阅读说明：本技术 一种掺镱硼酸钙钆钇混晶激光晶体及其制备方法和应用 (Ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal and preparation method and application thereof ) 是由 潘忠奔 唐开阳 戴晓军 张衍 居佳 袁浩 蔡华强 于 2019-10-17 设计创作，主要内容包括：本发明公开了一种掺镱硼酸钙钆钇混晶激光晶体及其制备方法和应用,掺镱硼酸钙钆钇混晶激光晶体的分子式为Ca<Sub>3</Sub>Gd<Sub>x</Sub>Y<Sub>y</Sub>Yb<Sub>2-x-y</Sub>(BO<Sub>3</Sub>)<Sub>4</Sub>,其中x＝0～2,y＝0～2,Yb<Sup>3+</Sup>离子的掺杂浓度为5at.％至30at.％。本发明所制备的Ca<Sub>3</Sub>Gd<Sub>x</Sub>Y<Sub>y</Sub>Yb<Sub>2-x-y</Sub>(BO<Sub>3</Sub>)<Sub>4</Sub>混晶较Yb:Ca<Sub>3</Sub>Gd<Sub>2</Sub>(BO<Sub>3</Sub>)<Sub>4</Sub>和Yb:Ca<Sub>3</Sub>Y<Sub>2</Sub>(BO<Sub>3</Sub>)<Sub>4</Sub>晶体具有更宽的吸收光谱以及更大的无序度,采用锁模技术,有望获得更短的超短脉冲激光输出。(The invention discloses a ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal and a preparation method and application thereof, wherein the molecular formula of the ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal is Ca 3 Gd x Y y Yb 2‑x‑y (BO 3 ) 4 Wherein x is 0-2, y is 0-2, Yb 3+ The doping concentration of the ions is 5 at.% to 30 at.%. Ca prepared by the invention 3 Gd x Y y Yb 2‑x‑y (BO 3 ) 4 Mixed crystal of Yb and Ca 3 Gd 2 (BO 3 ) 4 And Yb: Ca 3 Y 2 (BO 3 ) 4 The crystal has wider absorption spectrum and larger disorder degree, and is hopeful to obtain shorter ultrashort pulse laser output by adopting a mode locking technology.)

1. The ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal is characterized by being Yb³⁺Ion-doped Ca₃(Gd,Y)(BO₃)₄The molecular formula of the crystal is Ca₃Gd_xY_yYb_2-x-y(BO₃)₄Wherein x is 0-2, y is 0-2, Yb³⁺The doping concentration of the ions is 5 at.% to 30 at.%.

2. The ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal according to claim 1, wherein Gd, Y element can be doped by Yb^{3 +}And (4) substituting.

3. The preparation method of the ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal of claim 1 or 2, wherein the ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal is prepared by a Czochralski method after mixed crystals are obtained by a solid-phase reaction of the following raw materials:

raw materials: gd of 99.99% purity₂O₃Y of 99.99% purity₂O₃CaCO of 99.99% purity₃Yb of 99.99% purity₂O₃H with a purity of 99.99%₃BO₃；

Solid phase reaction chemical formula:

4. the preparation method of the ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal according to claim 3, wherein the solid phase reaction comprises the following steps of fully mixing the raw materials, carrying out solid phase reaction at 800-1000 ℃ for 10-12 h, and then heating to 1000-1200 ℃ for reaction for 10-14h to obtain the polycrystalline material.

5. The preparation method of the ytterbium-doped calcium gadolinium yttrium borate mixed crystal laser crystal according to claim 3, wherein the step of the pulling method is to place a polycrystalline material in a pulling furnace, the pulling speed of growth is 0.5-3 mm/h, and the rotating speed is 4-11 rpm.

6. The use of the ytterbium-doped calcium-gadolinium-yttrium borate mixed crystal laser crystal according to claim 1 or 2, wherein the crystal is used for generating ultrafast laser pulses in a 1 μm solid mode-locked laser.

Technical Field

The invention relates to the technical field of laser crystal materials, in particular to an ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal and a preparation method and application thereof.

Background

In the solid laser, limited by pumping source, experimental device, etc., the demand of people for short pulse laser is increasing, and the development of Q-switching and mode-locking technology makes nanosecond (10)^-9-10^-12) And femtosecond level (10)^-15) Is generated by a laser

Ultrafast laser has considerable usage, and its duration is short, spectrum is wider, and peak power output is big characteristics have unique use in fields such as communication, energy, military affairs, etc., have become one of the most extensively studied fields in laser technology at present. In the research of ultrafast laser, the research of laser materials has received extensive attention, and traditional crystal is because of its fluorescence spectral bandwidth reason, and the pulse laser output of obtaining femto second level is difficult to obtain, obtains the output of ultrafast laser, needs to have comparatively smooth, wider fluorescence spectrum. Unlike conventional ordered crystals, some disordered crystals doped with rare earth ions or transition ions have been developed slowly due to their broad fluorescence spectrum. The disordered crystal means that cations with different valences are randomly distributed on the same lattice point, so that a plurality of active ion centers can be formed. Compared with the traditional ordered crystal, the disordered crystal not only has a wider fluorescence spectrum, but also has better thermal property: high thermal conductivity coefficient, small thermal expansion coefficient and the like, and can be applied to high-power lasers. Therefore, the exploration of the disordered crystal growth method with large size, high quality and excellent comprehensive performance is a research and application hotspot at present. And on the basis of the disordered laser crystal, the preparation of the mixed crystal can further widen the spectrum of the laser crystal, and is more favorable for the generation of ultrashort pulse laser.

Disclosure of Invention

The invention aims to provide a laser crystal material which can generate 1 micron ultrashort pulse, the disorder of the material is larger, a wider absorption spectrum and an emission spectrum can be obtained, and then ultrashort pulse laser can be generated more favorably through a mode locking technology.

In order to achieve the technical effects, the invention adopts the following technical scheme:

an ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal, the molecular formula of the crystal is Ca₃Gd_xY_yYb_2-x-y(BO₃)₄Wherein x is 0-2, y is 0-2, Yb³⁺The doping concentration of the ions is 5 at.% to 30 at.%. at.% means atomic number percentage content. Through the verification of multiple experiments, when x is 0-2, y is 0-2, Yb³⁺The doping concentration of (A) is preferably 0 to 30 at% based on the crystal mass. The ytterbium-doped calcium borate gadolinium yttrium crystal belongs to an orthorhombic system.

The further technical proposal is that Yb in the crystal³⁺Ion substituted Gd³⁺And Y³⁺。

The invention also provides a preparation method of the ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal, wherein the crystal is prepared by carrying out solid phase reaction on the following raw materials to obtain a polycrystal material and carrying out a Czochralski method.

Raw materials: gd of 99.99% purity₂O₃Y of 99.99% purity₂O₃CaCO of 99.99% purity₃Yb of 99.99% purity₂O₃H with a purity of 99.99%₃BO₃；

Solid phase reaction chemical formula:

the further technical scheme is that the solid-phase reaction comprises the following steps: fully mixing the raw materials, carrying out solid-phase reaction for 10-12 h at the temperature of 800-1000 ℃, and then heating to 1000-1200 ℃ for reaction for 10-14h to obtain the polycrystalline material.

The technical scheme is that the solid phase reaction step comprises the steps of mixing raw materials, carrying out solid phase reaction for 10 hours at the temperature of 900 ℃, then grinding, mixing, tabletting, and carrying out solid phase reaction for 12 hours at the temperature of 1100 ℃ to obtain the polycrystalline material.

The further technical scheme is that the pulling step is to place the polycrystal material after the solid phase reaction in a single crystal furnace, wherein the pulling speed in the growth process is 0.5-3 mm/h and the rotating speed is 4-11 rpm.

The invention also provides the application of the ytterbium-doped calcium borate gadolinium yttrium mixed crystal, and the crystal is used for generating ultrafast laser pulses in a solid mode-locked laser.

The invention is further explained and illustrated below.

The ytterbium-doped calcium borate gadolinium yttrium mixed crystal can be abbreviated as Yb: CGYB, and the property of the mixed crystal is similar to CGB (Ca)₃Gd₂(BO₃)₄) And CYB (Ca)₃Y₂(BO₃)₄) All belong to the orthorhombic system and have a disordered structure, Ca²⁺And Gd³⁺Or Ca²⁺And Y³⁺The random occupation of two by two of the lattice sites results in a non-uniform broadening of the spectrum of the doped trivalent rare earth ions. Except that, in the crystal, Ca²⁺、Gd³⁺And Y³⁺The three randomly occupy lattice positions, so that the disorder of the crystal becomes larger, the spectrum is further widened on the basis of the nonuniform widening of the original spectrum, and the generation of ultrashort pulse laser is more favorably realized.

Compared with the prior art, the Ca prepared by the invention₃Gd_xY_yYb_2-x-y(BO₃)₄Mixed crystal of Yb and Ca₃Gd₂(BO₃)₄And Yb: Ca₃Y₂(BO₃)₄The crystal has wider absorption spectrum and larger disorder degree, and is hopeful to obtain shorter ultrashort pulse laser output by adopting a mode locking technology.

Drawings

FIG. 1 shows Ca of the present invention₃Gd_0.9Y_0.9Yb_0.2(BO₃)₄Mixed crystal, and Ca₃Y_1.8Yb_0.2(BO₃)₄And Ca₃Gd_1.8Yb_0.2(BO₃)₄XRD diffraction pattern of (a);

FIG. 2 shows Ca of the present invention₃Gd_0.9Y_0.9Yb_0.2(BO₃)₄Mixed crystal, and Ca₃Gd_1.8Yb_0.2(BO₃)₄And Ca₃Y_1.8Yb_0.2(BO₃)₄The absorption spectrum of (1).

Detailed Description

The invention will be further elucidated and described with reference to the embodiments of the invention described hereinafter.