CN103497766A

CN103497766A - Niobate CrxTmyHozBi1-x-y-zNbO4 luminescent material

Info

Publication number: CN103497766A
Application number: CN201310431944.XA
Authority: CN
Inventors: 石祥华
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-09-17
Filing date: 2013-09-17
Publication date: 2014-01-08

Abstract

The invention relates to a niobate CrxTmyHozBi1-x-y-zNbO4 luminescent material which is characterized in that the molecular formula is shown as CrxTmyHozBi1-x-y-zNbO4, wherein the value ranges of x, y and z are respectively that: x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.1, z is more than or equal to 0.0001 and less than or equal to 0.1. A crystal growth method comprises the steps: performing full mixing, press forming and high-temperature sintering to raw materials prepared according to a proportion, to obtain starting raw materials for the growth of a crystal; placing the starting raw materials into a crucible and then heating and fully melting to obtain melt-process grown initial melt, then growing by using a melt method such as a lifting method, a crucible descending method, a temperature gradient method and other melt methods. The CrxTmyHozBi1-x-y-zNbO4 can be used as a luminescent displaying material, a 2mu m laser working substance and the like.

Description

Niobate Cr xtm yho zbi 1-x-y-znbO 4luminescent material

Technical field

The present invention relates to luminescent material and field of crystal growth, the bismuth niobate luminescent material Cr of Cr, Tm, Tm doping _xtm _yho _zbi _1-x-y-znbO ₄, and their crystal growth method by melt method.

Technical background

In the crystal of low-symmetry, for the activation ion in low-symmetry as rare earth ion Ho ³⁺, Transition-Metal Ions Cr ³⁺, low-symmetry is conducive to remove the abstinence of transition parity, strengthens luminous efficiency, and the low-symmetry crystal has anisotropy physical property matter simultaneously, while utilizing it as working-laser material, can directly obtain polarization laser.Bismuth niobate belongs to triclinic(crystalline)system, and wherein the site symmetry of Bi ion is C ₁, when the doping active ions substitute the case of Bi ion, active ions will occupy C ₁symmetrical case, and two kinds of cases are arranged, be conducive to that the Crystal-field Energy Levels division is widened and the parity abstinence of luminescent transition is removed, and improves luminous efficiency, is expected to, as fluorescence and laserable material, in fields such as demonstrations, laser technologies, obtain and apply.

Summary of the invention

The purpose of this invention is to provide rare earth niobium hydrochlorate Cr _xtm _yho _zbi _1-x-y-znbO ₄luminescent material and crystal growth method by melt method thereof, the luminescent material of excellent, be expected to for showing and laser technology field.

For achieving the above object, the technical solution used in the present invention is as follows:

Niobate Cr _xtm _yho _zbi _1-x-y-znbO ₄luminescent material is characterized in that: molecular formula is expressed as: Cr _xtm _yho _zbi _1-x-y-znbO ₄, the span of x, y, z is: 0≤x≤0.2,0.0001≤y≤0.1,0.0001≤z≤0.1.

Described growing method is:

1), preparation of raw material: Cr ₂o ₃, Tm ₂o ₃, Ho ₂o ₃, Bi ₂o ₃, Nb ₂o ₅as raw material, by following chemical combination formula, prepared burden, after it is fully mixed, obtain the required polycrystal raw material of growing crystal after the generation solid state reaction under 800～1100 ℃:

Described solid state reaction is suppressed the raw material prepared and sintering, press forming; Sintering temperature is between 800～1100 ℃, and sintering time is 10～96 hours; Perhaps the raw material after press forming directly is used as the growing crystal raw material without extra sintering;

In the batching of described raw material, raw materials used Cr ₂o ₃, Tm ₂o ₃, Ho ₂o ₃, Bi ₂o ₃, Nb ₂o ₅, or replace with other compound that adopts corresponding Cr, Tm, Ho, Bi, Nb, the raw material synthetic method comprises that high temperature solid state reaction, liquid phase are synthesized, gas-phase synthesizing method, but needs satisfied foot can finally form Compound C r by chemical reaction _xtm _yho _zbi _1-x-y-znbO ₄this condition.

2), the growing crystal raw material is put into to growth crucible,, by heating fully fusing, obtain crystal growth initial melt; Then adopting crystal growth method by melt technique---crystal pulling method, falling crucible method, warm terraced method, heat-exchanging method, kyropoulos, top-seeded solution growth, fusing assistant growing method are grown, and obtain niobate Cr _xtm _yho _zbi _1-x-y-znbO ₄luminescent material.

Adopt the seed crystal oriented growth in described melting method or do not adopt the seed crystal oriented growth; For adopting the seed crystal oriented growth, seed crystal is Cr, Tm, Ho:BiNbO ₄or BiNbO ₄monocrystalline, the seed crystal direction is crystal<100>,<010 or<001>direction, and other any direction.

There is the component effect of segregation in described crystal growth method by melt process, establish described doping bismuth niobate Cr, Tm, Ho:BiNbO ₄in crystal, the segregation coefficient of certain element is k, and k=0.01-1, when in the chemical combination formula of Cr, Tm, Ho, Bi, Nb, the quality of the compound of this element is W in aforesaid batching, should be adjusted into W/k in batching.

The present invention, the Cr of preparation _xtm _yho _zbi _1-x-y-znbO ₄can be used as luminescence display material, 2 μ m working-laser materials etc.

Embodiment

Preparation Cr, Tm, Ho doping content are respectively 2at%, 3at%, 0.5% Cr, Tm, Ho:BiNbO ₄monocrystalline:

1, adopt Cr ₂o ₃, Tm ₂o ₃, Ho ₂o ₃, Bi ₂o ₃, Nb ₂o ₅as raw material, by following chemical combination formula, prepared burden:

The composition of this each component of raw material is as follows:

And these raw materials are fully mixed, obtain ingredients mixture.

2, the raw mix mixed is pressed into to pie, carries out sintering between 800～1100 ℃, sintering time is 10～96 hours, obtains the initial feed of crystal growth; Perhaps the raw material after press forming directly is used as the growing crystal raw material without extra sintering;

3, crystal growth initial feed is put into to growth crucible, by heating fully fusing, obtain crystal growth initial melt; Then adopting crystal growth method by melt technique---crystal pulling method, falling crucible method, warm terraced method, heat-exchanging method, kyropoulos, top-seeded solution growth, fusing assistant growing method are grown, and obtain Cr, Tm, Ho:BiNbO ₄monocrystalline.

Claims

1. niobate Cr _xtm _yho _zbi _1-x-y-znbO ₄luminescent material is characterized in that: molecular formula is expressed as: Cr _xtm _yho _zbi _1-x-y-znbO ₄, the span of x, y, z is: 0≤x≤0.2,0.0001≤y≤0.1,0.0001≤z≤0.1.

2. the growing method of a luminescent material according to claim 1 is characterized in that:

2), the growing crystal raw material is put into to growth crucible,, by heating fully fusing, obtain crystal growth initial melt; Then adopting crystal growth method by melt technique---crystal pulling method, falling crucible method, warm terraced method, heat-exchanging method, kyropoulos, top-seeded solution growth, fusing assistant growing method are grown, and obtain niobate Cr _xtm _vho _zbi _1-x-y-znbO ₄luminescent material.

3. the growing method of luminescent material according to claim 2, it is characterized in that: the solid state reaction described step 1) is suppressed the raw material prepared and sintering, press forming; Sintering temperature is between 800～1100 ℃, and sintering time is 10～96 hours; Perhaps the raw material after press forming directly is used as the growing crystal raw material without extra sintering.

4. the growing method of luminescent material according to claim 2 is characterized in that: in the feed proportioning described step 1), and raw materials used Cr ₂o ₃, Tm ₂o ₃, Ho ₂o ₃, Bi ₂o ₃, Nb ₂o ₅, or replace with other compound that adopts corresponding Cr, Tm, Ho, Bi, Nb, the raw material synthetic method comprises that high temperature solid state reaction, liquid phase are synthesized, gas-phase synthesizing method, finally forms Compound C r _xtm _yho _zbi _1-x-y-znbO ₄.

5. the growing method of luminescent material according to claim 2 is characterized in that: the melting method described step 2) adopts the seed crystal oriented growth or does not adopt the seed crystal oriented growth; For adopting the seed crystal oriented growth, seed crystal is Cr, Tm, Ho:BiNbO ₄or BiNbO ₄monocrystalline, the seed crystal direction is crystal<100>,<010 or<001>direction, and other any direction.

6. the growing method of luminescent material according to claim 2, is characterized in that: have the component effect of segregation in the crystal growth method by melt process described step 2), establish described doping bismuth niobate Cr, Tm, Ho:BiNbO ₄in crystal, the segregation coefficient of certain element is k, and k=0.01-1, when in the chemical combination formula of Cr, Tm, Ho, Bi, Nb, the quality of the compound of this element is W in aforesaid batching, should be adjusted into W/k in batching.