CN103073050A

CN103073050A - Application of mercuric iodobromide as infrared band second-order nonlinear optical material

Info

Publication number: CN103073050A
Application number: CN201310018836XA
Authority: CN
Inventors: 吴奇; 秦金贵
Original assignee: Wuhan University WHU
Current assignee: Wuhan University WHU
Priority date: 2013-01-18
Filing date: 2013-01-18
Publication date: 2013-05-01

Abstract

The invention discloses a novel second-order nonlinear optical material. The molecular formula of the novel second-order nonlinear optical material is HgBrI; and a crystallographic space group is Cmc21; a is 4.673(2); b is 7.130(3); c is 13.314(6); alpha is 900, beta is 900, gamma is 900 and Z is 4. The novel second-order nonlinear optical material has remarkable characteristics of strong second-order nonlinear optical effect which can be matched by phase, large light-transmitting windows in a visible light zone and an infrared light zone and favorable thermal stability. The crystal material can be widely applied to the fields of optics and the like.

Description

The mercuric iodobromide crystal is as the purposes of infrared band second-order non-linear optical materials

Technical field

The present invention relates to the mercuric iodobromide crystal as the purposes of infrared band second-order non-linear optical materials, belong to domain of inorganic chemistry, also belong to material science and optical field.

Background technology

Non-linear optical effect originates from the interaction of laser and medium.When laser when having the Propagation of non-zero second order susceptibility, can produce the non-linear optical effects such as frequency multiplication and frequency, difference frequency, parameter amplification.Utilize the second order nonlinear optical effect of crystal, can make the device for non-linear optical such as second harmonic generator, frequency converter, optical parametric oscillator, in a lot of fields, such as laser technology, national defence aspect, important using value is arranged.Inorganic Nonlinear Optical Materials occupies dominant position in the practical research of second-order non-linear optical materials.Divide according to transmission region and the scope of application, the inorganic nonlinear optical crystal material can be divided into ultraviolet region non-linear optical crystal material, visible region non-linear optical crystal material and infrared nonlinear optical crystal material.The inorganic nonlinear optical crystal material of existing excellent property as: the BBO(beta-barium metaborate), the LBO(lithium tetraborate), the KDP(potassium primary phosphate), the KTP(potassium titanium oxide phosphate), the LN(Lithium niobium trioxide) etc., mostly be applicable to the scope of ultraviolet, visible light and near-infrared band.And for infrared nonlinear optical crystal material, also have gap from practicality.Reason is existing infrared nonlinear optical crystal material, such as AgGaS ₂, AgGaSe ₂And ZnGeP ₂In crystal, although have very large nonlinear second-order optical susceptibility, the very wide scope that sees through is arranged also in the infrared light district, but synthesis condition is harsh, be not easy the high large single crystal of growing optics quality, particularly damage threshold is lower, thereby can not satisfy the practical requirement of non-linear optical crystal material.And the frequency inverted that realizes infrared laser has important value in fields such as national economy, national defense and military, as realizes continuously adjustable molecular spectrum, widens the scope of laser radiation wavelength, opens up new LASER Light Source etc.Thereby the research of infrared inorganic nonlinear optical material has become an important topic of current nonlinear optical material research field.

At present, the research of infrared inorganic nonlinear optical material mainly launches from two aspects, the one, by crystal technique, from known non-linear optical crystal material growth more perfect, more meet the crystal of application requiring; The 2nd, seek new non-linear optical crystal material, this comprises synthetic novel compound or seek the material with good nonlinear optical property from known compound.

Summary of the invention:

Problem to be solved by this invention provides the mercuric iodobromide crystal as the purposes of infrared band second-order non-linear optical materials.

The mercuric iodobromide crystal is as the infrared band second-order non-linear optical materials, transmission region is wider, nonlinear second-order optical susceptibility is larger, can realize phase matched, easily preparation and stability novel inorganic infrared nonlinear optical crystal material and its production and use preferably.

Described mercuric iodobromide crystal, its molecular formula are HgBrI, and the crystal space group is Cmc21, a=4.673 (2), b=7.130 (3), c=13.314 (6), α=90 ⁰, β=90 ⁰, γ=90 ⁰, Z=4.

This material just had bibliographical information before 100 years, but its non-linear optical property of Introduction of Literatures is never arranged.The present invention finds first, and above-mentioned mineral crystal is as the infrared non-linear optical material, and powder SHG effect is 1.4 * KTP(potassium titanium oxide phosphate), and can realize phase matched; The optical lens overrange is 0.46～40 micron.

The preparation method of above-mentioned mercuric iodobromide crystal is with HgBr ₂And I ₂Joined in 2: 1 in molar ratio in an amount of acetone soln, stir at normal temperatures the solution that becomes clear, continue to stir half an hour; After reaction finishes, by slow volatilization method or slow cooling method under the room temperature, obtain the crystal of yellow transparent.

Inorganic Nonlinear Optical Materials HgBrI disclosed in this invention has the very wide window that sees through at infrared region, and transparency range reaches 40 microns; The ultraviolet absorption edge observed value reaches 0.46 micron, calculates its band gap size and is about 2.70 electron-volts.Have larger nonlinear optical coefficients and bulk properties preferably, can be used as non-linear optical crystal material and be applied.

Compare the beneficial effect that has with background technology:

Of the present invention have following characteristics as non-linear optical crystal material:

1. adopt a kind of new synthetic method to prepare this compound crystal material, the crystal space group is Cmc21, a=4.673 (2), b=7.130 (3), c=13.314 (6), α=90 ⁰, β=90 ⁰, γ=90 ⁰, Z=4.Unit cell parameters is similar to bibliographical information, but the R value is provided first.Preparation method's mild condition, product purity is high, and is simple to operate;

2. the mercuric iodobromide crystal has larger frequency-doubled effect (SHG), and Kurtz powder frequency doubling test result shows that its powder SHG effect is the KTP(potassium titanium oxide phosphate) 1.4 times;

3. the mercuric iodobromide crystal has the very wide scope that sees through at visible region and infrared light district, and seeing through wave band fully is 0. 46～40 microns.

Description of drawings

Fig. 1 is the structure cell figure of HgBrI crystal of the present invention.

Fig. 2 is that HgBrI crystal of the present invention is at the structure cell figure of bc face accumulation graph.

Fig. 3 is the uv-visible absorption spectra of HgBrI powder of the present invention.

Fig. 4 is the Fourier transform attenuated total reflectance attenuated total refraction infrared spectra of HgBrI powder of the present invention.

Fig. 5 is the Raman spectrum of HgBrI powder of the present invention.

Fig. 6 is the thermal weight loss collection of illustrative plates of HgBrI powder of the present invention.

Fig. 7 is the frequency-doubled effect phase matched collection of illustrative plates of HgBrI powder of the present invention.

Embodiment

Below in conjunction with specific embodiment technical scheme of the present invention is further described:

The preparation of embodiment 1:HgBrI:

With 0.7208 g (2 mmol) HgBr ₂With 0.2538 g (1 mmol) I ₂Join in an amount of acetone soln, at normal temperatures, stir, to the solution that becomes clear, continue to react half an hour, after reaction finishes, naturally cooling.By slow volatilization method or slow cooling method under the room temperature, obtain the crystal of yellow transparent, through the Advances in crystal X-ray diffraction test, confirm as known compound HgBrI, be required crystalline material.

The powder SHG effect of embodiment 2:HgBrI:

The frequency doubling property of material obtains by Kurtz-Perry powder frequency doubling testing method.Concrete operation step is as follows:

The crystalline material of embodiment 1 gained is ground powder into about 80～100 micron grain sizes, then being contained in the two sides has in the sample pool of glass port, afterwards sample pool is placed on the laser optical path, using the Nd:YAG pulsed laser to produce wavelength as light source is that the fundamental frequency light of 1064 nanometers is injected sample pool, as standard specimen, signal is shown on the oscilloscope through photomultiplier with the KTP monocrystal of about 80～100 micron grain sizes.

The frequency-doubled effect phase matched test of embodiment 3:HgBrI:

The second-order non-linear optical crystal material of embodiment 1 gained is ground respectively and is sieved into the powder (20 ~ 40 of different grain size scope, 40 ~ 60,60 ~ 80,80 ~ 100,100 ~ 125,125 ~ 150 and 150 ~ 200 microns), then being contained in the two sides has in the sample pool of glass port, afterwards sample pool is placed on the laser optical path, using the Nd:YAG pulsed laser to produce wavelength as light source is that the fundamental frequency light of 1064 nanometers is injected sample pool, signal is shown on the oscilloscope through photomultiplier, the frequency-doubled signal intensity size of test different-grain diameter, and the mapping post analysis judges that can compound phase matched.

Fig. 1 and 2 is respectively that the structure cell figure of HgBrI crystal and structure cell are at the accumulation graph of bc face, HgBrI's is simple in structure, form by being similar to linear I-Hg-Br unit, the I-Hg-Br bond angle is 179.6(2) °, I atom and Hg atom form Hg-I bond distance be 2.568(4), and the Br atom of the other end and the formation of Hg atom Hg-Br bond distance is 2.547(4).Fig. 3 is the ultraviolet-visible spectrum of powdered material, and as can be seen from the figure, its ultraviolet absorption edge is at 0.46 micron, and the band gap size of calculating is 2.70 electron-volts.Fig. 4 and Fig. 5 are respectively the Fourier transform attenuated total reflectance attenuated total refraction FT-IR ﹠ FT-RAMAN spectras of material, from infrared spectrogram, can find out, material between 4000 wave number to 700 wave numbers without any absorption, from Raman spectrogram, material is from 800 wave numbers until 250 wave numbers also have no absorption peak, all without absorbing, so the infrared absorption limit of material reaches 250 wave numbers to this illustrative material, is converted into wavelength and then is 40 microns between 4000 wave number to 250 wave numbers.The result of comprehensive ultraviolet-visible spectrum, FT-IR ﹠ FT-RAMAN spectra can know the very wide transparency range that has of material by inference, and its transparency range is 0.46 micron to 40 microns.The heat analysis of material and the test result of powder frequency doubling phase matched are seen Fig. 6 and Fig. 7, and as seen from Figure 6, material just begins later on weightlessness at 200 degrees centigrade, has good thermostability, and as seen from Figure 7, material can phase matched.

Claims

1. the mercuric iodobromide crystal is as the purposes of infrared band second-order non-linear optical materials, described mercuric iodobromide crystal, and its molecular formula is HgBrI, the crystal space group is Cmc21, a=4.673 (2), b=7.130 (3), c=13.314 (6), α=90 ⁰, β=90 ⁰, γ=90 ⁰, Z=4.

2. the preparation method of the described mercuric iodobromide crystal of claim 1 is characterized in that, with HgBr ₂And I ₂Joined in 2: 1 in molar ratio in an amount of acetone soln, stir at normal temperatures the solution that becomes clear, continue to stir half an hour; After reaction finishes, by slow volatilization method or slow cooling method under the room temperature, obtain the crystal of yellow transparent.