CN114059169B - Ferroelectric deep ultraviolet transparent sulfate crystal and optical device - Google Patents
Ferroelectric deep ultraviolet transparent sulfate crystal and optical device Download PDFInfo
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Abstract
The invention provides a ferroelectric deep ultraviolet transparent sulfate crystal and an optical device. The chemical formula of the sulfate crystal is M x M′ y M″ z (SO 4 ) (x/2+y/2+z/2) M is selected from alkali metals, M 'is selected from alkali metal or ammonium ions, and M' is selected from alkali metal or ammonium ions; x is more than or equal to 1, y is more than or equal to 1, and z is more than or equal to 0. And carrying out periodic polarization on the sulfate crystal by using an electric field to obtain the quasi-phase matching optical device.
Description
Technical Field
The invention belongs to the field of crystal material application, and relates to a ferroelectric deep ultraviolet transparent sulfate crystal and an optical device.
Background
The nonlinear optical crystal material plays an important role in the fields of laser science and technology. Since the frequency doubling effect is discovered for the first time in 1961, researchers have carried out a lot of work on the research aspect of nonlinear optical crystal materials, and a series of novel nonlinear optical crystals are discovered in succession, so that the commercialization of ultraviolet-infrared band nonlinear optical crystals is realized, and the development task of deep ultraviolet nonlinear optical crystals is still very difficult. Although a large number of deep ultraviolet transparent nonlinear optical crystals are discovered at present, due to the mutual restriction relationship among material band gaps, birefringence and nonlinear optical coefficients, the large number of deep ultraviolet transparent nonlinear optical crystals are limited by factors with non-moderate birefringence per se, and deep ultraviolet phase matching cannot be realized.
The quasi-phase matching technology is another important technical approach for realizing frequency conversion of the nonlinear optical crystal, can effectively break through the limitation of the crystal with moderate birefringence, can get rid of the constraint of short-wave matching limit and walk-off effect, and can utilize the maximum nonlinear optical coefficient of the crystal. The quasi-phase matching is to compensate the phase mismatch between the fundamental light and the harmonic light caused by refractive index dispersion in the nonlinear frequency conversion process by periodically modulating the nonlinear polarizability of the crystal, thereby obtaining the effective enhancement of the nonlinear optical effect. Ferroelectric crystals are currently the most ideal material for achieving quasi-phase matching, all ferroelectrics exhibit spontaneous polarization characteristics below the curie temperature, and the direction of spontaneous polarization can be changed by an external electric field.
Disclosure of Invention
The invention provides a sulfate crystal, wherein the chemical formula of the sulfate crystal is M x M′ y M″ z (SO 4 ) (x/2+y/2+z/2) M is selected from alkali metals, M 'is selected from alkali metal or ammonium ions, and M' is selected from alkali metal or ammonium ions; x is more than or equal to 1, y is more than or equal to 1, and z is more than or equal to 0.
According to an embodiment of the present invention, the alkali metal is selected from at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs).
According to an embodiment of the invention, the alkali metal is selected from Li and K.
According to an embodiment of the invention, the sulfate crystals are LiKSO 4 Crystal, liNH 4 SO 4 Crystals or Li 2 KRbSO 4 And (4) crystals.
According to an embodiment of the invention, the LiKSO 4 The crystal is of an orthorhombic structure and the space group is P6 3 Cell parameter of
α＝β＝90°，γ＝120°。
Preferably, theThe LiKSO 4 The crystal is a deep ultraviolet transparent material.
Preferably, the LiKSO 4 The crystal has a transmission spectrum substantially as shown in a in fig. 1.
Preferably, the LiKSO 4 The crystal has a frequency doubling effect pattern substantially as shown in b in fig. 1.
Preferably, the sulphate crystals have a cut-off absorption edge of less than 200nm, for example 160nm. I.e. the sulphate crystals have deep uv properties.
Preferably, the LiKSO 4 The crystal has a ferroelectric hysteresis loop substantially as shown in figure 2.
According to an embodiment of the invention, the sulphate crystals are prepared by: weighing the sulfate raw materials according to the metering ratio, uniformly mixing, and preparing the sulfate crystal by adopting a molten salt method or an aqueous solution method.
According to an embodiment of the invention, the molten salt process comprises the steps of:
weighing the sulfate raw materials according to a metering ratio, uniformly mixing, loading into a platinum crucible, and heating, melting, preserving heat and cooling in a molten salt furnace to obtain the sulfate crystal;
according to an embodiment of the invention, the sulfate source is selected from (NH) 4 ) 2 SO 4 、Li 2 SO 4 、Na 2 SO 4 、K 2 SO 4 、Rb 2 SO 4 、Cs 2 SO 4 At least two of (a); preferably Li 2 SO 4 And K 2 SO 4 ；
According to an embodiment of the invention, the temperature increase is an increase of the temperature to 700 to 1100 ℃, for example 800 to 900 ℃;
according to an embodiment of the invention, the incubation time is 1 to 3 days, such as 1 to 2 days;
according to an embodiment of the invention, the temperature after said cooling is between 20 and 40 ℃, such as between 20 and 25 ℃;
according to an embodiment of the invention, the rate of warming and cooling may be the same or different and is independently selected from 5 to 60 ℃/hour, for example 10 to 50 ℃/hour.
According to an embodiment of the invention, the aqueous solution process comprises the steps of:
weighing sulfate raw materials according to a stoichiometric ratio, dissolving the sulfate raw materials in deionized water, uniformly stirring, and then heating, preserving heat and cooling in a drying oven to obtain target crystals;
according to an embodiment of the invention, the sulfate source is (NH) 4 ) 2 SO 4 、Li 2 SO 4 、Na 2 SO 4 、K 2 SO 4 、Rb 2 SO 4 、Cs 2 SO 4 At least two of (a); preferably Li 2 SO 4 And K 2 SO 4 ；
According to an embodiment of the invention, the temperature increase is an increase of the temperature to 50 to 80 ℃, such as 60 ℃, 80 ℃;
according to an embodiment of the invention, the incubation time is 2 to 5 days, such as 3 days;
according to an embodiment of the invention, the lowering of the temperature is a lowering of the temperature to 20-40 ℃, such as 20-30 ℃.
According to an embodiment of the invention, the rate of warming and cooling may be the same or different and is independently selected from 20 to 50 ℃/hour, for example 30 ℃/hour. For example, the temperature increase rate is 50 ℃/hr and the temperature decrease rate is 10 ℃/hr.
The present invention also provides the use of a sulphate compound or a sulphate crystal as described above, having the same chemical formula as the sulphate crystal, in the manufacture of an optical device.
According to an embodiment of the invention, the optical device is a deep ultraviolet non-linear optical device.
According to an embodiment of the invention, the optical device is a quasi-phase matching optical device.
According to the embodiment of the invention, the quasi-phase matching principle and the periodic polarization method are introduced into the sulfate crystal in the application, and the quasi-phase matching optical device is prepared.
The present invention also provides an optical device comprising the above sulfate compound or sulfate crystal.
According to an embodiment of the invention, the optical device is a deep ultraviolet non-linear optical device.
According to an embodiment of the invention, the optical device is a quasi-phase matching optical device.
According to an embodiment of the present invention, the quasi-phase matching optical device is prepared by the following method: and placing the optical device or element containing the sulfate crystal in an external electric field, and periodically polarizing the sulfate crystal to obtain the quasi-phase matching optical device.
The invention also provides a preparation method of the optical device, which comprises the steps of placing the optical device or the element containing the sulfate crystal in an external electric field, and carrying out periodic polarization on the sulfate crystal to obtain the optical device.
According to an embodiment of the invention, the periodic poling is preceded by a step of subjecting the sulphate crystals to an applied voltage, preferably 5-15kV, for example 10kV, for dwelling for monodomain formation. Preferably, the dwell time is 5-15min, for example 10min.
According to an embodiment of the invention, the periodic poling comprises applying a square wave electric field to the sulphate crystals using a high voltage pulsed poling power supply.
According to an embodiment of the invention, the optical device or element is, for example, an electrode, having a polarizing electrode structure.
According to an embodiment of the invention, the monodomain formation step takes place before the sulfate crystal forming electrode and the periodic polarisation takes place after the sulfate crystal forming electrode.
The quasi-phase matching principle specifically means that periodic modulation of a second-order nonlinear optical coefficient is realized by periodically polarizing the sulfate crystal through an external electric field, so that the phase of a wave vector of light waves passing through the sulfate crystal is regulated and controlled, and the conversion efficiency is continuously increased along with the increase of the transmission distance of the light waves.
The invention also provides an optical device, such as a deep ultraviolet optical device, prepared by the method.
Advantageous effects
The sulfate crystal provided by the invention is a ferroelectric deep ultraviolet transparent nonlinear optical crystal, and can realize periodic modulation of a second-order nonlinear optical coefficient in an external electric field periodic polarization mode, so that the wave vector phase of light waves passing through the crystal is regulated and controlled, and the conversion efficiency is continuously increased along with the increase of the light wave transmission distance. The invention introduces the quasi-phase matching principle and the periodic polarization method into the sulfate crystal to prepare the quasi-phase matching optical device.
The sulfate crystal provided by the invention has a short deep ultraviolet cut-off absorption edge, a wide light-transmitting wave band, a larger nonlinear effect, good ferroelectricity and stable physical and chemical properties, and is an excellent photoelectric functional crystal.
Drawings
FIG. 1 is LiKSO in the examples 4 The transmission spectrum (a) and the powder frequency doubling effect (b) of the crystal;
FIG. 2 is example LiKSO 4 The electric hysteresis loop of the crystal.
Fig. 3 is a schematic diagram of the operation of the nonlinear optical device prepared in example 7.
In the figure: 1-incident electromagnetic radiation, 2-nonlinear optics, 3-first emergent electromagnetic radiation, 4-optical filters, 5-second emergent electromagnetic radiation.
Detailed Description
Hereinafter, liKSO will be used 4 The technical scheme of the invention is further detailed by combining the crystal as an example with a specific embodiment. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the 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.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1LiKSO 4 Molten salt growth of crystals
With Li 2 SO 4 As a fluxing agentWill analyze pure Li 2 SO 4 (32.970 g) and K 2 SO 4 (14.200 g) starting Material according to LiKSO 4 Weighing and mixing the stoichiometric ratio and the ratio (1) of the stoichiometric ratio to the fluxing agent, putting the mixture into a platinum crucible, putting the crucible into the center of a molten salt furnace, and covering a furnace cover; heating to 900 ℃ at the speed of 50 ℃/hour, preserving the heat for two days, and then cooling to room temperature at the speed of 50 ℃/hour to obtain the LiKSO 4 And (4) crystals. The crystal is colorless and transparent, has an orthogonal structure at room temperature, and has a space group of P6 3 The cell parameter of which is
α＝β＝90°，γ＝120°。
Example 2LiKSO 4 Aqueous solution method for growing crystals
Will analyze pure Li 2 SO 4 (5.45 g) and K 2 SO 4 (8.715 g) starting Material according to LiKSO 4 Weighing and mixing according to a stoichiometric ratio, adding the mixture into a 200ml beaker, adding deionized water until the raw materials are completely dissolved, continuously adding the deionized water until the amount is doubled, uniformly stirring, heating the mixture to 80 ℃ at the speed of 50 ℃/h in a drying oven, keeping the temperature for two days, and then cooling the mixture to room temperature at the speed of 10 ℃/h to obtain the LiKSO 4 And (4) crystals.
Example 3LiKSO 4 Optical characterization of crystals
(1) The resulting LiKSO was characterized at room temperature using a McPherson2000 vacuum ultraviolet absorption spectrometer and a Lambda950 ultraviolet/visible/near infrared spectrophotometer 4 The transmission spectrum of the crystal (see a in FIG. 1) shows the LiKSO 4 The deep ultraviolet cut absorption edge of the crystal is 160nm.
(2) The Kurtz-Perry method is adopted to test the LiKSO at room temperature 4 The powder frequency doubling effect of the crystal (see b in figure 1) can be seen from the figure, and the LiKSO is known 4 The frequency doubling effect of the crystal is about KH 2 PO 4 4 times of crystal.
Example 4LiKSO 4 Characterization of ferroelectric properties of crystals
The LiKSO is characterized by adopting a TFAnalyzer2000 standard ferroelectric measuring system 4 Ferroelectric properties of the crystal.
And (3) testing conditions are as follows: the frequency of the alternating voltage was 3Hz and the test temperature was 100 ℃.
Referring to fig. 2, it can be seen that: liKSO 4 The coercive electric field of the crystal is 47.67kV/cm, and the remanent polarization is 1.61 mu C/cm 2 。
Example 5LiKSO 4 Stability and mechanical Properties characterization of the crystals
Growing the LiKSO at room temperature 4 After the crystal is placed in the air for one week, no obvious deliquescence phenomenon exists.
For the grown LiKSO 4 The crystal was subjected to cutting processing, and no cracking problem was found.
Description of LiKSO 4 The crystal has stable physical and chemical properties, is not easy to deliquesce, has good mechanical properties and is easy to process.
Example 6 contains LiKSO 4 Deep ultraviolet nonlinear optical device of crystal
The LiKSO obtained in example 2 was subjected to 4 Cutting and polishing the crystal in the direction vertical to the c direction to form an optical wafer with the thickness of 1 mm; coating silver paste on the upper surface and the lower surface of a wafer, putting the wafer into a sample box for polarization, heating to 100 ℃, applying an external voltage of 10kV, and maintaining the pressure for 10min to finish the single domain process; erasing the double-sided silver paste of the crystal, and marking the positive side and the negative side: + c surface and-c surface; plating a film on the + c surface of the crystal, wherein the metal for plating the film comprises Al, cr, au or other alloy materials, and the thickness of the plated film is 60-100 nm; carrying out photoetching, corrosion and other steps on the + c surface of the coated crystal according to coherence length data obtained by refractive index dispersion calculation to manufacture a polarized electrode structure and form a grating electrode; corroding the area of the + c surface except the electrode part for 1-2 minutes by using 40% hydrochloric acid, wherein the corrosion depth is 5-20 mu m, and obtaining the LiKSO 4 At the cavity of the crystal; the + c face is covered with a layer of SiO with a thickness of about 20 μm 2 A dielectric layer having a refractive index of 1.45 to 1.50; after the processes of alignment, development, corrosion and the like, the metal part of the polarized electrode structure is exposed for useApplying an external pulse voltage; in LiKSO 4 Plating a metal electrode with the thickness and the material consistent with those of the + c surface on the-c surface of the crystal, and taking the metal electrode as a negative electrode; applying square wave electric field to the crystal by using a high-voltage pulse polarization power supply to complete periodic polarization; and cleaning the metal electrode on the surface of the crystal to obtain the deep ultraviolet nonlinear optical device.
Example 7 contains LiKSO 4 Frequency doubling output of deep ultraviolet nonlinear optical device of crystal
The working principle is as follows: the wavelengths of the two beams are both lambda 1 And λ 1 By periodically polarized LiKSO in a non-linear optical device 2 4 Crystal generation wavelength is lambda 2 Of emitted electromagnetic radiation, wherein λ 1 And λ 2 The relationship of (1) is:
the product obtained in the manner of example 6 using LiKSO 4 The nonlinear optical device made of crystal is arranged in the light path shown in FIG. 3, and two beams of electromagnetic radiation with the wavelength of 355nm are incident to the periodically polarized LiKSO 4 On the crystal, a first emergent electromagnetic radiation 3 (355 nm and 177.5nm composite electromagnetic radiation) is generated, and a second emergent electromagnetic radiation 5 with the wavelength of 177.5nm is obtained after passing through a filter 4 (355 nm attenuation 99%,177.5nm transmission 80%).
One skilled in the art would expect that LiNH 4 SO 4 Crystals and Li 2 KRbSO 4 The crystal has a structure similar to LiKSO 4 The crystals have at least similar properties, so the LiKSO of example 6 4 Crystal substitution to LiNH 4 SO 4 Crystals or Li 2 KRbSO 4 After the crystal is crystallized, a quasi-phase-matched optical device can be prepared by applying external electric field periodic polarization to the crystal, so as to realize frequency-doubled output shown in embodiment 7.
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 (9)
1. The quasi-phase matching optical device is characterized by being obtained by introducing a quasi-phase matching principle and a periodic polarization method into a sulfate crystal, wherein the sulfate crystal is a ferroelectric deep ultraviolet transparent nonlinear optical crystal, and the sulfate crystal is LiKSO 4 A crystal;
the periodic polarization method comprises the following steps: mixing LiKSO 4 Cutting and polishing the crystal in the direction perpendicular to the c direction to form an optical wafer with the thickness of 1 mm; coating silver paste on the upper surface and the lower surface of a wafer, putting the wafer into a sample box for polarization, heating to 100 ℃, applying an external voltage of 10kV, and maintaining the pressure for 10min to finish the single domain process; erasing the double-sided silver paste of the crystal, and marking the positive and negative surfaces: + c-plane, -c-plane; coating the + c surface of the crystal, wherein the metal for coating comprises Al, cr, au or other alloy materials, and the coating thickness is 60 to 100nm; carrying out photoetching, corrosion and other steps on the + c surface of the coated crystal according to coherence length data obtained by refractive index dispersion calculation to manufacture a polarized electrode structure and form a grating electrode; corroding the area of the + c surface except the electrode part for 1-2 minutes by using 40% hydrochloric acid, wherein the corrosion depth is 5-20 mu m, and obtaining the LiKSO 4 At the cavity of the crystal; the + c face is covered with a layer of SiO with a thickness of about 20 μm 2 A medium layer with a refractive index of 1.45 to 1.50; exposing the metal part of the polarized electrode structure through the processes of alignment, development, corrosion and the like so as to be used for applying an external pulse voltage; in LiKSO 4 Plating a metal electrode with the thickness and the material consistent with those of the + c surface on the-c surface of the crystal, and taking the metal electrode as a negative electrode; a square wave electric field is applied to the crystal by a high-voltage pulse polarization power supply to complete periodic polarization.
2. The quasi-phase-matched optical device of claim 1, wherein the LiKSO 4 The crystal has a hexagonal structure and space group ofP6 3 Cell parameter ofa = b = 5.14280±0.02 Å，c = 8.63230±0.02 Å，α= β= 90 °，γ= 120 °。
3. Quasi-phase-matched optical device according to claim 1 or 2, characterized in that the LiKSO 4 The crystal is a deep ultraviolet transparent material.
4. Quasi-phase-matched optical device according to claim 1 or 2, characterized in that the LiKSO 4 The crystal has a transmission spectrum shown as a in fig. 1.
5. Quasi-phase-matched optical device according to claim 1 or 2, characterized in that the LiKSO 4 The crystal has a frequency doubling effect diagram as shown in b in figure 1.
6. Quasi-phase matching optics according to claim 1 or 2, characterized in that the cut-off absorption edge of the sulphate crystal is less than 200 nm.
7. The quasi-phase-matching optical device of claim 6, wherein said sulfate crystal has a cutoff absorption edge of 160nm.
8. Quasi-phase-matched optical device according to claim 1 or 2, characterized in that the LiKSO 4 The crystal has a ferroelectric hysteresis loop as shown in fig. 2.
9. The quasi-phase-matched optical device according to claim 1 or 2, wherein the sulfate crystal is prepared by: weighing the sulfate compound raw materials according to the metering ratio, uniformly mixing, and preparing the sulfate crystal by adopting a molten salt method or a water solution method.
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