CN1259462C

CN1259462C - Nd doped yttrium-barium borate laser crystal and its preparing method and use

Info

Publication number: CN1259462C
Application number: CN 02128742
Authority: CN
Inventors: 王国富; 潘尚可; 林州斌; 胡祖树
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: 2002-08-08
Filing date: 2002-08-08
Publication date: 2006-06-14
Anticipated expiration: 2022-08-08
Also published as: CN1473966A

Abstract

The present invention relates to a neodymium-doped yttrium barium borate laser crystal, a preparation method and a purpose thereof, particularly a laser crystal doped by neodymium and yttrium barium borate (Nd<3+>: YBa3(BO3)3), a preparation method and purpose thereof, which belongs to the field of an artificial crystal. The Nd<3+>: YBa3(BO3)3 crystal with high quality and large size is grown by adopting a crystal pulling method (Czochralski method) under the conditions that temperature is 1256 DEG C more or less, the rotary speed of the crystal is from 5 to 20 revolutions per minute, and pulling rate is from 0.5 to 2 mm/h; the crystal belongs to the space group of R<3>, density is 4.834 g/cm<3>, and refractivity is 1.76. The crystal is a novel laser crystal, and can generate laser with the wavelength of 1060 nm for output. A solid laser made from the crystal can be used for a plurality of fields of spectroscopy, biomedicine, military affairs, etc.

Description

Neodymium-doped barium yttrium borate laser crystal and preparation method and application thereof

A neodymium-doped barium yttrium borate laser crystal and a preparation method and application thereof relate to the field of artificial crystals and crystal growth in the technical field of photoelectron functional materials, in particular to a laser crystal material used as a working substance in a solid-state laser.

The solid laser working substance is composed of a matrix material and active ions, various physical and chemical properties of the solid laser working substance are mainly determined by the matrix material, and spectral characteristics, fluorescence lifetime and the like of the solid laser working substance are determined by the energy level structure of the active ions. Since the successful development of artificial ruby pulsed lasers in 1960, hundreds of laser crystals have been discovered so far, but for various reasons, only ten laser crystals are really available for practical use.

Currently, the most widely used laser crystal is a neodymium ion doped Yttrium Aluminum Garnet (YAG) crystal, which has various better physical and chemical properties and is easy to grow high optical quality and large-size high-quality crystals. However, it has the disadvantage of narrow absorption line, and is not suitable for pumping by LD, which will be the development direction of laser pumping source in future.

At present, various high-quality laser crystal materials with excellent physical and chemical properties and mechanical properties, high optical quality and large size are actively searched at home and abroad, and the crystal is suitable for LD pumping.

The invention discloses a neodymium-doped barium yttrium borate laser crystal, a preparation method and application thereof, and aims to develop a novel laser crystal which can be directly used as a flash lamp and an LD pump and is a laser crystal material with higher conversion efficiency.

Nd of the invention³⁺:YBa₃(BO₃)₃The crystal belongs to a trigonal system and has an R3 space group structure. Wherein neodymium ions are used as doping ions to replace the lattice position of yttrium ions, the doping concentration of neodymium is between 0.05 at% and 10 at%, the fluorescence lifetime (tau) is 17-120 mus, and the fluorescence of the neodymium ions isThe service life is a function of the concentration of neodymium ions, and the neodymium ions with different concentrations can be doped according to different requirements. The experimental result shows that the laser crystal can output laser with the wavelength of 1060nm and can be used as a laser crystal.

Nd of the invention³⁺:YBa₃(BO₃)₃The crystal is a compound melted with the same components, is grown by a pulling method and is prepared according to a chemical reaction formula: are weighed, mixed and tabletted in the proportions of (D) and (D)₂O₃Then adding the raw materials according to the required concentration, wherein the raw materials are as follows: nd (neodymium)₂O₃(purity 99.95%, institute of chemistry for Catharanthus of the Chinese academy of sciences), Y₂O₃(pure)99.99%, institute of chemistry for application of Changchun, department of Chinese academy of sciences), BaCO₃(purity 99.95%, Shanghai chemical reagent Co., Ltd., China pharmaceutical group), H₃BO₃(purity 99.99%, Beijing chemical plant) growth was carried out in a platinum crucible under an inert gas (e.g., N)₂Ar, etc.) under the atmosphere, the parameters of crystal growth are about 1256 ℃, the lifting speed is 0.5-2.0 mm/h, the crystal rotating speed is 5-20 r/min, and high-quality Nd is grown³⁺:YBa₃(BO₃)₃And (4) crystals.

Nd to be grown³⁺:YBa₃(BO₃)₃The crystal is obtained by collecting diffraction data on a four-circle diffractometer, and structural analysis shows that the crystal belongs to a trigonal system, the space group is R3, the unit cell parameters are a-13.028 (2) Å, c-9.4992 (2) Å and V-1396.1 (5) Å³Density of 4.834g/cm³(ii) a The refractive index was 1.76 as measured by oil immersion.

Nd to be grown³⁺:YBa₃(BO₃)₃The crystal is subjected to analysis tests of absorption spectrum, fluorescence lifetime and the like, and the result shows that: nd (neodymium)³⁺:YBa₃(BO₃)₃The main absorption peak of the crystal is 808nm, the half-peak width is 15nm, and the absorption transition section is 6.78 multiplied by 10^-21cm²The larger half-peak width at 808nm is very suitable for pumping by AsGaAl semiconductor laser, some of which areThe pump light absorption by the laser crystal is facilitated, and the pumping efficiency is improved. Its emission transition cross section sigma at 1060nm_emIs 2.91X 10^-20cm²The full width at half maximum (FWHM) is 17nm, the fluorescence lifetime is 70 μ s, and the crystal with long fluorescence lifetime can accumulate more particles at the upper energy level, thereby increasing the energy storage and being beneficial to improving the output power and the output energy of the device. Thus, Nd³⁺:YBa₃(BO₃)₃The crystal can obtain larger output, and is a laser crystal with high conversion efficiency, low cost, high optical quality and practical application prospect and use value.

Nd of the invention³⁺:YBa₃(BO₃)₃The crystal can be very easily grown into a crystal with excellent quality by a Czochralski method, has high growth speed, hard texture, good heat-conducting property and excellent optical characteristics, can be easily pumped by a flash lamp and an LD to obtain laser output with the laser output wavelength of 1060nm, and can be used as a better laser crystal.

The invention discloses a neodymium-doped barium yttrium borate laser crystal, a preparation method and application thereof, and the preferred mode of realizing the invention is as follows:

example 1: nd with doping concentration of 3.0 at.% for Czochralski growth³⁺Nd (iii) of³⁺:YBa₃(BO₃)₃Laser crystal

Accurately weighing BaCO according to the mixture ratio₃、Y₂O₃、H₃BO₃、Nd₂O₃Mixing, grinding, tabletting, and adding 60 × 40mm³The platinum crucible of (2) was subjected to a solid-phase reaction in a muffle furnace at 800 ℃ for 12 hours, and then heated to 1020 ℃ for 10 hours. Putting the synthesized sample into a pulling furnace, and adopting a pulling method in N₂In the atmosphere, the growth temperature is 1256 ℃, the crystal rotation speed is 10 r/min,at a pulling rate of 1 mm/h, a growth of 30X 28X 20mm in size was obtained³High quality Nd³⁺Nd content of 3.0 at%³⁺:YBa₃(BO₃)₃And (4) crystals.

Example 2: nd with doping concentration of 5.0 at.% for Czochralski growth³⁺Nd (iii) of³⁺:YBa₃(BO₃)₃Laser crystal

Accurately weighing BaCO according to the mixture ratio₃、Y₂O₃、H₃BO₃、Nd₂O₃Mixing, grinding, tabletting, and adding 60 × 40mm³The platinum crucible of (2) was subjected to a solid-phase reaction in a muffle furnace at 830 ℃ for 10 hours, and then heated to 1050 ℃ for 8 hours. Putting the synthesized sample into a pulling furnace, and growing the crystal with the size of 27 multiplied by 25 multiplied by 23mm by adopting a pulling method under the conditions that the growth temperature is 1250 ℃, the crystal rotating speed is 5 r/min and the pulling speed is 0.8 mm/h in Ar atmosphere³High quality Nd³⁺Nd content of 5.0 at%³⁺:YBa₃(BO₃)₃And (4) crystals.

Claims

1. A neodymium-doped yttrium barium borate laser crystal is characterized in that: the molecular formula of the crystal is Nd³⁺:YBa₃(BO₃)₃Belonging to trigonal system, space group is R3, unit cell parameter is a 13.028(2) Å, c 9.4992(2) Å, V1396.1 (5) Å³Density of 4.834g/cm³And a refractive index of 1.76.

2. The neodymium-doped yttrium barium borate laser crystal of claim 1, wherein: in the crystal, Nd³⁺Ion as doping ion to replace Y in crystal³⁺The doping concentration of the lattice position of the ion is between 0.05 at% and 10 at%.

3. A method for preparing a neodymium-doped yttrium barium borate laser crystal according to claim 1, which is characterized in that: the crystal is grown by a Czochralski method and is grown by Y₂O₃、BaCO₃、H₃BO₃And Nd₂O₃Is taken as a raw material and has a chemical reaction formula: weighing, mixing,Tablet press and Nd₂O₃Then adding the inert gas N into a platinum crucible according to the required concentration₂Or pulling the crystal in Ar atmosphere, wherein the growth temperature of the crystal is 1256 ℃, the pulling speed is 0.5-2.0 mm/h, and the crystal rotation speed is 5-20 r/min.

4. Use of a neodymium-doped yttrium barium borate laser crystal according to claim 1, characterized in that: the crystal is used as a laser working substance in a solid laser, and a flash lamp or a laser diode LD is used as a pumping source to excite and generate laser output with 1060nm wavelength.