CN102352533A - Novel nonlinear optical crystal beryllium-sodium-cesium borate - Google Patents

Novel nonlinear optical crystal beryllium-sodium-cesium borate Download PDF

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CN102352533A
CN102352533A CN201110347844XA CN201110347844A CN102352533A CN 102352533 A CN102352533 A CN 102352533A CN 201110347844X A CN201110347844X A CN 201110347844XA CN 201110347844 A CN201110347844 A CN 201110347844A CN 102352533 A CN102352533 A CN 102352533A
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boric acid
crystal
compound
sodium
linear optic
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CN102352533B (en
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叶宁
王时超
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The invention provides a novel nonlinear optical crystal beryllium-sodium-cesium borate of which the chemical formula is Na2CsBe6B5O15 (NCBB). The crystal structure of the novel nonlinear optical crystal belongs to a monoclinic system; the space group is C2; cell parameters are as follows: a=13.885 Angstrom, b=4.4332 Angstrom, c=10.874 Angstrom, alpha=gamma=90 DEG C, beta=103.141 DEG C, z=2, and the unit cell volume V=651.8 Angstrom<3>. A solid phase synthesis method is used for acquiring an NCBB compound by sintering at high temperature. A molten salt method is used for successfully growing a single crystal by taking Na2O-Cs2O-B2O3 or Na2O-Cs2O-B2O3-MF (M=Na or Cs) as a fluxing agent. The frequency-doubled effect of the Na2CsBe6B5O15 is 0.55 time of that of LiB3O5 (LBO), the ultraviolet absorption edge of the Na2CsBe6B5O15 is shorter than 190nm, and the Na2CsBe6B5O15 can not dissolve in dilute acid, has good chemical stability, can be widely applied to various nonlinear optical fields and develops the nonlinear optical application of deep ultraviolet bands.

Description

Novel nonlinear optical crystal boric acid beryllium sodium caesium
 
Technical field
The present invention relates to a kind of new type light electronic functional material and growth method and purposes, particularly relate to a kind of non-linear optical crystal material, i.e. boric acid beryllium sodium caesium, its chemical formula is Na 2CsBe 6B 5O 15, be called for short NCBB.
Background technology
The crystalline non-linear optical effect is meant a kind of like this effect: when a branch of laser with certain polarization direction passes through a non-linear optic crystal (like NCBB) by certain incident direction, the frequency of this light beam will change.
Crystal with non-linearity optical effect is called non-linear optic crystal.Utilize non-linear optic crystal to carry out the laser frequency conversion, widen the scope of optical maser wavelength, make the application of laser more extensive.Especially borate family non-linear optic crystal such as BaB 2O 4(BBO), LiB 3O 5(LBO), KBe 2BO 3F 2(KBBF), Sr 2Be 2B 2O 7(SBBO), Ba 2Be 2B 2O 7(TBO), K 2Al 2B 2O 7(KABO), BaAl 2B 2O 7(BABO) etc. crystal receives much attention with its excellent optical property.Development in photo-optics, photoengraving, precision instrument processing and other fields more and more needs ultraviolet and deep ultraviolet laser coherent source, promptly needs the ultraviolet and the deep ultraviolet non-linear optic crystal of excellent performance.
The substruction primitive of bbo crystal is (B 3O 6) 3-The plane group, this group has big conjugated, makes the ultraviolet absorption edge of BBO about 189nm, has limited the application of crystal in the ultraviolet region; And big conjugated also can cause bigger degree of birefringence (Δ n=0.12), thereby has limited its harmonic conversion efficient and the quality of the humorous glistening light of waves.
The substruction primitive of LBO is with (B 3O 6) 3-Thereby a B atom in the group becomes four-coordination by three-fold coordination and forms (B 3O 7) 5-Group.It has bigger Clock Multiplier Factor, and ultraviolet absorption edge is about 160nm, but the because (B in real crystal 3O 7) 5-Group is interconnection; Formation becomes 45 ° coiled strand with the z axle and can't in lattice, be arranged in parallel in the space; Make the crystalline degree of birefringence fall low (Δ n=0.04～0.05); Thereby make it be severely limited, make the wide advantage of band gap fail to give full play in the phase matched scope of ultraviolet region.
The substruction primitive of KBBF is (BO 3) 3-The plane group, this group and (BeO 3F) 5-Formed along the Be of z direction through shared Sauerstoffatom 2BO 3Plane layer.The existence of plane layer thus makes its ultraviolet absorption edge about 155nm, has moderate degree of birefringence (Δ n=0.07), can realize very wide phase matched scope, is classic so far deep ultraviolet non-linear optic crystal.But owing to lean on electrostatic attraction between layer and the layer rather than be connected through valence link, the stratiform habit is serious, and is very slow in the z direction speed of growth, and the single crystal demixing phenomenon that grows is obvious, and crystal is difficult for growing.
The substruction primitive of SBBO also is (BO 3) 3-The plane group, but it replaces fluorion with oxygen, makes to interconnect through oxo bridge between layer and the layer, and so that improve the stratiform habit of KBBF, it is constant basically that the structure of each layer then keeps.SBBO not only has bigger macroscopical Clock Multiplier Factor, low ultraviolet absorption edge (165nm), and moderate degree of birefringence (Δ n=0.06), and thoroughly overcome crystalline stratiform habit, solved the problem of crystal growth.On this basis, keep (BO 3) 3-The structural condition of group is constant basically, replacement kation S r 2+With the Be atom, developed a series of non-linear optic crystals such as TBO, KABO, BABO in succession, they are referred to as the SBBO group crystal.They have overcome the stratiform habit of KBBF single crystal growing; But up to the present these crystal can't replace the KBBF monocrystalline; Because SBBO and TBO crystalline structural integrity are bad, the non-constant of optical homogeneity that its macro property shows also can't be applied in practical devices at present.
Because there is the difficulty of growth aspect in the KBBF crystal, and it derives from Be in the excellent properties of deep ultraviolet wave band 2BO 3Plane layer, we think that the covalent linkage of available atom or group is with above-mentioned Be 2BO 3Plane layer couples together with layer, has so both kept the Be that produces excellent properties 2BO 3Plane layer has solved the difficulty of layer growth habit again, thereby forms brand-new anion frame, then with basic metal or alkaline earth metal ion as positively charged ion, obtain new compound, the application of developing deep ultraviolet non-linear optic crystal.Through solid phase synthesis, crystal growth, single crystal structure determination has confirmed that this imagination is possible.
Summary of the invention
The object of the present invention is to provide a kind of boric acid beryllium sodium caesium cpd, its chemical formula is Na 2CsBe 6B 5O 15
Another object of the present invention is to provide a kind of boric acid beryllium sodium caesium cpd preparation method.
Another object of the present invention is to provide a kind of boric acid beryllium sodium caesium non-linear optic crystal, its chemical formula is Na 2CsBe 6B 5O 15
A purpose more of the present invention is to provide a kind of growth method of boric acid beryllium sodium caesium non-linear optic crystal.
A further object of the invention is to provide the purposes of boric acid beryllium sodium caesium non-linear optic crystal.
Technical scheme of the present invention is following:
1. compound boric acid beryllium sodium caesium, it is characterized in that: its chemical formula is Na 2CsBe 6B 5O 15, be called for short NCBB, belong to oblique system, spacer is P2 1, unit cell parameters is a=13.885, b=4.4332, and c=10.874, α=γ=90 °, β=103.141 °, z=2, unit-cell volume is V=651.8 3
2. the preparation method of item 1 a described boric acid beryllium sodium caesium cpd; It is characterized in that: the raw materials of compound that will contain Na, Cs, Be and B is after the ratio uniform mixing of Na:Cs:Be:B=2:1:6:5 grinds in its mol ratio; After 400～500 ℃ of the slow intensifications, pre-burning 1～5 hour; Be cooled to room temperature, take out and grind; 650～750 ℃ of following sintering 12～20 hours, be cooled to room temperature and can obtain boric acid beryllium sodium caesium cpd then; The described Na of containing raw materials of compound is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or the borate that contains sodium; The described Cs of containing raw materials of compound is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or the borate that contains caesium; The described Be of containing raw materials of compound is BeO, and the described B of containing raw materials of compound is H 3BO 3Or B 2O 3
3. the non-linear optic crystal of item 1 a described compound boric acid beryllium sodium caesium.
4. the growth method of the non-linear optic crystal of item 3 described boric acid beryllium sodium caesiums adopts molten-salt growth, it is characterized in that: adopt Na 2O-Cs 2O-B 2O 3The fusing assistant system, the raw materials of compound that will contain Na, Cs, Be and B is that Na:Cs:Be:B=1～4:1～4:2:5～15 mix by its mol ratio, heats up 950～1050 ℃ to melt fully to raw material; Behind the constant temperature 1～20 hour; Be cooled to above 5～10 ℃ of temperature of saturation rapidly, then by every day 1～5 ℃ speed be cooled to 600 ℃, treat that sample is cooled to room temperature after; Remove fusing assistant with rare nitric acid and washing, promptly obtain boric acid beryllium sodium caesium non-linear optic crystal of the present invention; The raw materials of compound that adopts is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, the oxide compound that contains Cs or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, BeO and the H that contains Na 3BO 3Or B 2O 3
5. the growth method of item 3 described boric acid beryllium sodium caesium non-linear optic crystals adopts molten-salt growth, it is characterized in that: adopt Na 2O-Cs 2O-B 2O 3-MF fusing assistant system, wherein M is Na or Cs; Raw material is mixed in proportion, heat up 950～1050 ℃ and melt fully to raw material, constant temperature is after 1～20 hour; Be cooled to above 5～10 ℃ of temperature of saturation rapidly; The lower end that seed crystal is fixed on seed rod contacts the beginning crystal growth with melt liquid level, the speed of rotation of seed rod is 10～20 rev/mins, is cooled to temperature of saturation; Slowly lower the temperature by 1～5 ℃/day speed then; Cooling is lifted from liquid level with crystal after finishing, and reduces to room temperature with 10～30 ℃/hour speed, obtains boric acid beryllium sodium caesium non-linear optic crystal of the present invention; The raw materials of compound that adopts is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, the oxide compound that contains Cs or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, BeO and the H that contains Na 3BO 3Or B 2O 3
6. the growth method of item 5 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that, when M was Na, 5 a described raw material with the mol ratio that contains the fusing assistant of NaF was: Na 2CO 3: Cs 2CO 3: BeO:B 2O 3: NaF=1～4:1～4:4:5～15:0.5～1.
7. the growth method of item 5 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that, when M was Cs, 5 a described raw material with the mol ratio that contains the fusing assistant of CsF was: Na 2CO 3: Cs 2CO 3: BeO:B 2O 3: CsF=1～4:1～4:4:5～15:0.5～1.
8. the purposes of item 3 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that: this non-linear optic crystal is used for the frequency transformation of laser apparatus laser output.
9. the purposes of item 8 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that: it is that the laser beam of 1.064 μ m produces 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, the humorous glistening light of waves output of 5 frequencys multiplication that this crystal is used for wavelength.
10. the purposes of item 8 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that: this crystal is used to produce the humorous glistening light of waves output that wavelength is lower than 200nm.
11. the purposes of item 8 described boric acid beryllium sodium caesium non-linear optic crystals, it is characterized in that: described harmonic generator is the harmonic generator that is used for the ultraviolet region, optical parameter and amplifying device and fiber waveguide device.
12. the purposes of item 8 described boric acid beryllium sodium caesium non-linear optic crystals is characterized in that: described harmonic generator is optical parameter and amplifying device from infrared to the ultraviolet region.
It is Na that effect of the present invention is to provide a kind of chemical formula 2CsBe 6B 5O 15Compound, the non-linear optic crystal of this compound.Use powder frequency multiplication testing method to measure the phase matched ability of NCBB, its powder frequency-doubled effect is LiB 3O 5(LBO) 0.55 times.Its ultraviolet absorption edge is shorter than 190nm.The NCBB crystal can be realized 2 frequencys multiplication of Nd:YAG (λ=1.064 μ m), and, can predict that NCBB can be used in the harmonic generator of 3 frequencys multiplication of Nd:YAG, 4 frequencys multiplication, 5 frequencys multiplication, even be used to produce the humorous glistening light of waves output shorter than 200nm.In addition, NCBB monocrystalline water white transparency is non-congruent melting compound, about 855 ℃ of fusing point, and deliquescence not in air is insoluble to diluted acid, and chemicalstability is good.So can predict, NCBB will obtain widespread use in various non-linear optical fields, and will open up the nonlinear optics application of deep ultraviolet wave band.
Description of drawings
Fig. 1 is the canonical schema of NCBB crystal as frequency-doubling crystal application non-linear hour optical effect, and wherein 1 is laser apparatus, the 2nd, and incoming laser beam, the 3rd, through the NCBB single crystal of crystal aftertreatment and optics processing, the 4th, the outgoing laser beam that is produced, the 5th, filter plate.
Fig. 2 is a NCBB crystalline structure synoptic diagram, and wherein a is expression Na, Cs, B, Be, the O sciagraph along the b direction, b be expression Na, Cs, B, Be, O along ac planar sciagraph, c representes beryllium boron oxygen Be in the crystalline structure 2BO 3The two dimensional structure layer.
Fig. 3 is the x XRD X collection of illustrative plates of NCBB, and wherein a is the diffractogram of solid phase synthesis NCBB powdered sample, and b is the NCBB monocrystalline last diffractogram of pulverizing.
Embodiment
Embodiment 1
Adopt high temperature solid state reaction synthetic compound Na 2CsBe 6B 5O 15
Raw materials used: Na 2CO 31.0599 gram (0.01mol)
Cs 2CO 31.6292 gram (0.005mol)
BeO 1.5007 grams (0.06mol)
B 2O 31.7405 gram (0.025mol)
Its chemical equation is:
2Na 2CO 3?+?Cs 2CO 3?+?12BeO?+?5B 2O 3?=?2Na 2CsBe 6B 5O 15?+?3CO 2↑
The concrete operations step is following: after in operation box, above-mentioned raw materials being weighed up by above-mentioned dosage, put into that mortar mixes and carefully grind, in the platinum alloy crucible of the Φ 30 * 30mm that packs into then; With spoon it is compressed and to add a cover, put into retort furnace (retort furnace places stink cupboard, and the fume hood exhaust mouth is through the water tank exhaust); Slowly be warming up to 500 ℃ and constant temperature pre-burning 3 hours; The beginning temperature rise rate must be slow, prevents and treats the variation that causes proportioning because of decomposition, and solid state reaction is fully carried out.Crucible is taken out in the cooling back, and this moment, sample was more loose.Then take out sample and in operation box, grind again evenly, place crucible to compress again and add a cover, in 750 ℃ of following sintering 20 hours, took out the cooling back in retort furnace, and at this moment sample is formed one, sample is put into mortar smash grinding to pieces and promptly get product.This product is carried out X-ray analysis, and (Fig. 3 is consistent with the NCBB monocrystalline last X ray picture (Fig. 3 b) of pulverizing a) to the gained spectrogram.
Embodiment 2
Adopt high temperature solid state reaction synthetic compound Na 2CsBe 6B 5O 15
Raw materials used: Na 2CO 31.0599 gram (0.01mol)
Cs 2CO 31.6292 gram (0.005mol)
BeO 1.5007 grams (0.06mol)
H 3BO 33.0915 gram (0.05mol)
Its chemical equation is:
2Na 2CO 3?+?Cs 2CO 3?+?12BeO?+?10H 3BO 3?=?2Na 2CsBe 6B 5O 15?+?3CO 2↑+?15H 2O↑
The concrete operations step is following: after in operation box, above-mentioned raw materials being weighed up by above-mentioned dosage, put into that mortar mixes and carefully grind, in the platinum alloy crucible of the Φ 30 * 30mm that packs into then; With spoon it is compressed and to add a cover, put into retort furnace (retort furnace places stink cupboard, and the fume hood exhaust mouth is through the water tank exhaust); Slowly be warming up to 500 ℃ and constant temperature pre-burning 3 hours; The beginning temperature rise rate must be slow, prevents and treats the variation that causes proportioning because of decomposition, and solid state reaction is fully carried out.Crucible is taken out in the cooling back, and this moment, sample was more loose.Then take out sample and in operation box, grind again evenly, place crucible to compress again and add a cover, in 750 ℃ of following sintering 20 hours, took out the cooling back in retort furnace, and at this moment sample is formed one, sample is put into mortar smash grinding to pieces and promptly get product.This product is carried out X-ray analysis, and (Fig. 3 is consistent with the NCBB monocrystalline last X ray picture (Fig. 3 b) of pulverizing a) to the gained spectrogram.
Embodiment 3
Adopt molten-salt growth crystal Na 2CsBe 6B 5O 15
Crystal growing apparatus is homemade wire spiral process furnace, and temperature controlling instruments is a 908PHK20 type automatic temperature control instrument able to programme.Select Na for use 2O-Cs 2O-B 2O 3Make fusing assistant, sporadic nucleation obtains crystal.
Raw materials used: Na 2CO 321.198 gram (0.2mol)
Cs 2CO 397.749 gram (0.3mol)
BeO 10.004 grams (0.4mol)
B 2O 362.658 gram (0.9mol)
The concrete operations step is following: above-mentioned raw materials is weighed up by above-mentioned dosage; Pack into after mixing in the platinum alloy crucible of Φ 60 * 60mm, place in the self-control reactors, heat up 1000 ℃ and melt fully to raw material; Behind the constant temperature 10 hours; Be cooled to above 5～10 ℃ of temperature of saturation rapidly, then by every day 3 ℃ speed be cooled to 600 ℃, close stove.After treating the sample cooling, remove fusing assistant, promptly obtain transparent NCBB monocrystalline with rare nitric acid and washing.
Embodiment 4
Adopt molten-salt growth crystal Na 2CsBe 6B 5O 15
Crystal growing apparatus is homemade wire spiral process furnace, and temperature controlling instruments is a 908PHK20 type automatic temperature control instrument able to programme.Select Na for use 2O-Cs 2O-B 2O 3-NaF makees fusing assistant, and the crystal that instance 3 is obtained carries out orientation and cuts into the seed crystal that is designed.
Raw materials used: Na 2CO 321.198 gram (0.2mol)
Cs 2CO 397.749 gram (0.3mol)
BeO 10.004 grams (0.4mol)
B 2O 362.658 gram (0.9mol)
NaF 2.100 grams (0.05mol)
The concrete operations step is following: above-mentioned raw materials is weighed up by above-mentioned dosage, in the platinum alloy crucible of the Φ 60 * 60mm that packs into after mixing, place in the self-control reactors; Heat up 1000 ℃ and melt fully to raw material; Behind the constant temperature 10 hours, be cooled to above 5～10 ℃ of temperature of saturation rapidly, seed crystal be fixed on the lower end of seed rod; Import crucible from the aperture of furnace roof portion, make seed crystal contact the beginning crystal growth with melt liquid level.The speed of rotation of seed rod is 15 rev/mins, is cooled to temperature of saturation, slowly lowers the temperature by 1 ℃/day speed then.Cooling is lifted from liquid level with crystal after finishing, and reduces to room temperature with 20 ℃/hour speed, promptly obtains the NCBB monocrystalline of large-size.
Embodiment 5
Adopt molten-salt growth crystal Na 2CsBe 6B 5O 15
Crystal growing apparatus is homemade wire spiral process furnace, and temperature controlling instruments is a 908PHK20 type automatic temperature control instrument able to programme.Select Na for use 2O-Cs 2O-B 2O 3-CsF makees fusing assistant, and the crystal that instance 3 is obtained carries out orientation and cuts into the seed crystal that is designed.
Raw materials used: Na 2CO 321.198 gram (0.2mol)
Cs 2CO 397.749 gram (0.3mol)
BeO 10.004 grams (0.4mol)
B 2O 362.658 gram (0.9mol)
CsF 7.595 grams (0.05mol)
The concrete operations step is following: above-mentioned raw materials is weighed up by above-mentioned dosage, in the platinum alloy crucible of the Φ 60 * 60mm that packs into after mixing, place in the self-control reactors; Heat up 1000 ℃ and melt fully to raw material; Behind the constant temperature 10 hours, be cooled to above 5～10 ℃ of temperature of saturation rapidly, seed crystal be fixed on the lower end of seed rod; Import crucible from the aperture of furnace roof portion, make seed crystal contact the beginning crystal growth with melt liquid level.The speed of rotation of seed rod is 15 rev/mins, is cooled to temperature of saturation, slowly lowers the temperature by 1 ℃/day speed then.Cooling is lifted from liquid level with crystal after finishing, and reduces to room temperature with 20 ℃/hour speed, promptly obtains the NCBB monocrystalline of large-size.
Embodiment 6
With the crystal that instance 4 obtains, processing cutting, orientation; Polishing is placed on the position of 3 in the device shown in Figure 1; At room temperature, with transferring Q Nd:YAG laser to do the input light source, incident wavelength is 1064nm; Observe tangible 532nm frequency multiplication green glow output, output intensity is about 0.55 times of equal conditions LBO.

Claims (12)

1. compound boric acid beryllium sodium caesium, it is characterized in that: its chemical formula is Na 2CsBe 6B 5O 15, be called for short NCBB, belong to oblique system, spacer is C2, unit cell parameters is a=13.885, b=4.4332, c=10.874, α=γ=90 °, β=103.141 °, z=2, unit-cell volume is V=651.8 3
2. the preparation method of the described boric acid beryllium of claim 1 a sodium caesium cpd; It is characterized in that: the raw materials of compound that will contain Na, Cs, Be and B is after the ratio uniform mixing of Na:Cs:Be:B=2:1:6:5 grinds in its mol ratio; After 400～500 ℃ of the slow intensifications, pre-burning 1～5 hour; Be cooled to room temperature, take out and grind; 650～750 ℃ of following sintering 12～20 hours, be cooled to room temperature and can obtain boric acid beryllium sodium caesium cpd then; The described Na of containing raw materials of compound is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or the borate that contains sodium; The described Cs of containing raw materials of compound is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or the borate that contains caesium; The described Be of containing raw materials of compound is BeO, and the described B of containing raw materials of compound is H 3BO 3Or B 2O 3
3. the non-linear optic crystal of the described compound boric acid of claim 1 a beryllium sodium caesium.
4. the growth method of the non-linear optic crystal of the described boric acid beryllium of claim 3 a sodium caesium adopts molten-salt growth, it is characterized in that: adopt Na 2O-Cs 2O-B 2O 3The fusing assistant system, the raw materials of compound that will contain Na, Cs, Be and B is that Na:Cs:Be:B=1～4:1～4:2:5～15 mix by its mol ratio, heats up 950～1050 ℃ to melt fully to raw material; Behind the constant temperature 1～20 hour; Be cooled to above 5～10 ℃ of temperature of saturation rapidly, then by every day 1～5 ℃ speed be cooled to 600 ℃, treat that sample is cooled to room temperature after; Remove fusing assistant with rare nitric acid and washing, promptly obtain low temperature phase boric acid beryllium sodium caesium non-linear optic crystal of the present invention; The raw materials of compound that adopts is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, the oxide compound that contains Cs or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, BeO and the H that contains Na 3BO 3Or B 2O 3
5. the growth method of the described boric acid beryllium of claim 3 a sodium caesium non-linear optic crystal adopts molten-salt growth, it is characterized in that: adopt Na 2O-Cs 2O-B 2O 3-MF fusing assistant system, wherein M is Na or Cs; Raw material is mixed in proportion, heat up 950～1050 ℃ and melt fully to raw material, constant temperature is after 1～20 hour; Be cooled to above 5～10 ℃ of temperature of saturation rapidly; The lower end that seed crystal is fixed on seed rod contacts the beginning crystal growth with melt liquid level, the speed of rotation of seed rod is 10～20 rev/mins, is cooled to temperature of saturation; Slowly lower the temperature by 1～5 ℃/day speed then; Cooling is lifted from liquid level with crystal after finishing, and reduces to room temperature with 10～30 ℃/hour speed, obtains boric acid beryllium sodium caesium non-linear optic crystal of the present invention; The raw materials of compound that adopts is oxide compound or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, the oxide compound that contains Cs or oxyhydroxide or carbonate or nitrate salt or oxalate or borate, BeO and the H that contains Na 3BO 3Or B 2O 3
6. the growth method of the described boric acid beryllium of claim 5 a sodium caesium non-linear optic crystal is characterized in that, when M was Na, the described raw material of claim 5 with the mol ratio that contains the fusing assistant of NaF was: Na 2CO 3: Cs 2CO 3: BeO:B 2O 3: NaF=1～4:1～4:4:5～15:0.5～1.
7. the growth method of the described boric acid beryllium of claim 5 a sodium caesium non-linear optic crystal is characterized in that, when M was Cs, the described raw material of claim 5 with the mol ratio that contains the fusing assistant of CsF was: Na 2CO 3: Cs 2CO 3: BeO:B 2O 3: CsF=1～4:1～4:4:5～15:0.5～1.
8. the purposes of the described boric acid beryllium of claim 3 a sodium caesium non-linear optic crystal is characterized in that: this non-linear optic crystal is used for the frequency transformation of laser apparatus laser output.
9. the purposes of the described boric acid beryllium of claim 8 a sodium caesium non-linear optic crystal is characterized in that: it is that the laser beam of 1.064 μ m produces 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, the humorous glistening light of waves output of 5 frequencys multiplication that this crystal is used for wavelength.
10. the purposes of the described boric acid beryllium of claim 8 a sodium caesium non-linear optic crystal is characterized in that: this crystal is used to produce the humorous glistening light of waves output that wavelength is lower than 200nm.
11. the purposes of the described boric acid beryllium of claim 8 a sodium caesium non-linear optic crystal, it is characterized in that: described harmonic generator is the harmonic generator that is used for the ultraviolet region, optical parameter and amplifying device and fiber waveguide device.
12. the purposes of the described boric acid beryllium of claim 8 a sodium caesium non-linear optic crystal is characterized in that: described harmonic generator is optical parameter and amplifying device from infrared to the ultraviolet region.
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Publication number Priority date Publication date Assignee Title
CN106546332A (en) * 2016-11-17 2017-03-29 山西大学 Optical frequency measuring system and method based on formation of ultra-cold molecules photoassociation spectrum
CN107059109A (en) * 2017-04-13 2017-08-18 中国科学院理化技术研究所 Al-doped CsLiB6O10Crystal growth fluxing agent and crystal growth method
CN108957902A (en) * 2018-03-09 2018-12-07 中国科学院福建物质结构研究所 Device for non-linear optical comprising boracite crystal
CN108950687A (en) * 2018-03-09 2018-12-07 中国科学院福建物质结构研究所 Boracite crystal, preparation method and use
CN109706519A (en) * 2019-03-05 2019-05-03 中国科学院理化技术研究所 A kind of second-order non-linear optical crystal material and its preparation method and application
CN115717271A (en) * 2021-08-25 2023-02-28 中国科学院福建物质结构研究所 Lithium niobium tellurate compound and preparation method and application of nonlinear optical crystal thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106546332A (en) * 2016-11-17 2017-03-29 山西大学 Optical frequency measuring system and method based on formation of ultra-cold molecules photoassociation spectrum
CN107059109A (en) * 2017-04-13 2017-08-18 中国科学院理化技术研究所 Al-doped CsLiB6O10Crystal growth fluxing agent and crystal growth method
CN108957902A (en) * 2018-03-09 2018-12-07 中国科学院福建物质结构研究所 Device for non-linear optical comprising boracite crystal
CN108950687A (en) * 2018-03-09 2018-12-07 中国科学院福建物质结构研究所 Boracite crystal, preparation method and use
CN108957902B (en) * 2018-03-09 2021-05-11 中国科学院福建物质结构研究所 Nonlinear optical device comprising boracite crystal
CN109706519A (en) * 2019-03-05 2019-05-03 中国科学院理化技术研究所 A kind of second-order non-linear optical crystal material and its preparation method and application
CN109706519B (en) * 2019-03-05 2020-08-07 中国科学院理化技术研究所 Second-order nonlinear optical crystal material and preparation method and application thereof
CN115717271A (en) * 2021-08-25 2023-02-28 中国科学院福建物质结构研究所 Lithium niobium tellurate compound and preparation method and application of nonlinear optical crystal thereof

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