Nickel-doped transparent glass-ceramic microsphere laser with O-band lasing performance

Abstract

The present invention discloses a preparation and testing method for a Ni<supgt;2+< / supgt>-doped transparent microcrystalline glass microsphere laser with O-band laser emission performance, belonging to the technical field of micro-lasers. The preparation of the Ni<supgt;2+< / supgt>-doped microcrystalline glass microsphere cavity of the present invention includes the following steps: (1) externally doping transition metal Ni<supgt;2+< / supgt; ions and rare earth ions Yb<supgt;3+< / supgt> in a glass matrix, and melting to obtain a precursor glass; (2) grinding the precursor glass prepared in step (1) into glass powder with a particle size of 0.1 - 0.3 mm, and using the high-temperature melting method to make a precursor glass microsphere; (3) subjecting the precursor glass microsphere prepared in step (2) to in-situ crystallization heat treatment to generate a nanocrystalline phase, and preparing a Ni<supgt;2+< / supgt>-doped microcrystalline glass microsphere cavity. The Ni<supgt;2+< / supgt>-doped microcrystalline glass microsphere cavity prepared in step (3) is used to build an optical path by continuous optical pumping of a tapered fiber coupled to the microsphere and the laser performance is tested. The present invention realizes for the first time the preparation of a Ni<supgt;2+< / supgt>-doped microcrystalline glass microcavity and its effective laser emission in the low-loss O-band of optical fiber communication.

Description

Technical Field

[0001] The present invention relates to the field of micro laser technology, and in particular to a nickel (Ni) nanostructured carbon nanotube with O-band laser emission performance. 2+ ) doped transparent glass-ceramic microsphere laser. Background Art

[0002] Compared with the narrow-band luminescence characteristics of rare earth ions, transition metal Ni 2+ As doped optically active ions, due to dd electron transitions, it has unique near-infrared ultra-wideband spontaneous luminescence characteristics, which can cover the second optical biological window (1000-1350nm) and the important fiber optic communication window (1100-1700nm). However, transition metal ions are very sensitive to the crystal field environment, so a suitable matrix environment must be selected to produce ultra-wideband luminescence. If transition metal ions are directly doped in the glass, the probability of their non-radiative transitions will increase due to the distorted coordination field environment in the glass medium. Transparent microcrystalline glass has the appropriate crystal lattice environment for transition metal ions to attach, and it also has the properties of easy large-scale preparation and easy processing. Therefore, transparent microcrystalline glass doped with transition metal ions as activation ions as gain media has important application prospects in the field of modern fiber optic communications. In 2005, the research group of Professor Yasutake Ohishi of Toyota Institute of Technology in Japan reported Ni 2+ The classic ternary Li2O-Ga2O3-SiO2 glass-ceramic system was doped. LiGa5O8 nanocrystals were successfully precipitated in the glass system. Under the excitation of 976nm laser, near-infrared ultra-wideband fluorescence with a half-width of more than 300nm and a peak at 1300nm was observed. 2+ The fluorescence lifetimes are 500μs at 300K and 900μs at 5K, respectively. The luminescence is attributed to Ni 2+ Entering the environment of hexacoordinated octahedral LiGa5O8 nanocrystals 3 T 2g ( 3 F) → 3 A 2g ( 3 F) Energy level transition [T.Suzuki, GS.Murugan and Y.Ohishi, Appl.Phys.Lett.,2005,86:131903]. In 2006 and 2007, the research groups of Professor Qiu Jianrong, Professor Zhou Shifeng and Professor Wu Botao from Zhejiang University reported Ni 2+Ultra-broadband fluorescence of glass-ceramics doped with β-Ga2O3, ZnAl2O4, and MgAl2O4 nanocrystals [S.Zhou, H.Dong, G.Feng, B.Wu, H.Zeng and J.Qiu, Opt.Express, 2007, 15: 5477-5481]. In 2008 and 2009, the research groups of Professor Qiu Jianrong, Professor Zhou Shifeng, and Professor Wu Botao of Zhejiang University reported the ultra-broadband fluorescence of Yb 3+ / Ni 2+ ,Cr 3+ / Ni 2+ ,Bi / Ni 2+ Co-doped Ni 2+ The method of near-infrared ultra-broadband luminescence was developed, and the mechanism of energy transfer and enhancement was studied in detail [B.Wu, J.Ruan, J.Ren, D.Chen, C.Zhu, S.Zhou, and J.Qiu, Appl.Phys.Lett., 2008, 92:041110]. During this period, Professor Zhou Shifeng also reported the Ni 2+ The phenomenon of near-infrared light amplification in Ni-doped β-Ga2O3 transparent glass-ceramics 2+ The practical application of doped transparent glass-ceramics in optical fiber devices has taken an important step forward [S.Zhou, N.Jiang, H.Dong, H.Zeng, J.Hao and J.Qiu, Nanotechnology, 2008, 19: 015702]. In 2015 and 2016, Lin Changchu, a researcher at Ningbo University in China, reported Ni 2+ The near-infrared ultra-broadband luminescence of transparent glass-ceramics containing KZnF3, K2SiF6, and ZnF2 doped with Ni 2+ Doped hexacoordinated fluoride nanocrystals have a broader (1200-2400nm) near-infrared luminescence [C.Lin, L.Li, S.Dai, C.Liu, Z.Zhao, C.Bocker and C.Rüssel, J.Phys.Chem.C, 2016, 120:4556-4563]. In 2019, the applicant's research group reported that Nd 3+ / Yb 3+ / Ni 2+ Triple-doped transparent glass-ceramics containing γ-Ga2O3 nanocrystals, pumped by 808 nm laser 3+ , Yb 3+ As a bridge for energy transfer, Ni 2+Near-infrared broadband luminescence [Y.Zhang, X.Li, Z.Lai, R.Zhang, E.Lewis, AIAzmi, Z.Gao, X.Lu, Y.Chu, Y.Liu, Q.Chai, S.Sun, J.Ren and J.Zhang, J.Phys.Chem.C, 2019, 123: 10021-10027]. In 2020, the applicant's research group used the unique phase separation effect in supercooled gallium silicate glass and Au 3+ Ion self-reduction, Ni was prepared by a simple one-step heat treatment crystallization process 2+ The doped dual-phase transparent glass-ceramics containing Au / γ-Ga2O3 nanocrystals significantly enhances the Ni 2+ While measuring the luminous intensity, a dual-wavelength composite optical device was used to verify the feasibility of the light amplification phenomenon at a wavelength of 1310 nm in optical fiber communication [Z.Gao, H.Zhu, B.Sun, Y.Ji, X.Lu, H.Tian, ​​J.Ren, S.Guo, J.Zhang, J.Yang, X.Meng and K.Tanaka, Photonics Research, 2020, 8: 698-706].

[0003] Fiber optic communication uses light as an information carrier and transmits it in the fiber core for communication. However, not all light is suitable for fiber optic communication. Different wavelengths of light have different transmission losses in optical fibers. In order to minimize the loss and ensure the transmission effect, scientific researchers have been working hard to find the most suitable light. Researchers have found that light in the wavelength range of 1260nm-1360nm has the least signal distortion caused by dispersion and the lowest loss, so this wavelength range was adopted as the early optical communication band and named O-band.

[0004] Although there are currently efforts to increase the Ni content in glass-ceramics 2+ Important progress has been made in near-infrared broadband spontaneous luminescence, but to date, no research has been done on Ni 2+ Report on doped transparent microcrystalline glass laser. To achieve laser emission, it is necessary to have a pump source, a resonant cavity and a gain medium at the same time. Among them, the construction of the resonant cavity is crucial. The glass microsphere cavity based on the Whispering Gallery Mode (WGM) has a high quality factor, low threshold, simple preparation process, high stability, and easy laser mode control. It has gradually developed into a micro laser with excellent performance. Therefore, it is necessary to study how to realize Ni 2+ Doped transparent glass-ceramics laser emission is imminent. Summary of the invention

[0005] In view of the above prior art, the purpose of the present invention is to provide a Ni 2+ Doped transparent microcrystalline glass microsphere laser. This invention realizes Ni 2+ Efficient laser emission in the low-loss band of optical fiber communications.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] In a first aspect of the present invention, Ni having O-band laser emission performance 2+ The method for preparing a doped transparent microcrystalline glass microsphere laser comprises the following steps:

[0008] (1) Adding transition metal Ni into the glass matrix 2+ Ions and rare earth ions Yb 3+ , melting to obtain precursor glass;

[0009] (2) grinding the precursor glass prepared in step (1) into glass powder with a particle size of 0.1-0.3 mm, and preparing precursor glass microspheres by a high temperature melting method;

[0010] (3) subjecting the precursor glass microspheres prepared in step (2) to in-situ crystallization heat treatment to generate a nanocrystalline phase to prepare Ni 2+ Doped glass-ceramic microsphere cavity.

[0011] Preferably, in step (1), the transition metal Ni 2+ The molar percentage of the ions in the glass matrix is ​​0.1-0.5 mol.%; the rare earth Yb 3+ The amount of the ions used is 1.0-3.0 mol% based on the molar percentage of the glass matrix.

[0012] Transition Metal Ni 2+ Ions and rare earth Yb 3+ The ions can be added as a raw material using a compound containing the ions.

[0013] Preferably, in step (1), the glass matrix has a composition of any one of the following (A)-(C):

[0014] (A) a glass matrix, comprising SiO2, Ga2O3, and Li2O in a molar ratio of (60-70):(20-30):(10-15);

[0015] (B) a glass matrix, comprising SiO2, Al2O3, ZnO, and K2CO3 in a molar ratio of (55-60):(13-18):(15-20):(10-15);

[0016] (C) A glass matrix composed of SiO2, MgO, Al2O3, and Na2CO3 in a molar ratio of (50-55):(15-20):(10-15):(15-20).

[0017] Preferably, in step (1), the conditions for melting the precursor glass are: melting temperature 1500°C-1680°C, holding time 1.5-2.0h, then pouring the solution onto a preheated copper plate for quenching to form the precursor glass.

[0018] Preferably, in step (2), the conditions for preparing the precursor glass microspheres by the high temperature melting method are as follows: the glass powder is introduced into the furnace body for melting after being fully atomized and dispersed from the upper feeding port of the vertical tube furnace, and the melting temperature is 800-1200°C. After the glass powder is melted, it forms glass microspheres with smooth surfaces under the action of surface tension.

[0019] Preferably, in step (3), the temperature of the in-situ crystallization heat treatment is 600-800° C., and the heat treatment time is 5-10 h.

[0020] Preferably, in step (3), Ga2O3 or ZnAl2O4 or MgAl2O4 nanocrystalline phase is generated by in-situ crystallization heat treatment.

[0021] The second aspect of the present invention provides Ni prepared by the above preparation method 2+ Doped transparent glass-ceramic microsphere laser.

[0022] The Ni 2+ The size of doped transparent glass-ceramic microsphere lasers is 20-200μm.

[0023] The third aspect of the present invention provides a method for realizing the above-mentioned Ni 2+ The method for emitting laser light from a doped transparent microcrystalline glass microsphere laser comprises the following steps:

[0024] Using a 980nm continuous semiconductor laser as the pump light source and a tapered fiber for coupling, Ni 2+ Laser emission from doped transparent glass-ceramic microsphere lasers;

[0025] The taper diameter of the tapered optical fiber is 0.8-5 μm.

[0026] A fourth aspect of the present invention provides the Ni 2+ Application of doped transparent glass-ceramic microsphere lasers in O-band optical fiber communications.

[0027] Beneficial effects of the present invention:

[0028] (1) Ni prepared in this application 2+ Doping and Yb3+ / Ni 2+ The co-doped transparent glass-ceramic microspheres are both resonant cavities and gain media. Glass microspheres are a resonant cavity with obvious advantages and have extremely high quality factors (theoretical values ​​can reach 10 10 ) and extremely small mode volumes (on the order of 100 μm 3 ). Ni doped in it 2+ As a light-emitting center, it simultaneously serves as a resonant cavity and a gain medium, ensuring the feasibility of laser output.

[0029] (2) The supercooled silicate glass prepared by the present invention has a unique phase separation effect, which combines the good physical and chemical stability of the silicate glass phase with the strong crystal field environment of the Ga2O3 or ZnAl2O4 or MgAl2O4 nanocrystalline phase, ensuring the transition metal Ni 2+ The ions have excellent ultra-broadband near-infrared fluorescence emission characteristics. The most important thing is to prepare the micron-sized transition metal Ni by two steps of high-temperature melting of glass powder and in-situ crystallization by heat treatment. 2+ Ion-doped transparent glass-ceramic microspheres were used as resonators and gain media, and a continuous light-pumped tapered fiber-coupled microsphere laser test scheme was used to achieve the first Ni 2+ WGM laser is effectively emitted near 1310nm, a low-loss band in optical fiber communication. 3+ , significantly improving Ni 2+ Near the O band (1260-1360nm), the WGM laser emission efficiency is improved and the laser threshold is lowered.

[0030] (3) Compared with the Ni 2+ Compared with doped microcrystalline glass fiber, the glass microsphere cavity can confine light in the micrometer-scale cavity for a long time, and the tapered fiber-coupled microsphere cavity test method can achieve Ni 2+ The WGM laser is effectively emitted in the O band (1260-1360nm). 2+ Doped microcrystalline glass fiber cannot achieve Ni due to its high loss. 2 + Laser emission. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 : Actual photos taken under a cavity microscope of transparent glass-ceramic microspheres of different sizes containing Ga2O3 nanocrystalline phases prepared using the method proposed in the present invention.

[0032] Figure 2 : The continuous light pumped tapered fiber coupled Ni used in the present invention 2+ Optical path diagram of doped glass-ceramic microsphere cavity laser test.

[0033] Figure 3 : The present invention selects the 27μm microsphere cavity in comparative example 1 and the 26μm microsphere cavity in embodiment 1 for the quality factor Q value test results.

[0034] Figure 4 : Comparison of the laser performance of the transparent microcrystalline glass microsphere cavity containing Ga2O3 nanocrystalline phase at 27μm in comparative example 1 and 26μm in embodiment 1 under 500μW pump power of the present invention.

[0035] Figure 5 : The laser performance of the transparent microcrystalline glass microsphere cavity containing ZnAl2O4 nanocrystalline phase at 72μm in Example 2 under 200μW pump power of the present invention.

[0036] Figure 6 : The laser performance of the 128μm transparent microcrystalline glass microsphere cavity containing MgAl2O4 nanocrystalline phase in Example 3 under 200μW pump power of the present invention. DETAILED DESCRIPTION

[0037] It should be noted that the following detailed descriptions are illustrative and are intended to provide further explanation of the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present application belongs.

[0038] In order to enable those skilled in the art to more clearly understand the technical solution of the present application, the technical solution of the present application will be described in detail below in conjunction with specific embodiments.

[0039] The test materials used in the examples of the present invention are all conventional test materials in the art and can be purchased through commercial channels.

[0040] Example 1: Preparation of 64SiO2-23Ga2O3-13Li2O-1.0Yb2O3-0.15NiO multi-component transparent glass-ceramic microsphere laser and investigation of laser emission method

[0041] 1. Preparation of transparent glass-ceramic microsphere laser:

[0042] In the glass formula of this embodiment, SiO2, Ga2O3, and Li2O are used as glass matrices, and the numerical values ​​before each compound represent the molar ratio (mol.%); Yb2O3 is used as an externally doped sensitizer, and NiO is an externally doped transition metal Ni. 2+ For ionic compounds, the preceding numerical value represents the molar percentage of the compound incorporated relative to the entire glass matrix.

[0043] Specific preparation method:

[0044] (1) Weigh SiO2, Ga2O3, Li2O, Yb2O3 and NiO according to the measured mass, place the above raw materials in an agate pot, and use a ball mill to stir for 60 minutes to make them uniform. Transfer the mixed raw materials to a quartz crucible. Raise the temperature of the high-temperature furnace to 1600℃, then put the covered quartz crucible containing the raw materials into it and melt it for 60 minutes. Pour the molten glass onto a copper plate preheated at 200℃ to cool it to form a bulk glass, and immediately place it in a precision annealing furnace (400℃) for 3 hours to eliminate the internal stress of the glass.

[0045] (2) The prepared bulk glass was ground, and the ground powder sample was screened and filtered using a 0.1mm aperture sieve; the screened powder sample was introduced into the furnace body from the upper feeding port of the vertical tube furnace after being fully atomized and dispersed, and the temperature range of the tube furnace was 1450℃; nitrogen was introduced into the melting process to form the feeding air pressure, and the feeding air pressure was set to 0.9Pa, which prolonged the residence time of the glass powder in the furnace to ensure that the glass powder could be fully melted so that it could form glass microspheres with smooth surfaces under the action of the surface tension of the melt; the negative pressure of the collection system was set to 0.6Pa to reduce the impact force when the glass microspheres fell and avoid damage to the glass microspheres; the prepared glass microspheres were placed in a culture dish and transferred to a precision furnace for heat treatment at a rate of 2℃ / min, heated to 700℃, maintained for 5h, and then cooled to room temperature at 5℃ / min, and finally a transparent microcrystalline glass microsphere laser containing Ga2O3 nanocrystalline phase was prepared.

[0046] 2. Investigation of the laser emission method of transparent glass-ceramic microsphere laser:

[0047] In order to realize the laser emission of the prepared transparent microcrystalline glass microsphere laser, the present invention uses a 980nm continuous semiconductor laser as a pump light source and uses a tapered optical fiber for coupling to realize Ni 2+ Laser emission from doped transparent glass-ceramic microsphere lasers.

[0048] In order to obtain a better laser emission effect, the present invention uses the taper diameter of the tapered optical fiber as a variable, and investigates the pump light coupling efficiency and the maximum laser emission power as indicators. The results are as follows:

[0049] Taper diameter of tapered optical fiber Pump light coupling efficiency Laser output maximum power 0.8μm 30％ 4.8μW 1.0μm 45％ 7.5μW 2.5μm 32％ 5.6μW 5μm 27％ 4.5μW

[0050] Comparative Example 1: Preparation of 64SiO2-23Ga2O3-13Li2O-0.15NiO multi-component transparent glass-ceramic microsphere laser

[0051] In the glass formula of this embodiment, SiO2, Ga2O3, and Li2O are used as glass matrices, and the numerical values ​​before each compound represent the molar ratio (mol.%); NiO is the transition metal Ni doped externally. 2+ For ionic compounds, the preceding numerical value represents the molar percentage of the compound incorporated relative to the entire glass matrix.

[0052] Specific preparation method:

[0053] (1) Weigh SiO2, Ga2O3, Li2O and NiO according to the measured mass, place the above raw materials in an agate pot, and use a ball mill to stir for 60 minutes to make them uniform. Transfer the mixed raw materials to a quartz crucible. Raise the temperature of the high-temperature furnace to 1600℃, then put the covered quartz crucible containing the raw materials into it and melt it for 60 minutes. Pour the glass liquid onto a copper plate preheated at 200℃ to cool it to form a bulk glass, and immediately place it in a precision annealing furnace (400℃) for annealing for 3 hours to eliminate the internal stress of the glass.

[0054] (2) The prepared bulk glass was ground, and the ground powder sample was screened and filtered using a 0.1mm aperture sieve; the screened powder sample was introduced into the furnace body from the upper feeding port of the vertical tube furnace after being fully atomized and dispersed, and the temperature range of the tube furnace was 1450℃; nitrogen was introduced into the melting process to form the feeding air pressure, and the feeding air pressure was set to 0.9Pa, which prolonged the residence time of the glass powder in the furnace to ensure that the glass powder could be fully melted so that it could form glass microspheres with smooth surfaces under the action of the surface tension of the melt; the negative pressure of the collection system was set to 0.6Pa to reduce the impact force when the glass microspheres fell and avoid damage to the glass microspheres; the prepared glass microspheres were placed in a culture dish and transferred to a precision furnace for heat treatment at a rate of 2℃ / min, heated to 700℃, maintained for 5h, and then cooled to room temperature at 5℃ / min, and finally a transparent microcrystalline glass microsphere laser containing Ga2O3 nanocrystalline phase was prepared.

[0055] The laser performance of the transparent microcrystalline glass microsphere laser prepared in Example 1 and Comparative Example 1 was tested by using a method of continuous light pumping a tapered optical fiber coupled to the above-mentioned microsphere cavity. A 980nm continuous semiconductor laser was used as the pump light source. The diameter of the tapered optical fiber was 1.0μm, a tunable laser was used as the pump light source for testing the Q value, and an oscilloscope was used to record the data. When testing the laser spectrum, a 980nm continuous semiconductor laser was used as the pump light source, and a spectrometer was used to collect data.

[0056] Example 2: Preparation of 58SiO2-15Al2O3-16ZnO-11K2CO3-1.0Yb2O3-0.15NiO multi-component transparent glass-ceramic microsphere laser

[0057] In the glass formula of this embodiment, SiO2, Al2O3, ZnO, and K2CO3 are used as glass matrices, and the numerical values ​​before each compound represent the molar ratio (mol.%); Yb2O3 is used as an externally doped sensitizer, and NiO is an externally doped transition metal Ni. 2+ For ionic compounds, the preceding numerical value represents the molar percentage of the compound incorporated relative to the entire glass matrix.

[0058] Specific preparation method:

[0059] (1) Weigh SiO2, Al2O3, ZnO, K2CO3, Yb2O3 and NiO according to the measured mass, place the above raw materials in an agate pot, and use a ball mill to stir for 40 minutes to make them uniform. Transfer the mixed raw materials to a quartz crucible. Raise the temperature of the high-temperature furnace to 1580℃, then put the covered quartz crucible containing the raw materials into it and melt it for 60 minutes. Pour the molten glass onto a copper plate preheated at 200℃ to cool it to form a bulk glass, and immediately place it in a precision annealing furnace (450℃) for 3 hours to eliminate the internal stress of the glass.

[0060] (2) The prepared bulk glass was ground, and the ground powder sample was screened and filtered using a 0.20 mm aperture sieve; the screened powder sample was introduced into the furnace body from the upper feeding port of the vertical tube furnace after being fully atomized and dispersed, and the temperature range of the tube furnace was 1420°C; nitrogen was introduced during the melting process to form the feeding air pressure, and the feeding air pressure was set to 0.9 Pa, which prolonged the residence time of the glass powder in the furnace to ensure that the glass powder could be fully melted so that it could form glass microspheres with smooth surfaces under the action of the surface tension of the melt; the negative pressure of the collection system was set to 0.6 Pa to reduce the impact force when the glass microspheres fell and avoid damage to the glass microspheres; the prepared glass microspheres were placed in a culture dish and transferred to a precision furnace for heat treatment at a rate of 2°C / min, the temperature was raised to 680°C, maintained for 7h, and then cooled to room temperature at 5°C / min, and finally a transparent microcrystalline glass microsphere laser containing a ZnAl2O4 nanocrystalline phase was prepared.

[0061] (3) The laser performance was tested by using a continuous light pumped tapered fiber coupled to the above microsphere cavity. The pump light source used was a 980nm continuous semiconductor laser. The diameter of the tapered fiber was 1.2μm. A tunable laser was used as the pump light source for testing the Q value, and an oscilloscope was used to record the data. When testing the laser spectrum, a 980nm continuous semiconductor laser was used as the pump light source, and a spectrometer was used to collect the data.

[0062] Example 3: Preparation of 55SiO2-18MgO-10Al2O3-17Na2CO3-1.0Yb2O3-0.15NiO multi-component transparent glass-ceramic microsphere laser

[0063] In the glass formula of this embodiment, SiO2, MgO, Al2O3, and Na2CO3 are used as glass matrices, and the numerical values ​​before each compound represent the molar ratio (mol.%); Yb2O3 is used as an externally doped sensitizer, and NiO is an externally doped transition metal Ni 2+ For ionic compounds, the preceding numerical value represents the molar percentage of the compound incorporated relative to the entire glass matrix.

[0064] Specific preparation method:

[0065] (1) Weigh SiO2, MgO, Al2O3, Na2CO3, Yb2O3 and NiO according to the measured mass, place the above raw materials in an agate pot, and use a ball mill to stir for 50 minutes to make them uniform. Transfer the mixed raw materials to a quartz crucible. Raise the temperature of the high-temperature furnace to 1550℃, then put the covered quartz crucible containing the raw materials in and melt for 60 minutes. Pour the molten glass onto a copper plate preheated at 200℃ to cool it to form a bulk glass, and immediately place it in a precision annealing furnace (450℃) for 3 hours to eliminate the internal stress of the glass.

[0066] (2) The prepared bulk glass was ground, and the ground powder sample was screened and filtered using a 0.30 mm aperture sieve; the screened powder sample was introduced into the furnace body from the upper feeding port of the vertical tube furnace after being fully atomized and dispersed, and the temperature range of the tube furnace was 1400°C; nitrogen was introduced during the melting process to form the feeding air pressure, and the feeding air pressure was set to 0.9 Pa, which prolonged the residence time of the glass powder in the furnace to ensure that the glass powder could be fully melted so that it could form glass microspheres with smooth surfaces under the action of the surface tension of the melt; the negative pressure of the collection system was set to 0.6 Pa to reduce the impact force when the glass microspheres fell and avoid damage to the glass microspheres; the prepared glass microspheres were placed in a culture dish and transferred to a precision furnace for heat treatment at a rate of 2°C / min, the temperature was raised to 660°C, maintained for 8 hours, and then cooled to room temperature at 5°C / min, and finally a transparent microcrystalline glass microsphere laser containing MgAl2O4 nanocrystalline phase was prepared.

[0067] (3) The laser performance was tested by using a continuous light pumped tapered fiber coupled to the above microsphere cavity. The pump light source used was a 980nm continuous semiconductor laser. The diameter of the tapered fiber was 1.2μm. A tunable laser was used as the pump light source for testing the Q value, and an oscilloscope was used to record the data. When testing the laser spectrum, a 980nm continuous semiconductor laser was used as the pump light source, and a spectrometer was used to collect the data.

[0068] Figure 1 The following are photos of the transparent glass-ceramic microsphere cavities containing Ga2O3 nanocrystalline phase of different sizes prepared by the method proposed in the present invention in Example 1 (upper figure) and Comparative Example 1 (lower figure) taken under a microscope. From the results, it can be seen that the prepared microsphere cavities have good sphericity and smoothness.

[0069] Figure 2 The continuous light pumping tapered fiber coupled Ni used in the present invention is shown. 2+ Doped glass-ceramic microsphere cavity laser test optical path diagram. A tunable laser is used as the pump light source for testing the Q value, and an oscilloscope is used to record the data. A 980nm continuous semiconductor laser is used as the pump light source for testing the laser spectrum, and a spectrometer is used to collect data. Compared with pulsed spatial light pumping, this method uses a tapered optical fiber coupled to the microsphere and pumped with continuous light. This method has higher pump light coupling efficiency and higher laser emission collection efficiency. In the entire test process, the system is more stable, and the coupling efficiency and pump light polarization are adjustable. In addition, compared with femtosecond or even picosecond pulse laser pumping methods, this test system is lower in cost and easier to implement.

[0070] Figure 3 The figure above shows the test result of the quality factor Q value of a transparent microsphere cavity containing Ga2O3 nanocrystalline phase and a size of 27 μm in Comparative Example 1 of the present invention. From the test results, it can be seen that the quality factor Q value of the microsphere cavity prepared at a wavelength of 1572.8 nm is 3.29×10 5 The figure below shows the test result of the quality factor Q value of a Ga2O3 nanocrystalline transparent glass-ceramic microsphere cavity with a size of 26 μm selected in Example 1 of the present invention. From the test results, it can be seen that the quality factor Q value of the microsphere cavity prepared at a wavelength of 1570.62 nm is 4.37×10 5 It can be seen that the quality factor Q value of the prepared microsphere cavity is in the same order of magnitude, so the difference in laser performance can be judged to be caused by the sensitizing ion Yb 3+ caused by.

[0071] Figure 4 The results are shown in Figure 1. The present invention selects a Ga2O3 nanocrystalline phase transparent microcrystalline glass microsphere with a size of 27μm and 26μm in Example 1 and Comparative Example respectively. The pump wavelength is 980nm and the pump power is 500μW. It can be seen from the results that under the same test conditions, the addition of sensitizer Yb 3+ After the ions were added, the WGM laser output power near the 1310nm band increased by 4.2 times.

[0072] Figure 5The results of the comparative test of laser performance of a transparent microcrystalline glass microsphere cavity containing ZnAl2O4 nanocrystalline phase with a size of 72μm are shown in Example 2 of the present invention. The pump wavelength is 980nm and the pump power is 200μW. From the results, it can be seen that Ni can also be achieved in a transparent microcrystalline glass microsphere cavity containing ZnAl2O4 nanocrystalline phase. 2+ Effective laser output.

[0073] Figure 6 The results of the comparative test of the laser performance of a transparent microcrystalline glass microsphere cavity containing MgAl2O4 nanocrystalline phase with a size of 128μm are shown in Example 3 of the present invention. The pump wavelength is 980nm and the pump power is 200μW. From the results, it can be seen that Ni can also be achieved in the transparent microcrystalline glass microsphere cavity containing MgAl2O4 nanocrystalline phase. 2+ Effective laser output.

[0074] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method to realize Ni 2+ The method for emitting laser in O band by doped transparent microcrystalline glass microsphere laser is characterized in that: The following steps are involved: Using a 980nm continuous semiconductor laser as the pump light source and a tapered fiber for coupling, Ni 2+ Laser emission of doped transparent glass-ceramic microsphere laser in O-band; The taper diameter of the tapered optical fiber is 1.0 μm; The Ni 2+ Doped transparent glass-ceramic microsphere lasers are prepared by the following steps: (1) SiO2, Ga2O3, and Li2O are mixed in a molar ratio of 64:23:13 to form a glass matrix, and the transition metal Ni is doped into the glass matrix 2+ Ions and rare earth ions Yb 3+ , transition metal Ni 2+ The molar percentage of the ions doped in the entire glass matrix is ​​0.15; the rare earth ion Yb 3+ The doping amount accounts for 1.0 molar percentage of the entire glass matrix; the above raw materials are placed in an agate pot, and stirred by a ball mill for 60 minutes to make them uniform, and the uniformly mixed raw materials are transferred to a quartz crucible, and the temperature of the high-temperature furnace is raised to 1600°C, and then the quartz crucible with a cover containing the raw materials is placed in it, and it is melted for 60 minutes, and the molten glass liquid is poured on a copper plate preheated at 200°C to cool it to form a bulk glass, and it is immediately placed in a 400°C precision annealing furnace for annealing for 3 hours to eliminate the internal stress of the glass; (2) Grinding the prepared bulk glass, and filtering the ground powder sample with a 0.1 mm aperture sieve; introducing the screened powder sample into the furnace body from the upper feeding port of the vertical tube furnace after being fully atomized and dispersed, and the temperature range of the tube furnace is 1450°C; nitrogen is introduced into the melting process to form the feeding air pressure, and the feeding air pressure is set to 0.9 Pa, which prolongs the residence time of the glass powder in the furnace to ensure that the glass powder can be fully melted, so that it can form glass microspheres with smooth surfaces under the action of the surface tension of the melt; the negative pressure of the collection system is set to 0.6 Pa to reduce the impact force when the glass microspheres fall and avoid damage to the glass microspheres; placing the prepared glass microspheres in a culture dish and transferring them to a precision furnace for heat treatment at a rate of 2°C / min, heating to 700°C, maintaining for 5 hours, and then cooling to room temperature at 5°C / min to prepare a transparent microcrystalline glass microsphere laser containing a Ga2O3 nanocrystalline phase; The wavelength range of the O-band laser emission is 1260nm-1360nm.

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