CN117420716B - Infrared nonlinear optical crystal and preparation method and application thereof - Google Patents
Infrared nonlinear optical crystal and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
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- 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
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
Abstract
The invention provides an infrared nonlinear optical crystal, a preparation method and application thereof, and belongs to the technical field of optical crystal materials, wherein the chemical formula of the infrared nonlinear optical crystal is Cu 5 Cd 0.5 P 2 S 8 Belongs to an orthorhombic system, and the space group isPmn2 1 (No. 31) unit cell parameters area=7.32Å～7.33Å，b=6.33Å～6.34Å，c=6.07 a to 6.08 a, α=β=γ=90°; the infrared nonlinear optical crystal is prepared by adopting high-temperature solid phase reaction, can be applied to various nonlinear optical devices and optical information memories in a middle-far infrared region, and has good laser damage resistance.
Description
Technical Field
The invention relates to the technical field of optical crystal materials, in particular to an infrared nonlinear optical crystal, a preparation method and application thereof.
Background
The infrared nonlinear optical crystal is an extremely important middle-far infrared laser frequency conversion core element. The infrared laser has less absorption at the atmospheric windows (3-5 and 8-14 mu m), and has important application in the fields of communication, military, scientific research, engineering and the like. The development of nonlinear optical crystals for laser frequency conversion is the most effective means to obtain a stable and tunable mid-far infrared laser at high frequencies. The nonlinear optical crystal material is a crystal material having a frequency conversion effect, an electro-optical effect, a photorefractive effect, and the like. As light propagates in a medium (crystal), an optical frequency electric field causes it to produce an electrical polarization, thereby generating a polarized field that again produces radiated light over time. When the laser is strong, the second nonlinear term of the polarization coefficient is not negligible, and the radiation light generated by the nonlinear polarization field generated by the second nonlinear term is subjected to frequency conversion. The development of the novel high-performance infrared nonlinear optical crystal is key to obtaining stable continuous adjustable high-power middle-far infrared laser, and has important significance.
The metal chalcogen system compound is more suitable for the infrared nonlinear optical field because weaker interatomic bonds are less absorbed at the atmospheric window. But far infrared crystals such as CdSe, agGaS are commercially available 2 And AgGaSe 2 Etc., all have respective defects, such as damage thresholdLow nonlinear response, poor far infrared transmittance, small energy band, incapability of using 1 mu m pump light, and the like. Therefore, the synthesis of the novel infrared nonlinear optical material and the non-heart structural design aiming at nonlinear parameters are the difficult problems of the international leading-edge scientific research competitive phase breakthrough in the field.
Disclosure of Invention
The invention aims to provide an infrared nonlinear optical crystal, a preparation method and application thereof, wherein the infrared nonlinear optical crystal has a higher laser damage threshold.
To achieve the above object, the present invention provides an infrared nonlinear optical crystal having a chemical formula of Cu 5 Cd 0.5 P 2 S 8 Belongs to an orthorhombic system, and the space group is Pmn2 1 (No. 31) unit cell parameters area = 7.32 Å～7.33 Å，b = 6.33 Å～6.34 Å，c = 6.07 Å～6.08 Å，α = β = γ = 90°。
Optionally, the infrared nonlinear optical crystal is diamond-like in structure.
Optionally, the infrared nonlinear optical crystal comprises a rimcLayers arranged in layers and interconnected by an axis, each of said layers comprising a layer extending along the axisaFirst and second chains having axes alternately arranged and connected to each other; the first chain includes a rimbA first distorted tetrahedral structure and a second distorted tetrahedral structure having axes alternately arranged and connected to each other, said second chain comprising a plurality of chains extending along the length of the first chainbA third distorted tetrahedral structure with axes connected in sequence; the central atoms of the first distorted tetrahedral structure are P, the central atoms of the second distorted tetrahedral structure are 3/4 Cu and 1/4 Cd, the central atoms of the third distorted tetrahedral structure are 7/8 Cu, the coordination atoms of all distorted tetrahedral structures are S, and two adjacent distorted tetrahedral structures share the coordination atoms.
In order to achieve the above object, the present invention further provides a method for preparing an infrared nonlinear optical crystal, for preparing an infrared nonlinear optical crystal as described above, comprising: grinding and mixing a Cu source, a Cd source, a P source and an S source to obtain raw material powder; placing the raw material powder in a reaction tube, and vacuumizing and sealing the reaction tube; and (3) carrying out high-temperature solid-phase reaction on the raw material powder in the reaction tube, and then cooling to room temperature to obtain a reaction product.
Optionally, the vacuum degree of the reaction tube is less than or equal to 10 -2 mbar。
Optionally, the step of subjecting the raw material powder in the reaction tube to a high-temperature solid-phase reaction includes: and heating the reaction tube and the raw material powder to ensure that the temperature of the reaction tube and the raw material powder rises to a preset reaction temperature, and then preserving the heat of the reaction tube and the raw material powder.
Optionally, the reaction temperature is 650-900 ℃, and the heat preservation time is 1000-5000 min.
Optionally, the reaction tube is a quartz tube; the temperature rising rate of the reaction tube and the raw material powder is 50 ℃/h to 100 ℃/h.
Optionally, the cooling rate after the high temperature solid phase reaction is 1 ℃ to 10 ℃ per hour.
In order to achieve the above object, the present invention also provides an application of the infrared nonlinear optical crystal as described above.
Compared with the prior art, the infrared nonlinear optical crystal and the preparation method and application thereof have the following advantages: the chemical formula of the infrared nonlinear optical crystal is Cu 5 Cd 0.5 P 2 S 8 Belongs to an orthorhombic system, and the space group isPmn2 1 (No. 31) unit cell parameters area = 7.3211(4) Å, b = 6.3333(3) Å, c = 6.0742(3) Å，α = β = γThe energy band of the infrared nonlinear optical crystal is 2.35 eV, the two-photon absorption under 1064 nm pump light can be avoided, no strong absorption caused by chemical bond vibration exists in the infrared range of 3.0-25 μm, the infrared nonlinear optical crystal is suitable for middle-far infrared range application, the infrared nonlinear optical crystal also has a double frequency effect, and the laser damage threshold is AgGaS 2 Is 8.04 times of that of the laser frequency converter, the optical parametric oscillator and the optical parametric oscillator, and can be applied toVarious devices such as a quantity amplifier, a photoelectric rectifier, an electro-optical switch, an optical information storage and the like. In addition, the infrared nonlinear optical crystal is prepared through high-temperature solid-phase reaction, and is simple to operate and easy to realize.
Drawings
The drawings are included to provide a better understanding of the invention and are not to be construed as unduly limiting the invention.
Fig. 1 is a crystal structure diagram of a sample 1 prepared by a method for preparing an infrared nonlinear optical crystal according to a first embodiment of the present invention.
Fig. 2 is a crystal structure diagram of a sample 1 prepared by a method for preparing an infrared nonlinear optical crystal according to a first embodiment of the present invention, and the viewing direction of fig. 2 is different from that of fig. 1.
Fig. 3 is a schematic diagram of layer a of fig. 1.
Fig. 4 is a schematic diagram of the B chain in fig. 3.
Fig. 5 is a schematic diagram of the C chain of fig. 3.
The powder XRD pattern and fitted Cu of sample 1 prepared by the method for preparing an infrared nonlinear optical crystal according to the present invention, provided in the first embodiment, are shown in FIG. 6 5 Cd 0.5 P 2 S 8 XRD pattern of single crystal.
Fig. 7 is an ultraviolet-visible-diffuse reflection chart of a sample 1 prepared by the method for preparing an infrared nonlinear optical crystal according to the first embodiment of the present invention.
Fig. 8 is a graph of percent absorption versus wavelength curve of fig. 7.
Fig. 9 is an infrared spectrum of a sample 1 prepared by the method for preparing an infrared nonlinear optical crystal according to the first embodiment of the present invention.
Fig. 10 is a graph showing the frequency doubling performance of sample 1 prepared by the method for preparing an infrared nonlinear optical crystal according to the first embodiment of the present invention.
FIG. 11 shows a sample 1 and a commercial AgGaS prepared by the method for preparing an infrared nonlinear optical crystal according to the first embodiment of the present invention 2 Is a graph of partial performance comparisons of (c).
Fig. 12 is an XRD pattern of sample 2 prepared according to the method of preparing an infrared nonlinear optical crystal according to the second embodiment of the present invention.
Fig. 13 is an XRD pattern of sample 3 prepared according to the preparation method of an infrared nonlinear optical crystal according to the third embodiment of the present invention.
Fig. 14 is an XRD pattern of sample 4 prepared according to the method of preparing an infrared nonlinear optical crystal according to the fourth embodiment of the present invention.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
In addition, each embodiment of the following description has one or more features, respectively, which does not mean that the inventor must implement all features of any embodiment at the same time, or that only some or all of the features of different embodiments can be implemented separately. In other words, those skilled in the art can implement some or all of the features of any one embodiment or a combination of some or all of the features of multiple embodiments selectively, depending on the design specifications or implementation requirements, thereby increasing the flexibility of the implementation of the invention where implemented as possible.
The invention aims to provide an infrared nonlinear optical crystal, and a preparation method and application thereof. The chemical formula of the infrared nonlinear optical crystal is Cu 5 Cd 0.5 P 2 S 8 Belongs to an orthorhombic system, and the space group isPmn2 1 (No. 31) unit cell parameters area = 7.32 Å～7.33 Å，b = 6.33 Å～6.34 Å，c = 6.07 Å～6.08 Å，α = β = γ=90°. The infrared nonlinear optical crystal has a nonlinearThe sexual optical effect can be applied to mid-far infrared optical devices, has a considerable laser damage threshold, is not easy to generate cracks under laser irradiation, and has good service performance. For convenience of description, the "infrared nonlinear optical crystal" will be hereinafter simply referred to as "crystal".
The crystal can be applied to various nonlinear optical devices, including but not limited to any one of a laser frequency converter, an optical parametric oscillator, an optical parametric amplifier, a photoelectric rectifier and an electro-optical switch. The crystal can also be applied to an optical information storage device.
The preparation method of the crystal comprises the following steps of S10, S20 and S30, wherein the step of S10 comprises the steps of grinding and mixing a Cu source, a Cd source, a P source and an S source to obtain raw material powder. The step S20 includes placing the raw material powder in a reaction tube and vacuum-sealing. The step S30 includes subjecting the raw material powder in the reaction tube to a high-temperature solid-phase reaction, and then cooling the reaction tube and the substances therein to room temperature.
Wherein the Cu source can be Cu simple substance or Cu-containing compound such as Cu 2 S, S. The Cd source may be elemental Cd or a Cd-containing compound, such as CdS. The P source may be elemental P or a P-containing compound such as P 2 S 5 . The S source can be S simple substance or S-containing compound such as Cu 2 S、CdS、P 2 S 5 As long as the ratio of Cu atoms, cd atoms, P atoms, S atoms meets the preset requirements, for example, meets 5:0.5:2:8 (i.e., all the reaction raw materials are completely reacted). In one non-limiting embodiment, the Cu source is Cu 2 S, wherein the Cd source is CdS, and the P source is P 2 S 5 It is understood that the Cu source, the Cd source, and the P source are also the S source at the same time.
The reaction tube is typically a quartz tube. After the raw material powder is loaded on the quartz tube, the end part of the quartz tube is heated by oxyhydrogen flame while vacuumizing, so that the quartz tube is molten and can be sealed. The quartz isThe degree of vacuum in the tube is generally less than or equal to 10 -2 mbar。
The specific step of "making the raw material powder in the reaction tube perform a high-temperature solid-phase reaction" includes heating the reaction tube and the raw material separately so that the temperatures of the reaction tube and the raw material powder rise to a preset reaction temperature, and then keeping the temperature of the reaction tube and the raw material powder so that the high-temperature solid-phase reaction can be continuously performed. In practice, this step is performed by means of a muffle furnace, i.e. the reaction tube loaded with the raw powder is placed inside the muffle furnace and heated as the furnace heats up. Wherein the reaction temperature is 650-900 ℃ and the temperature rising rate is 50-100 ℃/h. In a specific embodiment, the reaction temperature is 750 ℃ and the rate of temperature rise is 75 ℃. It should be appreciated that the rate of temperature rise is not too fast, otherwise the S source may gasify resulting in an increase in pressure within the reaction tube causing the reaction tube to rupture. In addition, the duration of the heat preservation is 1000 min-5000 min, such as 1440 min and 2880 min, so that the reaction is fully carried out.
After the reaction is completed, the reaction tube and the substances therein are cooled with the furnace. The cooling rate is 1 ℃/h to 10 ℃/h, such as 3 ℃/h, 5 ℃/h, etc. Finally, breaking the quartz tube to obtain the crystal.
The preparation method of the crystal and the prepared crystal are further described below by specific examples.
The operation of the first embodiment of the present invention includes: 1.25 mmol Cu is weighed according to the stoichiometric ratio 2 S, 0.25 mmol CdS and 0.5 mmol P 2 S 5 . And mixing and grinding uniformly to obtain the raw material powder. Placing the raw material powder into a quartz tube, and vacuumizing the quartz tube loaded with the raw material powder to 10 by using a vacuum pump -2 mbar and the open end of the quartz tube was melt sealed using an oxyhydrogen flame gun. The quartz tube was then placed in a muffle furnace and a temperature program was set to raise the room temperature to 750 ℃ over 600 min, followed by a soak time of 2880 min (i.e., soak time of 48 h). Then, the muffle furnace is cooled at a cooling rate3 ℃/h up to room temperature. And finally, taking the quartz tube out of the muffle furnace, and breaking the quartz tube to obtain a large number of orange single crystal particles of sample 1.
The structural information of the sample 1 is collected by an X-ray single crystal diffractometer (D8 QUEST single crystal diffractometer, bloC, germany), the optical performance of the sample 1 is tested by an ultraviolet spectrometer and an infrared spectrometer, and the secondary frequency multiplication effect of the sample 1 is tested by a laser powder frequency multiplier.
FIGS. 1 to 5 show the crystal structure of the sample 1 obtained by the X-ray single crystal diffractometer with APEX3 software refinement analysis, wherein FIG. 1 shows the crystal structure alongaThe resulting crystal structure was observed on the axis,athe axis being perpendicular to the page and not shown, FIG. 2 shows alongcThe resulting crystal structure was observed on the axis,cthe axis is perpendicular to the paper and is not shown, FIG. 3 shows a schematic view of layer A in FIG. 1, layer A being ∞ 2 [Cu 2.5 Cd 0.25 PS 8 ] 8- The layer, FIG. 4 is a schematic view of the B chain of FIG. 3, B chain ∞ 1 [Cu 1.75 S 6 ] 8.5- FIG. 5 is a schematic view of the C chain of FIG. 3, the C chain being ∞ 1 [MPS 6 ] 5.75- (m=0.75 Cu/0.25 Cd) chains. As shown in fig. 1 to 5, the crystal is of a diamond-like structure, and includes three distorted tetrahedra therein, hereinafter referred to as a first distorted tetrahedra, a second distorted tetrahedra, and a third distorted tetrahedra, respectively. The central atoms of the first distorted tetrahedron are P, the central atoms of the second distorted tetrahedron are 3/4 Cu and 1/4 Cd, the central atoms of the third distorted tetrahedron are 7/8 Cu, the coordination atoms of all distorted tetrahedron structures are S, and two adjacent distorted tetrahedron structures share the coordination atoms. Wherein the Cu occupancy in the third distorted tetrahedra is 87.5%, in other words, the crystal is a vacancy-containing diamond-like structure, which is advantageous in enhancing the nonlinear optical effect of the crystal. As can be seen from fig. 1, the crystal comprises a rimcA plurality of layers arranged in a stacked manner and connected to each other, each of the layers having a structure as shown in FIG. 2 and FIG. 3Comprises a rimaFirst and second chains with axes alternately arranged and connected, the first chain having a structure as shown in chain B in FIG. 3 and FIG. 4, and the second chain having a structure as shown in chain C in FIG. 3 and FIG. 5, wherein the first chain comprises a chainbThe first distorted tetrahedron and the second distorted tetrahedron are alternately arranged along axes and are connected with each other, and the second chain comprises a chain edgebAnd a plurality of the third distorted tetrahedrons with axes connected in sequence. In addition, the crystal data and finishing data of the crystal are also given in table 1 below.
The powder XRD pattern and fitted Cu of sample 1 are shown in FIG. 6 5 Cd 0.5 P 2 S 8 XRD pattern of single crystal. As can be seen from fig. 6, the purity of sample 1 is 100%.
FIG. 7 shows the ultraviolet-visible-diffuse reflectance spectrum of the sample 1, in which (F #R)hv) 2 = (1-R) 2 /2R= B(hv – E g )，RIs the reflectivity. Fig. 8 is a plot of percent absorption versus wavelength for fig. 7. As can be seen from fig. 7 and 8, the energy band of the crystal is 2.35 eV. Those skilled in the art will recognize that when the energy band of the crystal is greater than 2.33 and eV, two-photon absorption by 1064 and nm pump light can be avoided, and the present invention can be applied to laser frequency converters of pump light above 1064 and nm. Thus, the crystal prepared in this example has the potential to be applied to optical devices and optical information storage devices in the infrared region.
Fig. 9 shows an infrared spectrogram of the sample 1. As shown in fig. 9, the sample 1 does not exhibit strong absorption by chemical bond vibration in the infrared range of 3.0 μm to 25 μm, and is suitable for mid-far infrared range application.
Fig. 10 shows a schematic diagram of the double frequency performance of the sample 1. As shown in fig. 10, the particle size of the sample 1 has a double frequency signal at least at less than 200 nm, and exhibits a nonlinear optical effect.
FIG. 11 shows the sample 1 with a commercial AgGaS 2 Is a graph of partial performance comparisons of (c). As can be seen from fig. 11, the laser damage threshold of the sample 1 is much larger than that of the sample 1 with a small difference in energy bandsCommercial AgGaS 2 Has good laser damage resistance.
TABLE 1
The operation of the second embodiment of the present invention includes: weighing 2.5 mmol of Cu, 0.25 mmol of Cd, 1 mmol of P and 4 mmol of S according to the stoichiometric ratio, grinding and uniformly mixing to obtain the raw material powder. After the raw material powder is filled into a quartz tube, the vacuum degree is 10 -2 The quartz tube is sealed at mbar. And placing the quartz tube loaded with the raw material powder in a muffle furnace, and controlling the muffle furnace to heat to 800 ℃ within 600 min. Then preserving heat for 2880 min. The muffle furnace is then controlled to cool to room temperature at a rate of no more than 5 ℃/h. And finally taking out and breaking the quartz tube to obtain a sample 2, wherein the sample 2 is orange single crystal particles. FIG. 12 shows the XRD pattern of sample 2, from which FIG. 12 it can be determined that sample 2 is Cu 5 Cd 0.5 P 2 S 8 。
The operations of the third embodiment of the present invention include: weighing 2.5 mmol Cu, 0.25 mmol Cd and 0.5 mmol P according to stoichiometric ratio 2 S 5 And 1.5 mmol S, grinding and uniformly mixing to obtain the raw material powder. After the raw material powder is filled into a quartz tube, the vacuum degree is 10 -2 The quartz tube is sealed at mbar. And placing the quartz tube loaded with the raw material powder in a muffle furnace, and controlling the muffle furnace to heat to 650 ℃ within 600 min. After that, the temperature was kept for 1440 minutes. The muffle furnace was then controlled to cool to room temperature at a rate of 3 ℃/h. And finally taking out and breaking the quartz tube to obtain a sample 3, wherein the sample 3 is orange single crystal particles. FIG. 13 shows the XRD pattern of sample 3, from which FIG. 13 it can be determined that sample 3 is Cu 5 Cd 0.5 P 2 S 8 。
The operations of the fourth embodiment of the present invention include: weighing 2.5 mmol Cu, 0.25 mmol CdS and 0.5 mmol P according to stoichiometric ratio 2 S 5 And 1.25 mmol S, grinding and uniformly mixing to obtain the raw material powder. Filling the raw material powder into stoneAfter the quartz tube, the vacuum degree is 10 -2 The quartz tube is sealed at mbar. And placing the quartz tube loaded with the raw material powder in a muffle furnace, and controlling the muffle furnace to heat to 900 ℃ within 600 min. After that, the temperature was kept for 1440 minutes. The muffle furnace was then controlled to cool to room temperature at a rate of 3 ℃/h. Finally, taking out and breaking the quartz tube to obtain a sample 3, wherein the sample 4 is orange single crystal particles. FIG. 14 shows the XRD pattern of sample 4, from which FIG. 14 it can be determined that sample 4 is Cu 5 Cd 0.5 P 2 S 8 。
Although the present invention is disclosed above, it is not limited thereto. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. An infrared nonlinear optical crystal is characterized in that the chemical formula of the infrared nonlinear optical crystal is Cu 5 Cd 0.5 P 2 S 8 Belongs to an orthorhombic system, and the space group isPmn2 1 (No. 31) unit cell parameters area = 7.32Å～7.33Å，b = 6.33 Å～6.34Å，c = 6.07Å～6.08 Å，α=β= γ = 90°；
The infrared nonlinear optical crystal is of a diamond-like structure, and the infrared nonlinear optical crystal comprises a rimcLayers arranged in layers and interconnected by an axis, each of said layers comprising a layer extending along the axisaFirst and second chains having axes alternately arranged and connected to each other; the first chain includes a rimbA first distorted tetrahedral structure and a second distorted tetrahedral structure having axes alternately arranged and connected to each other, said second chain comprising a plurality of chains extending along the length of the first chainbA third distorted tetrahedral structure with axes connected in sequence; the central atom of the first distorted tetrahedral structure is P, the central atom of the second distorted tetrahedral structure is 3/4 Cu and 1/4 Cd, the central atom of the third distorted tetrahedral structure is 7/8 Cu, and all the distorted tetrahedral structures are coordinatedThe atoms are S, and two adjacent distorted tetrahedral structures share coordination atoms.
2. A method for producing an infrared nonlinear optical crystal according to claim 1, comprising:
weighing a Cu source, a Cd source, a P source and an S source according to the proportion of the Cu atom, the Cd atom, the P atom and the S atom of 5:0.5:2:8;
grinding and mixing a Cu source, a Cd source, a P source and an S source to obtain raw material powder;
placing the raw material powder in a reaction tube, and vacuumizing and sealing the reaction tube;
and (3) carrying out high-temperature solid-phase reaction on the raw material powder in the reaction tube, and then cooling to room temperature to obtain a reaction product.
3. The method for producing an infrared nonlinear optical crystal according to claim 2, wherein the vacuum degree of the reaction tube is 10 or less -2 mbar。
4. The method for producing an infrared nonlinear optical crystal according to claim 2, wherein the step of subjecting the raw material powder in the reaction tube to a high-temperature solid phase reaction comprises:
and heating the reaction tube and the raw material powder to ensure that the temperature of the reaction tube and the raw material powder rises to a preset reaction temperature, and then preserving the heat of the reaction tube and the raw material powder.
5. The method for preparing an infrared nonlinear optical crystal according to claim 4, wherein the reaction temperature is 650-900 ℃ and the heat preservation time is 1000-5000 min.
6. The method for producing an infrared nonlinear optical crystal according to claim 4 or 5, wherein the reaction tube is a quartz tube; the temperature rising rate of the reaction tube and the raw material powder is 50 ℃/h to 100 ℃/h.
7. The method for producing an infrared nonlinear optical crystal according to claim 1, wherein the cooling rate after the high-temperature solid phase reaction is 1 ℃/h to 10 ℃/h.
8. Use of an infrared nonlinear optical crystal in accordance with claim 1 in a nonlinear optical device.
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| CN101545141A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Sulfurized gallium and barium monocrystal as well as growing method and infrared nonlinear optical device thereof |
| CN115216844A (en) * | 2022-04-25 | 2022-10-21 | 福州大学 | Preparation and application of mid-far infrared nonlinear optical crystal cadmium sulfur phosphate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101545141A (en) * | 2008-03-25 | 2009-09-30 | 中国科学院福建物质结构研究所 | Sulfurized gallium and barium monocrystal as well as growing method and infrared nonlinear optical device thereof |
| CN115216844A (en) * | 2022-04-25 | 2022-10-21 | 福州大学 | Preparation and application of mid-far infrared nonlinear optical crystal cadmium sulfur phosphate |
Non-Patent Citations (3)
| Title |
|---|
| Chalcophosphates: A Treasure House of Infrared Nonlinear Optical Materials;Zhuang Li等;Cryst. Growth Des.;20201023;全文 * |
| Structural Modulation from Cu 3 PS 4 to Cu 5 Zn 0.5 P 2 S 8 : Single-Site Aliovalent-Substitution-Driven Second-Harmonic-Generation Enhancement;Bang-Jun Song等;Inorg. Chem.;20210312;全文及SI * |
| Two Nonlinear Optical Thiophosphates Cu 5 Hg 0.5 P 2 S 8 and AgHg 3 PS 6 Activated by Their Tetrahedra-Stacking Architecture;Yang Wang等;Inorg. Chem.;20220111;全文 * |
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