CN115259175A - Potassium, sodium, calcium, yttrium, boron and oxygen compound, potassium, sodium, calcium, yttrium, boron and oxygen nonlinear optical crystal, and preparation method and application thereof - Google Patents

Potassium, sodium, calcium, yttrium, boron and oxygen compound, potassium, sodium, calcium, yttrium, boron and oxygen nonlinear optical crystal, and preparation method and application thereof Download PDF

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CN115259175A
CN115259175A CN202210735875.0A CN202210735875A CN115259175A CN 115259175 A CN115259175 A CN 115259175A CN 202210735875 A CN202210735875 A CN 202210735875A CN 115259175 A CN115259175 A CN 115259175A
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yttrium
calcium
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boron
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刘莉莉
胡兆炜
王欢
徐家跃
王俊博
朱萌萌
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Shanghai Institute of Technology
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    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • C01B35/128—Borates containing plural metal or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents
    • C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
    • C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
    • C30B9/12—Salt solvents, e.g. flux growth
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
    • H01S3/005—Optical devices external to the laser cavity, specially adapted for lasers, e.g. for homogenisation of the beam or for manipulating laser pulses, e.g. pulse shaping
    • H01S3/0092—Nonlinear frequency conversion, e.g. second harmonic generation [SHG] or sum- or difference-frequency generation outside the laser cavity
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The invention discloses a potassium-sodium-calcium-yttrium-boron-oxygen compound, a potassium-sodium-calcium-yttrium-boron-oxygen nonlinear optical crystal, and a preparation method and application thereof. The chemical formula of the compound is K6NaCaY2(B5O10)3The compound is synthesized by a solid-phase reaction method; the potassium-sodium-calcium-yttrium-boron-oxygen nonlinear optical crystal does not have a symmetric center, belongs to a trigonal system, has a space group R32 and has unit cell parameters of
Figure DDA0003715475420000011
α＝90°，β＝90°，γ＝120°，
Figure DDA0003715475420000012
Z =18, grows by adopting a high-temperature melt method, the crystal has the frequency doubling effect of 0.5 times of KDP, has high mechanical hardness, is easy to process and store, and can be widely applied to the preparation of nonlinear optical devices such as a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.

Description

Potassium, sodium, calcium, yttrium, boron and oxygen compound, potassium, sodium, calcium, yttrium, boron and oxygen nonlinear optical crystal, and preparation method and application thereof
Technical Field
The invention relates to a potassium-sodium-calcium-yttrium-boron-oxygen compound, a potassium-sodium-calcium-yttrium-boron-oxygen nonlinear optical crystal, and a preparation method and application thereof, belonging to the technical field of optical materials.
Background
Nonlinear optical (NLO) materials have attractive optical properties and are indispensable components in many optoelectronic fields, especially solid-state lasers, because they can extend the wavelength range through a frequency conversion process. From a commercial perspective, an ideal nonlinear crystal needs to have many properties, including a wide transparent window, a large Second Harmonic (SHG) response, and phase matching capability, to achieve an efficient coherent output; furthermore, a high laser damage threshold (LIDT), stable physicochemical properties and good growth habits are also essential. Thus, although many NLO crystals are explored, there are only a few crystals, such as KBe, due to the mutual constraints between optical properties2BO3F2、KTiOPO4And AgGaS2Etc. are practical. The nonlinear optical crystal material can be divided into nonlinear optical materials in ultraviolet region, visible region and infrared region according to the light-transmitting wave band and application range.
For a long time, the search for ultraviolet nonlinear optical materials with excellent properties has been a focus of attention of scientists at home and abroad. To date, scientists have discovered a series of ultraviolet nonlinear optical crystals with excellent properties, such as BBO (β -barium metaborate), LBO (lithium triborate), KBBF (potassium beryllium fluoroborate), and the like. Although the crystal growth technology of these materials is mature, there are still obvious disadvantages such as easy deliquescence of crystal, long growth period, serious lamellar growth habit and high price. Therefore, it is still a very important task to find new ultraviolet nonlinear optical crystal materials.
To further explore new ultraviolet nonlinear materials, rare earth borate systems are of great interest. Because of rare earth ions having a closed shell electron configuration, i.e. Sc3+、Y3+、La3+And Lu3+And the corresponding rare earth borate is expected to have higher optical transmittance in an ultraviolet region without f-f or d-d electronic transition. And the introduction of alkali metal or alkaline earth metal cations into the rare earth borate can further enrich the structural diversity of the borate and is beneficial to designing a new material with excellent ultraviolet nonlinear performance.
Disclosure of Invention
The invention aims to provide a potassium-sodium-calcium-yttrium-boron-oxygen compound and a potassium-sodium-calcium-yttrium-boron-oxygen nonlinear optical crystal, wherein the chemical formula of the compound is K6NaCaY2(B5O10)3Molecular weight 1117.62, prepared by solid-phase reaction, the nonlinear optical crystal has a chemical formula of K6NaCaY2(B5O10)3Is prepared by a high-temperature melt growth method, the crystal does not have a symmetrical center, belongs to a trigonal system, has a space group R32 and has unit cell parameters of
Figure BDA0003715475400000021
α＝90°，β＝90°，γ＝120°，
Figure BDA0003715475400000022
Z＝18。
In order to achieve the above object, the present invention provides a potassium-sodium-calcium-yttrium-boron-oxygen compound having a chemical formula of K6NaCaY2(B5O10)3The molecular weight of the compound is 1117.62, and the compound is prepared by taking a potassium source, a sodium source, a calcium source, an yttrium source and a boron source containing oxygen atoms as raw materials and adopting a solid-phase reaction method.
Preferably, the potassium source is KOH or K2CO3And KNO3The sodium source is at least one of NaOH and Na2CO3And NaNO3At least one of the calcium source is CaOH and CaCO3And Ca (NO)3)2·4H2O, the yttrium source is Y (NO)3)3·6H2O and/or Y2O3The boron source is H3BO3And/or B2O3。
The invention also provides a potassium-sodium-calcium-yttrium-boron-oxygen nonlinear optical crystal with the chemical formula of K6NaCaY2(B5O10)3The molecular weight is 1117.62, has no symmetric center, belongs to trigonal system, space group R32, and the unit cell parameter is
Figure BDA0003715475400000023
α＝90°，β＝90°，γ＝120°，
Figure BDA0003715475400000024
Z＝18。
The invention also provides a preparation method of the potassium sodium calcium yttrium boron oxygen nonlinear optical crystal, which comprises the following steps:
step 1: preparing the potassium sodium calcium yttrium boron oxygen mixed solution by the following method I or method II:
the method comprises the following steps: weighing a potassium source, a sodium source, a calcium source, a yttrium source and a boron source containing oxygen atoms according to a molar ratio of K, na, ca, Y and B of 6;
the second method comprises the following steps: mixing a potassium source, a sodium source, a calcium source, an yttrium source, a boron source and a fluxing agent, wherein the potassium source, the sodium source, the calcium source, the yttrium source and the boron source contain oxygen atoms, and the fluxing agent is mixed according to the ratio of K to Na to Ca to Y to B: the cosolvent has the molar ratio of 6;
step 2: preparing potassium sodium calcium yttrium boron oxygen seed crystal: cooling the mixed solution of potassium, sodium, calcium, yttrium, boron and oxygen obtained in the step (1) to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain potassium, sodium, calcium, yttrium, boron and oxygen seed crystals;
and 3, step 3: repeating the step 1 to prepare the potassium sodium calcium yttrium boron oxygen mixed solution, transferring the potassium sodium calcium yttrium boron oxygen mixed solution into a crystal growth furnace, fixing the seed crystal obtained in the step 2 on a seed crystal rod, preheating the seed crystal from the seed crystal below the top of the crystal growth furnace to the position above the liquid level of the mixed solution, preheating the seed crystal, then lowering the seed crystal to the surface of the mixed solution or lowering the seed crystal into the mixed solution for remelting, keeping the temperature for 5-60 minutes, and then reducing the temperature by 20-30 ℃ to 800-820 ℃ (namely the saturation point temperature);
and 4, step 4: cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the rotating speed of 0-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the crystals grow to the required size, cooling to room temperature, and taking out the crystals from a hearth to obtain the potassium sodium calcium yttrium boron oxygen nonlinear optical crystals.
Preferably, the potassium source in step 1 is KOH or K2CO3And KNO3The sodium source is at least one of NaOH and Na2CO3And NaNO3At least one of the calcium source is CaOH and CaCO3And Ca (NO)3)2·4H2At least one of O and Y (NO) as yttrium source3)3·6H2O and/or Y2O3The boron source is H3BO3And/or B2O3。
Preferably, the fluxing agent in the step 1 is LiF, KF, pbO and PbF2At least one of (1), or self-fluxing agent K2CO3、Na2CO3、H3BO3And B2O3At least one of (a).
The invention also provides application of the potassium sodium calcium yttrium boron oxygen nonlinear optical crystal in preparing a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator
The potassium, sodium, calcium, yttrium and boron oxide compound has a chemical formula of K6NaCaY2(B5O10)3The potassium sodium calcium yttrium boron oxide compound can be prepared by the following chemical reaction formula by adopting a solid-phase reaction method:
(1)6K2CO3+Na2CO3+2CaCO3+2Y2O3+30H3BO3→2K6NaCaY2(B5O10)3+9CO2↑+45H2O↑
(2)12K2CO3+Na2CO3+2CaCO3+4Y(NO3)3·6H2O+15B2O3→2K6NaCaY2(B5O10)3+15CO2↑+12NO2↑+24H2O↑
(3)12KNO3+Na2CO3+2CaCO3+4Y(NO3)3·6H2O+30H3BO3→2K6NaCaY2(B5O10)3+3CO2↑+24NO2↑+69H2O↑
(4)12KNO3+Na2CO3+2CaCO3+2Y2O3+15B2O3→2K6NaCaY2(B5O10)3+3CO2↑+12NO2↑
(5)12KNO3+2NaNO3+2CaCO3+4Y(NO3)3·6H2O+30H3BO3→2K6NaCaY2(B5O10)3+2CO2↑+26NO2↑+69H2O↑
(6)12KNO3+2NaNO3+2CaCO3+2Y2O3+15B2O3→2K6NaCaY2(B5O10)3+2CO2↑+14NO2↑
(7)12KNO3+2NaNO3+2Ca(NO3)2·4H2O+2Y2O3+30H3BO3→2K6NaCaY2(B5O10)3+18NO2↑+49H2O↑
(8)12KNO3+2NaNO3+2Ca(NO3)2·4H2O+2Y2O3+15B2O3→2K6NaCaY2(B5O10)3+18NO2↑+8H2O。
compared with the prior art, the invention has the beneficial effects that:
k of the invention6NaCaY2(B5O10)3The nonlinear optical crystal has the advantages of wider light-transmitting wave band reaching a deep ultraviolet region, higher crystal hardness, good mechanical property, difficult splitting, easy processing and storage and the like. The nonlinear optical device prepared by the compound potassium sodium calcium yttrium boron oxygen nonlinear optical crystal obtained by the method uses Nd-YAG Q-switched laser as a light source at room temperature, enters infrared light with the wavelength of 1064nm, outputs green laser with the wavelength of 532nm, and has the laser intensity equivalent to KDP (KH)2PO4) 0.5 times of the total weight of the powder.
Drawings
FIG. 1 shows the invention K6NaCaY2(B5O10)3X-ray diffraction pattern of the powder.
FIG. 2 shows the invention K6NaCaY2(B5O10)3Crystal structure of (2).
FIG. 3 shows the invention K6NaCaY2(B5O10)3Working principle diagram of nonlinear optical device made of crystal, wherein 1 is laser, 2 is emitted light beam, and 3 is K6NaCaY2(B5O10)3Crystal, 4 is emergent light beam, and 5 is filter.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1:
according to the reaction formula:
6K2CO3+Na2CO3+2CaCO3+2Y2O3+30H3BO3→2K6NaCaY2(B5O10)3+9CO2↑+45H2o ↓ ] synthetic compound K6NaCaY2(B5O10)3：
Putting a compound containing potassium, sodium, calcium, yttrium and boron into a mortar according to a molar ratio of K: na: ca: Y: B of 6. Taking out and grinding, putting into a muffle furnace, heating to 800 ℃, keeping the temperature for 18 hours, and grinding for multiple times during the heating. And finally, taking out and grinding to obtain the potassium sodium calcium yttrium boron oxide compound polycrystalline powder. Then the product is subjected to powder X-ray analysis, and the obtained powder X-ray spectrogram and K, na, ca, Y, B, O K6NaCaY2(B5O10)3Theoretical X-ray spectrograms obtained from the single crystal structures are consistent;
the obtained K, na, ca, Y, B, O and K6NaCaY2(B5O10)3Compound polycrystal powder and fluxing agent LiF according to mol ratio K6NaCaY2(B5O10)3LiF =1, mixing, placing into a platinum crucible with an opening of phi 80mm x 80mm, heating to 950 ℃ at a heating rate of 20 ℃/h, keeping the temperature for 10 hours to obtain a mixed melt, and cooling to 830 ℃;
preparing potassium sodium calcium yttrium boron oxygen seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain potassium sodium calcium yttrium boron oxygen seed crystals;
growing crystals in compound meltsBody: k to be obtained6NaCaY2(B5O10)3Fixing seed crystals on a seed crystal rod, discharging the seed crystals from the top of a crystal growing furnace, preheating the seed crystals on the surface of the mixed melt for 10 minutes, immersing the seed crystals in the liquid level, melting the seed crystals in the mixed melt, keeping the temperature for 40 minutes, and quickly reducing the temperature to 805 ℃;
cooling at the rate of 2 ℃/day, rotating the seed rod at the rotating speed of 10rpm, separating the crystal from the liquid surface after the crystal growth is finished, and cooling to room temperature at the rate of 10 ℃/hour to obtain the large-size K6NaCaY2(B5O10)3And (4) crystals.
The raw material potassium carbonate in the reaction formula can be replaced by potassium nitrate and potassium hydroxide; sodium carbonate can be replaced by sodium nitrate and sodium hydroxide; the calcium carbonate can be replaced by calcium nitrate tetrahydrate and calcium hydroxide; the yttrium oxide can be replaced by yttrium nitrate hexahydrate; boric acid may be replaced by boron oxide.
Example 2:
according to the reaction formula 12K2CO3+Na2CO3+2CaCO3+4Y(NO3)3·6H2O+15B2O3→2K6NaCaY2(B5O10)3+15CO2↑+6NO2↑+12H2O ↓ [ O ] synthetic compound K6NaCaY2(B5O10)3：
Will K2CO3、Na2CO3、CaCO3、Y(NO3)3·6H2O、B2O3Directly weighing raw materials according to a molar ratio of 122CO3Mixing according to the molar ratio of 1;
preparing potassium sodium calcium yttrium boron oxygen seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 1.5 ℃/h, and spontaneously crystallizing to obtain potassium-sodium-calcium-yttrium-boron-oxygen seed crystals;
k to be obtained6NaCaY2(B5O10)3Fixing the seed crystal on a seed crystal rod, placing the seed crystal from the top of a crystal growing furnace, preheating the seed crystal on the surface of the mixed melt for 10 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed melt, keeping the temperature for 30 minutes, and quickly cooling to 810 ℃;
slowly cooling at the speed of 1 ℃/day without rotating a seed rod, lifting the crystal away from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 20 ℃/h, and taking out the crystal from a hearth to obtain the large-size K6NaCaY2(B5O10)3And (4) crystals.
The raw material potassium carbonate in the reaction formula can be replaced by potassium nitrate and potassium hydroxide; sodium carbonate can be replaced by sodium nitrate and sodium hydroxide; the calcium carbonate can be replaced by calcium nitrate tetrahydrate and calcium hydroxide; the yttrium nitrate hexahydrate can be replaced by yttrium oxide; the boron oxide may be replaced by boric acid.
Example 3:
according to the reaction formula: 12KNO3+Na2CO3+2CaCO3+4Y(NO3)3·6H2O+30H3BO3→2K6NaCaY2(B5O10)3+3CO2↑+24NO2↑+69H2O ↓ ] synthetic compound K6NaCaY2(B5O10)3The specific procedure was carried out according to example 1:
to be synthesized K6NaCaY2(B5O10)3Compound and self fluxing agent H3BO3Loading the mixture into an opening platinum crucible with the diameter of 80mm multiplied by 80mm according to the mol ratio of 1;
fixing the obtained seed crystal on a seed crystal rod, preheating the seed crystal on the surface of the mixed melt for 10 minutes from the top of a crystal growth furnace, partially immersing the seed crystal below the liquid level, melting the seed crystal in the mixed melt back, keeping the temperature for 10 minutes, and quickly reducing the temperature to 800 ℃;
slowly cooling at the speed of 2 ℃/day, rotating the seed rod at the rotating speed of 30rpm, lifting the crystal from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 30 ℃/h, and taking out the crystal from the hearth to obtain the large-size K6NaCaY2(B5O10)3And (4) crystals.
Potassium nitrate in the reaction formula can be replaced by potassium carbonate and potassium hydroxide; the sodium carbonate can be replaced by sodium nitrate and sodium hydroxide; the calcium carbonate can be replaced by calcium nitrate tetrahydrate and calcium hydroxide; the yttrium nitrate hexahydrate can be replaced by yttrium oxide; boric acid may be replaced by boron oxide.
Example 4:
according to the reaction formula
12KNO3+Na2CO3+2CaCO3+2Y2O3+15B2O3→2K6NaCaY2(B5O10)3+3CO2↑+12NO2↓ [ synthetic compound K6NaCaY2(B5O10)3：
KNO (potassium zinc oxide)3、Na2CO3、CaCO3、Y2O3、B2O3Directly weighing raw materials according to a molar ratio of 12;
preparing potassium sodium calcium yttrium boron oxygen seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 1.5 ℃/h, and spontaneously crystallizing to obtain potassium sodium calcium yttrium boron oxygen seed crystals;
k to be obtained6NaCaY2(B5O10)3The seed crystal is fixed on the seed crystal rod, the seed crystal is arranged at the top of the crystal growing furnace, the seed crystal is preheated on the surface of the mixed solution for 10 minutes,immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed solution, keeping the temperature constant for 30 minutes, and quickly cooling to 800 ℃;
slowly cooling at the speed of 1 ℃/day without rotating a seed rod, lifting the crystal away from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 20 ℃/h, and taking out the crystal from a hearth to obtain the large-size K6NaCaY2(B5O10)3And (4) crystals.
The raw material potassium nitrate in the reaction formula can be replaced by potassium carbonate and potassium hydroxide; the sodium carbonate can be replaced by sodium nitrate and sodium hydroxide; the calcium carbonate can be replaced by calcium nitrate tetrahydrate and calcium hydroxide; the yttrium oxide can be replaced by yttrium nitrate hexahydrate; the boron oxide may be replaced by boric acid.
Example 5:
according to the reaction formula: 12KNO3+2NaNO3+2CaCO3+4Y(NO3)3·6H2O+30H3BO3→2K6NaCaY2(B5O10)3+2CO2↑+26NO2↑+69H2O ↓ [ O ] synthetic compound K6NaCaY2(B5O10)3The specific procedure was carried out as in example 1:
will synthesize K6NaCaY2(B5O10)3The compound and a fluxing agent PbO are put into an opening platinum crucible with phi 80mm multiplied by 80mm according to the mol ratio of 1 to 5, the temperature is raised to 1000 ℃, the temperature is kept for 8 hours, a mixed solution is obtained, the temperature is lowered to 840 ℃, then the temperature is slowly lowered to the room temperature at the speed of 1 ℃/h, and the potassium-sodium-calcium-yttrium-boron-oxygen seed crystal is obtained through spontaneous crystallization;
fixing the obtained seed crystal on a seed crystal rod, preheating the seed crystal on the surface of the mixed melt for 10 minutes from the top of a crystal growth furnace, partially immersing the seed crystal below the liquid level, melting the seed crystal in the mixed melt back, keeping the temperature for 10 minutes, and quickly cooling to 810 ℃;
slowly cooling at a speed of 2 ℃/day, rotating the seed rod at a rotating speed of 30rpm, and growing the crystal to a required sizeThe body is lifted from the surface of the melt, the temperature is reduced to the room temperature at the speed of 30 ℃/h, and then the crystal is taken out from the hearth, thus obtaining the large-size K6NaCaY2(B5O10)3And (4) crystals.
The raw material potassium nitrate in the reaction formula can be replaced by potassium carbonate and potassium hydroxide; the sodium nitrate can be replaced by sodium carbonate and sodium hydroxide; the calcium carbonate can be replaced by calcium nitrate tetrahydrate and calcium hydroxide; the yttrium nitrate hexahydrate can be replaced by yttrium oxide; boric acid may be replaced by boron oxide.
Example 6:
according to the reaction formula: 12KNO3+2NaNO3+2Ca(NO3)2·4H2O+2Y2O3+15B2O3→2K6NaCaY2(B5O10)3+18NO2↑+8H2O Synthesis of Compound K6NaCaY2(B5O10)3：
KNO (potassium zinc oxide)3、NaNO3、Ca(NO3)2·4H2O、Y2O3And B2O3The method comprises the following steps of (1) directly weighing raw materials in a molar ratio of 122Mixing according to the mol ratio of 1 to 2, putting the mixture into a platinum crucible with an opening diameter of 80mm multiplied by 80mm, heating to 940 ℃, keeping the temperature for 10 hours to obtain mixed melt, and cooling to 825 ℃;
preparing potassium sodium calcium yttrium boron oxygen seed crystal: slowly cooling the obtained mixed solution to room temperature at the speed of 2.5 ℃/h, and spontaneously crystallizing to obtain potassium sodium calcium yttrium boron oxygen seed crystals;
k to be obtained6NaCaY2(B5O10)3Fixing the seed crystal on a seed crystal rod, descending the seed crystal from the top of a crystal growing furnace, preheating the seed crystal on the surface of the mixed melt for 5 minutes, immersing the seed crystal below the liquid level to melt the seed crystal back in the mixed melt, keeping the temperature for 5 minutes, and quickly reducing the temperature to 805 ℃;
then slowly cooling at the speed of 1 ℃/day, rotating the seed rod at the rotating speed of 50rpm, and growing the crystal to the required sizeThe crystal is lifted off the surface of the melt, the temperature is reduced to room temperature at the speed of 20 ℃/h, and then the crystal is taken out from a hearth, so that the large-size K can be obtained6NaCaY2(B5O10)3And (4) crystals.
The raw material potassium nitrate in the reaction formula can be replaced by potassium carbonate and potassium hydroxide; the sodium nitrate can be replaced by sodium carbonate or sodium hydroxide; the calcium nitrate tetrahydrate can be replaced by calcium carbonate and calcium hydroxide; the yttrium oxide can be replaced by yttrium nitrate hexahydrate; the boron oxide may be replaced by boric acid.
Tested, K prepared in examples 1-6 above6NaCaY2(B5O10)3The crystal has no symmetry center, belongs to trigonal system, space group R32, and has unit cell parameter of
Figure BDA0003715475400000091
Figure BDA0003715475400000092
α＝90°，β＝90°，γ＝120°，
Figure BDA0003715475400000093
Z =18. The schematic diagram of the crystal structure is shown in fig. 2.
Example 7
K obtained in any of examples 1 to 66NaCaY2(B5O10)3Processing a frequency multiplier with 5mm × 5mm × 6mm size by crystal along matching direction, arranging at 3 position as shown in FIG. 2, using Q-switched Nd-YAG laser as light source with incidence wavelength of 1064nm at room temperature, and emitting infrared beam 2 with wavelength of 1064nm from Q-switched Nd-YAG laser 1 into K6NaCaY2(B5O10)3The single crystal 3 generates green frequency doubling light with the wavelength of 532nm, the output intensity is 0.5 time of KDP under the same condition, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and green laser with the wavelength of 532nm is obtained after filtering by the filter 5.

Claims (7)

1. AA potassium, sodium, calcium, yttrium, boron oxide compound characterized in that the compound has the chemical formula K6NaCaY2(B5O10)3The molecular weight of the compound is 1117.62, and the compound is prepared by taking a potassium source, a sodium source, a calcium source, an yttrium source and a boron source containing oxygen atoms as raw materials and adopting a solid-phase reaction method.
2. The K-Na-Ca-Y-B-O compound of claim 1 wherein the K source is KOH, K2CO3And KNO3The sodium source is at least one of NaOH and Na2CO3And NaNO3At least one of the calcium source is CaOH and CaCO3And Ca (NO)3)2·4H2O, the yttrium source is Y (NO)3)3·6H2O and/or Y2O3The boron source is H3BO3And/or B2O3。
3. A K-Na-Ca-Y-B-O nonlinear optical crystal is characterized in that the chemical formula of the crystal is K6NaCaY2(B5O10)3The molecular weight is 1117.62, has no symmetric center, belongs to trigonal system, space group R32, and the unit cell parameter is
Figure FDA0003715475390000011
α＝90°，β＝90°，γ＝120°，
Figure FDA0003715475390000012
Z＝18。
4. A method for preparing a nonlinear optical crystal of potassium, sodium, calcium, yttrium, boron and oxygen according to claim 3, comprising the steps of:
step 1: preparing potassium sodium calcium yttrium boron oxygen mixed solution by the following method one or method two:
the method comprises the following steps: weighing a potassium source, a sodium source, a calcium source, a yttrium source and a boron source containing oxygen atoms according to a molar ratio of K, na, ca, Y and B of 6;
the second method comprises the following steps: mixing a potassium source, a sodium source, a calcium source, an yttrium source, a boron source and a fluxing agent, wherein the potassium source, the sodium source, the calcium source, the yttrium source and the boron source contain oxygen atoms, and the fluxing agent is mixed according to the ratio of K to Na to Ca to Y to B: the cosolvent has the following molar ratio of 6;
and 2, step: preparing potassium sodium calcium yttrium boron oxygen seed crystal: cooling the mixed solution of potassium, sodium, calcium, yttrium, boron and oxygen obtained in the step (1) to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain potassium, sodium, calcium, yttrium, boron and oxygen seed crystals;
and 3, step 3: repeating the step 1 to prepare the potassium sodium calcium yttrium boron oxygen mixed solution, transferring the potassium sodium calcium yttrium boron oxygen mixed solution into a crystal growth furnace, fixing the seed crystal obtained in the step 2 on a seed crystal rod, preheating the seed crystal from the seed crystal below the top of the crystal growth furnace to the position above the liquid level of the mixed solution, preheating the seed crystal, then lowering the seed crystal to the surface of the mixed solution or lowering the seed crystal into the mixed solution for remelting, keeping the temperature for 5-60 minutes, and then reducing the temperature by 20-30 ℃ to 800-820 ℃;
and 4, step 4: cooling at the speed of 0.1-5 ℃/day, rotating the seed rod at the rotating speed of 0-60rpm to grow crystals, lifting the crystals away from the surface of the mixed melt after the crystals grow to the required size, cooling to room temperature, and taking out the crystals from a hearth to obtain the potassium sodium calcium yttrium boron oxygen nonlinear optical crystals.
5. The method for preparing K-Na-Ca-Y-B-O nonlinear optical crystal according to claim 4, wherein the K source in the step 1 is a K sourceIs KOH, K2CO3And KNO3At least one of NaOH and Na as the sodium source2CO3And NaNO3At least one of the calcium source is CaOH and CaCO3And Ca (NO)3)2·4H2O, the yttrium source is Y (NO)3)3·6H2O and/or Y2O3The boron source is H3BO3And/or B2O3。
6. The method for preparing K-Na-Ca-Y-B-O nonlinear optical crystal according to claim 4, wherein the flux in step 1 is LiF, KF, pbO and PbF2At least one of (1), or self-fluxing agent K2CO3、Na2CO3、H3BO3And B2O3At least one of (1).
7. Use of the K-Na-Ca-Y-B-O nonlinear optical crystal of claim 3 in the preparation of a frequency doubling generator, an upper frequency converter, a lower frequency converter or an optical parametric oscillator.
CN202210735875.0A 2022-06-27 2022-06-27 Potassium, sodium, calcium, yttrium, boron and oxygen compound, potassium, sodium, calcium, yttrium, boron and oxygen nonlinear optical crystal, and preparation method and application thereof Pending CN115259175A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006048036A1 (en) * 2005-10-07 2007-04-12 Chemetall Gmbh New asymmetrical or asymmetrical borate salts are useful as additives, stabilizers, flame protectors and/or conductivity enhancers in polymers and as electrolytes
CN107699948A (en) * 2017-09-08 2018-02-16 中国科学院新疆理化技术研究所 Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006048036A1 (en) * 2005-10-07 2007-04-12 Chemetall Gmbh New asymmetrical or asymmetrical borate salts are useful as additives, stabilizers, flame protectors and/or conductivity enhancers in polymers and as electrolytes
CN107699948A (en) * 2017-09-08 2018-02-16 中国科学院新疆理化技术研究所 Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes

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