CN114808132A - Oxysulfide nonlinear optical crystal and preparation method and application thereof - Google Patents
Oxysulfide nonlinear optical crystal and preparation method and application thereof Download PDFInfo
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- 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
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- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
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- 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
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Abstract
The invention relates to an oxysulfide nonlinear optical crystal, a preparation method and application thereof, wherein the chemical general formula of the infrared nonlinear optical crystal is A 2 CdGe 2 OS 6 Wherein A is selected from one or more of alkaline earth metal Ca, Sr, Ba or rare earth metal Eu, the infrared nonlinear optical crystal belongs to a tetragonal system, and the space group is
Having a layered structure of [ CdGe ] 2 OS 6 ] 4‑ The alkaline earth metal or rare earth metal ions between the layers are stacked along the c-axis direction, and Cd coordinates with four adjacent S to form [ CdS ] 4 ] 6‑ Tetrahedron, Ge coordinated to three S-O surrounding [ GeOS ] 3 ] 4‑ Tetrahedron, [ CdS 4 ] 6‑ Tetrahedron by sharing vertices with four [ GeOS ] 3 ] 4‑ Tetrahedral interconnection, [ GeOS 3 ] 4‑ The tetrahedra are connected to each other by a common vertex O.
Description
Technical Field
The invention relates to an inorganic crystal material, a preparation method and an application thereof as a nonlinear optical crystal, belonging to the field of inorganic materials.
Background
Medium-far infrared laser with wavelength range of 3-20 μm in laser guidance, photoelectric countermeasure and infrared laser communicationThe system plays a very important role in various aspects such as environmental monitoring, drug inspection and the like. The infrared nonlinear optical crystal is a core component for determining the output power and the tunable range of infrared laser, and is a crystal material with high strategic value. The ideal infrared nonlinear optical crystal needs to have the characteristics of large nonlinear response, high laser damage threshold, wide optical transmission range, easy crystal growth and the like. However, ZnGeP practical in infrared band at present 2 、AgGaS 2 And AgGaSe 2 And the crystal has the defects of small nonlinear response, low laser damage resistance threshold value and the like, so that the large-scale use of the crystal is limited. Therefore, the exploration of novel high-performance infrared nonlinear optical crystals has important strategic significance and application value.
Disclosure of Invention
The invention aims to provide a novel oxysulfide infrared nonlinear optical crystal and a preparation method thereof.
In a first aspect, the present invention provides an infrared nonlinear optical crystal having a chemical formula A 2 CdGe 2 OS 6 Wherein A is selected from one or more of alkaline earth metal Ca, Sr, Ba or rare earth metal Eu, the infrared nonlinear optical crystal belongs to a tetragonal system, and the space group is
The infrared nonlinear optical crystal has a layered structure consisting of [ CdGe ] 2 OS 6 ] 4- The alkaline earth metal or rare earth metal ions (Ca ion, Sr ion, Ba ion, Eu ion) between the layers are stacked along the c-axis direction, and Cd coordinates with four adjacent S to form [ CdS ] 4 ] 6- Tetrahedron, Ge coordinated to three S-O surrounding [ GeOS ] 3 ] 4- Tetrahedron, [ CdS 4 ] 6- Tetrahedron by sharing vertices with four [ GeOS ] 3 ] 4- Tetrahedral interconnection, [ GeOS 3 ] 4- The tetrahedra are connected to each other by a common vertex O.
In a second aspect, the present invention provides a method for preparing any one of the above infrared nonlinear optical crystals, comprising: placing raw materials containing an alkaline earth or rare earth metal source, a cadmium source, a germanium source, an oxygen source and a sulfur source under a vacuum condition, preserving the temperature at 700-900 ℃ for more than 24 hours by adopting a high-temperature solid-phase reaction method, and then cooling.
The molar ratio of the alkaline earth or rare earth metal elements, the cadmium elements, the germanium elements, the oxygen elements and the sulfur elements in the raw materials can be (2-3) to 1:2 (1-2) to (6-8). The oxygen and sulfur elements may be derived from the same compound as the alkaline earth or rare earth metal elements, cadmium elements, germanium elements, e.g. the feedstock comprises alkaline earth or rare earth metal oxides, alkaline earth or rare earth metal sulfides, cadmium sulfide (CdS) and germanium disulfide (GeS) 2 )。
The high temperature solid phase reaction method may include raising the temperature to 750-850 ℃ at a rate of 75-85 ℃/hr.
The high-temperature solid-phase reaction method comprises the steps of heating to 750-850 ℃, preserving heat for 48-72 hours, then cooling to 650 ℃ at a cooling rate of 3-8 ℃/hour, and then naturally cooling to room temperature.
In a third aspect, the invention provides an infrared detector comprising the infrared nonlinear optical crystal.
In a fourth aspect, the present invention provides an infrared laser, which comprises the above infrared nonlinear optical crystal.
In a fifth aspect, the present invention provides a use of the above infrared nonlinear optical crystal, which can realize visible, near-infrared and mid-far infrared laser frequency conversion output, and is used for infrared countermeasure, resource detection, spatial counterguidance, laser communication, medical diagnosis and treatment, or molecular spectroscopy (including forming a device/system with at least one of the uses).
The invention provides a novel oxysulfide infrared nonlinear optical crystal with a chemical general formula A 2 CdGe 2 OS 6 Wherein A is selected from alkaline earth metal Ca, Sr, Ba or rare earth metal Eu, has large nonlinear response, high laser damage threshold, wide optical transmission range and easy crystal growth, and has wide application prospect in various fields such as infrared detectors, infrared lasers, infrared countermeasure, resource detection, space reflection, laser communication, medical diagnosis and treatment, or molecular spectroscopy and the like. Class A 2 CdGe 2 OS 6 The crystal has a layered structure consisting of [ CdGe ] 2 OS 6 ] 4- The alkaline earth or rare earth metal ions between the layers are stacked (see fig. 1). The valence of alkaline earth or rare earth metal, Cd, Ge, O and S in the crystal structure is respectively +2, +4, -2 and-2. Cd coordinated to four adjacent S to form [ CdS ] 4 ] 6- Tetrahedron, Ge coordinated to three S-O surrounding [ GeOS ] 3 ] 4- Tetrahedrons, which are connected to each other by a common vertex. The existence of oxygen ions in the structure is beneficial to increasing the band gap so as to improve the laser damage threshold, and the asymmetry of the coordination polyhedron can be increased so as to be beneficial to generating larger nonlinear optical effect. Tests show that Sr is used 2 CdGe 2 OS 6 For example, the powder has an optical band gap of about 3.0eV, a wide optical transmission window of 0.4 to 13.6 μm, and a laser damage threshold of about commercial AgGaS 2 11.6 times of the crystal powder sample, under 1570nm fundamental frequency light irradiation, the crystal grain diameter is in the range of 150-212 mu m, and the frequency doubling capability of the crystal powder sample is commercial AgGaS 2 0.9 times of.
Drawings
FIG. 1 shows the present invention A 2 CdGe 2 OS 6 The infrared nonlinear optical crystal structure schematic diagram;
FIG. 2 shows Sr in example 2 of the present invention 2 CdGe 2 OS 6 The powder X-ray diffraction pattern of (a) is an experimental pattern, and b is a theoretical pattern;
FIG. 3 shows Sr in example 2 of the present invention 2 CdGe 2 OS 6 Ultraviolet-visible diffuse reflectance map of;
FIG. 4 shows Sr in example 2 of the present invention 2 CdGe 2 OS 6 An infrared spectrum of (1);
FIG. 5 shows Sr in embodiment 2 of the present invention 2 CdGe 2 OS 6 、AgGaS 2 Graph of the doubled frequency intensity versus the sample particle size.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
Book of JapaneseRelates to an infrared nonlinear optical crystal and a preparation method thereof, and the chemical general formula of the infrared nonlinear optical crystal is A 2 CdGe 2 OS 6 Wherein A is one or more selected from alkaline earth metal Ca, Sr, Ba or rare earth element Eu, belongs to tetragonal system, and has space group of
Has a layered structure. The crystal material has excellent nonlinear optical property and is used as A 2 CdGe 2 OS 6 Sr as one example of (1) 2 CdGe 2 OS 6 The powder frequency doubling intensity at 1570nm is AgGaS 2 0.9 times of the total laser damage threshold value of the laser, and the laser damage threshold value is AgGaS 2 11.6 times of the total surface area of the glass, and has a wide optical transmission window of 0.4 to 13.6 μm. The crystal can be used for manufacturing nonlinear optical devices, has wide application prospect in multiple fields, and can be used for infrared countermeasure, infrared laser communication, medical diagnosis and treatment and the like.
Embodiment 1
The infrared nonlinear optical crystal A of the present embodiment 2 CdGe 2 OS 6 (A ═ Ca, Sr, Ba, Eu) belongs to the tetragonal system, and the space group is
Further, the nonlinear optical crystal A of the present embodiment 2 CdGe 2 OS 6 Having a layered structure consisting of [ CdGe ] 2 OS 6 ] 4- The alkaline earth or rare earth metal ions between the layers are stacked (see fig. 1). The valence of alkaline earth or rare earth metal, Cd, Ge, O and S in the crystal structure is respectively +2, +4, -2 and-2. Cd coordinated to four adjacent S to form [ CdS ] 4 ] 6- Tetrahedron, Ge coordinated to three S-O surrounding [ GeOS ] 3 ] 4- Tetrahedrons, which are connected to each other by a common vertex. Specifically, [ CdS 4 ] 6- Tetrahedron by sharing vertices with four [ GeOS ] 3 ] 4- Tetrahedral interconnection, [ GeOS 3 ] 4- The tetrahedra are connected to each other by a common vertex O. As A 2 CdGe 2 OS 6 Sr as one example of (1) 2 CdGe 2 OS 6 The unit cell parameters are as follows:
α ═ β ═ γ ═ 90 °, Z ═ 2 (measurement temperature 180K), and its crystallographic data are shown in table 1.
TABLE 1 Sr 2 CdGe 2 OS 6 Crystallographic data of
Hereinafter, the nonlinear optical crystal A of the present invention is exemplarily described 2 CdGe 2 OS 6 The preparation method of (1).
The raw materials containing alkaline earth or rare earth metal source, cadmium source, germanium source, oxygen source and sulfur source can be placed under vacuum condition, and prepared by adopting high-temperature solid-phase reaction method. The raw materials can be well ground and mixed uniformly in, for example, a mortar. The vacuum condition is, for example, vacuum pumping to 0.1 to 0.3Pa, and the mixed raw materials can be sealed in, for example, a quartz tube. The molar ratio of the alkaline earth or rare earth metal elements, the cadmium elements, the germanium elements, the oxygen elements and the sulfur elements in the raw materials can be (2-3) to 1:2 (1-2) to (6-8), so that a product with high purity can be further obtained. The oxygen and sulfur elements may be derived from the same compound as the alkaline earth or rare earth metal elements, cadmium elements, germanium elements, e.g. the feedstock comprises alkaline earth or rare earth metal oxides, alkaline earth or rare earth metal sulfides, cadmium sulfide (CdS) and germanium disulfide (GeS) 2 )。
The mixed raw materials can be placed under the vacuum condition, the temperature is raised to 700-900 ℃, and the temperature is reduced and cooled after the temperature is kept for more than 24 hours. In the high-temperature solid-phase reaction method, the temperature is preferably raised to 750-850 ℃ at a rate of 75-85 ℃/hour, so that the preparation of crystals with higher quality and purity can be realized. In some embodiments, the reaction vessel may be a quartz tube, which is vacuumed to 0.1Pa, melted and sealed, and then placed in a muffle furnace to be heated to 750-850 ℃ at a rate of 75-85 ℃/hr. In addition, the temperature is preferably raised to 750-850 ℃, then the temperature is kept for 48-72 hours, then the temperature is lowered to 650 ℃ at the cooling rate of 3-8 ℃/hour, and then the temperature is naturally cooled to room temperature, so that the growth of crystals with larger size can be realized.
In some embodiments, the nonlinear optical crystal A 2 CdGe 2 OS 6 The preparation method of (2) may comprise:
(a) uniformly mixing raw materials containing alkaline earth or rare earth elements, cadmium elements, germanium elements, oxygen elements and sulfur elements in a molar ratio of 2-3: 1:2: 1-2: 6-8, putting the raw materials into a reaction container, vacuumizing and sealing the container.
(b) Placing the sealed reaction vessel in the step (a) into a muffle furnace, heating to 700-900 ℃, preserving the temperature for a period of time, and then cooling to room temperature to obtain the product A 2 CdGe 2 OS 6 。
The invention provides a novel infrared nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the novel infrared nonlinear optical crystal is A 2 CdGe 2 OS 6 Wherein A is selected from alkaline earth or rare earth metals. The crystal has larger nonlinear response intensity and high laser damage threshold. The infrared nonlinear optical crystal A of the invention 2 CdGe 2 OS 6 The structure does not have a symmetry center, so that the nonlinear optical effect generating condition is provided, two anions exist in the material, and the existence of oxygen ions in the structure is beneficial to increasing the band gap so as to improve the laser damage threshold, and the asymmetry of the coordination polyhedron can be increased so as to be beneficial to generating a larger nonlinear optical effect. As A 2 CdGe 2 OS 6 Sr as one example of (1) 2 CdGe 2 OS 6 The nonlinear response intensity and the laser damage threshold value of the laser are AgGaS respectively under the same condition 2 0.9 times and 11.6 times of the crystal. The crystal is a novel oxysulfide infrared nonlinear optical crystal, has wide application prospect in various fields, such as infrared countermeasure, infrared laser, infrared detector, medical diagnosis and other application fields, and can realize visible, near infrared and middle and far infrared laser frequency conversion output.
The infrared nonlinear optical crystal A of the invention 2 CdGe 2 OS 6 The middle A site ion plays the role of a structural template to support the crystal structure, and the alkaline earth metal Ca ion, Sr ion, Ba ion and the rare earth metal Eu ion have the same structureThe charge quantity and strong ionic property can be mutually replaced to occupy the A site, such as Sr 2 CdGe 2 OS 6 (
α ═ β ═ γ ═ 90 °, Z ═ 2) (measurement temperature 180K), Eu 2 CdGe 2 OS 6 (
α ═ β ═ γ ═ 90 °, Z ═ 2) (measurement temperature 180K). The nonlinear optical property of the crystal mainly consists of covalent [ CdGe ] 2 OS 6 ]The layers are produced so that the crystals have nonlinear optical properties after the substitution of the A-site ions.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
In the following examples, the reagents, materials and instruments used are all conventional reagents, conventional materials and conventional instruments, which are commercially available, unless otherwise specified, and the reagents involved therein may also be synthesized by conventional synthesis methods.
Example 1
Sr 2 CdGe 2 OS 6 Preparation of crystals: weighing 0.1036g SrO, 0.1197g SrS, 0.1445g CdS and 0.1368g GeS 2 (i.e. SrO, SrS, CdS, GeS with a molar ratio of 1:1:1:2 2 ) After fully grinding and uniformly mixing in a mortar, transferring the mixture into a quartz tube with the inner diameter of 1cm for vacuum packaging, and vacuumizing to 0.1 Pa. Stone to be sealedThe quartz tube is placed into a muffle furnace, and the heat preservation program is set as follows: heating to 850 ℃ within 10 hours, preserving the heat for 48 hours at 850 ℃, then cooling to 650 ℃ at the cooling rate of 3 ℃ per hour, and then naturally cooling to room temperature. The product is taken out from the quartz tube to obtain Sr 2 CdGe 2 OS 6 Crystals, wherein the size of part of the crystals can reach millimeter level.
Example 2
And (3) performance testing:
1) the obtained crystal was ground and then subjected to a powder X-ray diffraction test, and the results are shown in FIG. 2. The obtained powder X-ray diffraction pattern and the single crystal structure are analyzed to obtain Sr 2 CdGe 2 OS 6 The theoretical X-ray diffraction patterns of the crystal are consistent, and the obtained crystal is proved to have higher purity.
2) Determination of Sr using UV-Vis-NIR Diffuse reflectance Spectroscopy 2 CdGe 2 OS 6 The crystal had a band gap of 3.0eV, as shown in FIG. 3. Compared with AgGaS 2 The band gap of the crystal is 2.64eV, and the compound has a wider band gap.
3) To the obtained Sr 2 CdGe 2 OS 6 The crystal was characterized by IR spectroscopy, and the results are shown in FIG. 4, where it can be seen that the crystal obtained had an IR absorption cutoff of 13.6 μm, an optical transmission range of 0.4-13.6 μm, covering an atmospheric transmission window of 3-5, 8-12 μm.
4) Sr with the grain diameter of 150- 2 CdGe 2 OS 6 Crystal and AgGaS 2 Nb at 1064nm with a pulse time of 10 ns: under the irradiation of YAG laser, the laser energy is continuously increased until a crystal damage trace is observed under a microscope, and the formula LDT is E/(S multiplied by PW), wherein E is the laser energy, S is the laser beam area, and PW is the laser pulse width. The test shows that Sr 2 CdGe 2 OS 6 The laser damage threshold of the crystal is AgGaS 2 11.6 times of the total weight of the powder.
5) Sr prepared in example 1 2 CdGe 2 OS 6 Sieving the crystal to obtain samples with the particle size ranging from small to large, carrying out frequency doubling response test (SHG) on the samples with different particle sizes under the irradiation of 1570nm fundamental frequency light,the concrete result is shown in FIG. 5, Sr with a particle size of 150-212 μm 2 CdGe 2 OS 6 Crystal SHG strength of AgGaS 2 0.9 times of. Fig. 5 is an effect diagram of laser frequency conversion, and the nonlinear optical effect is generally generated by a structure without a symmetrical center, namely, the crystal in the invention has a noncentral structure.
Example 3
Eu 2 CdGe 2 OS 6 Preparation of crystals: weighing 0.1680g EuO, 0.1840g EuS, 0.1445g CdS and 0.1368g GeS 2 (i.e. a molar ratio of 1:1:1:2 EuO, EuS, CdS, GeS 2 ) After sufficiently grinding and uniformly mixing in a mortar, the mixture was transferred to a quartz tube having an inner diameter of 1cm and vacuum-sealed. And (3) putting the sealed quartz tube into a muffle furnace, and setting a heat preservation program as follows: heating to 850 ℃ within 10 hours, preserving the heat for 48 hours at 850 ℃, then cooling to 650 ℃ at the cooling rate of 3 ℃ per hour, and then naturally cooling to room temperature. Taking out the product from the quartz tube to obtain Eu 2 CdGe 2 OS 6 And (4) crystals.
Claims (8)
1. An infrared nonlinear optical crystal is characterized in that the chemical general formula is A 2 CdGe 2 OS 6 Wherein A is selected from one or more of alkaline earth metal Ca, Sr, Ba or rare earth metal Eu, the infrared nonlinear optical crystal belongs to a tetragonal system, and the space group is
Having a layered structure consisting of [ CdGe ] 2 OS 6 ] 4- The alkaline earth metal or rare earth metal ions between the layers are stacked along the c-axis direction, and Cd coordinates with four adjacent S to form [ CdS ] 4 ] 6- Tetrahedra, Ge coordinated with three S-O of the surroundings [ GeOS 3 ] 4- Tetrahedron, [ CdS 4 ] 6- Tetrahedron by sharing vertices with four [ GeOS ] 3 ] 4- Tetrahedral interconnection, [ GeOS 3 ] 4- The tetrahedra are connected to each other by a common vertex O.
2. A method for preparing an infrared nonlinear optical crystal according to claim 1, comprising: placing raw materials containing an alkaline earth or rare earth metal source, a cadmium source, a germanium source, an oxygen source and a sulfur source under a vacuum condition, preserving the temperature at 700-900 ℃ for more than 24 hours by adopting a high-temperature solid-phase reaction method, and then cooling.
3. The preparation method according to claim 2, wherein the molar ratio of the alkaline earth or rare earth metal element, the cadmium element, the germanium element, the oxygen element and the sulfur element in the raw materials is (2-3): 1:2, (1-2): 6-8.
4. The method according to claim 2 or 3, wherein the high temperature solid phase reaction method comprises raising the temperature to 750-850 ℃ at a rate of 75-85 ℃/hr.
5. The preparation method according to any one of claims 2 to 4, wherein the high-temperature solid-phase reaction method comprises the steps of heating to 750-850 ℃, then preserving heat for 48-72 hours, then cooling to 650 ℃ at a cooling rate of 3-8 ℃/hour, and then naturally cooling to room temperature.
6. An infrared detector comprising the infrared nonlinear optical crystal according to claim 1.
7. An infrared laser comprising the infrared nonlinear optical crystal according to claim 1.
8. Use of the infrared nonlinear optical crystal according to claim 1, for infrared countermeasure, resource detection, spatial inversion, laser communication, medical diagnosis, or molecular spectroscopy.
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