CN102031562A

CN102031562A - Non-linear optical crystal bismuth cadmium borate

Info

Publication number: CN102031562A
Application number: CN2009101125840A
Authority: CN
Inventors: 程文旦; 张炜龙
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: 2009-09-28
Filing date: 2009-09-28
Publication date: 2011-04-27
Anticipated expiration: 2029-09-28
Also published as: CN102031562B

Abstract

A kind of three color rolls into a ball the optical crystal bismuth borate cadmium of compound composition, is related to nonlinear optical material field. Bismuth borate cadmium, its chemical formula is Cd4BiO (BO3) 3, and molecular weight 851.05 belongs to monoclinic system, space group Cm, cell parameter is a=8.044 (2), b=15.913 (5), c=3.4891 (10) , alpha=90.00 °, beta=100.08 (2) °, gamma=90.00 °, V=439.7 (2)

Z=2. It is prepared using high temperature solid-state method. Bismuth borate cadmium has excellent non-linear optical property, and powder SHG coefficient is equivalent to six times of KDP.

Description

A kind of nonlinear optical crystal boric acid bismuth cadmium

Technical field

The invention belongs to nonlinear optical material and synthetic.

Background technology

Non-linear optic crystal has frequency-doubled effect (SHG), sells off information processing at laser frequency conversion, Electro-optical Modulation, light, and high-tech areas such as nonlinear optics imaging have significant application value.Nonlinear optical material is in modern science and technology, in particularly some military and civilian high-tech areas, for example submarine deep water communication, blinding laser weapons, the ocean locating fish, video disc recording, color laser printing, laser projection tv, photometry calculation and optical-fibre communications etc. all have a series of important application.The non-linear optic crystal of practical application at present comprises LiB ₃O ₅(LBO), β-BaB ₂O ₄(BBO), KH ₂PO ₄(KDP), KTiOPO ₄(KTP), LiNbO ₃(LNO) and BaTiO ₃(BTO) etc.Studies show that recently the bismuth positively charged ion that contains lone-pair electron combines the nonlinear optical material that also available can be superior with the borate with non-core structure, as BiB ₃O ₆, BaBiBO ₄, Bi ₂ZnOB ₂O ₆Deng.In exploring nonlinear optical material, we find Ca from the structure of known materials ₄M ^(III)O (BO ₃) ₃(A=Ca; M=La, Nd, Sm, Gd, Er, and Y) this serial compound spacer is Cm, belong to non-core structure, have good nonlinear optical property, we wish by replace the rare earth element in this system with bismuth, come the Clock Multiplier Factor of strongthener, obtained the novel non-linearity optical material of superior performance.The research of relevant this respect does not still have bibliographical information.

Summary of the invention

One of purpose of the present invention is to prepare the bismuth boracic acid cadmic compound.

Two of purpose of the present invention is to prepare bismuth boracic acid Cd monocrystal body.

The bismuth boracic acid cadmic compound of the present invention's preparation, its chemical formula is Cd ₄BiO (BO ₃) ₃, molecular weight is 851.05.

The bismuth boracic acid cadmic compound adopts pyroprocess synthetic.Particularly, be 4: 1: 3 by the mol ratio of Cd: Bi: B, take by weighing CdO, Bi ₂O ₃With H ₃BO ₃Grind, mix, put into platinum crucible, in 800 to 820 ℃ of stoichiometric numbers hour in chamber type electric resistance furnace can obtain light yellow polycrystal powder, and purity can reach 100%.

The bismuth boracic acid Cd monocrystal body of the present invention's preparation, its chemical formula is Cd ₄BiO (BO ₃) ₃, molecular weight is 851.05, belongs to oblique system, spacer Cm, cell parameter are a=8.044 (2), b=15.913 (5), c=3.4891 (10)

Alpha=90.00 °, beta=100.08 (2) °, gamma=90.00 °, V=439.7 (2)

Z=2.Its structure is by CdO ₆And CdO ₇Polyhedron by in twos altogether the limit form a two strands along the c direction, chain and chain have the three-dimensional structure in eight yuan and quaternary tunnel by summit and then formation altogether.B1 and Bi then are positioned at by four CdO ₆With four CdO ₇In the middle of the tunnel that polyhedron surrounded, B2 then is positioned at by two CdO ₆With two CdO ₇Polyhedron surrounds in the tetra-atomic ring.The B atom all is that the formation of three-fold coordination has polar plane triangle structure, and the Bi atom is because lone-pair electron have irregular octahedron to the influence and then the formation of its three-dimensional arrangement.It should be noted that the B2O in the structure ₃And BiO ₆The polar orientation of two configurations is consistent basically, all is towards a direction, and this is just to the enhancement that played of nonlinear optical property.

Bismuth boracic acid Cd monocrystal body prepares by pyroprocess.Particularly, with CdO, Bi ₂O ₃With H ₃BO ₃Be raw material, mix grinding, grind after the pre-burning, and then 900 ° of constant temperature of high temperature, then slowly cooling, it naturally cools to room temperature relief, obtains light yellow transparent tabular crystal.

The nonlinear optics measurement shows, bismuth boracic acid cadmium (Cd ₄BiO (BO ₃) ₃) have good non-linear optical property, the very strong 532nm green glow of output under the 1064nm laser radiation, its powder SHG coefficient roughly is equivalent to 6 times of KDP.Be expected at laser frequency conversion, Electro-optical Modulation, light is sold off high-tech areas such as information processing that significant application value is arranged.This type of nonlinear optical material is in modern science and technology, in particularly some military and civilian high-tech areas, for example submarine deep water communication, blinding laser weapons, the ocean locating fish, video disc recording, color laser printing, laser projection tv, photometry calculation and optical-fibre communications etc. all have a series of important application.

Description of drawings:

Fig. 1. the bismuth boracic acid cadmium along the axial structure iron of c;

Fig. 2. the pure phase coatings of bismuth boracic acid cadmium;

Fig. 3. the uv-visible absorption spectra figure of bismuth boracic acid cadmium.

Embodiment

The preparation of embodiment 1 bismuth boracic acid cadmium dust

In the mol ratio of Cd: Bi: B is the CdO that 4: 1: 3 ratios weigh up, Bi ₂O ₃With H ₃BO ₃Grind, mix, put into the Pt crucible, place chamber type electric resistance furnace,, can obtain productive rate and be 100% buff powder pure phase 820 ℃ of reactions 24 hours.

The preparation of embodiment 2 bismuth boracic acid Cd monocrystal bodies

To be the CdO that 4: 1: 4 ratios weigh up in the mol ratio of Cd: Bi: B, Bi ₂O ₃With H ₃BO ₃Grind, mix, put into the Pt crucible, put into box-type furnace, grind 300 ℃ of pre-burnings.At last at 900 ℃ of constant temperature 10h, cool to 600 ℃ with 3 ℃ speed per hour then, and then reduce to 300 ℃ with 6 ℃ speed per hour, it naturally cools to room temperature relief, obtains many light yellow transparent tabular crystals in crucible bottom.This crystal has been carried out monocrystalline X-ray diffraction crystallographic analysis has known that it is the bismuth boracic acid cadmium, its crystallographic parameter as mentioned above, structure is as shown in Figure 1.

Claims

1. bismuth boracic acid cadmic compound, its chemical formula is Cd ₄BiO (BO ₃) ₃, molecular weight is 851.05.

2. the preparation method of the described bismuth boracic acid cadmic compound of claim 1 is characterized in that: adopt high temperature solid-state method synthetic, the mol ratio that adopts Cd: Bi: B is that 4: 1: 3 mixture is a raw material, and temperature of reaction is 800 to 820 ℃.

3. nonlinear optical crystal boric acid bismuth cadmium, it is characterized in that: its chemical formula is Cd ₄BiO (BO ₃) ₃, molecular weight is 851.05, belongs to oblique system, spacer Cm, cell parameter are a=8.044 (2), b=15.913 (5), c=3.4891 (10)

Alpha=90.00 °, beta=100.08 (2) °, gamma=90.00 °, V=439.7 (2)

Z=2.

4. the preparation method of the described bismuth boracic acid Cd monocrystal of claim 3 body is characterized in that: with CdO, and Bi ₂O ₃With H ₃BO ₃Be raw material, grinding mixes it, and first low temperature presintering grinds, and at 900 ℃ of constant temperature, reduces to room temperature with given pace then at last, obtains light yellow transparent crystals.

5. the purposes of the non-linear optical crystal material bismuth boracic acid cadmium of a claim 3 is characterized in that: this crystal is used for the communication of submarine deep water, blinding laser weapons, the ocean locating fish, video disc recording, color laser printing, laser projection tv, photometry and calculates or optical-fibre communications.