CN1600906A - Large-size boron phosphate nonlinear optical crystal and fused salt growth method and application thereof - Google Patents
Large-size boron phosphate nonlinear optical crystal and fused salt growth method and application thereof Download PDFInfo
- Publication number
- CN1600906A CN1600906A CN 03154423 CN03154423A CN1600906A CN 1600906 A CN1600906 A CN 1600906A CN 03154423 CN03154423 CN 03154423 CN 03154423 A CN03154423 A CN 03154423A CN 1600906 A CN1600906 A CN 1600906A
- Authority
- CN
- China
- Prior art keywords
- crystal
- boron phosphate
- nonlinear optical
- compound
- size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 125
- 229910000149 boron phosphate Inorganic materials 0.000 title claims abstract description 85
- 230000003287 optical effect Effects 0.000 title claims abstract description 64
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 22
- 150000003839 salts Chemical class 0.000 title claims description 7
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000004907 flux Effects 0.000 claims abstract description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 39
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- -1 boron phosphate compound Chemical class 0.000 claims description 8
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 7
- 230000001427 coherent effect Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000005520 cutting process Methods 0.000 abstract description 4
- 238000005498 polishing Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical group [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
Abstract
A large-size boron phosphate nonlinear optical crystal: from the chemical formula BPO4The expression, transparent, the volume has at least centimeter-level large size, and the optical property: ultraviolet absorption edge 130 nm; coefficient of non-linearity d36≈0.98pm/v；d310.36 pm/v; negative uniaxial crystal o＞ne) (ii) a The Mohs hardness is 4, and the cutting, polishing and storage are easy without deliquescence. The preparation method comprises the following steps: 1) mixing boron phosphate and fluxing agent in proportion, heating to melt, keeping the temperature for 24-72 hours, and cooling to 2-10 ℃ above the saturation temperature to obtain a mixed melt; the mixing molar ratio of the boron phosphate to the flux is as follows: BPO4∶Li4P2O7∶Li2O is 1: 0.35: 0.24-0.12; 2) putting seed crystals arranged on seed crystal rods into the mixed melt in the step 1) for growth, wherein the conditions are as follows: rotating the seed crystal rod, keeping the temperature for 1-6 hours, quickly cooling to the saturation temperature, and then cooling at the cooling rate of 1-0.2 ℃/day; and (4) growing the crystal to a required size, quickly lifting the crystal away from the liquid level, and quickly cooling to room temperature to obtain the large-size boron phosphate nonlinear optical crystal. Can be used for manufacturing devices in frequency doubling generators, up/down frequency converters and optical parametric oscillators.
Description
Technical Field
The invention belongs to a nonlinear optical crystal, a growth method and application, and particularly relates to large-size Boron Phosphate (BPO)4) Nonlinear optical crystal and fused salt growth method and application thereof。
Background
In the laser technology, the laser wavelength which can be directly obtained by using a laser crystal is limited, and a blank waveband exists from an ultraviolet spectrum region to an infrared spectrum region. The nonlinear optical crystal is used, and limited laser wavelength can be converted into coherent light of a new waveband through nonlinear optical effects such as frequency doubling, frequency mixing, optical parametric oscillation and the like. The technology can fill the blank spectral region of the laser wavelength emitted by various laser devices, so that the laser device can be widely applied, and has huge application prospect and economic value in the technical field of laser.
At present, borate-type and phosphate-type nonlinear optical crystals such as BBO, LBO, KTP, and the like are attracting attention for their excellent nonlinear optical properties. The boron oxygen group and the phosphorus oxygen group in the materials play an important role in the nonlinear optical properties of the crystal. If the phosphorus-oxygen group and the boron-oxygen group are in the same compound, new properties can be generated, and the nonlinear optical materials of the compound are less reported at present.
German journal Zeitschrift fur Physikache Chemie, Abteilung B: BPO is reported by Chemie der Vol.B24, 215, 19344Crystal structure belonging to tetragonal system, I4 space group, unit cell parameters a-b-4.332 (6) Å, c-6.640 (8) Å, Z-2 BPO4Having BO only in the lattice4And PO4The two tetrahedral groups are mutually connected through oxygen atoms at the vertex angle to form a three-dimensional network structure. BPO is reported in "Manual Crystal school newspaper" Vol.20, 309, 1991 of China4And selection of fluxing agents therefor. BPO4The decomposition point of the molten compound is 1470 ℃, and the growth of the crystal is carried out by a flux method. According to BPO4-Li4P2O7Binary system phase diagram (see journal of U.S. J.am.C. Soc., vol.44, 393, 1961), BPO4And Li4P2O7Form a simple low co-soluble binary system, so Li can be used4P2O7Growth as fluxBPO4However, this system has a large viscosity, and it has not been possible to obtain BPO having a size sufficient for physical property testing4Crystals, which are even less commercially available, and further, BPO4Reporting of results of single crystal nonlinear optical property tests or BPO4Single crystals are reported for use in the fabrication of nonlinear optical devices. For the application of nonlinear optical crystals, it is necessary to grow single crystals of high optical quality with dimensions of the order of centimeters. Therefore, there is a need for a large-sized, high optical quality BPO4A method for growing a single crystal. There have been many theories on the flux-method growth technology, and the key is to find a suitable flux system. The crystal has high hardness, no moisture absorption and wide band gap, B-O and P-O bonds are favorable for the transmission of ultraviolet light, the ultraviolet absorption edge of the crystal reaches 130nm, and the crystal has application prospect in a deep ultraviolet spectrum region.
Disclosure of Invention
The invention aims to provide a BPO4The nonlinear optical crystal and its growth method and use, the method has the advantages of high growth speed, low cost, simple operation, and easy obtainment of large-size BPO4Nonlinear optical crystal and large-size BPO with high optical quality4Method for growing nonlinear optical crystal, and method for using BPO4The non-linear optical crystal is used to produce quasi-phase matched non-linear optical device, so that it can generate deep ultraviolet harmonic light output.
The technical scheme of the invention is as follows:
the invention provides a large-size boron phosphate nonlinear optical crystal, which is characterized in that: the crystal is transparent and has the chemical formula BPO4Expressed, its volume has at least a large dimension in the order of centimetres and has the following linear and nonlinear optical characteristics:
A. ultraviolet absorption edge 130 nm;
B. coefficient of non-linearity d36≈0.98pm/v；d31≈0.36pm/v；
C. The crystal is a negative uniaxial crystal (n)o＞ne)；
D. The Mohs hardness is 4, the cutting, polishing and storage are easy, the deliquescence is avoided, and the preparation method is suitable for manufacturing nonlinear optical devices.
The invention provides a molten salt growth method of a large-size boron phosphate nonlinear optical crystal, which comprises the following steps:
(1) mixing boron phosphate and a fluxing agent uniformly according to a proportion, heating and melting, keeping the temperature for 24-72 hours, and cooling to 2-10 ℃ above the saturation temperature to obtain a mixed melt containing boron phosphate and the fluxing agent;
the fluxing agent contains Li4P2O7And Li2A composite fluxing agent of O;
the boron phosphate and Li4P2O7And Li2The molar ratio of the mixed compound fluxing agent of O is as follows:
BPO4∶Li4P2O7∶Li2O＝1∶0.35∶0.24-0.12；
(2) and (2) putting the seed crystal arranged on the seed rod into the mixed melt prepared in the step (1) for growth at the temperature of 2-10 ℃ above the saturation temperature, wherein the growth conditions are as follows: rotating the seed rod at a rotating speed of 9-15 rpm, keeping the temperature at 2-10 ℃ above the saturation temperature for 1-6 hours, rapidly cooling to the saturation temperature, and then slowly cooling at a cooling rate of 1-0.2 ℃/day; when the crystal grows to the required size, the crystal is quickly lifted from the melt to the liquid level, and the temperature is reduced to the room temperature at the cooling rate of 20-40 ℃/hour, thus obtaining the large-size boron phosphate nonlinear optical crystal.
B in the boron phosphate compound is from a B-containing compound with the same equivalent ratio as the boron phosphate compound, and the B-containing compound is B2O3Or H3BO3；
P in the boron phosphate compound is from a P-containing compound with the same equivalent ratio as the boron phosphate compound, and the P-containing compound is P2O5、NH4H2PO4Or (NH)4)2HPO4。
The Li4P2O7Li in flux comes from Li4P2O7A compound containing Li in the same equivalent ratio, wherein the compound containing Li is lithium oxide, lithium hydroxide, lithium oxalate or lithium carbonate;
the Li4P2O7P in the flux is derived from Li4P2O7The compound contains P compound with the same equivalent ratio, and the P compound is P2O5、NH4H2PO4Or (NH)4)2HPO4。
The Li2Li in O flux comes from Li2And the O compound is a Li-containing compound with the same equivalent ratio, and the Li-containing compound is lithium hydroxide, lithium oxalate or lithium carbonate.
The application of the large-size boron phosphate nonlinear optical crystal of the invention is as follows: the quasi-phase matching nonlinear optical device is used for manufacturing a frequency doubling generator, an upper/lower frequency converter and an optical parametric oscillator, and generates at least one beam of coherent light with the frequency different from that of incident light after penetrating through at least one beam of incident fundamental wave light; the wavelength of the coherent light reaches the deep ultraviolet region and is shortest to 130 nm.
The equipment for growing the large-size boron phosphate nonlinear optical crystal is a heating furnace, the heating temperature of the heating furnace can be at least 1100 ℃, a certain temperature gradient is formed in a heating cavity, the temperature control precision is +/-0.5 ℃, a seed crystal rod is arranged above the furnace, a seed crystal is clamped at the lower end of the seed crystal rod, the upper end of the seed crystal rod is connected with a rotating mechanism, and the seed crystal rod can axially rotate around a shaft and move up and down;
preparing raw materials in the step (1):
BPO4the starting material may be prepared by any one of the following reactions:
(a)
(b)
(c)
(d)
(e)
(f)
wherein, the compound containing P is P2O5、NH4H2PO4Or (NH)4)2HPO4；
The compound containing B is B2O3Or H3BO3；
The preparation method comprises the following steps: accurately weighing the reagents according to the stoichiometric ratio, putting the reagents into an agate mortar for even grinding, putting the mixture into a corundum crucible, presintering the corundum crucible in a muffle furnace for 10 hours (presintering temperature is 500 ℃), putting the corundum crucible into the mortar for grinding, and then sintering the mixture for 48 hours at 900 ℃ to obtain the BPO4A compound polycrystalline powder;
Li4P2O7the preparation of (1):
Li4P2O7the starting material may be prepared by any one of the following reactions:
namely Li4P2O7The flux may be formed of Li4P2O7The compound is prepared by reacting a mixture of Li and a P-containing compound with the same equivalent ratio, wherein the Li-containing compound is lithium oxide, lithium hydroxide, lithium oxalate or lithium carbonate; the compound containing P is P2O5、NH4H2PO4Or (NH)4)2HPO4；
The preparation method comprises the following steps: accurately weighing the above reagents according to stoichiometric ratio, grinding in agate mortar, placing into corundum crucible, and directly sintering in muffle furnace at 700 deg.C for 24 hr to obtain Li4P2O7A polycrystalline powder;
(3) the Li2The O flux may be lithium oxide from a Li-containing compoundLithium hydroxide, lithium oxalate or lithium carbonate are obtained by heating and decomposing, and the reaction formula is as follows:
such as
In a weight ratio of WLi2CO3∶WLi2O＝1∶0.4044
The mol ratio is 1: 1,
the above (2) and (3) can be combined together to complete the synthesis of Li4P2O7Then according to Li4P2O7-Li2Adding a certain amount of Li-containing compound into the O composite fluxing agent, and sintering and synthesizing according to the method in the step (2).All of the above-mentioned B-, P-and Li-containing compounds can be commercially available reagent-grade raw materials;
the BPO-containing4On one hand, the mixed melt of the fluxing agent and the raw materials respectively prepared by the method can be prepared by mixing and heating the raw materials according to the proportion in the step 1; or may be combined to prepare BPO4Reaction with its flux to obtain BPO in one pass4And its fluxing agent.
Large-size BPO prepared by the invention4The application of the nonlinear optical crystal is as follows: the device is used for manufacturing devices in frequency doubling generators, up/down frequency converters and optical parametric oscillators; according to BPO4Crystallographic data of the crystal, orienting the crystal blank; cutting the crystal according to the required thickness and section size along the phase matching direction; and polishing the crystal light-passing surface to obtain the non-linear optical device.
BPO4The transmission curve of the crystal in the ultraviolet region is given by FIG. 4, the ultraviolet absorption edge is 130nm, and we also measured the refractive index at 7 wavelengths in the visible region, the data of which are given in Table 1, and BPO4Refractive index dispersion equation of crystal:
ne 2＝2.50739+0.01212/(λ2-0.00242)-0.01128λ2
no 2＝2.52049+0.01408/(λ2-0.01663)-0.00901λ2
wherein λIn μm for the incident wavelength. Since n iso＞ne，BPO4The crystal is a negative uniaxial crystal;
BPO4the crystal has 4 non-zero frequency multiplication coefficients: d14，d15，d31，d36Since the UV absorption edge of the crystal reaches 130nm, the Kleinman symmetry requirement is satisfied (D.A. Kleinman, phys.Rev.126, 1977-1979(1962)), and d15＝d31，d14＝d36. The measurement results show that36≈0.98(pm/v)；d310.36 (pm/v). This illustrates BPO4The crystal has a moderate frequency multiplication coefficient. According to BPO4Since the crystal has a refractive index and a birefringence of about 0.0055 in the visible light region, phase matching cannot be achieved using a common angle tuning and temperature tuning method.
BPO was made according to the quasi-phase matching method (see vol.127, 1918, 1962, the journal of physics4The principle of the quasi-phase matching device is given by the figure (1). In the figure, each small rectangular grid represents a layer of BPO4The effective nonlinear coefficient d of the crystal layer is shown by the upward arrow in the small squareeffPositive, the arrow indicates downwards the effective nonlinear coefficient d of the layer crystaleffBeing negative, BPO layers4Effective nonlinear coefficient d of crystaleffAre equal in absolute value, i.e. deff(odd layers) ═ deff(even number of layers).
Each layer of BPO4The orientation of the crystal is determined by the following method:
BPO4the crystal symmetry belongs to a 4-point group, and the effective nonlinear coefficient expression is
deff＝(d36sin2φ+d31cos2 phi) sin theta (class I phase matching)
deff＝(d36cos2φ-d31sin2 phi) sin2 theta (class II phase matching)
Wherein θ is BPO4Phase-matching angle of the crystal, i.e. the optical axis of the crystal (parallel to the BPO) when phase-matched4Crystallographic c-axis of the crystal) and the direction of the incident light,phi is the included angle between the projection of the matching direction on the X (parallel to the a axis) plane and the Y (parallel to the b axis) plane and the X axis, namely the azimuth angle.
The phase matching angle θ can be obtained by the following equation:
class I phase matching θ ═ 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 θ ═ 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 the BPO described above4And calculating the refractive index dispersion equation of the crystal.
The azimuth angle phi may be in accordance with the above BPO4Effective nonlinear coefficient expression of crystal and condition deff(odd layers) ═ deff(even layers). For example, when the 1 st, 3 rd, 5 th and other odd-numbered layers BPO4The azimuth angle phi of the crystal is 45 DEG, and 2 nd,4. 6 equal even layer BPO4When the azimuth angle phi of the crystal is 135 degrees, quasi-phase matching can be realized. As another example, the BPO layers4The crystals are superposed in the positive and negative directions along the c-axis direction, and quasi-phase matching can be realized.
BPO per layer4The thickness of the crystal is determined by the formula (2n +1) Lc, where Lc is BPO4The coherence length of the crystal is given by the formula: lc ═ λ/4 (n)2ω-nω) Where λ is the wavelength of fundamental light incident on the crystal, nωIs the refractive index of fundamental light, n2ωIs the refractive index of the frequency doubled light, the value of Lc is therefore related to the wavelength λ.
For the determined wavelength lambda, the Lc value is firstly measured by a Maker stripe method, and then each piece is calculated according to the formula of (2n +1) LcBPO4The thickness of the crystal. The value of n can be derived from BPO4Is determined by the hardness of (c). BPO4The hardness of (a) is about Morse hardness Standard 4, and thus the value of n is about such that each BPO piece is4The thickness is controlled between 0.1 mm and 0.5 mm. Using optical contact crystal surface polishing technique to make BPO4The wafers are stacked in the manner of fig. 1, with optical contact between the sheets. BPO thus produced4The quasi-phase matching nonlinear optical device can realize the frequency doubling and sum frequency output of the laser.
Effects of the invention
The invention provides a preparation method of a large-size boron phosphate nonlinear optical crystal, which comprises the following steps: the used fluxing agent has low viscosity, is beneficial to mass transmission, is easy to grow crystals, is transparent and free of package, and has the advantages of high growth speed, low cost, easiness in obtaining crystals with larger size and the like. The obtained crystal has the advantages of wide light-transmitting wave band, high hardness, good mechanical property, difficult cracking, no deliquescence, easy processing and storage and the like.
Boron phosphate BPO4The nonlinear optical crystal is used for manufacturing a frequency doubling generator, an up/down frequency converter and a quasi-phase matching nonlinear optical device in an optical parametric oscillator, and the wavelength of coherent light generated by the device can reach a deep ultraviolet region and can be as short as 130 nm.
Drawings
FIG. 1 is a quasi-phase matched BPO4Schematic diagram of the device;
FIG. 2 is a schematic diagram of a quasi-phase-matching nonlinear optical device
FIG. 3 is a second schematic diagram of a quasi-phase-matching nonlinear optical device
FIG. 4 is BPO4Ultraviolet transmission spectrum of the nonlinear optical crystal;
Detailed Description
Example 1 Crystal growth
(1) Mixing the pre-synthesized boron phosphate and the fluxing agent in proportion, loading the mixture into a platinum crucible with an opening of phi 60mm multiplied by 60mm, placing the crucible into a vertical heating furnace, sealing the opening at the top of the furnace by using a heat-insulating material, reserving a small hole for a seed rod to go in and out at the corresponding position of the top of the furnace and the center of the crucible, quickly heating to 880 ℃ for melting, quickly cooling to 815 ℃ (10 ℃ above the saturation temperature) after keeping the temperature for 24 hours, and obtaining a mixed melt containing the boron phosphate and the fluxing agent;
the fluxing agent contains Li4P2O7And Li2A composite fluxing agent of O;
the boron phosphate and Li4P2O7And Li2The molar ratio of the mixed compound fluxing agent of O is as follows: BPO4∶Li4P2O7∶Li2O＝1∶0.35∶0.24；
(2) BPO cut along the c-axis at 815 deg.C (10 deg.C above saturation temperature)4The seed crystal is fixed at the lower end of the seed rod by a platinum wire, the seed crystal is guided into a crucible from a small hole at the top of the furnace and is immersed into the melt for crystal growth, and the seed crystal is prepared in the step (1)The mixed melt of (2) is grown under the following growth conditions: rotating the seed rod at a rotating speed of 15 rpm, keeping the temperature of 10 ℃ above the saturation temperature for 1 hour, quickly cooling to 805 ℃ (saturation temperature), and then slowly cooling at a cooling rate of 0.5 ℃/day; when the crystal grows to the required size, the crystal is quickly lifted from the melt to the liquid level, and the temperature is reduced to the room temperature at the cooling rate of 40 ℃/hour, thus obtaining the transparent boron phosphate nonlinear optical crystal with the size of 15mm multiplied by 10mm multiplied by 12 mm.
Example 2 Crystal growth
Pre-synthesized boron phosphate and Li4P2O7And Li2And O, compounding a composite fluxing agent, wherein the molar ratio is as follows: BPO4∶Li4P2O7∶Li2O is 1: 0.35: 0.18; loading into a platinum crucible with a diameter of 60mm × 60mm, placing the crucible into a vertical heating furnace, sealing the opening at the top of the furnace with heat insulating material, leaving a small hole at the top of the furnace corresponding to the center of the crucible for seed rod to enter and exit, and rapidly heating to 890 deg.C for meltingMelting, keeping the temperature for 48 hours, and then rapidly cooling to 816 ℃ (5 ℃ above the saturation temperature) to obtain a mixed melt containing boron phosphate and the fluxing agent. BPO to be cut along the c-axis4Fixing seed crystals at the lower end of a seed crystal rod by using a platinum wire, guiding the seed crystals into a crucible from a small hole at the top of the furnace, immersing the crucible into a melt for crystal growth, rotating the seed crystal rod at a rotating speed of 12 revolutions per minute, keeping the temperature for 3 hours, rapidly cooling to 811 ℃ (saturation temperature), and then slowly cooling at a cooling rate of 0.3 ℃/day; when the crystal grows to the required size, the crystal is quickly lifted from the melt to the liquid level, and the temperature is reduced to the room temperature at the cooling rate of 20 ℃/hour, thus obtaining the transparent boron phosphate nonlinear optical crystal with the size of 16mm multiplied by 10 mm.
EXAMPLE 3 Crystal growth
And growing the crystal by adopting a top seed crystal method. By a one-step synthesis method, analytically pure H is directly selected3BO3、NH4H2PO4And Li2CO3The preparation method comprises the following steps of: h3BO3∶NH4H2PO4∶Li2CO31: 1.7: 0.82 (actual BPO)4Compounds and Li4P2O7And Li2The molar ratio of the O composite fluxing agent is as follows: BPO4∶Li4P2O7∶Li2O1: 0.35: 0.12), accurately weighing the reagents according to the stoichiometric ratio, putting the reagents into an agate mortar for grinding uniformly, putting the mixture into a corundum crucible, presintering the corundum crucible in a muffle furnace at 400 ℃ for 10 hours, putting the corundum crucible into the mortar for grinding, sintering the mixture at 650 ℃ for 48 hours, putting the corundum crucible into an open platinum crucible, putting the open platinum crucible on a determined position of a heating furnace, sealing the opening of the furnace by using a proper heat insulation material, heating the mixture to 900 ℃ for melting, keeping the temperature for 72 hours to fully melt and homogenize the raw materials, cooling the mixture to 816 ℃ (the temperature is 3 ℃ above the saturation temperature), and cutting the BPO along the c axis4The seed crystal is fixed at the lower end of a seed rod by a platinum wire, the seed crystal is guided into a crucible from a small hole at the top of the furnace to be contacted with the liquid level, the seed crystal rotates at the speed of 9 r/min, the temperature is kept for 5 hours, the temperature is rapidly reduced to 813 ℃, and then the temperature is reduced at the speed of 0.7 ℃/day. After the growth of the crystal is finished,the crystals were allowed to fall off the liquid surface and cooled to room temperature at a rate of 30 ℃/hour to obtain transparent BPO having dimensions of 17mm by 10mm by 14mm4And (4) crystals.
Example 4 quasi-phase-matching nonlinear optics
According to the design of the figure (1), Lc is 10 mu-30 mu, n is 5, the thickness of each sheet is 55 mu-180 mu, 4 sheets are superposed, optical contact is realized between each sheet, the wavelength of 386nm is fundamental wave light, the light is vertically incident into the device, and 193nm frequency doubling light is generated after the light passes through the device (see figure 2).
Example 5 quasi-phase matching device
According to the design of fig. 1, Lc is 5 μ to 10 μ, n is 10, the thickness of each sheet is 55 μ to 110 μ, 4 sheets are superposed, optical contact is realized between each sheet, two fundamental wave lights with the wavelengths of 788nm and 197nm respectively are vertically incident into the device, and 157.6nm sum frequency light is obtained at the other end of the device (see fig. 3).
Claims (7)
1. A large-size boron phosphate nonlinear optical crystal is characterized in that: the crystal is transparent and has the chemical formula BPO4Expressed, its volume has at least a large dimension in the order of centimetres and has the following linear and nonlinear optical characteristics:
A. ultraviolet absorption edge 130 nm;
B. coefficient of non-linearity d36≈0.98pm/v；d31≈0.36pm/v；
C. The crystal is a negative uniaxial crystal (n)o＞ne)；
D. The Mohs hardness was 4.
2. A molten salt growth method of the large-size boron phosphate nonlinear optical crystal as claimed in claim 1, which comprises the following steps:
(1) mixing boron phosphate and a fluxing agent uniformly according to a proportion, heating and melting, keeping the temperature for 24-72 hours, and cooling to 2-10 ℃ above the saturation temperature to obtain a mixed melt containing boron phosphate and the fluxing agent;
the fluxing agent contains Li4P2O7And Li2A composite fluxing agent of O;
the boron phosphate and Li4P2O7And Li2The molar ratio of the mixed compound fluxing agent of O is as follows:
BPO4∶Li4P2O7∶Li2O＝1∶0.35∶0.24-0.12；
(2) and (2) putting the seed crystal arranged on the seed rod into the mixed melt prepared in the step (1) for growth at the temperature of 2-10 ℃ above the saturation temperature, wherein the growth conditions are as follows: rotating the seed rod at a rotating speed of 9-15 rpm, keeping the temperature at 2-10 ℃ above the saturation temperature for 1-6 hours, rapidly cooling to the saturation temperature, and then slowly cooling at a cooling rate of 1-0.2 ℃/day; when the crystal grows to the required size, the crystal is quickly lifted from the melt to the liquid level, and the temperature is reduced to the room temperature at the cooling rate of 20-40 ℃/hour, thus obtaining the large-size boron phosphate nonlinear optical crystal.
3. The method for growing large-size nonlinear optical boron phosphate crystals as claimed in claim 2, wherein B in the boron phosphate compound is derived from a B-containing compound in the same equivalent ratio as the boron phosphate compound, and the B-containing compound is B2O3Or H3BO3；
P in the boron phosphate compound is from a P-containing compound with the same equivalent ratio as the boron phosphate compound, and the P-containing compound is P2O5、NH4H2PO4Or (NH)4)2HPO4。
4. The method of claim 2 for molten salt growth of large size boron phosphate nonlinear optical crystals, wherein the Li is Li4P2O7Li in flux comes from Li4P2O7A compound containing Li in the same equivalent ratio, wherein the compound containing Li is lithium oxide, lithium hydroxide, lithium oxalate or lithium carbonate;
the Li4P2O7P in the flux is derived from Li4P2O7The compound contains P compound with the same equivalent ratio, and the P compound is P2O5、NH4H2PO4Or (NH)4)2HPO4。
5. The method of claim 2 for molten salt growth of large size boron phosphate nonlinear optical crystals, wherein the Li is Li2Li in O flux comes from Li2The O compound is a Li-containing compound with the same equivalent ratio; the Li-containing compound is lithium hydroxide, lithium oxalate or lithium carbonate.
6. Use of the large-size boron phosphate nonlinear optical crystal of claim 1, wherein: the quasi-phase matching nonlinear optical device is used for manufacturing a frequency doubling generator, an up/down frequency converter and an optical parametric oscillator, and generates at least one beam of coherent light with the frequency different from that of incident light after penetrating at least one beam of incident fundamental wave light.
7. Use of a large-size boron phosphate nonlinear optical crystal according to claim 6, characterized in that: the wavelength of the coherent light reaches the deep ultraviolet region and is shortest to 130 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03154423 CN1269997C (en) | 2003-09-28 | 2003-09-28 | Molten salt growth method of large-size boron phosphate nonlinear optical crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03154423 CN1269997C (en) | 2003-09-28 | 2003-09-28 | Molten salt growth method of large-size boron phosphate nonlinear optical crystal |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100578869A Division CN100361354C (en) | 2003-09-28 | 2003-09-28 | Application of large-size boron phosphate nonlinear optical crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1600906A true CN1600906A (en) | 2005-03-30 |
| CN1269997C CN1269997C (en) | 2006-08-16 |
Family
ID=34659977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03154423 Expired - Fee Related CN1269997C (en) | 2003-09-28 | 2003-09-28 | Molten salt growth method of large-size boron phosphate nonlinear optical crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1269997C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340485C (en) * | 2005-08-30 | 2007-10-03 | 云南省化工研究院 | Boron phosphate preparation method |
| CN100572615C (en) * | 2006-11-27 | 2009-12-23 | 中国科学院理化技术研究所 | Alkali metal boroaluminate compound and single crystal and preparation method thereof |
| CN101435109B (en) * | 2007-11-14 | 2011-08-31 | 中国科学院理化技术研究所 | Fluxing agent growth method of boron phosphate single crystal |
| CN110143610A (en) * | 2019-05-22 | 2019-08-20 | 天津理工大学 | Compound lithium potassium titanium germanate and lithium potassium titanium germanate nonlinear optical crystal and preparation method and purposes |
| WO2020220391A1 (en) * | 2019-04-30 | 2020-11-05 | 山东大学 | Visible to ultraviolet band optical frequency converter |
-
2003
- 2003-09-28 CN CN 03154423 patent/CN1269997C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340485C (en) * | 2005-08-30 | 2007-10-03 | 云南省化工研究院 | Boron phosphate preparation method |
| CN100572615C (en) * | 2006-11-27 | 2009-12-23 | 中国科学院理化技术研究所 | Alkali metal boroaluminate compound and single crystal and preparation method thereof |
| CN101435109B (en) * | 2007-11-14 | 2011-08-31 | 中国科学院理化技术研究所 | Fluxing agent growth method of boron phosphate single crystal |
| WO2020220391A1 (en) * | 2019-04-30 | 2020-11-05 | 山东大学 | Visible to ultraviolet band optical frequency converter |
| JP7006989B2 (en) | 2019-04-30 | 2022-02-10 | 山東大学 | Optical frequency converter in the visible to ultraviolet frequency band |
| CN110143610A (en) * | 2019-05-22 | 2019-08-20 | 天津理工大学 | Compound lithium potassium titanium germanate and lithium potassium titanium germanate nonlinear optical crystal and preparation method and purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1269997C (en) | 2006-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | A new congruent-melting oxyborate, Pb 4 O (BO 3) 2 with optimally aligned BO 3 triangles adopting layered-type arrangement | |
| Yang et al. | Li4Cs3B7O14: Synthesis, crystal structure, and optical properties | |
| US9715160B2 (en) | Barium tetraborate compound and barium tetraborate non-linear optical crystal, and preparation method and use thereof | |
| WO2017121024A1 (en) | K3ba3li2al4b6o20f compound, nonlinear optical crystal thereof, and preparation method therefor and use thereof | |
| CN1904148A (en) | Beryllium fluoroborate nonlinear optical crystal, and growing method and application thereof | |
| US20120189524A1 (en) | Barium fluoroborate, nonlinear optical crystal of barium fluoroborate, preparation method and use thereof | |
| CN101435108B (en) | Large size nonlinear optical crystal lead bromoborate preparation method | |
| CN101799609B (en) | Nonlinear optical crystal BaZnBO3F, preparation method and application thereof | |
| CN101545138A (en) | Non-linear optical crystal-sodium beryllate borate, growth method and application thereof | |
| JP2010503879A (en) | Beryllium fluoride borate non-linear optical crystal and its growth method and application | |
| US6391229B1 (en) | Borate crystal, growth method of the same and laser equipment using the same | |
| US20150225251A1 (en) | Cesium borosilicate compound, nonlinear optical crystal of cesium borosilicate, and preparation method therefor and use thereof | |
| RU2112089C1 (en) | Nonlinearly optical crystal of strontium berillatoborate, method of growing of nonlinarly optical single crystals of strontium berillatoborate and nonlinearly optical device | |
| Sekar et al. | An Overview on Recent Trends in Deep‐Ultraviolet (DUV) and Ultraviolet (UV) Nonlinear Optical Crystals | |
| CN1958883A (en) | Crystal of barium tellurium aluminate, preparation method and application | |
| CN1269997C (en) | Molten salt growth method of large-size boron phosphate nonlinear optical crystal | |
| CN102828245B (en) | Calcium sodium fluoroboroberyllate nonlinear optical crystal and growth method and application thereof | |
| CN102828246B (en) | Strontium sodium fluoroboroberyllate nonlinear optical crystal and growth method and application thereof | |
| CN101295118A (en) | Nonlinear optical crystal boric acid lutetium lanthanum scandium | |
| US10005675B2 (en) | Li4Sr(BO3)2 compound, Li4Sr(BO3)2 nonlinear optical crystal, preparation method and use thereof | |
| CN1835307A (en) | Application of large-size boron phosphate nonlinear optical crystal | |
| CN114000201B (en) | K 4 (HC 3 N 3 S 3 ) 2 ·H 2 O compound, crystal, and production method and use thereof | |
| CN1207451C (en) | Large size strontium borophosphate nonlinear optical crystal and its growth method and use | |
| Liu et al. | Ba 2.5 Pb 1.5 B 12 O 22: structural transformation from a centrosymmetric to a noncentrosymmetric space group by introducing Pb into Ba 2 B 6 O 11 | |
| Wang et al. | Growth and properties of KBe2BO3F2 crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060816 Termination date: 20120928 |