CN102912433B

CN102912433B - Ba3P3O10Br single crystal and preparation method thereof

Info

Publication number: CN102912433B
Application number: CN201210421506.0A
Authority: CN
Inventors: 陈玲; 于鹏; 吴立明; 吴新涛
Original assignee: Fujian Institute of Research on the Structure of Matter of CAS
Current assignee: Fujian Institute of Research on the Structure of Matter of CAS
Priority date: 2012-10-26
Filing date: 2012-10-26
Publication date: 2015-05-13
Anticipated expiration: 2032-10-26
Also published as: CN102912433A

Abstract

The invention discloses a Ba3P3O10Br single crystal and a preparation method thereof. The molecular formula of the material is Ba3P3O10Br and the material belongs to an orthorhombic crystal system and P212121 space group; and crystal cell parameters of the material are as follows: a is 7.1722 (18) angstroms, b is 11.364(3) angstroms, c is 13.998(4) angstroms, V is 1140.9 (5) angstroms (3), and Z is 4. The compound shows good nonlinear optical property, is a matched compound and is 0.5 times of KDP (potassium dihydrogen phosphate) in second-order frequency-doubled effect strength; meanwhile, short-wave absorption edges of the compound can reach less than 200 nm, so that potential nonlinear optical application values may exist. Meanwhile, the compound also shows excellent thermal stability; and through synthetical thermal analysis, a testing result is that the compound is a consistent melted compound.

Description

Ba 3p 3o 10br monocrystalline and preparation method thereof

Technical field

The present invention relates to novel deep ultraviolet nonlinear optical crystal material containing isolated tripolyphosphate of a class and preparation method thereof, belong to Inorganic Nonlinear Optical Materials field.

Background technology

Along with 193 nm photoetching techniques and development that is micro-, the meticulous laser processing of nanometer, the modern equipments such as superenergy resolving power photoelectron spectrograph and photoelectron emissions microscope are for the tight demand of deep ultraviolet laser source (being less than 200 nm), and the fundamental research such as chemical kinetics is to an urgent demand of deep ultraviolet coherent source, development all-solid-state deep ultraviolet laser light source has become focus and the difficult point of scientific circles' research.The approach that can produce deep ultraviolet coherent source at present mainly contains: synchrotron radiation light source and excimer laser, but two kinds of modes all exist the bottleneck of application, the former can not miniaturization, and the monochromaticity of light beam is bad, the efficiency that obtain specific herring bone wavelength is too low.And the latter's subject matter be the live width of light beam, pattern do not reach the requirement of above-mentioned instrument, and operation is very inconvenient.Therefore, how present stage obtains good beam quality, the deep ultraviolet coherent laser light source of line width is the subject matter that laser science interface is faced.Last century the nineties, scientists finds to utilize that superpower is visible, near infrared all solid state laser is fundamental frequency light source, by the multistage frequency conversion technology of non-linear optic crystal, can produce deep ultraviolet coherent source, and be a very effective approach.Therefore finding the non-linear optic crystal that can produce deep ultraviolet coherent source, is a hot and difficult issues of current research.Research shows that this crystalloid should meet following requirement: (1) crystal, on the cut-off limit of ultraviolet region, at least should reach near 150 nm; (2) crystal must have large degree of birefringence, thus can realize broadband phase matched, is generally greater than or equals 0.06.

Known non-linear optic crystal is nearly all discontented is enough to two conditions, as β – BaB ₂o ₄(BBO), LiB ₃o ₅(LBO), CsB ₃o ₅(CBO), CsLiB ₆o ₁₀(BRBO), KTiPO ₄(KTP), KH ₂pO ₄and LiNbO (KDP) ₃be discontented with Deng all and be enough to upper two conditions.The non-linear optic crystal that present stage can produce deep ultraviolet coherent light only has KBe ₂bO ₃f ₂, but grow difficulty because the growth of its macrocrystal is subject to the impact of its laminate structure, therefore also have with a certain distance from large-scale application.Therefore find that novel deep ultraviolet nonlinear optical crystal is extremely urgent science major issue.Because this type of Crystal study mainly concentrates on borate salt system, we pay close attention to phosphate system, utilize the compound of tripolyphosphate radical ion and halide-ions, alkaline-earth metal, have synthesized the novel non-linear optic crystal may with application prospect.

Summary of the invention

Object of the present invention: (1) provides a kind of compound, this compound is represented by following molecular formula: Ba ₃p ₃o ₁₀br; (2) compd B a is provided ₃p ₃o ₁₀the preparation method of Br; (3) provide a kind of single crystal, its chemical formula is Ba ₃p ₃o ₁₀br; (4) compd B a is provided ₃p ₃o ₁₀the purposes of Br single crystal

Technical scheme of the present invention is as follows:

The invention provides chemical formula is Ba ₃p ₃o ₁₀the compound of Br, this compound belongs to rhombic system, and spacer is P2 ₁2 ₁2 ₁, unit cell parameters is , α=β=γ=90 °, Z=4, unit cell volume is .

The invention provides the preparation method of this compound, comprise the steps: that this compound is by the reactant B aO of stoichiometric ratio, P ₂o ₅and BaBr ₂obtained by high temperature process heat under fusing assistant CsBr helps, at 850 DEG C of sintering, after cooling, compd B a can be obtained ₃p ₃o ₁₀br.The innovative point of this synthetic method is to utilize fusing assistant to reduce temperature of reaction, simultaneously because this reaction carries out in closed system, and then restrained effectively P ₂o ₅volatilization.

Concrete preparation process is: the reactant B aO by total amount being 300 mg, P ₂o ₅and BaBr ₂weigh according to 5:3:1, weigh the CsBr fusing assistant of 300 mg simultaneously, it is loaded in plumbago crucible together, transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then programme controlled tube furnace is put into, 250 oC are heated to from room temperature with 15 h, and one day is incubated under 250 oC, then 620 oC are heated to 20 h from 250 oC, 850 oC are being heated to 30 h, and 100 h are incubated at its temperature, then 450 oC are cooled to 5 oC/h, finally turn off temperature controller, crystal that the present invention introduces and fusing assistant just can be obtained after being down to room temperature, Ba can be obtained after washed with de-ionized water ₃p ₃o ₁₀br crystal.Confirm through XRD.

The invention provides compd B a ₃p ₃o ₁₀the single crystal of Br.

Ba ₃p ₃o ₁₀the compound of Br, this compound belongs to rhombic system, and spacer is P2 ₁2 ₁2 ₁, unit cell parameters is , α=β=γ=90 °, Z=4, unit cell volume is .

This single crystal, belongs to rhombic system, and spacer is P2 ₁2 ₁2 ₁, unit cell parameters is , α=β=γ=90 °, Z=4, unit cell volume is .Crystalline structure as shown in Figure 1.This compound is by the tripolyphosphate salt ion P isolated ₃o ₁₀ ^5-, Br ^-negatively charged ion and Ba ²⁺cation composition, wherein, tripolyphosphate salt ion P ₃o ₁₀ ^5-only there is C ₁symmetry, and have one 2 along a, b, c-axis respectively ₁screw shaft.

The invention provides the growth method of this single crystal, comprise the steps: to adopt molten-salt growth method, using CsBr as fusing assistant, pyrosol is 2/1 preparation according to solute and solvent quality ratio; Crystal growth heating top temperature is: 800 DEG C, cooling rate is 0.5 oC/h, is cooled to 450 DEG C, then Temperature fall.

Concrete process of growth is: by the Ba of 3.7 g ₃p ₃o ₁₀br loads in platinum crucible together with the CsBr of 1.8 g, then transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then put into chamber type electric resistance furnace, be heated to 800 oC with 20 h from room temperature, and be incubated 70 h at this temperature, then 450 oC are cooled to 0.5 oC/h, turn off temperature controller, after being down to room temperature, obtain very little Ba ₃p ₃o ₁₀br monocrystalline.

The invention provides this single crystal and be used as deep ultraviolet nonlinear optical material.

The invention provides the purposes of this single crystal, it is characterized in that: this crystal, for realizing the multiplied frequency harmonic output that wavelength is the laser beam of 1.064 μm, is applied to deep ultraviolet and ultraviolet band.

It is Ba that effect of the present invention there are provided a kind of chemical formula ₃p ₃o ₁₀the compound of Br, and the single crystal of this compound, and compounds process for production thereof, growing method and purposes.We adopt molten-salt growth method, and using CsBr as solubility promoter, growth obtains smaller crystal.The wavelength utilizing the Nd:YAG laser apparatus of tune Q to export is that the laser of 1.064 μm carries out the test of powder frequency doubling method as fundamental frequency light, shows Ba ₃p ₃o ₁₀br non-linear optic crystal has good frequency-doubled effect, and its powder SHG effect is about KH ₂pO ₄(KDP) 0.5 times, and can 1.064 μm → 0.532 μm laser freuqency doubling process implementation phase matched.The limit of its deep ultraviolet cut-off simultaneously can be less than 200nm (Fig. 3).This compound also shows excellent thermostability in addition, shows that two compounds are congruent melting compound through Thermal Synthetic Analysis test.Estimate important using value to be had at deep ultraviolet and ultraviolet non-linear optical field.

Accompanying drawing explanation

Fig. 1 is Ba ₃p ₃o ₁₀the structure iron of Br

Fig. 2 is Ba ₃p ₃o ₁₀powder diffraction spectrum

Fig. 3 is Ba ₃p ₃o ₁₀br UV-permeable figure

Fig. 4 is Ba ₃p ₃o ₁₀br Thermal Synthetic Analysis figure

Embodiment

Embodiment 1

Adopt high temperature solid phase synthesis synthetic compound Ba ₃p ₃o ₁₀br

Raw materials used: BaO 0.1544g

P ₂O ₅0.0857 g

BaBr ₂0.0599 g

CsBr 0.3000g

Its chemical equation is:

5BaO + 3P ₂O ₅+ BaBr ₂= 2Ba ₃P ₃O ₁₀Br

Concrete operation step is as follows: after being weighed up by above-mentioned dosage by above-mentioned raw materials, it is loaded in plumbago crucible together, transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then programme controlled tube furnace is put into, 250 oC are heated to from room temperature with 15 h, and one day is incubated under 250 oC, then 620 oC are heated to 20 h from 250 oC, 850 oC are being heated to 30 h, and 100 h are incubated at its temperature, then 450 oC are cooled to 5 oC/h, finally turn off temperature controller, crystal that the present invention introduces and fusing assistant just can be obtained after being down to room temperature, Ba can be obtained after washed with de-ionized water ₃p ₃o ₁₀br crystal.(Fig. 2) is confirmed through XRD.

Embodiment 2

Adopt molten-salt growth Ba ₃p ₃o ₁₀br crystal

Crystal growth heating unit is chamber type electric resistance furnace, and temperature controlling instruments is Xiamen space electricity AI-808P type temperature controller, and hotness equipment is platinum rhodium thermocouple.Select CsBr as fusing assistant, slow cooling spontaneous crystallization goes out Ba ₃p ₃o ₁₀br crystal.

Raw materials used: Ba ₃p ₃o ₁₀br 3.7 g

CsBr 1.8 g

Concrete operation step is as follows: after being weighed up by above-mentioned dosage by above-mentioned raw materials, mix, load in platinum crucible together, then transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then put into chamber type electric resistance furnace, be heated to 800 oC with 20 h from room temperature, and be incubated 70 h at this temperature, then 450 oC are cooled to 0.5 oC/h, turn off temperature controller, after being down to room temperature, obtain smaller BPOB monocrystalline.

Claims

1. the compound of deep ultraviolet nonlinear optical crystal material, is characterized in that: molecular formula is Ba ₃p ₃o ₁₀br, belongs to rhombic system, P2 ₁2 ₁2 ₁spacer, its unit cell parameters is z=4.

2. the preparation method of compound according to claim 1, comprises the steps: total amount to be the reactant B aO of 300mg, P ₂o ₅and BaBr ₂weigh according to mol ratio 5:3:1, weigh the CsBr fusing assistant of 300mg simultaneously, it is loaded in plumbago crucible together, transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then programme controlled tube furnace is put into, 250 DEG C are heated to from room temperature with 15h, and one day is incubated at 250 DEG C, be then heated to 620 DEG C with 20h from 250 DEG C, be heated to 850 DEG C with 30h, and 100h is incubated at its temperature, then be cooled to 450 DEG C with 5 DEG C/h, finally turn off temperature controller, after being down to room temperature, obtain Ba ₃p ₃o ₁₀br compound and fusing assistant, obtain compound according to claim 1 after washed with de-ionized water.

3. the growth method of the crystal of compound described in claim 1, comprises the steps: the Ba of 3.7g ₃p ₃o ₁₀br compound loads in platinum crucible together with the CsBr of 1.8g, then transfer in large silica tube, use oxyhydrogen flame tube sealing under a high vacuum, then put into chamber type electric resistance furnace, be heated to 800 DEG C with 20h from room temperature, and be incubated 70h at this temperature, then 450 DEG C are cooled to 0.5 DEG C/h, turn off temperature controller, after being down to room temperature, obtain less Ba ₃p ₃o ₁₀br monocrystalline.