阅读说明：本技术 基于钬铥离子共掺杂的zbya玻璃微球的三波长激光器 (Three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres ) 是由 王鹏飞 赵海燕 王顺宾 于 2020-06-02 设计创作，主要内容包括：本发明公开了一种基于钬铥离子共掺杂的ZBYA玻璃微球的三波长激光器,具体公开了一种钬铥离子共掺杂的ZBYA玻璃材料,所述玻璃材料的摩尔组成按化学式表示为：50ZrF<Sub>4</Sub>-33BaF<Sub>2</Sub>-8.5YF<Sub>3</Sub>-7AlF<Sub>3</Sub>,并掺杂浓度0.5 mol%的Ho<Sup>3+</Sup>离子和1 mol%的Tm<Sup>3+</Sup>离子,以上各组成摩尔百分比之和为100%。还公开了一种钬铥离子共掺杂的ZBYA玻璃微球的制备方法以及一种基于钬铥离子共掺杂的ZBYA玻璃微球的三波长激光器的制备方法和调节方法。本发明具有低阈值、高Q值,且结构简单,可在低阈值下实现激光器的小型化和集成化,并可以应用于集成光子学、低阈值激光、高灵敏度生物传感、腔光力学等诸多领域。(The invention discloses a three-wavelength laser based on a holmium and thulium ion co-doped ZBYA glass microsphere, and particularly discloses a holmium and thulium ion co-doped ZBYA glass material, wherein the molar composition of the glass material is expressed as the following chemical formula: 50ZrF 4 ‑33BaF 2 ‑8.5YF 3 ‑7AlF 3 And is doped with Ho at a concentration of 0.5 mol% 3+ Ion and 1mol% Tm 3+ And ions, wherein the sum of the mole percentages of the components is 100%. Also discloses a preparation method of the holmium and thulium ion co-doped ZBYA glass microsphere, and a preparation method and a regulation method of a three-wavelength laser based on the holmium and thulium ion co-doped ZBYA glass microsphere. The invention has low threshold, high Q value, simple structure, can realize miniaturization and integration of the laser under low threshold, and can be applied to the fields of integrated photonics, low threshold laser, high sensitivity biosensing, cavity optomechanics and the like.)

1. A holmium and thulium ion co-doped ZBYA glass material is characterized in that the molar composition of the glass material is expressed by the chemical formula: 50ZrF₄-33BaF₂-8.5YF₃-7AlF₃And is doped with Ho at a concentration of 0.5 mol%³⁺Ion and 1mol% Tm³⁺And ions, wherein the sum of the mole percentages of the components is 100%.

2. The holmium thulium ion co-doped zkya glass material of claim 1, wherein the Ho is characterized by³⁺Ion by HoF₃The form is doped.

3. The holmium thulium ion co-doped zkya glass material of claim 1, wherein the Tm is³⁺Ion at TmF₃The form is doped.

4. A preparation method of a holmium and thulium ion co-doped ZBYA glass microsphere is characterized by comprising the following steps:

step 1, according to a chemical formula of 50ZrF₄-33BaF₂-8.5YF₃-7AlF₃And is doped with Ho at a concentration of 0.5 mol%³⁺Ion and 1mol% Tm³⁺Calculating the mass ratio of the high-purity raw materials according to the molar composition of ions, weighing, grinding in an agate mortar, and fully and uniformly mixing;

step 2, pouring the uniformly mixed raw materials into a platinum crucible, and placing the platinum crucible into a high-temperature furnace of a glove box to keep the temperature of 800-900 ℃ for 1-3 hours;

step 3, pouring the solution glass on a preheated copper plate, drawing and cooling the solution glass from molten glass liquid to prepare the holmium and thulium ion co-doped ZBYA glass fiber;

step 4, using CO₂And heating the ZBYA glass fiber by a laser to prepare the microsphere.

5. The method of preparing the holmium and thulium ion co-doped zkya glass microspheres of claim 4, wherein the Ho in the step 1 is performed³⁺Ion by HoF₃The form is doped.

6. The method of preparing the holmium thulium ion co-doped ZBYA glass microspheres of claim 4, wherein the Tm in step 1 is³⁺Ion at TmF₃The form is doped.

7. The method for preparing the holmium and thulium ion co-doped ZBYA glass microspheres according to claim 4, wherein the diameter of the microspheres prepared in the step 4 is 40-80 microns.

8. A preparation method of a three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres is characterized by comprising the following steps:

step 1, tapering a single mode optical fiber to a diameter of 1-3 mu m to prepare a tapered optical fiber;

step 2, connecting two ends of the tapered optical fiber with a pumping light source and a spectrum analyzer respectively;

and 3, enabling the biconical tapered optical fiber and the holmium and thulium ion codoped ZBYA glass microsphere to be in a near contact state, and coupling laser into and out of the microsphere by utilizing an evanescent field generated by the optical fiber taper.

9. The method according to claim 8, wherein the pump light source in step 2 is a 793nm semiconductor laser.

10. A method for adjusting a three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres is characterized by comprising the following steps:

step 1, coupling a tapered optical fiber and a holmium and thulium ion co-doped ZBYA glass microsphere, and adjusting the coupling position to enable the tapered optical fiber and the holmium and thulium ion co-doped ZBYA glass microsphere to be in a near contact state;

and 2, improving the pumping power of the pumping light source to enable the three-wavelength laser to appear successively.

Technical Field

The invention relates to the technical field of fiber lasers, in particular to a three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres.

Background

On the way of the development of optical information science, higher and higher requirements are put on the perception, transmission and control of light, while the traditional photonic devices obviously cannot meet the requirements, and novel photonic devices capable of transmitting and manipulating optical information are paid attention to. Among numerous photonic platforms, Whispering Gallery Mode (WGM) microcavities have extremely high quality factors (Q values) and extremely small Mode volumes (V), enhancing the interaction between light and substances, providing a very excellent platform for a large number of basic physical studies and the development of photonic devices, and having important applications in the fields of optical communication, sensing, microwave photonics, quantum computing, and the like. Based on the WGM microcavity platform, light information can be generated, sensed, transmitted and regulated, and with the improvement of micro-nano processing and packaging technology, the microcavity platform can be developed towards miniaturization and practicability. Low-absorption dielectric glass microspheres with diameters of several microns to several hundred microns are natural optical resonators with very high quality factor Q (quartz matrix up to 10)¹⁰) And extremely small mode volume V_mAnd has attracted a great deal of attention. The excellent characteristic of the optical fiber is derived from the existence of Whispering Gallery Modes (WGMs) in a cavity, namely an incident light beam is subjected to total internal reflection in the cavity, is confined near an equatorial plane and rounds a great circle, and can be mutually superposed to be enhanced when the phases of the incident light beam meet a certain phase matching condition. The glass microsphere cavity has characteristics superior to those of traditional resonant cavities such as F-B cavity and the like, and optical resonance of other structures such as micro-ring, micro-column and micro-diskThe vibration cavity and the microsphere cavity also have the characteristics of simple preparation, longest light energy storage time and the like. Based on the excellent characteristics, the glass microsphere has wide application prospect in the fields of extremely low threshold laser, high-sensitivity sensor, nonlinear optics, cavity quantum electrodynamics effect and the like. At present, the glass substrates developed at home and abroad for the microsphere cavity experiment mainly comprise quartz glass, phosphate glass, fluoride glass, tellurate glass, chalcogenide glass and the like.

For rare earth doped glasses, host glasses possessing low phonon energy are an important factor in achieving high efficiency luminescence, thereby reducing the occurrence of non-radiative relaxation processes. Fluoride glasses have the advantage of lower phonon energy (about 580 cm)^-1) The doped activator has high quantum efficiency. In addition, since the coordination fields of rare earth ions are different in different glass matrixes such as fluoride, sulfate, phosphate, silicate and the like, the fluorescence characteristics and the spectral properties of the rare earth ions are also different, and the influence of the matrixes on the luminescence properties of the rare earth ions is generally reflected in the following two directions: one is to widen the energy level, including phonon broadening and perturbation of the energy level by the matrix electric field, and the other is to cause Stark level splitting due to the non-uniform distribution of the electric field to eliminate the degeneracy of the energy level of rare earth ions. Therefore, the selection of the matrix glass is very important, and the selection of the matrix glass generally follows the following points: 1. has excellent mechanical performance, thermal stability and physical and chemical properties. 2. The rare earth ions can have high solubility in the matrix and have good spectral properties. 3. The maximum phonon energy of the matrix glass is small. The advantages of fluorozirconate glasses over other matrix glasses are: low phonon energy, good physical and chemical properties, high solubility to rare earth, large stimulated emission cross section and the like, so the microsphere has very high gain effect and low melting point, and can be prepared at low temperature. With ZBLAN (ZrF)₄-BaF₂-LaF₃-AlF₃NaF) fluoride glass, for example, ZBLAN glass fibers have been widely studied and developed in recent years and have been commercialized, and ZBLAN fiber-based mid-infrared lasers have been widely studied by foreign and domestic students. Nevertheless, ZBLAN is chemically stablePoor mechanical strength, easy deliquescence and the like, mainly because the ZBLAN glass component contains NaF and Na ions have the chemical property of easy water absorption. Therefore, we made ZBYA (ZrF) by oneself₄-BaF₂-YF₃-AlF₃) The fluoride glass not only keeps the advantages of fluorozirconate glass, but also overcomes the defects of easy deliquescence and the like.

For the rare earth ion doped matrix glass material, the melting point is lower, so that the microsphere preparation mode is relatively more. There are three balling methods in the laboratory. Including direct heating using alcohol lamps or oxyhydrogen flames to form balls, arc discharge to form balls, and CO₂The laser is processed into balls. In the three methods, because the heating source thermal field range of the first two methods is large, and the temperature is difficult to regulate, a microsphere cavity with the diameter less than 200 mu m is difficult to add, when the size of the active microsphere cavity is too high, the surface quality is easy to deteriorate, and the main sources of surface deterioration are crystallization, adhesion, surface cracks and the like. Therefore, the invention mainly adopts CO₂Preparation of microsphere cavity by laser micromachining method, CO₂A laser is a heating source with a very small and controllable heating field. Coupling is a critical step in order to produce microsphere lasers. The coupling mode of the microsphere cavity is various, including prism coupling, space optical coupling, micro-nano fiber evanescent field coupling and the like. The micro-nano optical fiber has the advantages of high coupling efficiency, low cost, easiness in preparation and the like, so that the micro-nano optical fiber is a waveguide structure widely used in the field of microsphere cavity coupling at present. At present, the demand for communication capacity is rapidly increased, and the miniaturization trend of optical devices is increasingly obvious, the glass microspheres have wide development prospects in the fields of low-threshold laser emission, integrated optics, nonlinear optical fibers, sensing, quantum communication and the like by virtue of extremely high quality factors and extremely small mode volume characteristics. At present, the research overall level of the microsphere micro-cavity resonator is still in a theoretical and experimental stage, but with continuous improvement and perfection of related preparation processes, coupling and integration technologies and the like, the microsphere micro-cavity resonator can be widely applied.

Therefore, those skilled in the art are devoted to develop a three-wavelength laser based on a holmium and thulium ion co-doped ZBYA glass microsphere, which can be applied to the fields of integrated photonics, low-threshold laser, high-sensitivity biosensing, cavity optomechanics and the like.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is how to prepare a catalyst based on Ho doping³⁺/Tm³⁺The ZBYA fluoride glass matrix microsphere laser realizes laser emission of 3 wave bands and realizes output of 1507 nm, 1833 nm and 2074 nm lasers.

In order to achieve the above object, the present invention provides a holmium and thulium ion co-doped ZBYA glass material, wherein the molar composition of the glass material is represented by the chemical formula: 50ZrF₄-33BaF₂-8.5YF₃-7AlF₃And is doped with Ho at a concentration of 0.5 mol%^{3 +}Ion and 1mol% Tm³⁺And ions, wherein the sum of the mole percentages of the components is 100%.

Further, the Ho³⁺Ion by HoF₃The form is doped.

Further, the Tm is³⁺Ion at TmF₃The form is doped.

In another aspect, the invention provides a preparation method of a holmium and thulium ion co-doped ZBYA glass microsphere, which comprises the following steps:

step 1, according to a chemical formula of 50ZrF₄-33BaF₂-8.5YF₃-7AlF₃And is doped with Ho at a concentration of 0.5 mol%³⁺Ion and 1mol% Tm³⁺Calculating the mass ratio of the high-purity raw materials according to the molar composition of ions, weighing, grinding in an agate mortar, and fully and uniformly mixing;

step 2, pouring the uniformly mixed raw materials into a platinum crucible, and placing the platinum crucible into a high-temperature furnace of a glove box to keep the temperature of 800-900 ℃ for 1-3 hours;

step 3, pouring the solution glass on a preheated copper plate, drawing and cooling the solution glass from molten glass liquid to prepare the holmium and thulium ion co-doped ZBYA glass fiber;

step 4, using CO₂And heating the ZBYA glass fiber by a laser to prepare the microsphere.

Further, the Ho in the step 1³⁺Ion by HoF₃The form is doped.

Further, the Tm in the step 1³⁺Ion at TmF₃The form is doped.

Further, the diameter of the microsphere prepared in the step 4 is 40-80 microns.

In another aspect, the invention provides a preparation method of a three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres, which comprises the following steps:

step 1, tapering a single mode optical fiber to a diameter of 1-3 mu m to prepare a tapered optical fiber;

step 2, connecting two ends of the tapered optical fiber with a pumping light source and a spectrum analyzer respectively;

and 3, enabling the biconical tapered optical fiber and the holmium and thulium ion codoped ZBYA glass microsphere to be in a near contact state, and coupling laser into and out of the microsphere by utilizing an evanescent field generated by the optical fiber taper.

Further, the pump light source in the step 2 is a 793nm semiconductor laser.

In another aspect, the invention provides a method for tuning a three-wavelength laser based on holmium and thulium ion co-doped ZBYA glass microspheres, which comprises the following steps:

step 1, coupling a tapered optical fiber and a holmium and thulium ion co-doped ZBYA glass microsphere, and adjusting the coupling position to enable the tapered optical fiber and the holmium and thulium ion co-doped ZBYA glass microsphere to be in a near contact state;

and 2, improving the pumping power of the pumping light source to enable the three-wavelength laser to appear successively.

The invention has the beneficial effects that:

the invention has low threshold value, high Q value, simple structure, and can realize miniaturization and integration of laser under low threshold value.

The 1.5 micron, 1.8 micron and 2.1 micron lasers obtained by the invention can be applied to the fields of integrated photonics, low threshold laser, high-sensitivity biosensing, cavity optomechanics and the like.

Drawings

FIG. 1 is a schematic optical path diagram of a microsphere laser according to a preferred embodiment of the present invention;

FIG. 2 is the laser emission spectrum of the microsphere laser at three wavelength bands of 1507 nm, 1833 nm and 2074 nm according to a preferred embodiment of the present invention;

FIG. 3 is a slope efficiency spectrum of a three wavelength laser of a microsphere laser according to a preferred embodiment of the present invention.

Wherein: the device comprises a semiconductor laser 1, a notebook computer 2, a CCD camera 3, microspheres 4, tapered optical fibers 5 and a spectrum analyzer 6.

Detailed Description

The preferred embodiments of the present invention will be described below with reference to the accompanying drawings for clarity and understanding of technical contents. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.

In the drawings, structurally identical elements are represented by like reference numerals, and structurally or functionally similar elements are represented by like reference numerals throughout the several views. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components may be exaggerated where appropriate in the figures to improve clarity.