WO2021087717A1 - Composite single-crystal optical fiber clad with multi-component phosphate glass and preparation method thereof - Google Patents

Composite single-crystal optical fiber clad with multi-component phosphate glass and preparation method thereof Download PDF

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WO2021087717A1
WO2021087717A1 PCT/CN2019/115532 CN2019115532W WO2021087717A1 WO 2021087717 A1 WO2021087717 A1 WO 2021087717A1 CN 2019115532 W CN2019115532 W CN 2019115532W WO 2021087717 A1 WO2021087717 A1 WO 2021087717A1
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cladding
optical fiber
fiber
crystal
crucible
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PCT/CN2019/115532
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French (fr)
Chinese (zh)
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沈荣存
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南京同溧晶体材料研究院有限公司
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Priority to PCT/CN2019/115532 priority Critical patent/WO2021087717A1/en
Publication of WO2021087717A1 publication Critical patent/WO2021087717A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/02—Optical fibres with cladding with or without a coating

Definitions

  • the invention relates to the technical field of optical fibers, in particular to a clad single crystal optical fiber and a preparation method thereof.
  • the traditional optical fiber is prepared with inorganic glass or organic polymer as the raw material by the method of melting control.
  • the single crystal fiber as the name suggests, not only has the slender structure and light guiding ability of traditional optical fiber, but also has the unique ordered structure of single crystal material and the physical properties of light, electricity, heat and magnetism. It is made of single crystal material. Commonly used single crystal fibers include Nd:YAG, Ti:Al2O3, Cr:Al2O3, LiNbO3, KBr, Mn2SiO4, etc. In recent years, single crystal optical fiber has received extensive attention due to its unique physical properties and its important application potential in laser technology, sensor technology, integrated optoelectronic systems and other fields.
  • the parameters reflecting the quality of single crystal fiber include diameter, length, intensity, etc.
  • Optical parameters include absorption and emission characteristics, absorption and scattering light conduction loss, which are related to the growth conditions and the internal and surface defects of the fiber. It is of great significance to explore and research the physical properties of single crystal fibers based on different materials.
  • Single crystal fibers are currently mainly made of crystalline materials by drawing and growing, which have the dual characteristics of crystals and fibers.
  • Single crystal fiber has the characteristics of high strength and high temperature resistance, and can be used in a wide range of fields such as conduction, sensing, frequency doubling and holographic data storage.
  • Due to the high refractive index of the crystal it is difficult for the single crystal fiber to be made into a core-cladding structure.
  • the existing single crystal fiber usually has an unclad structure.
  • the single crystal fiber without cladding structure has large transmission loss, its characteristics are easily affected by environmental changes, and the integrity of the fiber surface is also vulnerable to damage.
  • magnesium-doped lithium niobate LiNbO3
  • LiNbO3 pure lithium niobate crystal
  • the present invention provides a clad single crystal optical fiber and a preparation method thereof.
  • the invention provides a multi-component phosphate glass-clad composite single crystal optical fiber, which includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass,
  • the fiber core material is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
  • the fiber core material is a single crystal selenium-tellurium compound.
  • the molar ratio of Eu 4+ , Lu 3+ , and Tb 3+ is (2-4): (1-3):1 .
  • the composition of the multi-component phosphate glass is: P 2 O 5 : 45 ⁇ 65 parts by weight; K 2 O: 10 ⁇ 20 parts by weight; BaO: 5 ⁇ 10 parts by weight; Al 2 O 3 : 10 ⁇ 20 parts by weight.
  • the ratio of the total number of moles of Eu 4+ , Lu 3+ , and Tb 3+ to the number of moles of BaTiO 3 is (1-5):100.
  • the present invention also provides a method for preparing the above-mentioned multi-component phosphate glass-clad composite single crystal optical fiber, which is prepared by using a crystal fiber and its cladding synchronous preparation equipment, and includes the following steps:
  • the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
  • the crystal fiber and its cladding synchronous preparation equipment includes a lower crucible (1), an upper crucible (2), a crucible support column (3), and a cladding column (4);
  • the upper crucible (2) is located The top of the lower crucible (1) and the lower crucible (1) and the upper crucible (2) are connected by a crucible support column (3);
  • one end of the cladding column (4) is located in the lower crucible (1) and penetrates vertically Pass the upper crucible (2), and the other end is located above the upper crucible (2);
  • the cladding column (4) is provided with a crystal fiber supply forming tube (5) and a cladding supply forming tube (6).
  • the cladding feeding forming tube (6) is a ring-shaped pipe and is ringed outside the crystal optical fiber feeding forming tube (5).
  • the raw material of the crystal fiber is BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , and Tb 2 O 3 .
  • the cladding material is multi-component phosphate glass.
  • the multi-component phosphate glass clad composite single crystal fiber provided by the present invention adopts the fiber core and the clad material covering the fiber core.
  • the preparation process of the fiber core is simple, and it has excellent absorption characteristics and up-conversion.
  • the strength greatly improves the application range of BaTiO3 single crystal fiber;
  • the cladding material uses multi-component phosphate glass, which is low in cost and can meet the requirements of total reflection.
  • the synchronous preparation equipment of the crystal fiber and its cladding layer of the present application has a simple structure and low cost.
  • the equipment can be used to prepare the cladding layer on the surface of the crystal fiber while growing the crystalline fiber, which greatly reduces the production cost and increases the efficiency of device preparation;
  • the cladding layer is a single crystal cladding, which can be the same matrix as the crystalline fiber or a different matrix.
  • the single crystal cladding has more excellent physical and chemical properties.
  • Figure 1 is a schematic diagram of the structure of the crystal fiber and its cladding synchronous preparation equipment.
  • the composite single crystal optical fiber and the preparation method thereof include the following steps:
  • the seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
  • the composite single crystal optical fiber and the preparation method thereof include the following steps:
  • the seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
  • the composite single crystal optical fiber and the preparation method thereof include the following steps:
  • the seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
  • the sample is made into a cylindrical optical fiber with a diameter of 1.0mm and a length of 4mm. The two sides are carefully polished and placed in a fiber coupler.
  • the quartz lamp is used as the light source for measurement.
  • the measurement spectrum ranges from 500 to 1000 nm.
  • a 650nm semiconductor laser was used as the pump light source to pump the sample and measure the up-conversion spectrum of each sample.
  • the results show: the BaTiO 3 has a spectral conversion, but the intensity is very weak; however, the Eu complex crystal fiber of Examples 1 to 3 4+ / Lu 3+ / Tb 3+: converting the spectral intensity significantly higher than 3 BaTiO BaTiO 3 Enhance a lot.
  • Crystal fiber and its cladding synchronous preparation equipment including a lower crucible (1), an upper crucible (2), a crucible support column (3), and a cladding column (4);
  • the upper crucible (2) is located in the lower crucible (1)
  • the top and the lower crucible (1) and the upper crucible (2) are connected by a crucible support column (3);
  • one end of the cladding column (4) is located in the lower crucible (1) and vertically passes through the upper crucible (2) ), the other end is located above the upper crucible (2);
  • the cladding column (4) is provided with a crystal optical fiber feeding forming tube (5) and a cladding feeding forming tube (6), the cladding feeding forming
  • the tube (6) is a ring-shaped pipe and is looped outside the crystal fiber supply forming tube (5).
  • a multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
  • the composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
  • the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass;
  • the composition of multi-component phosphate glass is: P 2 O 5 : 55 parts by weight; K 2 O: 15 parts by weight; BaO: 7.5 parts by weight; Al 2 O 3 : 15 parts by weight;
  • the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
  • a multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
  • the composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
  • the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass;
  • the composition of multi-component phosphate glass is: P 2 O 5 : 45 parts by weight; K 2 O: 20 parts by weight; BaO: 10 parts by weight; Al 2 O 3 : 20 parts by weight;
  • the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
  • a multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
  • the composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
  • the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass;
  • the composition of multi-component phosphate glass is: P 2 O 5 : 65 parts by weight; K 2 O: 10 parts by weight; BaO: 5 parts by weight; Al 2 O 3 : 10 parts by weight;
  • the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
  • Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube, until the crystal contacts the cladding material melt in the cladding supply forming tube, and the cladding is supplied The cladding material melt in the material forming tube adheres to the outer wall of the fiber crystal to grow; thus, the fiber crystal and the cladding material grow simultaneously.

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  • Organic Chemistry (AREA)
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Abstract

Provided is a composite single-crystal optical fiber clad with multi-component phosphate glass, comprising an optical fiber core and a cladding material covering the optical fiber core. The cladding material is a multi-component phosphate glass. The optical fiber core material is a composite single-crystal optical fiber, where the composite single-crystal optical fiber is Eu4+/Lu3+/Tb3+:BaTiO3. Also provided is a method for preparing the aforementioned composite single-crystal optical fiber clad with multi-component phosphate glass. The composite single-crystal optical fiber clad with multi-component phosphate glass provided in the present invention adopts an optical fiber core and a cladding material covering the optical fiber core. The preparation process of the optical fiber core is simple. The optical fiber core has excellent absorption characteristics and up-conversion strength, thereby significantly increasing the application range of BaTiO3 single-crystal optical fiber. The multi-component phosphate glass is used as the cladding material, such that the cost is low, and the requirements of total reflection can be achieved.

Description

一种多组分磷酸盐玻璃包层的复合单晶光纤及其制备方法Multi-component phosphate glass clad composite single crystal optical fiber and preparation method thereof 技术领域Technical field
本发明涉及光纤技术领域，特别一种包层单晶光纤及其制备方法。The invention relates to the technical field of optical fibers, in particular to a clad single crystal optical fiber and a preparation method thereof.
背景技术Background technique
传统的光纤是以无机玻璃或有机聚合物为原料，通过烙融控制的方法制备的。而单晶光纤，顾名思义，就是既具备传统光纤的细长结构和导光能力，又具备单晶材料特有的有序结构和光、电、热、磁等物理性质，其是由单晶材料制成的光学纤维，常用的单晶光纤有Nd:YAG、Ti:Al2O3、Cr:Al2O3、LiNbO3、KBr、Mn2SiO4等。近年来，单晶光纤由于其独特的物理性能，在激光技术、传感技术、集成光电***等领域具有重要的应用潜力而受到广泛的关注。The traditional optical fiber is prepared with inorganic glass or organic polymer as the raw material by the method of melting control. The single crystal fiber, as the name suggests, not only has the slender structure and light guiding ability of traditional optical fiber, but also has the unique ordered structure of single crystal material and the physical properties of light, electricity, heat and magnetism. It is made of single crystal material. Commonly used single crystal fibers include Nd:YAG, Ti:Al2O3, Cr:Al2O3, LiNbO3, KBr, Mn2SiO4, etc. In recent years, single crystal optical fiber has received extensive attention due to its unique physical properties and its important application potential in laser technology, sensor technology, integrated optoelectronic systems and other fields.
    单晶光纤反映单晶光纤质量的参数有直径、长度、强度等，光学参数有吸收和发射特性，吸收和散射光传导损耗，这些与其生长条件和光纤内在及表面缺陷都有关系。对基于不同材料的单晶光纤的制备技术巧物理性能开展探索和研究具有十分重要的意义。... The parameters reflecting the quality of single crystal fiber include diameter, length, intensity, etc. Optical parameters include absorption and emission characteristics, absorption and scattering light conduction loss, which are related to the growth conditions and the internal and surface defects of the fiber. It is of great significance to explore and research the physical properties of single crystal fibers based on different materials.
    单晶光纤目前主要由晶体材料拉丝生长而成，具有晶体和纤维的双重特性。单晶光纤具有高强度、耐高温等特点，可应用于传导、传感、倍频和全息数据存储等广泛领域。但由于晶体折射率较高，单晶光纤很难做成纤芯-包层结构，现有的单晶光纤通常为无包层结构。无包层结构的单晶光纤传输损耗大，特性易受环境变化影响，光纤表面的完整性也易受到破坏。... Single crystal fibers are currently mainly made of crystalline materials by drawing and growing, which have the dual characteristics of crystals and fibers. Single crystal fiber has the characteristics of high strength and high temperature resistance, and can be used in a wide range of fields such as conduction, sensing, frequency doubling and holographic data storage. However, due to the high refractive index of the crystal, it is difficult for the single crystal fiber to be made into a core-cladding structure. The existing single crystal fiber usually has an unclad structure. The single crystal fiber without cladding structure has large transmission loss, its characteristics are easily affected by environmental changes, and the integrity of the fiber surface is also vulnerable to damage.
    对于单晶光纤的包层结构，也有一些研究设计。主要是利用掺镁铌酸锂（MgO：LiNbO3）折射率比纯铌酸锂晶体（LiNbO3）折射率低的原理，使用MgO或者MgF通过扩散的方式将镁离子由外层向中心扩散，从而降低外层铌酸锂晶体的折射率，形成包层。1995年，西安交大阙文修等人在1995年《西安交通大学学报》29卷第9期中公布了利用此方法制作铌酸锂材料单晶光纤包层。这种方法仅适用于铌酸锂（LiNbO3）晶体生长的单晶光纤，对其它晶体材料并不适用，限制了包层应用的范围。另外，这种方法可控性差，扩散程度不均匀，扩散深度不宜控制，产品性能稳定性较差。... For the cladding structure of single crystal fiber, there are also some research designs. It mainly uses the principle that magnesium-doped lithium niobate (MgO: LiNbO3) has a lower refractive index than pure lithium niobate crystal (LiNbO3), and uses MgO or MgF to diffuse magnesium ions from the outer layer to the center through diffusion, thereby reducing The refractive index of the outer layer of lithium niobate crystal forms the cladding layer. In 1995, Que Wenxiu of Xi'an Jiaotong University and others announced the use of this method to make lithium niobate material single crystal optical fiber cladding in the 1995 "Journal of Xi'an Jiaotong University", Volume 29, Issue 9. This method is only suitable for single crystal fibers grown by lithium niobate (LiNbO3) crystals, and is not suitable for other crystal materials, which limits the scope of cladding applications. In addition, this method has poor controllability, uneven diffusion, unsuitable control of diffusion depth, and poor product performance stability.
技术问题technical problem
了解决现有技术的缺陷，本发明提供了一种包层单晶光纤及其制备方法。To solve the defects of the prior art, the present invention provides a clad single crystal optical fiber and a preparation method thereof.
技术解决方案Technical solutions
本发明提供的一种多组分磷酸盐玻璃包层的复合单晶光纤，包括光纤纤芯以及包覆于光纤纤芯外的包层材料；所述包层材料为多组分磷酸盐玻璃，所述光纤纤芯材料为复合单晶光纤，所述复合单晶光纤为Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 The invention provides a multi-component phosphate glass-clad composite single crystal optical fiber, which includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, The fiber core material is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
优选地，光纤纤芯材料为单晶态硒碲化合物所述复合单晶光纤中，Eu 4+、Lu 3+、Tb 3+的摩尔比为（2-4）：（1-3）：1。 Preferably, the fiber core material is a single crystal selenium-tellurium compound. In the composite single crystal fiber, the molar ratio of Eu 4+ , Lu 3+ , and Tb 3+ is (2-4): (1-3):1 .
优选地，所述多组分磷酸盐玻璃组成为：P 2O 5：45~65重量份；K 2O：10~20重量份；BaO：5~10重量份；Al 2O 3：10~20重量份。 Preferably, the composition of the multi-component phosphate glass is: P 2 O 5 : 45~65 parts by weight; K 2 O: 10~20 parts by weight; BaO: 5~10 parts by weight; Al 2 O 3 : 10~ 20 parts by weight.
优选地，所述Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为（1-5）：100。 Preferably, the ratio of the total number of moles of Eu 4+ , Lu 3+ , and Tb 3+ to the number of moles of BaTiO 3 is (1-5):100.
本发明还提供了上述多组分磷酸盐玻璃包层的复合单晶光纤的制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：The present invention also provides a method for preparing the above-mentioned multi-component phosphate glass-clad composite single crystal optical fiber, which is prepared by using a crystal fiber and its cladding synchronous preparation equipment, and includes the following steps:
（1）在下坩埚内装入晶体光纤原料，在上坩埚内装入包层原料；加热下坩埚和上坩埚；(1) Load the crystal fiber raw material in the lower crucible, and load the cladding material in the upper crucible; heat the lower crucible and the upper crucible;
（2）待晶体光纤原料和包层原料融化后在包层柱顶部种籽晶，由于毛细管作用，下坩埚内的晶体光纤原料熔体通过晶体光纤供料成形管达到包层柱顶，籽晶先接触到晶体光纤供料成形管内的晶体光纤原料熔体，开始放肩；(2) After the crystal fiber raw material and the cladding material are melted, the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
（3）晶体不断生长，由于毛细管作用，上坩埚内的包层原料熔体通过包层供料成形管达到包层柱顶，至晶体接触到包层供料成形管内的包层原料熔体，包层供料成形管内的包层原料熔体附着在光纤晶体外壁生长；从而光纤晶体和包层材料同步生长。(3) Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube until the crystal contacts the cladding material melt in the cladding feeding forming tube. The cladding material melt in the cladding supply forming tube is attached to the outer wall of the fiber crystal to grow; thus the fiber crystal and the cladding material grow simultaneously.
       优选地，所述晶体纤维及其包层同步制备设备，包括下坩埚（1）、上坩埚（2）、坩埚支撑柱（3）、包层柱（4）；所述上坩埚（2）位于下坩埚（1）顶部且下坩埚（1）和上坩埚（2）之间通过坩埚支撑柱（3）连接；所述包层柱（4）一端位于下坩埚（1）内，且竖直穿过上坩埚（2），另一端位于上坩埚（2）上方；所述包层柱（4）内设有晶体光纤供料成形管（5）和包层供料成形管（6），所述包层供料成形管（6）为环形管道且环设于晶体光纤供料成形管（5）外。... Preferably, the crystal fiber and its cladding synchronous preparation equipment includes a lower crucible (1), an upper crucible (2), a crucible support column (3), and a cladding column (4); the upper crucible (2) is located The top of the lower crucible (1) and the lower crucible (1) and the upper crucible (2) are connected by a crucible support column (3); one end of the cladding column (4) is located in the lower crucible (1) and penetrates vertically Pass the upper crucible (2), and the other end is located above the upper crucible (2); the cladding column (4) is provided with a crystal fiber supply forming tube (5) and a cladding supply forming tube (6). The cladding feeding forming tube (6) is a ring-shaped pipe and is ringed outside the crystal optical fiber feeding forming tube (5).
优选地，步骤（1）中，所述晶体光纤原料为BaTiO 3、Eu 2O 3、Lu 2O 3、Tb 2O 3。 Preferably, in step (1), the raw material of the crystal fiber is BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , and Tb 2 O 3 .
优选地，步骤（1）中，所述包层原料为多组分磷酸盐玻璃。Preferably, in step (1), the cladding material is multi-component phosphate glass.
有益效果Beneficial effect
本发明提供的多组分磷酸盐玻璃包层的复合单晶光纤采用包括光纤纤芯以及包覆于光纤纤芯外的包层材料，光纤纤芯制备工艺简单，具有优异的吸收特性和上转换强度，大大提高了BaTiO3单晶光纤的应用范围；包层材料使用多组分磷酸盐玻璃，成本低，而且可以能够满足全反射的要求。The multi-component phosphate glass clad composite single crystal fiber provided by the present invention adopts the fiber core and the clad material covering the fiber core. The preparation process of the fiber core is simple, and it has excellent absorption characteristics and up-conversion. The strength greatly improves the application range of BaTiO3 single crystal fiber; the cladding material uses multi-component phosphate glass, which is low in cost and can meet the requirements of total reflection.
采用本申请的晶体纤维及其包层同步制备设备结构简单，成本低廉，利用该设备可在生长晶体纤维时同时制备晶体纤维表面的包层，大大降低了生产成本、增加器件制备效率；制备出的包层为单晶包层，可以与晶体纤维同基质，也可以不同基质，单晶包层拥有更加优异的物化性能。The synchronous preparation equipment of the crystal fiber and its cladding layer of the present application has a simple structure and low cost. The equipment can be used to prepare the cladding layer on the surface of the crystal fiber while growing the crystalline fiber, which greatly reduces the production cost and increases the efficiency of device preparation; The cladding layer is a single crystal cladding, which can be the same matrix as the crystalline fiber or a different matrix. The single crystal cladding has more excellent physical and chemical properties.
附图说明Description of the drawings
图1为晶体纤维及其包层同步制备设备的结构示意图。Figure 1 is a schematic diagram of the structure of the crystal fiber and its cladding synchronous preparation equipment.
本发明的最佳实施方式The best mode of the present invention
下面对本发明作出进一步说明。The present invention will be further explained below.
       制备复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 Preparation of composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
实施例1 Example 1
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为3：2：1，Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为3：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 3:2:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 3:100.
    上述复合单晶光纤及其制备方法，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof include the following steps:
    （1）在坩埚中部放置中部设有毛细管的晶体生长模具，将原料BaTiO 3、Eu 2O 3、Lu 2O 3、Tb 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体； (1) Place a crystal growth mold with a capillary in the middle of the crucible, place the raw materials BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , and Tb 2 O 3 in the crucible, and heat the crucible to melt the raw materials to form a melt;
    （2）在模具顶部接籽晶提拉熔体，使籽晶在熔体的交界面上不断进行原子或分子重排，随降温逐渐凝固而生长出与模具边缘形状相同的单晶。... (2) The seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
实施例2Example 2
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为4：1：1，Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为1：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 4:1:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 1:100.
       上述复合单晶光纤及其制备方法，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof include the following steps:
    （1）在坩埚中部放置中部设有毛细管的晶体生长模具，将原料BaTiO 3、Eu 2O 3、Lu 2O 3、Tb 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体； (1) Place a crystal growth mold with a capillary in the middle of the crucible, place the raw materials BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , and Tb 2 O 3 in the crucible, and heat the crucible to melt the raw materials to form a melt;
    （2）在模具顶部接籽晶提拉熔体，使籽晶在熔体的交界面上不断进行原子或分子重排，随降温逐渐凝固而生长出与模具边缘形状相同的单晶。... (2) The seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
实施例3Example 3
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为2：3：1，Eu 4+、Lu 3+、Tb 3+的总摩尔  数与BaTiO3摩尔数之比为5：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 2:3:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 5:100.
    上述复合单晶光纤及其制备方法，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof include the following steps:
    （1）在坩埚中部放置中部设有毛细管的晶体生长模具，将原料BaTiO 3、Eu 2O 3、Lu 2O 3、Tb 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体； (1) Place a crystal growth mold with a capillary in the middle of the crucible, place the raw materials BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , and Tb 2 O 3 in the crucible, and heat the crucible to melt the raw materials to form a melt;
    （2）在模具顶部接籽晶提拉熔体，使籽晶在熔体的交界面上不断进行原子或分子重排，随降温逐渐凝固而生长出与模具边缘形状相同的单晶。... (2) The seed crystal is connected to the top of the mold to pull the melt, so that the seed crystal continuously rearranges atoms or molecules at the interface of the melt, and gradually solidifies as the temperature drops to grow a single crystal with the same shape as the edge of the mold.
    测试BaTiO 3、实施例1至3的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3的吸收特性。 Test BaTiO 3, 4+ / Lu 3+ / Tb 3+ complex to Example 1 of the single crystal fiber Eu 3: BaTiO 3 absorption characteristics.
    将样品制成直径1.0mm，长4mm的圆柱形光纤，两面经过仔细抛光后放到光纤耦合器中，以石英灯光源作为光源进行测量，测量光谱范围500-1000nm。结果显示，BaTiO 3、实施例1至3的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3在650nm附近均具有明显的吸收峰，而且，实施例1的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3在650nm附近的吸收峰最大，实施例2和3的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3在650nm附近的吸收峰少小；证明：复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3具有比BaTiO 3更优异的吸收特性。 The sample is made into a cylindrical optical fiber with a diameter of 1.0mm and a length of 4mm. The two sides are carefully polished and placed in a fiber coupler. The quartz lamp is used as the light source for measurement. The measurement spectrum ranges from 500 to 1000 nm. The results show, BaTiO 3, to the composite in Example 1 Single Crystal Fiber Eu 3 embodiment 4+ / Lu 3+ / Tb 3+: BaTiO 3 have obvious absorption peak around 650nm, and the composite single crystal of Embodiment 1 of the embodiment of the optical fiber Eu 4+ / Lu 3+ / Tb 3+ : BaTiO 3 maximum absorption peak in the vicinity of 650nm, a composite embodiment of Examples 2 and 3 the single crystal fiber Eu 4+ / Lu 3+ / Tb 3+ : BaTiO 3 in the vicinity of 650nm The absorption peak is small; it is proved that the composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 has better absorption characteristics than BaTiO 3.
       测试BaTiO 3、实施例1至3的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3的上转换效率。 Conversion efficiency of BaTiO 3: Test BaTiO 3, 4+ / Lu 3+ / Tb 3+ complex to Example 1 of the single crystal fiber Eu 3.
       用650nm的半导体激光器作为泵浦光源，对样品泵浦，并测量个样品的上转换光谱。结果显示：BaTiO 3有上转换光谱，但强度非常弱；然而，但是实施例1至3的复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3上转换光谱强度比BaTiO 3明显增强很多。 A 650nm semiconductor laser was used as the pump light source to pump the sample and measure the up-conversion spectrum of each sample. The results show: the BaTiO 3 has a spectral conversion, but the intensity is very weak; however, the Eu complex crystal fiber of Examples 1 to 3 4+ / Lu 3+ / Tb 3+: converting the spectral intensity significantly higher than 3 BaTiO BaTiO 3 Enhance a lot.
 To
       晶体纤维及其包层同步制备设备，包括下坩埚（1）、上坩埚（2）、坩埚支撑柱（3）、包层柱（4）；所述上坩埚（2）位于下坩埚（1）顶部且下坩埚（1）和上坩埚（2）之间通过坩埚支撑柱（3）连接；所述包层柱（4）一端位于下坩埚（1）内，且竖直穿过上坩埚（2），另一端位于上坩埚（2）上方；所述包层柱（4）内设有晶体光纤供料成形管（5）和包层供料成形管（6），所述包层供料成形管（6）为环形管道且环设于晶体光纤供料成形管（5）外。... Crystal fiber and its cladding synchronous preparation equipment, including a lower crucible (1), an upper crucible (2), a crucible support column (3), and a cladding column (4); the upper crucible (2) is located in the lower crucible (1) The top and the lower crucible (1) and the upper crucible (2) are connected by a crucible support column (3); one end of the cladding column (4) is located in the lower crucible (1) and vertically passes through the upper crucible (2) ), the other end is located above the upper crucible (2); the cladding column (4) is provided with a crystal optical fiber feeding forming tube (5) and a cladding feeding forming tube (6), the cladding feeding forming The tube (6) is a ring-shaped pipe and is looped outside the crystal fiber supply forming tube (5).
       制备多组分磷酸盐玻璃包层的复合单晶光纤。... Preparation of multi-component phosphate glass clad composite single crystal fiber.
实施例4 Example 4
       多组分磷酸盐玻璃包层的复合单晶光纤，包括光纤纤芯以及包覆于光纤纤芯外的包层材料；所述包层材料为多组分磷酸盐玻璃，所述光纤纤芯材料为复合单晶光纤，所述复合单晶光纤为Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 A multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为3：2：1，Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为3：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 3:2:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 3:100.
    上述复合单晶光纤及其制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
（1）在下坩埚内装入晶体光纤原料，在上坩埚内装入包层原料；加热下坩埚和上坩埚；所述晶体光纤原料为BaTiO3、Eu2O3、Lu2O3、Tb2O3，所述包层原料为多组分磷酸盐玻璃；多组分磷酸盐玻璃组成为：P 2O 5：55重量份；K 2O：15重量份；BaO：7.5重量份；Al 2O 3：15重量份； (1) Fill the lower crucible with crystal fiber raw materials, and load the upper crucible with cladding raw materials; heat the lower crucible and the upper crucible; the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass; the composition of multi-component phosphate glass is: P 2 O 5 : 55 parts by weight; K 2 O: 15 parts by weight; BaO: 7.5 parts by weight; Al 2 O 3 : 15 parts by weight;
（2）待晶体光纤原料和包层原料融化后在包层柱顶部种籽晶，由于毛细管作用，下坩埚内的晶体光纤原料熔体通过晶体光纤供料成形管达到包层柱顶，籽晶先接触到晶体光纤供料成形管内的晶体光纤原料熔体，开始放肩；(2) After the crystal fiber raw material and the cladding material are melted, the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
（3）晶体不断生长，由于毛细管作用，上坩埚内的包层原料熔体通过包层供料成形管达到包层柱顶，至晶体接触到包层供料成形管内的包层原料熔体，包层供料成形管内的包层原料熔体附着在光纤晶体外壁生长；从而光纤晶体和包层材料同步生长。(3) Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube until the crystal contacts the cladding material melt in the cladding feeding forming tube. The cladding material melt in the cladding supply forming tube is attached to the outer wall of the fiber crystal to grow; thus the fiber crystal and the cladding material grow simultaneously.
实施例5Example 5
       多组分磷酸盐玻璃包层的复合单晶光纤，包括光纤纤芯以及包覆于光纤纤芯外的包层材料；所述包层材料为多组分磷酸盐玻璃，所述光纤纤芯材料为复合单晶光纤，所述复合单晶光纤为Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 A multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为4：1：1，Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为1：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 4:1:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 1:100.
       上述复合单晶光纤及其制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
（1）在下坩埚内装入晶体光纤原料，在上坩埚内装入包层原料；加热下坩埚和上坩埚；所述晶体光纤原料为BaTiO3、Eu2O3、Lu2O3、Tb2O3，所述包层原料为多组分磷酸盐玻璃；多组分磷酸盐玻璃组成为：P 2O 5：45重量份；K 2O： 20重量份；BaO： 10重量份；Al 2O 3： 20重量份； (1) Fill the lower crucible with crystal fiber raw materials, and load the upper crucible with cladding raw materials; heat the lower crucible and the upper crucible; the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass; the composition of multi-component phosphate glass is: P 2 O 5 : 45 parts by weight; K 2 O: 20 parts by weight; BaO: 10 parts by weight; Al 2 O 3 : 20 parts by weight;
（2）待晶体光纤原料和包层原料融化后在包层柱顶部种籽晶，由于毛细管作用，下坩埚内的晶体光纤原料熔体通过晶体光纤供料成形管达到包层柱顶，籽晶先接触到晶体光纤供料成形管内的晶体光纤原料熔体，开始放肩；(2) After the crystal fiber raw material and the cladding material are melted, the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
（3）晶体不断生长，由于毛细管作用，上坩埚内的包层原料熔体通过包层供料成形管达到包层柱顶，至晶体接触到包层供料成形管内的包层原料熔体，包层供料成形管内的包层原料熔体附着在光纤晶体外壁生长；从而光纤晶体和包层材料同步生长。(3) Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube until the crystal contacts the cladding material melt in the cladding feeding forming tube. The cladding material melt in the cladding supply forming tube is attached to the outer wall of the fiber crystal to grow; thus the fiber crystal and the cladding material grow simultaneously.
实施例6Example 6
       多组分磷酸盐玻璃包层的复合单晶光纤，包括光纤纤芯以及包覆于光纤纤芯外的包层材料；所述包层材料为多组分磷酸盐玻璃，所述光纤纤芯材料为复合单晶光纤，所述复合单晶光纤为Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 A multi-component phosphate glass-clad composite single crystal optical fiber includes an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, and the optical fiber core material It is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
       复合单晶光纤Eu 4+/Lu 3+/Tb 3+: BaTiO 3；其中，Eu 4+、Lu 3+、Tb 3+的摩尔比为2：3：1，Eu 4+、Lu 3+、Tb 3+的总摩尔  数与BaTiO3摩尔数之比为5：100。 Composite single crystal fiber Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 ; wherein the molar ratio of Eu 4+ , Lu 3+ , Tb 3+ is 2:3:1, Eu 4+ , Lu 3+ , The ratio of the total number of moles of Tb 3+ to the number of moles of BaTiO3 is 5:100.
    上述复合单晶光纤及其制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：... The composite single crystal optical fiber and the preparation method thereof are prepared by the simultaneous preparation equipment of the crystal fiber and its cladding, including the following steps:
（1）在下坩埚内装入晶体光纤原料，在上坩埚内装入包层原料；加热下坩埚和上坩埚；所述晶体光纤原料为BaTiO3、Eu2O3、Lu2O3、Tb2O3，所述包层原料为多组分磷酸盐玻璃；多组分磷酸盐玻璃组成为：P 2O 5： 65重量份；K 2O：10重量份；BaO：5重量份；Al 2O 3：10重量份； (1) Fill the lower crucible with crystal fiber raw materials, and load the upper crucible with cladding raw materials; heat the lower crucible and the upper crucible; the crystal fiber raw materials are BaTiO3, Eu2O3, Lu2O3, Tb2O3, and the cladding raw materials are multi-component Phosphate glass; the composition of multi-component phosphate glass is: P 2 O 5 : 65 parts by weight; K 2 O: 10 parts by weight; BaO: 5 parts by weight; Al 2 O 3 : 10 parts by weight;
（2）待晶体光纤原料和包层原料融化后在包层柱顶部种籽晶，由于毛细管作用，下坩埚内的晶体光纤原料熔体通过晶体光纤供料成形管达到包层柱顶，籽晶先接触到晶体光纤供料成形管内的晶体光纤原料熔体，开始放肩；(2) After the crystal fiber raw material and the cladding material are melted, the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube. First touch the crystal fiber raw material melt in the crystal fiber supply forming tube, and begin to shoulder;
晶体不断生长，由于毛细管作用，上坩埚内的包层原料熔体通过包层供料成形管达到包层柱顶，至晶体接触到包层供料成形管内的包层原料熔体，包层供料成形管内的包层原料熔体附着在光纤晶体外壁生长；从而光纤晶体和包层材料同步生长。Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube, until the crystal contacts the cladding material melt in the cladding supply forming tube, and the cladding is supplied The cladding material melt in the material forming tube adheres to the outer wall of the fiber crystal to grow; thus, the fiber crystal and the cladding material grow simultaneously.

Claims (7)

  1. 一种多组分磷酸盐玻璃包层的复合单晶光纤，其特征在于：包括光纤纤芯以及包覆于光纤纤芯外的包层材料；所述包层材料为多组分磷酸盐玻璃，所述光纤纤芯材料为复合单晶光纤，所述复合单晶光纤为Eu 4+/Lu 3+/Tb 3+: BaTiO 3。 A multi-component phosphate glass-clad composite single crystal optical fiber, which is characterized in that it comprises an optical fiber core and a cladding material covering the fiber core; the cladding material is a multi-component phosphate glass, The fiber core material is a composite single crystal fiber, and the composite single crystal fiber is Eu 4+ /Lu 3+ /Tb 3+ : BaTiO 3 .
  2. 根据权利要求1所述的一种多组分磷酸盐玻璃包层的复合单晶光纤，其特征在于：所述复合单晶光纤中，Eu 4+、Lu 3+、Tb 3+的摩尔比为（2-4）：（1-3）：1。 The multi-component phosphate glass clad composite single crystal fiber according to claim 1, wherein the molar ratio of Eu 4+ , Lu 3+ , and Tb 3+ in the composite single crystal fiber is (2-4): (1-3):1.
  3. 根据权利要求1所述的一种多组分磷酸盐玻璃包层的复合单晶光纤，其特征在于：所述Eu 4+、Lu 3+、Tb 3+的总摩尔数与BaTiO3摩尔数之比为（1-5）：100。 The multi-component phosphate glass clad composite single crystal optical fiber according to claim 1, characterized in that: the ratio of the total number of moles of Eu 4+ , Lu 3+ , and Tb 3+ to the number of moles of BaTiO3 For (1-5): 100.
  4. 根据权利要求1所述的一种多组分磷酸盐玻璃包层的复合单晶光纤，其特征在于：所述多组分磷酸盐玻璃组成为：P 2O 5：45~65重量份；K 2O：10~20重量份；BaO：5~10重量份；Al 2O 3：10~20重量份。 The multi-component phosphate glass clad composite single crystal optical fiber according to claim 1, wherein the composition of the multi-component phosphate glass is: P 2 O 5 : 45-65 parts by weight; K 2 O: 10-20 parts by weight; BaO: 5-10 parts by weight; Al 2 O 3 : 10-20 parts by weight.
  5. 权利要求1所述的多组分磷酸盐玻璃包层的复合单晶光纤的制备方法，其特征在于：利用晶体纤维及其包层同步制备设备制得，包括以下步骤：The method for preparing a multi-component phosphate glass-clad composite single crystal optical fiber according to claim 1, characterized in that it is prepared by using a crystal fiber and its cladding synchronous preparation equipment, and comprises the following steps:
    在下坩埚内装入晶体光纤原料，在上坩埚内装入包层原料；加热下坩埚和上坩埚；Fill the lower crucible with crystal fiber raw materials, and load the upper crucible with cladding raw materials; heat the lower crucible and the upper crucible;
    待晶体光纤原料和包层原料融化后在包层柱顶部种籽晶，由于毛细管作用，下坩埚内的晶体光纤原料熔体通过晶体光纤供料成形管达到包层柱顶，籽晶先接触到晶体光纤供料成形管内的晶体光纤原料熔体，开始放肩；After the crystal fiber raw material and the cladding material are melted, the seed crystal is seeded on the top of the cladding column. Due to the capillary action, the crystal fiber raw material melt in the lower crucible reaches the top of the cladding column through the crystal fiber supply forming tube, and the seed crystal first touches The crystal fiber raw material melt in the crystal fiber feed forming tube begins to shoulder;
    晶体不断生长，由于毛细管作用，上坩埚内的包层原料熔体通过包层供料成形管达到包层柱顶，至晶体接触到包层供料成形管内的包层原料熔体，包层供料成形管内的包层原料熔体附着在光纤晶体外壁生长；从而光纤晶体和包层材料同步生长。Crystals continue to grow. Due to capillary action, the cladding material melt in the upper crucible reaches the top of the cladding column through the cladding supply forming tube, until the crystal contacts the cladding material melt in the cladding supply forming tube, and the cladding is supplied The cladding material melt in the material forming tube adheres to the outer wall of the fiber crystal to grow; thus, the fiber crystal and the cladding material grow simultaneously.
  6. 根据权利要求3所述的多组分磷酸盐玻璃包层的复合单晶光纤的制备方法，其特征在于：所述晶体纤维及其包层同步制备设备，包括下坩埚（1）、上坩埚（2）、坩埚支撑柱（3）、包层柱（4）；所述上坩埚（2）位于下坩埚（1）顶部且下坩埚（1）和上坩埚（2）之间通过坩埚支撑柱（3）连接；所述包层柱（4）一端位于下坩埚（1）内，且竖直穿过上坩埚（2），另一端位于上坩埚（2）上方；所述包层柱（4）内设有晶体光纤供料成形管（5）和包层供料成形管（6），所述包层供料成形管（6）为环形管道且环设于晶体光纤供料成形管（5）外。The method for preparing a multi-component phosphate glass-clad composite single crystal optical fiber according to claim 3, characterized in that: the crystal fiber and its cladding synchronous preparation equipment includes a lower crucible (1) and an upper crucible ( 2) Crucible support column (3), cladding column (4); the upper crucible (2) is located on the top of the lower crucible (1) and the crucible support column (1) and the upper crucible (2) pass between the lower crucible (1) and the upper crucible (2). 3) Connection; one end of the cladding column (4) is located in the lower crucible (1) and passes through the upper crucible (2) vertically, and the other end is located above the upper crucible (2); the cladding column (4) A crystal optical fiber supply forming tube (5) and a cladding supply forming tube (6) are arranged inside. The cladding supply forming tube (6) is an annular pipe and is looped around the crystal optical fiber supply forming tube (5) outer.
  7. 根据权利要求3所述的多组分磷酸盐玻璃包层的复合单晶光纤的制备方法，其特征在于：步骤（1）中，所述晶体光纤原料为BaTiO 3、Eu 2O 3、Lu 2O 3、Tb 2O 3。 The method for preparing a multi-component phosphate glass clad composite single crystal optical fiber according to claim 3, characterized in that: in step (1), the raw material of the crystal optical fiber is BaTiO 3 , Eu 2 O 3 , Lu 2 O 3 , Tb 2 O 3 .
     To
PCT/CN2019/115532 2019-11-05 2019-11-05 Composite single-crystal optical fiber clad with multi-component phosphate glass and preparation method thereof WO2021087717A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4315667A (en) * 1978-03-20 1982-02-16 Kokusai Denshin Denwa Kabushiki Kaisha Fiber for optical transmission having single crystal core
JPH0656595A (en) * 1992-08-13 1994-03-01 Fujikura Ltd Production of optical fiber made of barium titanate single crystal
US20140119692A1 (en) * 2012-11-01 2014-05-01 National Sun Yat-Sen University Optical fiber and method for manufacturing same
CN104797531A (en) * 2012-11-13 2015-07-22 关东电化工业株式会社 Coated barium titanate particulate and production method for same
CN109238499A (en) * 2018-08-31 2019-01-18 南京同溧晶体材料研究院有限公司 A kind of high-temperature resistant optical fiber temperature sensor
CN109269666A (en) * 2018-08-31 2019-01-25 南京同溧晶体材料研究院有限公司 A kind of cladded-fiber temperature sensor
CN110320592A (en) * 2019-07-04 2019-10-11 山东海富光子科技股份有限公司 A kind of single crystal glass composite fiber and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4315667A (en) * 1978-03-20 1982-02-16 Kokusai Denshin Denwa Kabushiki Kaisha Fiber for optical transmission having single crystal core
JPH0656595A (en) * 1992-08-13 1994-03-01 Fujikura Ltd Production of optical fiber made of barium titanate single crystal
US20140119692A1 (en) * 2012-11-01 2014-05-01 National Sun Yat-Sen University Optical fiber and method for manufacturing same
CN104797531A (en) * 2012-11-13 2015-07-22 关东电化工业株式会社 Coated barium titanate particulate and production method for same
CN109238499A (en) * 2018-08-31 2019-01-18 南京同溧晶体材料研究院有限公司 A kind of high-temperature resistant optical fiber temperature sensor
CN109269666A (en) * 2018-08-31 2019-01-25 南京同溧晶体材料研究院有限公司 A kind of cladded-fiber temperature sensor
CN110320592A (en) * 2019-07-04 2019-10-11 山东海富光子科技股份有限公司 A kind of single crystal glass composite fiber and preparation method thereof

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