing the light intensity modulator.
According to the technical scheme of the invention, the polarization directions of the two polarizing plates or the polarizing prisms in the light intensity modulator are parallel or vertical.
According to the technical scheme of the invention, the preparation method of the electro-optical deflection device comprises the following specific steps:
adopting two right-angle prism KNBO crystals with the same model, and optically polishing the inclined planes of the two crystals; combining the bevel edge planes of the two crystals; an electro-optic deflector was prepared by applying a voltage to the Z-plane.
According to the technical scheme of the invention, the bevel edge plane combination mode can adopt gluing.
According to the technical scheme of the invention, after an electric field is applied to one right-angle side, a light beam is transmitted perpendicular to the other right-angle side.
The invention has the beneficial effects that:
(1) The KNBO electro-optic crystal material provided by the invention has the advantages of no deliquescence, easy growth, good mechanical property, no voltage electric ringing effect and the like. The electro-optic coefficient of the KNBO crystal is 3.3pm/V, which is 2.7pm/V higher than that of the BBO of the existing commercial electro-optic crystal. This means that for the same conditions of use, the same crystal pass length and thickness, the applied voltage required for the KNBO crystal is significantly lower than for the BBO crystal.
(2) The electro-optic crystal material provided by the invention can be used for preparing electro-optic modulators, electro-optic switches, integrated electro-optic devices and the like, and is applied to the field of laser technology or optical communication.
Drawings
FIG. 1 shows K prepared in example 1 of the present invention 3 Nb 3 B 2 O 12 A photograph of the crystal;
FIG. 2 shows K prepared in example 1 of the present invention 3 Nb 3 B 2 O 12 XRD spectrum of the crystal;
FIG. 3 is K prepared according to example 1 of the present invention 3 Nb 3 B 2 O 12 A structure of a crystal;
fig. 4 is a crystal photograph of a KNBO electro-optical Q-switch device prepared in example 2;
FIG. 5 is a graph of the KNBO crystal voltage versus the light intensity as measured with the light intensity modulator in example 4 over time;
FIG. 6 is a schematic diagram of a KNBO crystal electro-optical Q-switch device prepared in example 2;
FIG. 7 is a schematic view of a KNBO crystal phase modulator prepared in example 3;
FIG. 8 is a schematic view of a KNBO crystal light intensity modulator prepared in example 4;
FIG. 9 is a schematic view of a KNBO crystal electro-optical deflector prepared in example 5.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Example 1
Growing K by top seed crystal method 3 Nb 3 B 2 O 12 Crystal
Weighing an initial reaction raw material K in a molar ratio of 41 2 O、Nb 2 O 3 And B 2 O 3 I.e. K 3 Nb 3 B 2 O 12 With a fluxing agent K 2 O and B 2 O 3 The ratio of (1) to (2) is 8. Mixing and grinding the initial raw materials uniformly, putting the mixture into a platinum crucible, and putting the platinum crucible into a crystal growth furnace. Heating to 1000 deg.C for melting, keeping the temperature at 1000 deg.C for 30h, cooling to a temperature above saturation point 950 deg.C by 5-10 deg.C, placing seed crystal suspended on platinum wire in the center of liquid surface, cooling to saturation point temperature for 30 min, cooling at a rate of 1 deg.C/day, finishing growth, lifting crystal off the liquid surface, cooling at 20 deg.C/h for annealing to obtain K 3 Nb 3 B 2 O 12 An antiferroelectric crystal. The structure and the performance of the material are determined by powder X-ray diffraction, dielectric and ferroelectric property tests and analysis.
K prepared in this example 3 Nb 3 B 2 O 12 The crystals were colorless transparent crystals (as shown in FIG. 1).
FIG. 2 shows K prepared in this example 3 Nb 3 B 2 O 12 XRD pattern of the crystals, explanation K 3 Nb 3 B 2 O 12 The crystal is successfully prepared.
FIG. 3 shows K prepared in this example 3 Nb 3 B 2 O 12 Structural diagram of the crystal, the KNBO crystal being in orthorhombic system at room temperature, P2 1 ma point group, cell parameters are:
Figure BDA0002777646190000071
Figure BDA0002777646190000072
α＝β＝γ＝90°。
example 2
Manufacture of KNBO electro-optical Q-switch
Firstly, processing the KNBO crystal into two cuboid crystals with the same size according to different tangential directions, and respectively marking the two cuboid crystals as a first crystal and a second crystal, wherein as shown in figure 1, the sizes of the two crystals are as follows: the width d =5mm in the Z direction, the width w =5mm in the Y direction, the length l =20mm in the X direction, the Y direction of the first crystal is parallel to the X direction of the second crystal, and the light passing direction is along the X direction. And (4) polishing the X end faces of the two crystal samples, and plating an anti-reflection film. A gold-plated film is used as an electrode on the Z surface, and the gold-plated film can be coated to a thickness capable of realizing electric conduction; and respectively applying voltages along the Z directions of the first crystal and the second crystal, wherein the voltages applied to the two crystals are 1400V, and as shown in figure 3, the electro-optical Q-switch device with the wavelength of 632.8nm is prepared and can be applied to a laser.
Fig. 4 is a photograph of a KNBO electro-optical Q-switch crystal prepared in example 2.
Fig. 6 is a schematic diagram of a KNBO electro-optical Q-switch prepared in example 2.
Example 3
Making KNBO phase modulators
The KNBO crystal is processed into a cuboid block according to different tangential directions, the width of the KNBO crystal in the Z direction is d =3mm, the length of the KNBO crystal in the X direction is w =20mm, the width of the KNBO crystal in the Y direction is l =4mm, the light transmission direction is along the X direction, the wavelength of light is 300 nanometers to 5 micrometers, a gold-plated film on the Z surface is used as an electrode, voltage is applied along the Z direction of the crystal, and the voltage modulation range is 0V to 6000V, so that the electro-optic phase modulation device is prepared.
Fig. 7 is a schematic diagram of a KNBO electro-optic crystal phase modulator prepared in this example.
Example 4
Manufacturing of KNBO light intensity modulator
Using a KNBO crystal, firstly processing the KNBO crystal into a cuboid block according to different tangential directions, wherein the width of the KNBO crystal in the Z direction is d =2.3mm, the width of the KNBO crystal in the X direction is w =2.5mm, the length of the KNBO crystal in the Y direction is l =26mm, light is transmitted in the Y direction, a gold-plated film on the Z surface is used as an electrode, voltage is applied along the Z direction of the crystal, and the voltage modulation range is 0-4000 volts; and in the light transmission direction, polarizing plates 1 and 3 are arranged on two sides of the crystal, and the polarization directions of the polarizing plates 1 and 3 are vertical to each other, so that the electro-optic modulation device is prepared.
FIG. 5 is a curve of the light intensity of the KNBO crystal measured with a light intensity modulator as a function of voltage, example 4 using a wavelength of 632.8nm, calculated according to equation (1), and the electro-optic coefficient of the KNBO crystal was 3.3pm/V.
Fig. 8 is a schematic diagram of a prepared KNBO electro-optic crystal light intensity modulator.
Example 5
Making KNBO electro-optic deflectors
Firstly, processing the KNBO crystal into two right-angle prisms with the same size according to different tangential directions, and marking the two right-angle prisms as a first crystal and a second crystal, wherein as shown in figure 6, the sizes of the two crystals are as follows: a Z-direction width d =5mm, a y-direction width w =5mm, and an x-direction length l =5mm; and gluing the bevel edges of the two right-angle prism KNBO crystals in parallel. And applying a voltage along the Z direction of the first crystal by using the Z-surface gold-plated film as an electrode, wherein the voltage is changed from 0 volt to 9000 volts. After an electric field is applied to the Z surface of the first crystal, a light beam is transmitted in a direction vertical to the Z direction; an electro-optical deflector is prepared.
Fig. 9 is a schematic view of a KNBO electro-optic deflector of the present embodiment.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (20)

1. The application of electro-optical crystal boron potassium niobate is characterized in that the chemical formula of the electro-optical crystal boron potassium niobate is K 3 Nb 3 B 2 O 12 KNBO crystal in orthorhombic system at room temperature, P2 1 ma space group, unit cell parameters are: a =17.506 (2), b =15.162 (3) a, c =3.9680 (4) a, α = β = γ =90 °;
the electro-optical crystal boron potassium niobate is applied to manufacturing an electro-optical device; the electro-optical device is selected from a phase modulator, an electro-optical Q-switch device, an optical intensity modulator and an electro-optical deflection device.
2. Use according to claim 1, wherein the KNBO crystals are colorless transparent crystals.
3. The use according to claim 1, wherein the electro-optical coefficient of the KNBO crystal at room temperature is 3.3pm/V, the electro-optical coefficient of the KNBO crystal is obtained by measuring by a half-wave voltage method, and the relationship between the electro-optical coefficient of the crystal and the half-wave voltage is shown in formula (1):
Figure DEST_PATH_IMAGE001
（1）
wherein, λ is the laser wavelength, n is the crystal refractive index, d is the thickness between the electrodes, and L is the length of the crystal in the light passing direction.
4. The use of claim 1, wherein, in the manufacture of an electro-optic device, the electro-optic crystal of potassium boroniobate is cut into cubes, and an electric field is applied in the direction of the physical Z of the electro-optic crystal, the direction of light transmission being perpendicular to the direction of the physical Z.
5. Use according to claim 4, wherein the electro-optical device is made in the wavelength range of 300 nm to 5 μm.
6. The use according to claim 4, wherein, in the preparation of an electro-optical device, both end faces perpendicular to the direction of light transmission are polished and coated with an antireflection film.
7. Use according to claim 6, characterized in that the surface of the Z-end of the crystal is plated with a conductive film.
8. Use according to claim 7, wherein the conductive film is a gold film, a silver film or a copper film.
9. The use of claim 8, wherein the conductive film and/or the anti-reflection film is plated by one or more of ion sputtering, vacuum evaporation and coating of conductive adhesive.
10. The use according to claim 1, wherein the preparation method of the KNBO crystal comprises:
according to K 3 Nb 3 B 2 O 12 And weighing a potassium-containing compound, a niobium-containing compound, a boron-containing compound and a fluxing agent according to a stoichiometric ratio, mixing, and preparing the KNBO crystal by adopting a high-temperature molten salt method or a top seed crystal method.
11. The use according to claim 10, wherein the high temperature molten salt process for preparing KNBO crystals comprises the steps of:
according to K 3 Nb 3 B 2 O 12 Weighing a potassium-containing compound, a niobium-containing compound and a boron-containing compound according to a stoichiometric ratio, mixing the potassium-containing compound, the niobium-containing compound and the boron-containing compound with a fluxing agent, and heating, melting, preserving heat and cooling in a molten salt furnace to obtain the KNBO crystal;
the preparation of the KNBO crystal by the top seed crystal method comprises the following steps:
according to K 3 Nb 3 B 2 O 12 Weighing a potassium-containing compound, a niobium-containing compound and a boron-containing compound according to a stoichiometric ratio, mixing the potassium-containing compound, the niobium-containing compound and the boron-containing compound with a fluxing agent, and obtaining the KNBO crystal after heating, melting, heat preservation, seed crystal introduction, cooling and annealing in a molten salt furnace.
12. Use according to claim 10, characterized in that K is 3 Nb 3 B 2 O 12 The molar ratio of the stoichiometric raw materials to the fluxing agent is (1~4): 1-12);
the fluxing agent is a mixture of a potassium-containing compound and a boron-containing compound, wherein the molar ratio of the potassium-containing compound to the boron-containing compound is (1~8): (1~8);
the potassium-containing compound is K 2 CO 3 、K 2 At least one of O, KCl and KOH;
the niobium-containing compound isNb 2 O 5 ；
The boron-containing compound is B 2 O 3 、H 3 BO 3 At least one of (1).
13. The use according to claim 11, wherein the temperature is raised to 800 to 1200 ℃ at a rate of 10 to 300 ℃/h;
the heat preservation time is 0.5 to 5 days;
the temperature reduction is carried out at a speed of 0.1 to 100 ℃/day, wherein the temperature is reduced to 15 to 100 ℃;
the annealing rate is 5 to 40 ℃/hour.
14. The use according to any of claims 1 to 13, wherein a method of manufacturing an electro-optical Q-switch device comprises the steps of:
taking two KNBO crystals I and two KNBO crystals II with the same size to realize the natural birefringence compensation of the crystals, wherein the light passing direction is along the X direction or the Y direction of the physics of the crystals, or the other directions parallel to the X/Y plane; polishing two end faces perpendicular to the light transmission direction, and plating an antireflection film; and plating a conductive film on the Z-end surfaces of the two crystals as electrodes, and applying an electric field along the Z direction of the crystal physics to prepare the electro-optical Q-switch device.
15. The use according to any of claims 1 to 13, wherein a method for manufacturing a phase modulator comprises the steps of: processing the KNBO crystal into a cube, applying an electric field along the Z direction of the crystal physics, pressurizing the surface of the KNBO crystal to form a metal electrode, and preparing the phase modulator along the X direction or the Y direction of the crystal physics or other directions parallel to the XY plane in the light passing direction.
16. The use according to any one of claims 1 to 13, wherein a method for manufacturing a light intensity modulator comprises the steps of:
plating metal on the KNBO crystal along the Z end face of the crystal physics, preparing electrodes, applying an electric field along the Z direction of the crystal physics, placing two polaroids or polarizing prisms on two sides of the crystal and in the light passing direction respectively along the X direction or the Y direction of the crystal physics or other directions parallel to the XY plane, and preparing the light intensity modulator.
17. Use according to claim 16, wherein the polarization directions of the two polarizers or polarizing prisms of the light intensity modulator are parallel or perpendicular.
18. Use according to any of claims 1-13, characterized in that a method for manufacturing an electro-optical deflection device comprises the steps of:
adopting two right-angle prism KNBO crystals with the same model, and optically polishing the inclined planes of the two crystals; combining the bevel edge planes of the two crystals; an electro-optic deflector was prepared by applying a voltage to the Z-plane.
19. The use according to claim 18, wherein the combination of beveled surfaces is by gluing.
20. The use according to claim 19, wherein the light beam propagates perpendicularly to one of the legs after the electric field is applied to the other leg.
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