CN114084880B - K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compound, nonlinear optical crystal, and preparation method and application thereof - Google Patents
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compound, nonlinear optical crystal, and preparation method and application thereof Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
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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 K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compounds, nonlinear optical crystals, and methods of making and using the same. The invention has the following beneficial effects: the crystal is easy to grow and transparent without inclusion, and has the advantages of high growth speed, low cost, easy obtaining of larger-size crystal and the like; the obtained crystal has the advantages of short ultraviolet absorption cut-off edge, moderate nonlinear optical effect, stable physical and chemical properties, good mechanical properties, easy processing and the like; the crystal can be used for manufacturing nonlinear optical devices; the nonlinear optical device manufactured by the nonlinear optical crystal can be used in a plurality of military and civil high-tech fields, such as laser blind weapons, optical disk recording, laser projection televisions, optical computation, optical fiber communication and the like.
Description
Technical Field
The invention relates to a K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compounds, K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal, K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Crystal preparation method and K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Use of a crystal for the manufacture of a nonlinear optical device.
Background
The nonlinear optical effect of a crystal refers to such an effect: when a laser beam having a certain polarization direction passes through a nonlinear optical crystal in a certain direction, the frequency of the beam changes. Crystals with nonlinear optical effects are referred to as nonlinear optical crystals. The nonlinear optical effect of the crystal can be used for manufacturing nonlinear optical devices such as a second harmonic generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and the like. All-solid-state lasers using nonlinear optical crystals for frequency conversion are one direction of development of future lasers, and the key is to obtain excellent nonlinear optical crystals.
At present, nonlinear optical crystals applied to ultraviolet and deep ultraviolet bands are borates, mainly including beta-BaB 2 O 4 (BBO)、LiB 3 O 5 (LBO)、RbLiB 6 O 10 (CLBO) and K 2 Be 2 BO 3 F 2 (KBBF) and the like, but they all have respective disadvantages. For example, both LBO and CBO have relatively small birefringence and cannot achieve a quadruple frequency output of 1064nm wavelength laser light; the BBO has larger double refractive index, and has photorefractive effect when being used for quadrupling frequency output of 1064nm wavelength laser, so that the output power and the beam quality are limited; CLBO is very deliquescent and difficult to realize commercial applications; KBBF is difficult to obtain crystals with a large c-direction thickness due to its severe lamellar growth habit. Therefore, it is still urgent and necessary to explore novel ultraviolet and deep ultraviolet nonlinear optical crystals excellent in combination properties.
In recent years, phosphate ultraviolet deep ultraviolet nonlinear optical crystal systems have received much attention. In 2014, researchers reported two new phosphate nonlinear optical crystals Ba 3 P 3 O 10 X (x=cl, br) (see j.am.chem.soc., vol 136,480-487, 2014). The ultraviolet absorption cut-off edges of the two crystals reach the deep ultraviolet region, the powder frequency doubling effect is about 0.6 times and 0.5 times of KDP respectively, and the phases at 1064nm and 532nm are matched. This finding shows that phosphates are promising as uv deep uv nonlinear optical materials. Subsequently, a series of phosphate deep ultraviolet nonlinear optical crystals were found, e.g., rbNaMgP 2 O 7 、Rb 2 Ba(PO 3 ) 5 、Ba 5 P 6 O 10 、CsLi 2 PO 4 Etc. The phosphate deep ultraviolet nonlinear optical crystals all show good nonlinear optical performance, which indicates that a brand new deep ultraviolet nonlinear optical crystal system can be found and has great potential to be excavated.
The fluorophosphate group contains a P-F bond, and the motif has large polarization anisotropy, a wide HOMO-LUMO gap and a high hyperpolarizability, and is determined as an excellent structural building block. By replacing conventional PO 4 The elements can enhance the birefringence of the material while producing a large frequency doubling effect and a short uv cut-off. Fluorophosphates are considered promising alternatives to phosphates as ideal candidates for deep ultraviolet nonlinear optical materials. Therefore, the discovery of new fluorophosphate deep ultraviolet nonlinear optical crystals has great potential.
Disclosure of Invention
The invention aims to provide a compound with a chemical formula of K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Compound (iv), process for producing the same, nonlinear optical crystal, process for producing the crystal, and K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Use of a nonlinear optical crystal. K of the invention 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal has the advantages of short ultraviolet absorption cut-off edge, large nonlinear optical effect, stable physical and chemical properties, good mechanical properties, difficult deliquescence and fragmentation, easy processing and storage and the like.
The technical scheme of the invention is as follows:
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 compounds, said K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The chemical formula of the compound is K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Or written as K 3 Sc 3 P 3 O 10 F 7 。
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A process for the preparation of a compound comprising the steps of:
the molar ratio is 1-2:1-3:1-3: 6-10K-containing + Compounds, containing Sc 3+ Compounds, P-containing compounds and F-containing compounds - After the compounds are evenly mixed, the temperature is increased to 180-230 ℃ at the speed of 10-200 ℃/hour, then the heat preservation reaction is carried out for 72-120 hours, and the mixture is taken out after the temperature is reduced to the room temperature, thus obtaining the K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal.
Preferably, the K-containing + The compound is KF or KNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Sc-containing + The compound is Sc (NO) 3 ) 3 ·xH 2 O、Sc 2 O 3 Or ScF 3 The method comprises the steps of carrying out a first treatment on the surface of the The P-containing compound is H 3 PO 4 Or H 2 PO 3 F, performing the process; said F-containing - The compound being NH 4 F or HPF 6 。
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal, K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal does not contain a symmetrical center, belongs to a monoclinic Cc space group, and has unit cell parameters of
α＝90°，β＝115.58°，γ＝90°，/>
Z＝4。
The basic structure of the crystal is composed of PO 3 F、PO 4 Tetrahedra and Sc 3 O 10 F 5 The trimers are connected at the same vertex to form a three-dimensional framework structure, K + Filled in the hollows of the three-dimensional frame to maintain the balance of the entire three-dimensional structure.
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The preparation method of the nonlinear optical crystal comprises the following steps: the method comprises the following steps:
adopting a medium-temperature hydrothermal method to make the mixture contain K + Compounds, containing Sc 3+ Mixing the compound, the P-containing compound or the fluorine-containing compound in a certain molar ratio (the molar ratio is 1-2:1-3:1-3:6-10), adding 1-13mL of distilled water and 1-6mL of triethylamine, uniformly stirring, heating to 180-230 ℃ at the speed of 10-200 ℃/h, preserving heat for 72-120 h, and cooling to room temperature at the speed of 10-200 ℃/h to obtain K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A compound.
Preferably, the distilled water is used in an amount of 5-6mL; the dosage of triethylamine is 1-2mL.
K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Use of a nonlinear optical crystal, said K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal is used as a nonlinear optical device.
A nonlinear optical device comprising said K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal.
Preferably, the nonlinear optical device is prepared by passing at least one beam of incident electromagnetic radiation through at least one block K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 And means for generating at least one beam of output radiation having a frequency different from the frequency of the incident electromagnetic radiation after the nonlinear optical crystal.
Compared with the prior art, the invention has the following beneficial effects: (1) The reagent and the raw materials used in the method have small toxicity to human bodies, short growth period and low cost;
(2) Obtained K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal has the advantages of short ultraviolet absorption cut-off edge, large nonlinear optical effect, stable physical and chemical properties, good mechanical properties, difficult deliquescence and fragmentation, easy processing and storage and the like;
(3) The K is 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal can be used for manufacturing nonlinear optical devices;
(4) The nonlinear optical device manufactured by the nonlinear optical crystal can be used in a plurality of military and civil high-tech fields, such as laser blind weapons, optical disk recording, laser projection televisions, optical computation, optical fiber communication and the like.
Drawings
FIG. 1 is a schematic diagram of K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A typical nonlinear optical device of crystal manufacture works in a schematic diagram where 1 is a laser, 2 is an incident laser beam, 3 is K after crystal post-treatment and optical processing 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The crystal, 4, is the generated laser beam and 5 is the filter.
FIG. 2 is a diagram of the invention K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Polycrystalline powder X-ray diffraction pattern and K-based 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 X-ray diffraction pattern of the crystal structure simulation.
FIG. 3 is a diagram of the invention K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Crystal structure diagram.
Detailed Description
The invention is further described below with reference to examples and figures. It will be appreciated by persons skilled in the art that the following examples are not intended to limit the scope of the invention, and that any modifications and variations made on the basis of the present invention are within the scope of the invention.
Examples 1 to 9 relate to K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Preparation of the CompoundsAnd (5) preparing.
Example 1
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(a)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.14 g (2.5 mmol), sc (NO) 3 ) 2 ·xH 2 O0.338 g (1.5 mmol), H 3 PO 4 0.3mL(4.5mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed according to the above doses, placed in a polytetrafluoroethylene liner of 23mL volume and 2mL TEA, 6mL H were added, respectively 2 O, which was then charged into the reaction kettle and placed in an oven, was warmed to 200 ℃ at a rate of 10 ℃/hour. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 2
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(b)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.425 g (7 mmol), sc (NO) 3 ) 3 ·xH 2 O0.724 g (3 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: at the dosage aboveThe reagents were weighed separately, placed in a polytetrafluoroethylene liner of 23mL volume and 1mL of H was added separately 2 O, 6mL TEA, was then charged to the reaction kettle and placed in an oven and warmed to 200℃at a rate of 10℃per hour. Keeping the temperature for 3-5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, taking out the reaction product, and filtering and separating colorless transparent blocky crystals by using filter paper to obtain KMgSO 4 F。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 3
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(c)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.991 g (17 mmol), sc (NO) 3 ) 3 ·xH 2 O0.563 g (2.5 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 4
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(d)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.142 g (2.5 mmol), sc (NO) 3 ) 3 ·xH 2 O0.282 g (1 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,1mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 5
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(e)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.496 g (8.5 mmol), sc (NO) 3 ) 3 ·xH 2 O0.282 g (1.2 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,1mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr.Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 6
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(f)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.271 g (4.7 mmol), sc (NO) 3 ) 3 ·xH 2 O0.307 g 1.3mmol, H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 7
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(f)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 1.275 g (22 mmol), sc (NO) 3 ) 3 ·xH 2 O0.563 g (2 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 8
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(f)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.425 g (22 mmol), sc (NO) 3 ) 3 ·xH 2 O0.563 g (0.298 mmol), H 3 PO 4 0.5mL(7mmol)、NH 4 F0.12 g (3 mmol).
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals,obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 9
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(f)3KF+3Sc(NO 3 ) 3 ·xH 2 O+3H 3 PO 4 +4NH 4 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+4NH 3 ↑+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.14 g (2.5 mmol), sc (NO) 3 ) 2 ·xH 2 O0.338 g (1.5 mmol), H 3 PO 4 0.3mL(4.5mmol)、NH 4 F0.13 g (3.5 mmol).
The specific operation steps are as follows: the reagents were weighed according to the above doses, placed in a polytetrafluoroethylene liner of 23mL volume and 1mL TEA, 5mL H were added, respectively 2 O, which was then charged into the reaction kettle and placed in an oven, was warmed to 200 ℃ at a rate of 10 ℃/hour. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 10
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(g)3KNO 3 +3ScF 3 +3H 3 PO 4 +2HPF 6 ＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KNO (KNO) 3 1.263 g (12.5 mmol))、ScF 3 1.275 g (12.5 mmol), H 3 PO 4 0.3mL(4.5mmol)、HPF 6 0.4mL(9mmol)。
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 11
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(h)3KNO 3 +3Sc 2 O 3 +3H 2 PO 3 F+4HPF 6 ＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KNO (KNO) 3 0.404 g (4 mmol), sc 2 O 3 0.828 g (6 mmol), H 2 PO 3 F 0.3mL(3mmol)、HPF 6 0.6mL(7mmol)。
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,1mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 12
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(i)3KF+3Sc 2 O 3 +3H 3 PO 4 +4HPF 6 ＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.58 g (10 mmol), sc 2 O 3 0.345 g (2.5 mmol), H 3 PO 4 0.5mL(7mmol)、HPF 6 0.3mL(3.5mmol)。
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O,2mL TEA, was then charged to the reaction kettle and placed in an oven and heated to 200deg.C at a rate of 10deg.C/hr. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
Example 13
By adopting a hydrothermal reaction method, the reaction equation is as follows:
(j)3KF+3ScF 3 +3H 3 PO 4 +4H 2 PO 3 F＝K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 ↓+H 2 O↑+NO 2 ↑
the three reagent feeding amounts are as follows: KF 0.58 g (10 mmol), scF 3 0.510 g (5 mmol), H 3 PO 4 0.5mL(7mmol)、H 2 PO 3 F 0.5mL(6mmol)。
The specific operation steps are as follows: the reagents were weighed separately in the above doses, placed in a polytetrafluoroethylene liner 23mL in volume and 6mL H was added 2 O，2mL TEA, which was then charged into the reaction kettle and placed in an oven, was warmed to 200 ℃ at a rate of 10 ℃/hour. Constant temperature for 5 days, and slowly cooling to room temperature at a speed of 1 ℃/h. After the reaction is finished, the reaction product is taken out and filtered by filter paper to separate colorless transparent blocky crystals, thus obtaining K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 。
As shown in fig. 2, the powder X-ray diffraction pattern obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof.
K obtained in example 1 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal is subjected to diffuse reflection spectrum test, and the ultraviolet absorption cut-off edge of the crystal is lower than 200nm and transmits in the wavelength range of 200-800 nm; the crystal is not easy to crack and not absorb moisture; k obtained in example 1 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal is placed at the position of the device with the reference number of 3 shown in the figure 1, and at room temperature, a Q-switched Nd-YAG laser is used as a fundamental frequency light source, near infrared light with the incident wavelength of 1064nm is used for outputting green laser with the wavelength of 532 nm.
FIG. 1 shows the use of K for the present invention 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A simple illustration of a crystal-fabricated nonlinear optical device. The laser 1 emits a light beam 2 to be injected into K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The crystal 3, the generated outgoing beam 4 passes through a filter 5, thereby obtaining the desired laser beam. The nonlinear optical laser can be a frequency multiplication generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator or the like.
The above detailed description is only for explaining the technical solution of the present invention in detail, the present invention is not limited to the above examples, and it should be understood that those skilled in the art should all modifications and substitutions based on the above principles and spirit are within the scope of the present invention.
Claims (8)
1.K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A compound characterized by: the K is 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The chemical formula of the compound is K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Or written as K 3 Sc 3 P 3 O 10 F 7 。
2.K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A nonlinear optical crystal characterized by: the K is 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal does not contain a symmetrical center, belongs to a monoclinic Cc space group, and has unit cell parameters of
α＝90°，β＝115.58°，γ＝90°，
Z＝4。
3. K according to claim 2 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The preparation method of the nonlinear optical crystal is characterized by comprising the following steps: the method comprises the following steps:
the molar ratio is 1-2:1-3:1-3: 6-10K-containing + Compounds, containing Sc 3+ Uniformly mixing the compound, the compound containing P and the compound containing F-and heating to 180-230 ℃ at the speed of 10-200 ℃/h, then carrying out heat preservation reaction for 72-120 h, cooling to room temperature and taking out to obtain the K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal.
4. K according to claim 2 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Of non-linear optical crystalsThe preparation method is characterized by comprising the following steps:
the molar ratio is 1-2:1-3:1-3: 6-10K-containing + Compounds, containing Sc 3+ Compounds, P-containing compounds and F-containing compounds - Adding the compound into the liner of the reaction kettle, mixing, adding distilled water and triethylamine to make the total volume of the solution be one third to one half of the volume of the liner of the reaction kettle, uniformly stirring, heating to 180-230 ℃ at the speed of 10-200 ℃/hour, preserving heat for 72-120 hours, and finally cooling to room temperature at the speed of 1-200 ℃/hour to obtain K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 A nonlinear optical crystal, wherein the volume ratio of distilled water to triethylamine is 1-13:1-6.
5. K as claimed in claim 3 or 4 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The preparation method of the nonlinear optical crystal is characterized by comprising the following steps: the K-containing + The compound is KF or KNO 3 The method comprises the steps of carrying out a first treatment on the surface of the The Sc-containing 3+ The compound is Sc (NO) 3 ) 3 ·xH 2 O、Sc 2 O 3 Or ScF 3 The method comprises the steps of carrying out a first treatment on the surface of the The P-containing compound is H 3 PO 4 Or H 2 PO 3 F, performing the process; said F-containing - The compound being NH 4 F or HPF 6 。
6. K according to claim 4 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The preparation method of the nonlinear optical crystal comprises the following steps: the volume ratio of distilled water to triethylamine is 5-6:1-2.
7. k according to claim 2 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The use of a nonlinear optical crystal, characterized in that the K 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 The nonlinear optical crystal is used as a nonlinear optical device.
8. A nonlinear optical device comprising the K of claim 2 3 Sc 3 (PO 4 )(PO 3 F) 2 F 5 Nonlinear optical crystal.
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