Preparation method and application of composite material of antimony bismuth selenate / antimony bismuth oxide compound

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a preparation method and application of a selenium-oxygen antimony bismuth / oxygen antimony bismuth compound composite material, and the preparation method comprises the following steps: S1, before a sample is sintered, filling inert gas into a furnace body, carrying out air burning for high-temperature impurity removal, and ensuring that the interior of the furnace body is in an inert environment; s2, raw materials of Bi2O3, Bi2Se3 and Sb2Se3 are fully mixed and then put into a quartz crucible, and then the quartz crucible is put into chemical vapor deposition; and S3, after the furnace is put into the crucible, the furnace is subjected to inert gas washing, after gas washing is completed, inert gas is used as carrier gas, the temperature is increased to be not lower than 630 DEG C, and the composite material of the selenium-oxygen antimony bismuth / oxygen antimony bismuth compound is obtained. The composite material can be used as an optical material by means of its excellent stability and nonlinear optical properties.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials, and particularly relates to a preparation method and application of a selenium-antimony-bismuth / antimony-bismuth compound composite material. BACKGROUND

[0002] The emergence of laser technology promotes the transition of signal carriers from electrons to photons, leading mankind into the information age. At present, ultrafast laser technology has been widely used in information, manufacturing and other fields. Since the advent of wideband tunable laser crystals and self-mode-locked technology in the 1980s, femtosecond laser technology has developed rapidly, and its application potential in ultra-precision machining has attracted much attention. In the mode-locked technology, stable generation of high-quality ultrashort pulses is the key to realizing high-precision applications, and the performance of the saturable absorber as a core device directly determines the output characteristics of the laser. At present, SA is mainly divided into two categories: solid saturable absorbers based on material optical absorption (such as semiconductor saturable absorber mirrors (SESAM)), and equivalent saturable absorbers based on fiber nonlinear effects. SESAM has been commercialized, but its preparation is complex and adjustable. Based on the above limitations, the development of new saturable absorbers with high performance and wideband characteristics has become a research hotspot, providing an important direction for realizing efficient and economical ultrashort pulse lasers.

[0003] Traditional selenides (such as zinc selenide) have achieved good results in saturable absorber research. For example, Ge-doped zinc selenide can realize ultrashort pulses below 2 microns, and Fe-doped zinc selenide exhibits excellent nonlinear characteristics above 2 microns. However, the preparation of selenides faces challenges: selenium has a high vapor pressure at low temperatures and is prone to volatilization during high-temperature reactions, and the crystal growth and diffusion of selenides usually require high temperatures and long reaction times. Therefore, how to design and prepare selenides that are easier to synthesize and have excellent performance has become a key research point. SUMMARY

[0004] In order to solve the problems existing in the prior art, the application provides a selenium-antimony-bismuth / antimony-bismuth composite material, which can be used as an optical material due to its excellent stability and nonlinear optical characteristics. The technical scheme is as follows:

[0005] A preparation method of a selenium-antimony-bismuth / antimony-bismuth compound composite material, comprising the following steps:

[0006] S1. Before sintering the sample, inert gas is filled into the furnace body, high-temperature impurity removal is performed by empty burning, and it is ensured that the furnace body is in an inert environment;

[0007] S2. After the Bi2O3, Bi2Se3 and Sb2Se3 raw materials are thoroughly mixed, they are placed in a quartz crucible, and then the quartz crucible is placed in a chemical vapor deposition apparatus;

[0008] S3. After being put into the crucible, the furnace is washed with inert gas again. After the washing is completed, the inert gas is used as the carrier gas to heat to not less than 630℃, and the selenium-antimony-bismuth oxide compound composite material is obtained.

[0009] Preferably, before sintering the sample, the furnace body is heated to not less than 800℃ in an air atmosphere to remove impurities by air sintering. Then, the inert gas is switched to constant temperature at 800℃ to ensure the inert environment. Finally, the furnace is cooled to room temperature, and the inert gas is maintained below 200℃.

[0010] Preferably, the inert gas is any one of helium, neon, and argon.

[0011] Preferably, the molar ratio of Bi2O3, Bi2Se3, and Sb2Se3 is 10:3:2.

[0012] Preferably, in step S3, after being put into the crucible, the furnace is washed with inert gas multiple times. After the washing is completed, the inert gas is used as the carrier gas to flow at a rate of 100sccm, and the chemical vapor deposition is heated to 630℃ at a rate of 10℃ / min, and the selenium-antimony-bismuth oxide compound, i.e., Bi 2-x Sb x O2Se / BiSbO4, is obtained by maintaining the temperature for 2 hours.

[0013] A method for preparing a saturable absorber, which uses ethanol to disperse Bi 2-x Sb x O2Se / BiSbO4 powder, and then deposits the dispersed Bi 2-x Sb x O2Se / BiSbO4 powder on a tapered optical fiber to obtain the saturable absorber.

[0014] A micro-mode-locked laser experimental device using a saturable absorber, which includes a saturable absorber prepared using Bi 2-x Sb x O2Se / BiSbO4 powder, an erbium-doped optical fiber, a wavelength division multiplexer, a pump source, a polarization controller, a single-mode optical fiber, an optoelectronic coupler, and a polarization-independent isolator. The pump source provides a light source. The laser passes through the wavelength division multiplexer and enters the erbium-doped optical fiber, and then enters the saturable absorber. The saturable absorber has high transmittance or reflectivity for strong light and has absorption or loss for weak light. The light signal passing through the saturable absorber enters the polarization controller and the single-mode optical fiber in sequence, and then enters the optoelectronic coupler, which is connected to an external oscilloscope.

[0015] Preferably, when the light signal circulates in the resonant cavity of the saturable absorber, the weak light component is continuously suppressed by the amplification of the gain medium and the nonlinear selection of the saturable absorber, and the strong light component is continuously accumulated, so that the phase locking between longitudinal modes is finally achieved.

[0016] Preferably, when the light intensity reaches the threshold value, the absorption coefficient sharply decreases due to carrier filling, thereby forming a periodic modulation in the cavity, prompting the laser to spontaneously enter a mode-locked state, and by adjusting the polarization controller, three mode-locked mechanisms are realized in the 1.5-micron waveband, including traditional soliton mode-locking, traditional soliton harmonic mode-locking and bound-state soliton mode-locking, and a stable ultra-short pulse sequence can be output.

[0017] Preferably, the group velocity dispersion of the erbium-doped optical fiber at 1550 nanometers is 21.9 ps 2 km -1 ; the group velocity dispersion of the single-mode optical fiber at 1550 nanometers is -22.3 ps 2 km -1 ; and the coupling ratio of the optoelectronic coupler is 10%.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] 1. The synthesis method is simple and the performance is excellent.

[0020] 2. The composite material can be used as an optical material due to its excellent stability and nonlinear optical properties. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a selenium-antimony bismuth / antimony bismuth powder XRD pattern (selenium-antimony bismuth / antimony bismuth is compounded from antimony-doped selenium-antimony bismuth and antimony bismuth);

[0022] Figure 2 is a selenium-antimony bismuth / antimony bismuth powder actual object picture, and the material is a black opaque powder;

[0023] Figure 3 is a crystal picture of selenium-antimony bismuth / antimony bismuth (scanning electron microscope image, micron level);

[0024] Figure 4 is a crystal picture of selenium-antimony bismuth / antimony bismuth (transmission electron microscope image, nanometer level);

[0025] Figure 5 is a nanometer-level element distribution of selenium-antimony bismuth / antimony bismuth (transmission electron microscope mapping analysis, in order to show that the elements are uniformly mixed in the material without obvious segregation);

[0026] Figure 6 is an X-ray photoelectron spectrogram of selenium-antimony bismuth / antimony bismuth (elements: Bi, O, Se, Sb);

[0027] Figure 7is a schematic diagram of a 1.5-micron passively mode-locked fiber laser experimental device of selenium-antimony bismuth oxide / antimony bismuth oxide saturable absorber;

[0028] ① pump source (976 nm), ② wavelength division multiplexer, ③ erbium-doped optical fiber, ④ saturable absorber, ⑤ polarization controller, ⑥ single-mode optical fiber, ⑦ optoelectronic coupler, ⑧ polarization-independent isolator;

[0029] Figure 8 is a mode-locked result of a conventional soliton;

[0030] Figure 9 is a harmonic mode-locked result of a conventional soliton.

[0031] Figure 10 is a mode-locked result of a bound-state soliton. DETAILED DESCRIPTION

[0032] The technical solutions of the present application will be described in detail below through specific embodiments and drawings. It should be understood that the embodiments of the present application and the specific features in the embodiments are detailed descriptions of the technical solutions of the present application, rather than limitations of the technical solutions of the present application, and the specific technical features can be combined with each other.

[0033] A preparation method of a selenium-antimony bismuth / antimony bismuth compound composite material, comprising the following steps:

[0034] Raw materials: Bi2O3 with a purity of 99.99%, Bi2Se3 with a purity of 99.99%, Sb2Se3 with a purity of 99.99%, and argon (an inert gas selected as argon) with a purity of 99.999%.

[0035] (a) Before sintering the sample, first heat the furnace body to 800℃ at 10℃ / min under air atmosphere, and remove impurities by air sintering for 8 hours; then switch to high-purity argon gas with a flow rate of 100sccm, and ensure the inert environment by constant temperature at 800℃ for another 8 hours. The temperature rising program is set to 10℃ / min, constant temperature for 8 hours after reaching the target temperature, and finally the furnace is cooled to room temperature (argon is maintained below 200℃).

[0036] (b) After mixing Bi2O3, Bi2Se3 and Sb2Se3 raw materials with a molar ratio of about 10:3:2 in a sufficient manner (more than ten minutes) using a agate mortar, the mixture is placed in a quartz crucible, and then the quartz crucible is placed in a chemical vapor deposition (CVD).

[0037] (c) Procedure setting: After putting into the crucible, the furnace was washed with argon for 3 times again. After washing, argon was used as the carrier gas with a flow rate of 100 sccm. The chemical vapor deposition (CVD) was performed at a temperature increasing rate of 10 ℃ / min to 630 ℃. After keeping the temperature for 2 hours, the selenium-antimony-bismuth / antimony-bismuth oxide compound was obtained by cooling to room temperature. The sample was taken out and ground in a mortar to obtain black Bi 2- x Sb x O2Se / BiSbO4 powder.

[0038] A method for preparing a saturable absorber, which uses ethanol to disperse Bi 2-x Sb x O2Se / BiSbO4 powder, and then the dispersed Bi 2-x Sb x O2Se / BiSbO4 powder is deposited on a tapered optical fiber with a radius of 12.5 microns and an intrinsic loss of 8.5%.

[0039] An experimental device of a saturable absorber micrometer mode-locked laser, which comprises a saturable absorber 4 prepared by using Bi 2-x Sb x O2Se / BiSbO4 powder, an erbium-doped optical fiber 3 (an erbium-doped optical fiber Er110-4 / 125 with a length of 0.3 meters and a group velocity dispersion of 21.9 ps 2 km -1 at 1550 nanometers), a wavelength division multiplexer 2, a reflective wavelength division multiplexer (980 / 1550 nanometers), a pump source 1, a polarization controller 5, a single-mode optical fiber 6 (a single-mode optical fiber SM28e with a length of 16.9 meters and a group velocity dispersion of -22.3 ps 2 km -1 at 1550 nanometers), a photoelectric coupler 7, and a polarization-independent isolator 8; the pump source provides a light source, the laser enters the erbium-doped optical fiber 3 after passing through the wavelength division multiplexer 2, enters the saturable absorber 4 from the erbium-doped optical fiber 3, and the saturable absorber 4 has high transmittance or reflectivity to strong light and has absorption or loss to weak light; the light signal passing through the saturable absorber 4 enters the photoelectric coupler 7 in turn through the polarization controller 5 and the single-mode optical fiber 6, and the photoelectric coupler 7 is connected with an external oscilloscope.

[0040] The erbium-doped optical fiber has a group velocity dispersion of 21.9 ps 2 km -1 at 1550 nanometers; the single-mode optical fiber has a group velocity dispersion of -22.3 ps 2 km -1 at 1550 nanometers; and the coupling ratio of the photoelectric coupler is 10%.

[0041] The working principle of passively mode-locked fiber lasers relies on the introduction of a saturable absorber into the laser cavity. This element acts as a nonlinear "optical switch" that exhibits high transmission or reflection for intense light and absorption or loss for weak light. When the optical signal circulates in the resonant cavity, the weak light components are continuously suppressed by the amplification of the gain medium and the nonlinear selection of the saturable absorber, while the intense light components are continuously accumulated, eventually realizing the phase locking between longitudinal modes. The nonlinear effect of the saturable absorber is due to the saturation characteristics of its excited-state carriers: when the light intensity reaches a threshold, the absorption coefficient drops sharply due to carrier filling, thereby forming a periodic modulation in the cavity, which promotes the laser to spontaneously enter the mode-locked state. Experiments show that by adjusting the polarization controller, the laser system successfully realizes three kinds of mode-locked mechanisms (traditional soliton mode-locking, traditional soliton harmonic mode-locking and bound-state soliton mode-locking) in the 1.5 micron waveband, and can stably output ultra-short pulse sequences.

[0042] Figure 8 In (a1), the optical spectrum is depicted with clear Kelly sidebands. The central wavelength is 1564 nm, and the 3dB spectral width is 1.6 nm. Figure (a2) is a traditional soliton mode-locked pulse sequence, with a uniform interval of 100 ns between adjacent pulses, which aligns with the fundamental repetition rate of 10.0 MHz. Figure (a3) shows the radio frequency spectrum with a central frequency of 10.0 MHz and a signal-to-noise ratio (SNR) of approximately 62.9 dB, and the inset shows the RF spectrum from 0 to 1 GHz, demonstrating the good stability of the traditional soliton mode-locked laser based on the selenium-antimony bismuth oxide / antimony bismuth oxide saturable absorber. Figure (a4) is the autocorrelation trace, and the hyperbolic secant function fitting yields an estimated pulse duration of approximately 1.06 ps,

[0043] Figure 9 In (b1), the optical spectrum is depicted with clear Kelly sidebands. The central wavelength is 1564 nm, and the 3dB spectral width is 3.04 nm. Figure (b2) is a harmonic soliton mode-locked pulse sequence, with a uniform interval of 5 ns between adjacent pulses, which is the 20th harmonic of the traditional soliton fundamental frequency, and aligns with the fundamental repetition rate of 200 MHz. Figure (b3) shows the radio frequency spectrum with a central frequency of 200 MHz and a signal-to-noise ratio of approximately 68.5 dB, and the inset shows the RF spectrum from 0 to 1 GHz, demonstrating the good stability of the traditional soliton harmonic mode-locked laser based on the selenium-antimony bismuth oxide / antimony bismuth oxide saturable absorber, and figure (b4) is the autocorrelation trace, and the hyperbolic secant function fitting yields an estimated pulse duration of approximately 1.24 ps.

[0044] Figure 10In the middle, Fig. (c1) depicts the optical spectrum. The central wavelength is 1564 nm, and the modulation period is 2.06 nm. Fig. (c2) is the sequence of harmonic soliton mode-locked pulses with a uniform spacing of 100 ns between adjacent pulses, which aligns with a fundamental repetition rate of 10.0 MHz. Fig. (c3) shows the radio frequency spectrum with a central frequency of 10.0 MHz and a signal-to-noise ratio of ~68.5 dB, and the inset shows the RF spectrum from 0 to 1 GHz, demonstrating the good stability of the bound-state soliton mode-locked laser based on the Bi- doped selenium-antimony-bismuth / Bi-antimony-selenide saturable absorber. Fig. (c4) is the autocorrelation trace with a peak separation of ~4 ps.

[0045] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the technical principles of the present application, a number of improvements and modifications can be made, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims

1. A method for preparing a composite material of selenium antimony bismuth oxide / antimony bismuth oxide compound, characterized in that: The steps include: S1. Before sintering the sample, fill the furnace with inert gas and burn it empty to remove impurities at high temperature, ensuring that the furnace is in an inert environment. S2. The Bi2O3, Bi2Se3 and Sb2Se3 raw materials were fully mixed and placed in a quartz crucible, and then the quartz crucible was placed in a chemical vapor deposition process; S3. After placing the crucible, the furnace is purged with an inert gas. After the purging is completed, the inert gas is used as a carrier gas and the temperature is raised to not less than 630° C. to obtain a composite material of selenium oxide antimony bismuth / oxyantimony bismuth compound.

2. The method for preparing the composite material of selenium antimony bismuth oxide / antimony bismuth oxide compound according to claim 1, characterized in that: Before sintering the sample, the furnace body is first heated to no less than 800°C in an air atmosphere and burned in air to remove impurities; then it is switched to inert gas and kept at a constant temperature at 800°C to ensure an inert environment. Finally, it is cooled to room temperature with the furnace, and the inert gas is maintained below 200°C.

3. The method for preparing the composite material of selenium antimony bismuth oxide / antimony bismuth oxide compound according to claim 1, characterized in that: The inert gas may be any one of helium, neon, and argon.

4. The method for preparing the composite material of selenium antimony bismuth oxide / antimony bismuth oxide compound according to claim 1, characterized in that: The molar ratio of Bi2O3, Bi2Se3 and Sb2Se3 is 10:3:

2.

5. The method for preparing the composite material of selenium antimony bismuth oxide / antimony bismuth oxide compound according to claim 1, characterized in that: In step S3, after the crucible is placed, the furnace is purged with inert gas several times. After the purging is completed, the inert gas is used as a carrier gas with a flow rate of 100 sccm. The chemical vapor deposition is heated to 630°C at 10°C / min and kept at this temperature for 2 hours to obtain selenium oxide antimony bismuth / oxygen antimony bismuth compound, namely Bi 2-x Sb x O2Se / BiSbO4.

6. A method for preparing a saturable absorber, characterized in that: Bi prepared by any one of the methods described in claims 1 to 5 is dispersed using ethanol 2-x Sb x O2Se / BiSbO4 powder, and then dispersed Bi 2-x Sb x O2Se / BiSbO4 powder is deposited on a tapered optical fiber to obtain a saturable absorber.

7. An experimental device for micron mode-locked laser using a saturable absorber, characterized in that: Including the use of Bi 2- x Sb x A saturable absorber, erbium-doped optical fiber, wavelength division multiplexer, pump source, polarization controller, single-mode optical fiber, photoelectric coupler and polarization-independent isolator are prepared from O2Se / BiSbO4 powder. The pump source provides a light source. The laser enters the erbium-doped optical fiber after passing through the wavelength division multiplexer, and then enters the saturable absorber from the erbium-doped optical fiber. The saturable absorber exhibits high transmittance or reflectivity for the strong light portion, but absorbs or loses the weak light portion. The optical signal passing through the saturable absorber sequentially enters the polarization controller and the single-mode optical fiber and then enters the photoelectric coupler. The photoelectric coupler is connected to an external oscilloscope.

8. The experimental device using a saturable absorber micron mode-locked laser according to claim 7, characterized in that: When the optical signal circulates in the resonant cavity of the saturable absorber, the weak light component is continuously suppressed through the amplification of the gain medium and the nonlinear selection of the saturated absorber, while the strong light component continues to accumulate, ultimately achieving phase locking between longitudinal modes.

9. The experimental device using a saturable absorber micron mode-locked laser according to claim 7, characterized in that: When the light intensity reaches the threshold, the absorption coefficient drops sharply due to carrier filling, thereby forming periodic modulation in the cavity, prompting the laser to spontaneously enter the mode-locked state. By adjusting the polarization controller, three mode-locking mechanisms are realized in the 1.5-micron band. The three mode-locking mechanisms include traditional soliton mode-locking, traditional soliton harmonic mode-locking, and bound-state soliton mode-locking, which can stably output ultrashort pulse sequences.

10. The experimental device using a saturable absorber micron mode-locked laser according to claim 7, characterized in that: The group velocity dispersion of erbium-doped fiber at 1550 nm is 21.9 ps 2 km -1 ; The group velocity dispersion of single-mode fiber at 1550 nm is -22.3ps 2 km -1 ; Coupling ratio of the photocoupler: 10%.

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