CN1320725A - Non-linear optical crystal of large-size high-temp zinc borophosphate and its preparing process and use - Google Patents
Non-linear optical crystal of large-size high-temp zinc borophosphate and its preparing process and use Download PDFInfo
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Abstract
A monocrystal beta-Zn3BPO7, its preparing process and its usage are disclosed. Said crystal has the size of at least cm class, 0.69 pm/v of non-linear coefficient, light-transmission wave range of 250nm-2500nm, negative single axis and 5.0 of Mohs hardness. It is prepared through pretreating raw materials, loading in crucible, melting and growing. Said crystal can be used to make frequency multiplier, frequency converter, and photoparametric oscillator. Its advantages are low viscosity of its molten body, easy growth at high speed, high transparency and low cost.
Description
The invention relates to a nonlinear optical crystal and a growing method thereof, in particular to a method for growing a nonlinear optical crystal from Zn3BPO7Large size high quality high temperature phase zinc borophosphate (β -Zn) grown in melt3BPO7) Single crystal and its preparation and use β -Zn3BPO7Made of crystalsUse of a non-linear optical device.
In the laser technology, the laser band obtained by directly utilizing the laser crystal is limited, and blank bands exist from ultraviolet to infrared spectral regions. The nonlinear optical crystal is used, and limited laser wavelength can be converted into laser with a new waveband through nonlinear optical effects such as frequency doubling, frequency mixing, optical parametric oscillation and the like. The technique can fill the blank spectral region of the laser wavelength emitted by various laser devices, so that the laser device can be widely applied. The full-curing blue-green laser system can be realized by generating near-infrared laser by a solid laser and then performing frequency conversion by a nonlinear optical crystal, and has huge application prospect and economic value in various high-technology fields such as optical data storage, biomedical instruments, laser printing, full-color display and the like.
The main nonlinear optical materials currently applied to the blue-green light waveband frequency conversion include KTP ((KTiOPO4) crystal disclosed in United states patent 5,684,813 and BBO (β -BaB) introduced in Chinese science B28,235,19852O4) Crystal and LBO (LiB) disclosed in "Chinese invention patent" 881020843O5) And (4) crystals. These materials have disadvantages in crystal growth: as KTP and LBO are molten compounds with different components, a fluxing agent method is needed for growth; BaB2O4There is a phase transition, BBO is a low temperature phase BaB2O4Therefore, the growth by flux method is also required. The nonlinear optical crystals with excellent performance need to be grown by a fluxing agent method, so that the growth speed is slow, large-size crystals are not easy to obtain, the cost is high, and the large-scale application of the fully-cured blue-green laser is influenced. Therefore, in recent years, when developing a novel nonlinear optical crystal, not only optical properties and mechanical properties of the crystal but also production characteristics of the crystal have been more and more emphasized, and it is desired that a novel crystal material be easily produced, preferably a homomelting compound, and that a single crystal be grown by a melt method, so that a large-sized high-quality nonlinear optical crystal with low cost can be obtained. There are various techniques for growing by the melt method, such as the Czochralski method, the Bridgman method, the kyropoulos method, and the likeThere have been many theories.
The Z.Kristallogr. journal of Germany (Vol.160,135-137,1982) reports the compound zinc borophosphate Zn3BPO7The existence of (A) indicates that the melting point of the compound is 927 ℃ and that there is a high temperature phase (β -Zn)3BPO7) And a low temperature phase (α -Zn)3BPO7) Two polymorphs, β -Zn3BPO7Belongs to a hexagonal crystal system, and the point group is D3hUnit cell parameters a =8.439(3) Å, c =13.030(3) Å. generally, to test the fundamental physical properties (also including nonlinear optical properties) of a crystal requires a single crystal of several millimeters or even centimeters in size, and it has not been found until now that β -Zn of a size sufficient for physical property testing is prepared3BPO7Single crystals are even impossible to be commercially available, and β -Zn is not reported3BPO7Report of results of single crystal nonlinear optical property test or β -Zn3BPO7Single crystals are reported for use in the fabrication of nonlinear optical devices.
The invention aims to make up the blank spectral region of laser wavelength emitted by various lasers, thereby providing a transparent high-temperature phase β -Zn with centimeter-level large size3BPO7A nonlinear optical crystal, and a preparation method which does not require the use of flux and is simple in operation, and a process using β -Zn3BPO7Use of a nonlinear optical device made of a single crystal.
The purpose of the invention is realized as follows:
the large-size high-temperature phase zinc borophosphate nonlinear optical crystal provided by the invention has a chemical formula of β -Zn3BPO7Expressed, its volume has a large dimension of at least the order of centimetres, the crystal is transparent (as shown in figure 1) and has the following linear and nonlinear optical characteristics:
1. the light transmission wave band is 250nm to 2500nm (shown in figure 2);
2. coefficient of non-linearity d22≈0.69pm/V；
3. The crystal is a negative uniaxial crystal (n)o＞ne) The Sellmeire equation is:
me 2=2.82069+0.0220393/(λ2-0.00898032)
no 2=2.92674+0.0268122/(λ2-0.00298647)
where λ is the incident wavelength in μm.
Large-size high-temperature phase β -Zn of the invention3BPO7The Mohs hardness of the crystal is 5.0, the crystal is easy to cut, polish, process and store, does not deliquesce, and is suitable for manufacturing nonlinear optical devices.
The invention provides large-size high-temperature β -Zn3BPO7The preparation method of nonlinear optical crystal is characterized by that it adopts compound melt method to grow crystal, and places the prepared and pretreated raw material into crucible, melts said raw material and makes the crystal grow on the surface of melt or in the melt, and the crystal grown in the compound melt also can adopt pulling method, kyropoulos method and crucible descent method, and can be used for preparing large-size high-temperature phase β -Zn3BPO7The method of the nonlinear optical crystal comprises the following steps:
1 first a compound melt is prepared: mixing Zn, B and P compounds according to a molar ratio of 3: 1, grinding and uniformly mixing the raw materials, heating the raw materials in a crucible to be molten, keeping the temperature for 1-24 hours at a temperature higher than the melting point, and cooling the mixture to a temperature 1-5 ℃ higher than the melting point for later use;
2, growing the crystal in the compound melt quickly, including using seed crystal to grow, fixing the seed crystal on a seed crystal rod when using the seed crystal, contacting the seed crystal with the surface of the compound melt prepared in the crucible in the step 1 from the top, cooling to 927 ℃, or directly cooling the compound melt prepared in the crucible in the step 1 to 927 ℃, rotating the seed crystal and/or the crucible at the rotating speed of 0-80 rpm, pulling the crystal upwards at the speed of not more than 12mm/h, increasing the pulling speed after the single crystal grows to the required size, separating the crystal from the melt liquid level, annealing to 550-650 ℃ at the speed of not more than 120 ℃/h, and then annealing the prepared high-temperature phase β -Zn3BPO7The nonlinear optical crystal is slowly taken out of the hearth;
3 growing crystals in the compound melt by any one of the following reactions:
(1)
(2)
(3)
(4)
(5)
(6)
(7) the compound raw material can be ZnO or H3BO3And P2O5In which ZnO can be replaced by the corresponding chloride, carbonate, nitrate, oxalate or hydroxide of zinc, H3BO3Can be used as B2O3Replacing; p2O5May use NH4H2PO4、(NH4)2HPO4Instead. Zn can be obtained by using any one of the compound raw materials and a reaction3BPO7And (4) melting the melt.
Or growing the crystal in the compound melt by adopting a kyropoulos method, namely, under the basic condition of growing the crystal by adopting the pulling technology, the pulling speed is zero, the temperature is reduced at the speed of 0-5 ℃/day, and β -Zn is reduced3BPO7Growing the single crystal to a required size; either with or without a seed crystal.
Or growing the crystal in the compound melt by adopting a crucible moving method, wherein the crucible or the heater can be moved and can be moved horizontally or vertically; either with or without a seed crystal. Moving the crucible or the heater at a speed of 0.01-10 mm/h to enable the melt to pass through a temperature gradient area for solidification to generate the single crystal. The process can also be realized by slowly cooling the crystallization furnace, and the heating mode can be resistance wire heating, and also can be silicon carbon rod or silicon molybdenum rod heating; the crucible can be cylindrical, the bottom of the crucible is provided with a conical sharp corner, the crucible is boat-shaped, and the crucible can also be in other shapes.
In principle, existing compound melt growth techniques can be used to prepare the β -Zn of the present invention3BPO7The β -Zn with a corresponding larger size can be obtained when a large-size crucible is adopted for the crystal3BPO7However, β -Zn can be prevented only by using the conditions for growing crystals in a compound melt used in the present invention3BPO7Cracking of crystals due to phase transformation. The method adopts proper thermal conditions, namely, after the crystal growth is finished, the crystal is separated from the surface of the melt, is cooled to 550-650 ℃ at the speed of not more than 120 ℃/h, and is slowly taken out of a hearth.
Large-size high-temperature phase β -Zn prepared by the invention3BPO7Use of crystal for making non-linear optical device, including frequency doubling generator, upper or lower frequency converter, optical parametric oscillator, etc. according to β -Zn3BPO7Crystallography data of crystal, orienting the blank, cutting along phase matching direction to needed thickness and cross-section, polishing the light-passing surface of crystal, and processing β -Zn3BPO7The crystal can be used as a nonlinear optical device because of β -Zn3BPO7The crystal is a uniaxial crystal, the phase of which is matched only with the optical axis of the crystal (parallel to β -Zn)3BPO7Crystallographic c-axis of the crystal) and angle theta between incident light directions, phase-matching angle thetamCan be obtained according to the following formula:
class I phase matching thetam=sin-1((ne 2ω/no ω)2((no 2ω)2-(no ω)2)/((no 2ω)2-(ne 2ω)2)))1/2
Class II phase matching thetam=sin-1((2no 2ω)2/(ne ωθm+no ω)2-1)/((no 2ω/ne 2ω)2-1))1/2
Wherein the refractive index no ω,ne ω,no 2ωAnd ne 2ωCan be prepared from β -Zn3BPO7The Sellmeire equation of the crystal is calculated.
For example, the nonlinear optical crystal of the present invention is made into a nonlinear optical device with a cross-sectional size of 4X 4mm and a thickness of 12mm in the light-transmitting direction, and at room temperature, a Q-switched Nd: YAG laser is used as a light source to emit infrared light with a wavelength of 1064nm and green laser light with a wavelength of 532 nm.
The optical processing method of the nonlinear optical crystal is familiar to the technical personnel in the field, and the crystal provided by the invention has no special requirement on the optical processing precision.
Effects of the invention
The invention provides a method for preparing high-temperature phase boron-zinc phosphate (β -Zn) by adopting various melt growth technologies3BPO7) And β -Zn3BPO7Compared with the prior nonlinear optical crystal KTP, BBO and LBO preparation technology applied to the blue-green light waveband frequency conversion, the crystal preparation method of the invention has β -Zn3BPO7The melting of the same components is suitable for growing single crystals by using a melt method, the common melt growing method can be used, and β -Zn is used in the invention3BPO7The melt viscosity is lower than that of general borate, the mass transmission is facilitated, the crystal is extremely easy to grow and is transparent and free of package, the method has the advantages of no need of using fluxing agent, simplicity in operation, high growth speed, low cost, easiness in obtaining larger-size crystals and the like, the growth cycle of the crystals such as BBO, LBO, KTP and the like is as long as 1 month to several months, and the β -Zn of the invention3BPO7The crystal growth period instrument needs several days, compared with the common non-linear optical crystals such as BBO, LBO, KTP and the like in the prior art, β -Zn3BPO7The crystal has better crystal preparation characteristics, and can grow single crystal by using a melt method to obtain large-size high-quality crystal with low price. Crystals obtainedHas the advantages of good mechanical property, difficult cracking, no deliquescence, easy processing and storage, and the like. The nonlinear optical crystal is made into a nonlinear optical device with the cross section size of 4 multiplied by 4mm and the thickness of 12mm in the light transmission direction, and at room temperature, a Q-switched Nd: YAG laser is used as a light source, infrared light with the incident wavelength of 1064nm is emitted, and green laser with the output wavelength of 532nm is output.
The invention is described in detail below with reference to the following figures and examples:
FIG. 1 shows large size β -Zn prepared by the present invention3BPO7A crystal picture;
FIG. 2 shows large size β -Zn prepared by the present invention3BPO7Crystal transmission spectrum;
FIG. 3 is a typical large size β -Zn prepared by the present inventors3BPO7Working principle diagram of nonlinear optical device made of crystal, light beam 2 emitted by laser 1 is injected into β -Zn3BPO7A single crystal 3, the resulting output beam 4 passing through a filter 5 to obtain the desired laser beam, the non-linear optical device may be a frequency doubling generator, an upper and lower frequency converter, an optical parametric oscillator, etc. the laser 1 may be a neodymium-doped yttrium aluminum garnet (Nd: YAG) laser or other laser, and for frequency doubling devices using a Nd: YAG laser as the light source, the input beam 2 is infrared light with a wavelength of 1064nm passing through β -Zn3BPO7The single crystal generates a green double-frequency light with a wavelength of 532nm, the emergent light beam 4 contains an infrared light with a wavelength of 1064nm and a green light with a wavelength of 532nm, and the filter 5 functions to filter the infrared light component and only allow the green double-frequency light to pass through.
Example 1:
growing large-size high-temperature phase β -Zn by adopting a pulling technology in a melt3BPO7And (4) crystals.
Firstly, preparing a melt: 146.484 g of ZnO and 20.886 g of B2O3And 42.582 g P2O5Mixing, placing into a platinum crucible with a diameter of 60mm × 40mm, placing the crucible into a crystal growth furnace, heating to 980 deg.C, holding the temperature for 12 hrCooling to 930 deg.C, fixing β -Zn on the lower end of seed rod and cutting along the plane perpendicular to (001)3BPO7Introducing seed crystal into crucible from small hole at furnace top to make seed crystal contact with melt surface, cooling to 927 deg.C, seed rod rotating speed of 15rpm, pulling speed of 0.5mm/h, increasing pulling speed when growth is finished to make crystal separate from melt surface, annealing at 80 deg.C/h to 610 deg.C, and slowly taking out crystal from furnace to obtain β -Zn with size of phi 20mm × 34mm3BPO7And (3) single crystal.
Using the same procedure as above, 146.484 g of ZnO was replaced with 245.28 g of ZnCl2β -Zn is also obtained3BPO7And (3) single crystal.
Example 2:
β -Zn prepared by kyropoulos method3BPO7And (4) crystals.
225.702 g of ZnCO337.098 g of H3BO3And 69.012 g NH4H2PO4Mixing, placing into a platinum crucible with a diameter of 60mm × 45mm, placing the crucible into a crystal growth furnace, heating to 980 deg.C, holding for 20 hr, cooling to 930 deg.C, and cutting β -Zn along c-axis3BPO7Fixing seed crystal at the lower end of a seed crystal rod by using a platinum wire, guiding the seed crystal into a crucible from a small hole at the top of the furnace to enable the seed crystal to be in contact with the liquid level of a melt, reducing the temperature at the speed of 0.5 ℃/day at the rotation speed of 25rpm of the seed crystal rod, finishing the growth of the crystal after a few days, lifting the crystal away from the liquid level of the melt, annealing at the speed of 100 ℃/h to reduce the temperature to 580 ℃, and then slowly taking out the crystal from a hearth to obtain β -Zn with the side length of 40mm and the thickness of 11mm in the shape3BPO7。
Using the same procedure as described above, 225.702 g of ZnCO were added3Replacement was carried out with 276.12 g ZnC2O4β -Zn is also obtained3BPO7And (3) single crystal.
Example 3:
β -Zn prepared by adopting Bridgman-Stockbarge method3BPO7And (4) crystals.
30.343 g of Zn (NO)3)2·6H2O, 1.051 g of B2O3And 4.49 g (NH)4)2HPO4Mixing uniformly, placing into a platinum crucible with a diameter of 10mm, placing the seed crystal at the bottom of the crucible with a conical sharp angle, placing the crucible into a vertical heating furnace, heating until the raw material is completely melted, keeping the heating power constant, descending the crucible at a speed of 1mm/h to solidify the melt from bottom to top to generate a single crystal, annealing at a speed of 70 ℃/h to reduce the temperature to 600 ℃ after the crystallization is finished, and slowly taking out the crucible from a hearth to obtain β -Zn with a size of 10mm x 33mm3BPO7And (3) single crystal.
Using the same method as above, 30.343 g of Zn (NO) were added3)2·6H2O was replaced with 8.392 g of Zn (OH)2β -Zn is also obtained3BPO7And (3) single crystal.
Example 4:
β -Zn obtained in example 23BPO7Processing a frequency multiplier with 4 × 4 × 12mm size in the direction of θ =49.8 deg. by using a Q-switched Nd: YAG laser as light source at room temperature at the position of 3, and emitting infrared beam 2 with 1064nm wavelength from the Q-switched Nd: YAG laser 1 into β -Zn at room temperature3BPO7The single crystal 3 generates green frequency doubling light with the wavelength of 532nm, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and the filter 5 filters the infrared light component to obtain green laser with the wavelength of 532 nm.
Example 5:
β -Zn obtained in example 23BPO7An optical parametric oscillation device with the size of 4 multiplied by 8mm is processed by the crystal according to the direction of theta =42.5 degrees, and is pumped by 532nm laser at room temperature according to the position of 3 of the device shown in the attached figure 3, so that the parametric oscillation tuning output is obtained.
β -Zn is readily available to one of ordinary skill in the art using similar methods3BPO7The crystal produces other non-linear optical devices such as upper and lower frequency converters, etc., all without departing from the spirit and scope of the present invention.
Claims (9)
1. Large-size high-temperature phase zinc borophosphate β -Zn3BPO7A nonlinear optical crystal characterized by β -Zn represented by the following chemical formula3BPO7Crystals having a volume of at least a large dimension in the order of centimetres, which are transparent and have the following linear and nonlinear optical properties:
A. the light-transmitting wave band is 250nm to 2500 nm;
B. coefficient of non-linearity d22≈0.69pm/V；
C. The crystal is a negative uniaxial crystal (n)o＞ne) (ii) a D. The Mohs hardness was 5.0.
2. Preparation of large-size high-temperature phase zinc borophosphate β -Zn according to claim 13BPO7A non-linear optical crystal growing method features that the compound melt method is used to grow crystal, the prepared and pretreated raw material is put in crucible, and the raw material is molten to grow crystal on the surface of melt or in the melt.
3. The large size high temperature phase zinc borophosphate β -Zn of claim 23BPO7A nonlinear optical crystal method, characterized by comprising the steps of:
a. first, a compound melt was prepared: mixing Zn, B and P compounds according to a molar ratio of 3: 1, grinding and uniformly mixing the raw materials, heating the raw materials in a crucible to be molten, keeping the temperature for 1-24 hours at a temperature higher than the melting point, and cooling the mixture to a temperature 1-5 ℃ higher than the melting point for later use;
b. rapid crystal growth in compound melt: comprises the steps of growing by using seed crystals, fixing the seed crystals on a seed crystal rod when using the seed crystals, contacting the seed crystals from the top with the surface of the compound melt prepared in the crucible in the step 1, and cooling to 927 ℃; or directly cooling the compound melt prepared in the crucible in the step 1 to 927 ℃; rotating the seed crystal and/or the crucible at the rotating speed of 0-80 rpm, and pulling up the crystal at the speed of not more than 12 mm/h; after the single crystal grows to the required size, increasing the pulling speed to ensure that the crystal is separated from the liquid level of the melt, and controlling the pulling speed to be not more than 120 ℃/hAnnealing at a speed of 550-650 ℃, and then carrying out β -Zn on the prepared high-temperature phase3BPO7The nonlinear optical crystal is slowly taken out of the hearth.
4. The large size high temperature phase zinc borophosphate β -Zn of claim 23BPO7The nonlinear optical crystal method is characterized in that the method for growing the crystal in the compound melt method comprises a pulling method, a kyropoulos method and a crucible descending method.
5. The large size high temperature phase zinc borophosphate β -Zn of claim 23BPO7The nonlinear optical crystal method is characterized in that the Zn-containing compound raw material comprises: ZnO, or the corresponding chloride, carbonate, nitrate, oxalate or borate with zinc.
6. The large size high temperature phase zinc borophosphate β -Zn of claim 23BPO7Nonlinear optical crystalThe method is characterized in that the compound raw material containing B comprises: h3BO3、B2O3。
7. The large size high temperature phase zinc borophosphate β -Zn of claim 23BPO7A nonlinear optical crystal method, characterized by: the compound raw material containing P comprises: p2O5、NH4H2PO4、(NH4)2HPO4。
8. The large-size high-temperature phase zinc borophosphate β -Zn of claim 13BPO7Use of a nonlinear optical crystal characterized by: the method comprises the steps of manufacturing a frequency doubling generator, an upper frequency converter or a lower frequency converter and an optical parametric oscillator.
9. The large size high temperature phase zinc borophosphate β -Zn of claim 83BPO7Use of a nonlinear optical crystal characterized by:the crystal is used in a non-linear optical device comprising means for passing at least one beam of incident electromagnetic radiation through at least one non-linear optical crystal to produce at least one output radiation having a frequency different from that of the incident electromagnetic radiation, wherein the non-linear optical crystal is a high temperature phase zinc borophosphate β -Zn3BPO7A single crystal.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361354C (en) * | 2003-09-28 | 2008-01-09 | 中国科学院理化技术研究所 | Application of large-sized boron phosphate non-linear optical crystal |
| CN101876772B (en) * | 2009-11-19 | 2011-12-28 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
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2000
- 2000-04-27 CN CN 00106163 patent/CN1115430C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100361354C (en) * | 2003-09-28 | 2008-01-09 | 中国科学院理化技术研究所 | Application of large-sized boron phosphate non-linear optical crystal |
| CN101876772B (en) * | 2009-11-19 | 2011-12-28 | 中国科学院新疆理化技术研究所 | Compound potassium lead borophosphate nonlinear optical crystal as well as preparation method and application thereof |
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN103173859B (en) * | 2011-12-20 | 2015-05-13 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN106835263A (en) * | 2017-02-20 | 2017-06-13 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of lithium fluoroborate nonlinear optical crystal |
| CN106835263B (en) * | 2017-02-20 | 2020-01-03 | 中国科学院新疆理化技术研究所 | Preparation method and application of lithium fluoroborate nonlinear optical crystal |
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