WO2021087716A1 - 一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法 - Google Patents

一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法 Download PDF

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WO2021087716A1
WO2021087716A1 PCT/CN2019/115531 CN2019115531W WO2021087716A1 WO 2021087716 A1 WO2021087716 A1 WO 2021087716A1 CN 2019115531 W CN2019115531 W CN 2019115531W WO 2021087716 A1 WO2021087716 A1 WO 2021087716A1
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crystal
cladding
lutetium
phosphate glass
europium
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PCT/CN2019/115531
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English (en)
French (fr)
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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/CN2019/115531 priority Critical patent/WO2021087716A1/zh
Publication of WO2021087716A1 publication Critical patent/WO2021087716A1/zh

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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 sapphire crystal material doped with europium and lutetium coated with phosphate glass 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 sapphire crystal material doped with europium and lutetium coated with phosphate glass and a preparation method thereof.
  • the invention provides a phosphate glass-coated europium-lutetium-doped sapphire crystal material comprising a europium-lutetium-alumina sapphire crystal and a cladding material coated on the europium-lutetium-alumina sapphire crystal; the cladding material is A multi-component phosphate glass doped with polycrystalline alumina, the europium lutetium-alumina sapphire crystal material is Eu 4+ /Lu 3+ : Ti 3+ : Al 2 O 3 .
  • the molar ratio of Eu 4+ and Lu 3+ is (8-12):1.
  • the ratio of the total number of moles of Eu 4+ and Lu 3+ to the number of moles of Ti 3+ :Al 2 O 3 is (1-5):100.
  • the content of polycrystalline alumina is 5-15%.
  • composition of the multi-component phosphate glass is: P 2 O 5 : 45 to 65 parts by weight; K 2 O: 10 to 20 parts by weight; BaO: 5 to 10 parts by weight; Al 2 O 3 : 10 to 20 parts by weight Parts by weight.
  • the present invention also provides a method for preparing the phosphate glass-coated europium-lutetium-doped sapphire crystal material, which is prepared by using the crystal fiber and its cladding synchronous preparation equipment, including 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 raw materials are Al 2 O 3 , Ti 2 O 3 , Eu 2 O 3 , and Lu 2 O 3 .
  • the cladding material is a multi-component phosphate glass doped with polycrystalline alumina.
  • the phosphate glass-coated europium-lutetium-doped sapphire crystal material provided by the present invention adopts an optical fiber core and a cladding material covering the fiber core.
  • the optical fiber core has a simple preparation process and has excellent absorption characteristics and up-conversion The strength greatly improves the application range of the sapphire fiber;
  • the cladding material uses multi-component phosphate glass doped with polycrystalline alumina, 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.
  • Sapphire laser crystal material material Eu 4+ /Lu 3+ :Al 2 O 3 .
  • the molar ratio of Eu 4+ and Lu 3+ is 8:1; the ratio of the total number of moles of Eu 4+ and Lu 3+ to the number of moles of Ti 3+ :Al 2 O 3 is 3. : 100.
  • the preparation method of the sapphire laser crystal material includes 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.
  • Sapphire laser crystal material material Eu 4+ /Lu 3+ :Al 2 O 3 .
  • the molar ratio of Eu 4+ and Lu 3+ is 12:1; the ratio of the total molar number of Eu 4+ and Lu 3+ to the molar number of Ti 3+ :Al 2 O 3 is 1. : 100.
  • the preparation method of the sapphire laser crystal material includes 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.
  • Sapphire laser crystal material material Eu 4+ /Lu 3+ :Al 2 O 3 .
  • the molar ratio of Eu 4+ and Lu 3+ is 10:1; the ratio of the total molar number of Eu 4+ and Lu 3+ to the molar number of Ti 3+ :Al 2 O 3 is 5. : 100.
  • the preparation method of the sapphire laser crystal material includes 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 was made into a cylindrical optical fiber with a diameter of 1.0mm and a length of 4mm. The two sides were carefully polished and placed in a fiber coupler. The quartz lamp was used as the light source for measurement. The measurement spectrum range was 400-1000nm.
  • a 560nm 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 that Ti 3+ :Al 2 O 3 has an up-conversion spectrum; the sapphire laser crystal material Eu 4+ /Lu 3+ :Al 2 O 3 of Examples 1 to 3 has an up-conversion spectrum intensity ratio Ti 3+ :Al 2 O 3 is obviously enhanced a lot.
  • a sapphire crystal material doped with europium and lutetium coated with phosphate glass was prepared.
  • Phosphate glass coated europium-lutetium-doped sapphire crystal material including europium-lutetium-alumina sapphire crystal and a cladding material coated on the europium-lutetium-alumina sapphire crystal; the cladding material is doped polycrystalline oxide
  • a multi-component phosphate glass of aluminum, the europium lutetium-alumina sapphire crystal material is Eu 4+ /Lu 3+ :Al 2 O 3 .
  • the method for preparing the phosphate glass-coated europium-lutetium-doped sapphire crystal material is prepared by the simultaneous preparation equipment of crystal fiber and its cladding, and includes the following steps:
  • the cladding material is a multi-component phosphate glass doped with polycrystalline alumina, the content of polycrystalline alumina is 10 parts by weight, and the content of Er 3+ is 1 part by weight, based on parts by weight
  • the composition of the 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;
  • Phosphate glass coated europium-lutetium-doped sapphire crystal material including europium-lutetium-alumina sapphire crystal and a cladding material coated on the europium-lutetium-alumina sapphire crystal; the cladding material is doped polycrystalline oxide
  • a multi-component phosphate glass of aluminum, the europium lutetium-alumina sapphire crystal material is Eu 4+ /Lu 3+ :Al 2 O 3 .
  • the ratio of 3+ :Al 2 O 3 moles is 1:100.
  • the method for preparing the phosphate glass-coated europium-lutetium-doped sapphire crystal material is prepared by the simultaneous preparation equipment of crystal fiber and its cladding, and includes the following steps:
  • the cladding material is a multi-component phosphate glass doped with polycrystalline alumina, the content of polycrystalline alumina is 5 parts by weight, and the content of Er 3+ is 0.5 parts by weight, based on parts by weight
  • 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;
  • Phosphate glass coated europium-lutetium-doped sapphire crystal material including europium-lutetium-alumina sapphire crystal and a cladding material coated on the europium-lutetium-alumina sapphire crystal; the cladding material is doped polycrystalline oxide
  • a multi-component phosphate glass of aluminum, the europium lutetium-alumina sapphire crystal material is Eu 4+ /Lu 3+ :Al 2 O 3 .
  • Sapphire laser crystal material Eu 4+ /Lu 3+ :Al 2 O 3 among them, the molar ratio of Eu 4+ and Lu 3+ is 2:3:1, and the total number of moles of Eu 4+ and Lu 3+ is the same as Ti 3 + : The ratio of the number of moles of Al 2 O 3 is 5:100.
  • the phosphate glass-coated europium-lutetium-doped sapphire crystal material and its preparation method are prepared by using crystal fiber and its cladding synchronous preparation equipment, including the following steps:
  • the cladding material is a multi-component phosphate glass doped with polycrystalline alumina, the content of polycrystalline alumina is 15 parts by weight, and the content of Er 3+ is 1.5 parts by weight, based on parts by weight
  • 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;

Abstract

本发明提供的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+:Al 2O 3。本发明还提供了上述磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料的制备方法。本发明提供的磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料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，大大提高了蓝宝石材料的应用范围；包层材料使用掺杂多晶氧化铝的多组分磷酸盐玻璃，成本低，而且可以能够满足全反射的要求。

Description

一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法 技术领域
本发明涉及光纤技术领域，特别一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法。
 背景技术
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、集成光电系统等领域具有重要的应用潜力而受到广泛的关注。
    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。
    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。
    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。
 技术问题
为了解决现有技术的缺陷，本发明提供了一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法。
 技术解决方案
本发明提供的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+: Ti 3+:Al 2O 3。
其中，Eu 4+、Lu 3+的摩尔比为（8-12）：1。
其中，所述Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为（1-5）：100。
其中，所述多组分磷酸盐玻璃中，多晶氧化铝的掺量为5-15%。
其中，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。
本发明还提供了上述磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料的制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：
（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；
（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；
（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。
步骤（1）中，所述晶体光纤原料为Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3。
步骤（1）中，所述包层原料为掺杂多晶氧化铝的多组分磷酸盐玻璃。
 有益效果
本发明提供的磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料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，大大提高了蓝宝石光纤的应用范围；包层材料使用掺杂多晶氧化铝的多组分磷酸盐玻璃，成本低，而且可以能够满足全反射的要求。
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。
 本发明的最佳实施方式
下面对本发明作出进一步说明。
       制备蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3。
实施例1
蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3。
蓝宝石激光晶体材料材料中，Eu 4+、Lu 3+的摩尔比为8：1；所述Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为3：100。
所述蓝宝石激光晶体材料材料的制备方法，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体；
       （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。
实施例2
蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3。
蓝宝石激光晶体材料材料中，Eu 4+、Lu 3+的摩尔比为12：1；所述Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为1：100。
所述蓝宝石激光晶体材料材料的制备方法，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体；
       （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。
实施例3
蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3。
蓝宝石激光晶体材料材料中，Eu 4+、Lu 3+的摩尔比为10：1；所述Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为5：100。
所述蓝宝石激光晶体材料材料的制备方法，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3置于坩埚中，加热坩埚使原料熔化形成熔体；
       （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。
 
    测试Ti 3+:Al 2O 3、实施例1至3的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3的吸收特性。
    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400-1000nm。结果显示，Ti 3+:Al 2O 3、实施例1至3的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3在560nm附近均具有明显的吸收峰，而且，实施例1的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3在560nm附近的吸收峰最大，实施例2和3的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3在560nm附近的吸收峰少小；证明：蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3具有比Ti 3+:Al 2O 3更优异的吸收特性。
      
    测测试Ti 3+:Al 2O 3、实施例1至3的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3的上转换效率。
       用560nm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：Ti 3+:Al 2O 3有上转换光谱；实施例1至3的蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3上转换光谱强度比Ti 3+:Al 2O 3明显增强很多。
 
       制备磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料。
实施例4
       磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+:Al 2O 3。
       蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3；其中，Eu 4+、Lu 3+的摩尔比为3：2：1，Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为3：100。
    上述磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3，所述包层原料为掺杂多晶氧化铝的多组分磷酸盐玻璃，多晶氧化铝的掺量为10重量份，Er 3+的掺量为1重量份，以重量份计；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；
（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；
（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。
实施例5
       磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+:Al 2O 3。
       蓝宝石激光晶体材料材料Eu 4+/Lu 3+:Al 2O 3；其中，Eu 4+、Lu 3+的摩尔比为4：1：1，Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为1：100。
       上述磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3，所述包层原料为掺杂多晶氧化铝的多组分磷酸盐玻璃，多晶氧化铝的掺量为5重量份，Er 3+的掺量为0.5重量份，以重量份计；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；
（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；
（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。
实施例6
       磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+:Al 2O 3。
       蓝宝石激光晶体材料Eu 4+/Lu 3+:Al 2O 3；其中，Eu 4+、Lu 3+的摩尔比为2：3：1，Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为5：100。
    上述磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法，利用晶体纤维及其包层同步制备设备制得，包括以下步骤：
（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Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3，所述包层原料为掺杂多晶氧化铝的多组分磷酸盐玻璃，多晶氧化铝的掺量为15重量份，Er 3+的掺量为1.5重量份，以重量份计；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；
（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；
（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。
 

Claims (8)

  1. 一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，其特征在于：包括铕镥-氧化铝蓝宝石晶体以及包覆于铕镥-氧化铝蓝宝石晶体外的包层材料；所述包层材料为掺杂多晶氧化铝的多组分磷酸盐玻璃，所述铕镥-氧化铝蓝宝石晶体材料为Eu 4+/Lu 3+: Ti 3+:Al 2O 3。
  2. 根据权利要求1所述的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，其特征在于：Eu 4+、Lu 3+的摩尔比为（8-12）：1。
  3. 根据权利要求1所述的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，其特征在于：所述Eu 4+、Lu 3+的总摩尔数与Ti 3+:Al 2O 3摩尔数之比为（1-5）：100。
  4. 根据权利要求1所述的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，其特征在于：所述多组分磷酸盐玻璃中，多晶氧化铝的掺量为5-15%。
  5. 根据权利要求1所述的一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料，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。
  6. 权利要求1所述的磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料的制备方法，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：
    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；
    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；
    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。
  7. 根据权利要求3所述的磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料的制备方法，其特征在于：步骤（1）中，所述晶体光纤原料为Al 2O 3、Ti 2O 3、Eu 2O 3、Lu 2O 3。
  8. 根据权利要求3所述的磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料的制备方法，其特征在于：步骤（1）中，所述包层原料为掺杂多晶氧化铝的多组分磷酸盐玻璃。
PCT/CN2019/115531 2019-11-05 2019-11-05 一种磷酸盐玻璃包覆铕镥掺杂的蓝宝石晶体材料及其制备方法 WO2021087716A1 (zh)

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