| 52 | 0 | 113 |
| 下载次数 | 被引频次 | 阅读次数 |
1.5～1.7μm人眼安全波段激光在激光测距、激光雷达和光通信等领域具有重要应用。然而，现有的Er:YAG、Er:LuYO3等激光晶体受限于较小的发射截面或晶体尺寸，难以满足高功率、大型化激光器的需求。因此，开发兼具大尺寸和高发射截面的新型激光晶体已成为当前研究的热点。本工作采用冷坩埚法生长了稀土掺杂钇稳定氧化锆(YSZ)晶体，晶体呈<111>择优生长取向，单体直径和长度都超过150 mm(6英寸)，是目前所知最大的YSZ单晶。研究了Er掺杂YSZ晶体的吸收、发射光谱。结果表明，在971 nm波长激发下，YSZ:Er晶体在1530 nm处表现出强发射峰，对应~4I13/2→~4F15/2跃迁；发射截面随Er3+含量变化，Er3+含量为1.60%(摩尔分数，下同)时为4.811×10–20 cm2；荧光寿命随着Er3+含量增加逐渐减小，Er3+含量为1.60%时荧光寿命为1.149 ms。通过掺杂离子和掺杂浓度的优化，YSZ:Er晶体有望成为一种潜在的激光晶体材料。
Abstract：Introduction Lasers operating within a spectral range of 1.5-1.7 μm are essential for eye-safe applications like laser ranging, lidar, and optical communications, etc.. Nevertheless, conventional laser crystals such as Er:YAG and Er:LuYO3 have limitations in emission cross-sections or attainable crystal dimensions, thereby constraining their utilization in high-power, large-scale laser systems. To address these challenges, the development of novel laser crystals with substantial crystal sizes and high emission cross-sections is thus imperative. Yttria-stabilized zirconia(YSZ) doped with rare-earth ions emerges as a promising candidate due to its disordered crystalline structure that enables a broader wavelength tunability and a reduced thermal loading under resonant pumping conditions. Specifically, erbium(Er3+) doped YSZ crystals have a significant potential due to its intense emission at 1.5 μm(~4I13/2→~4F15/2 transition) for eye-safe laser. This study was to investigate the growth of large-scale Er3+-doped YSZ crystals by a skull melting technique, and the optical and spectral properties were systematically investigated to explore a novel laser gain medium in the infra-red region. Methods Pure YSZ and Er3+-doped YSZ crystals(i.e., 0.36%, 1.60% and 2.54% in mole) were grown by a skull melting method(or a cold crucible technique), and a radio frequency(RF) generator was used to heat up the charges. A large-scale furnace with a diameter of approximately 150 cm was employed to accommodate the spontaneous nucleation. Graphite electrodes were used for initial arcing due to the poor conductivity of ZrO2 at < 1200 ℃. At >1200 ℃, raw materials became an electric conductor to form the melting pool. The lowering mechanism started to work at a lowering rate of 2 mm/h, and the melt crystallized from the bottom to the top. After the growth, annealing process was performed to release the internal stresses. The phase and crystal structures of as-grown crystals were characterized by X-ray diffraction(XRD). The transmittance and absorption properties were analyzed by UV-Vis-NIR spectroscopy. The luminescence and decay curve were also systematically evaluated. Results and Discussion The results show that Large-sized YSZ and Er-doped YSZ crystals with the diameters and lengths of exceeding 150 mm(6 inches) are grown, representing the largest YSZ single crystals reported. The XRD patterns indicate the cubic structure with a preferred <111> preferred orientation. The lattice parameters increase slightly with Er3+ concentration, indicating the effective incorporation of Er3+ into the YSZ lattice. The transmission of exceeding 74% in the range of 400-1650 nm occurs for pure YSZ crystals, confirming relatively high crystalline qualities. The absorption spectra for Er-doped crystals show some characteristic peaks at 378, 408, 451, 489, 518, 546, 654, 971, 1460 nm and 1530 nm, corresponding to Er3+ transitions from the ground state ~4F15/2 to excited states such as ~4G11/2 and ~4F11/2. The most intense absorption band occurs at 971 nm, which is attributed to the ~4F15/2→~4F11/2 transition. Under 971 nm excitation, the emission spectra exhibit a dominant peak at 1530 nm for the ~4I13/2→~4F15/2 transition, which is ideal for eye-safe lasers. The great emission intensity appears at an Er3+ mole concentration of 1.60%, with an emission cross-section of 4.811×10--20 cm2, which is significantly higher than that of Er:YAG(i.e., 0.6×10-20 cm2) and Er:LuYO3(i.e., 0.261×10-20 cm2). Correspondingly, the decay time of YSZ: 0.36, YSZ: 1.60 and YSZ: 2.54 crystals is 1.836 ms, 1.149 ms and 0.797 ms, respectively. Conclusions This study demonstrated the effective growth of large-scale(6-inch) YSZ and Er-doped YSZ crystals by a skull melting method. YSZ: Er crystals exhibited an intense emission at 1530 nm under 971 nm excitation. In particular, a high emission cross-section of 4.811×10-20 cm2 and suitable fluorescence lifetime of 1.149 ms appeared for Er3+ of 1.60% in mole. YSZ:Er crystals could be used as a highly promising gain medium for high-power, eye-safe lasers at 1.5 μm due to the ultra-large crystal size and relatively large emission cross-section.
[1] MALASHKEVICH G E, SIGAEV V N, GOLUBEV N V, et al.Luminescence of borogermanate glasses activated by Er3+and Yb3+ions[J]. J Non Cryst Solids, 2011, 357(1):67–72.
[2] LISIECKI R, RYBA-ROMANOWSKI W, CAVALLI E, et al. Optical spectroscopy of Er3+-doped LaVO4 crystal[J]. J Lumin, 2010, 130(1):131–136.
[3] JABA N, AJROUD M, PANCZER G, et al. Optical characterizations of Er3+-doped KLa(PO3)4 phosphate crystals[J]. Opt Mater, 2010, 32(3):479–483.
[4] GHEORGHE C, GEORGESCU S, LUPEI V, et al. Absorption intensities and emission cross section of Er3+in Sc2O3 transparent ceramics[J]. J Appl Phys, 2008, 103(8):083116.
[5] SETZLER S D, FRANCIS M P, YOUNG Y E, et al. Resonantly pumped eyesafe erbium lasers[J]. IEEE J Sel Top Quantum Electron,2005, 11(3):645–657.
[6] POLLACK S A, CHANG D B, MCFARLANE R A, et al. Infrared(Er)BaY2F8 laser pumped through di-and tri-ionic upconversion processes[J]. J Appl Phys, 1990, 67(2):648–653.
[7] HEHLEN M P, COCKROFT N J, GOSNELL T R, et al. Spectroscopic properties of Er3+-and Yb3+-doped soda-lime silicate and aluminosilicate glasses[J]. Phys Rev B, 1997, 56(15):9302–9318.
[8] SHOJIYA M, TAKAHASHI M, KANNO R, et al. Upconversion luminescence of Er3+in chloride glasses based on ZnCl2 or CdCl2[J].Appl Phys Lett, 1994, 65(15):1874–1876.
[9] POLLACK S A, CHANG D B. Ion-pair upconversion pumped laser emission in Er3+ions in YAG, YLF, SrF2, and CaF2 crystals[J]. J Appl Phys, 1988, 64(6):2885–2893.
[10] SARDAR D K, BRADLEY W M, PEREZ J J, et al. Judd–Ofelt analysis of the Er3+(4f11)absorption intensities in Er3+-doped garnets[J]. J Appl Phys, 2003, 93(5):2602–2607.
[11] SPARIOSU K, BIRNBAUM M. Intracavity 1.549-μm mu/m pumped1.634-μm mu/m Er:YAG lasers at 300 K[J]. IEEE J Quantum Electron,1994, 30(4):1044–1049.
[12] GARBUZOV D, KUDRYASHOV I, DUBINSKII M. Resonantly diode laser pumped 1.6-μm-erbium-doped yttrium aluminum garnet solid-state laser[J]. Appl Phys Lett, 2005, 86(13):131115.
[13]于浩海,潘忠奔,张怀金,等.无序激光晶体及其超快激光研究进展[J].人工晶体学报, 2021, 50(4):648–668.YU Haohai, PAN Zhongben, ZHANG Huaijin, et al. J Synth Cryst,2021, 50(4):648–668.
[14] KAMINSKII A A. Achievements of modern crystal-laser physics[J].Ann Phys Fr, 16(6):639–706.
[15] ALEKSANDROV V I, VISHNYAKOVA M A, VO?TSITSKI?V P,et al. Fianite(ZrO2–Y2O3:Er3+)laser emitting the 3-μm range[J]. Sov J Quantum Electron, 1989, 19(12):1555–1556.
[16] VORON’KO Y K, VISHNYAKOVA M A, LOMONOVA E E, et al.Spectroscopy of Yb3+in cubic ZrO2 crystals[J]. Inorg Mater, 2004,40(5):502–508.
[17] RYABOCHKINA P A, BORIK M A, KULEBYAKIN A V, et al.Structure and spectral-luminescence properties of yttrium-stabilized zirconia crystals activated with Tm3+ions[J]. Opt Spectrosc, 2012,112(4):594–600.
[18] ZHANG D B, HE X M, CHEN J P, et al. Research on crystal growth and defects in cubic zirconia[J]. J Cryst Growth, 1986, 79(1–3):336–340.
[19]徐家跃,展宗贵,张道标,等.壳熔法生长技术及其应用[J].人工晶体学报, 2009, 38(1):101–106.XU Jiayue, ZHAN Zonggui, ZHANG Daobiao, et al. J Synth Cryst,2009, 38(1):101–106.
[20]徐家跃,周鼎,李志超.超高温氧化物晶体及其生长技术[J].应用技术学报, 2017, 17(4):283–288.XU Jiayue, ZHOU Ding, LI Zhichao. J Technol, 2017, 17(4):283–288.
[21] XU J Y, LEI X Y, JIANG X, et al. Industrial growth of yttria-stabilized cubic zirconia crystals by skull melting process[J]. J Rare Earths, 2009,27(6):971–974.
[22]徐家跃,蒋新,陈宇轩,等.冷坩埚法生长5t批量钇稳定立方氧化锆晶体[J].应用技术学报, 2024, 24(4):385–389.XU Jiayue, JIANG Xin, CHEN Yuxuan, et al. J Technol, 2024, 24(4):385–389.
[23]张保童,王燕,李坚富,等.共掺稀土离子对Er3+激活中红外激光晶体光谱性能的影响[J].应用化学, 2016, 33(9):994–1001.ZHANG Baotong, WANG Yan, LI Jianfu, et al. Chin J Appl Chem,2016, 33(9):994–1001.
[24] WANG S, LI C L, LI Y Z, et al. Orthogonally polarized dual-wavelength Nd:LiYF4 laser at 903 and 908 nm on 4F3/2→4I9/2transition[J]. Opt Laser Technol, 2025, 180:111510.
[25] ZHANG Y, HU S C, TIAN T, et al. Growth and spectral properties of Er3+and Yb3+co-doped bismuth silicate single crystal[J]. Crystals,2022, 12(11):1532.
[26] YANG Y H, XU S L, LI S Y, et al. Luminescence properties of Ho2O3-doped Y2O3 stabilized ZrO2 single crystals[J]. Crystals, 2022,12(3):415.
[27]陈旭阳,周婉玲,胡辉,等. Er掺杂Cs2AgBiBr6薄膜光电探测性能研究[J].材料科学, 2023, 13(4):270-281.CHEN X Y, ZHOU W L, HU H, et al. Performance Study of Er-Doped Cs2AgBiBr6 Thin Film Photodetectors[J]. Mater Sci, 2023, 13(4):270–281.
[28] RUIZ-CARIDAD A, MARCAUD G, DURAN-VALDEIGLESIAS E,et al. Heterogeneous integration of doped crystalline zirconium oxide for photonic applications[J]. IEEE J Sel Top Quantum Electron, 2022,28(3:Hybrid Integration for Silicon Photonics):6100413.
[29] RUIZ-CARIDAD A, MARCAUD G, RAMIREZ J M, et al.Erbium-doped yttria-stabilised zirconia thin films grown by pulsed laser deposition for photonic applications[J]. Thin Solid Films, 2020,693:137706.
[30] MARCAUD G, MATZEN S, ALONSO-RAMOS C, et al.High-quality crystalline yttria-stabilized-zirconia thin layer for photonic applications[J]. Phys Rev Materials, 2018, 2(3):035202.
[31] SCHWEIZER T, JENSEN T, HEUMANN E, et al. Spectroscopic properties and diode pumped 1.6μm laser performance in Yb-codoped Er:Y3Al5O12 and Er:Y2SiO5[J]. Opt Commun, 1995, 118(5–6):557–561.
[32] CHEN G Z, LI S M, FANG Q N, et al. Growth and spectroscopy of Er:LuYO3 single crystal[J]. J Lumin, 2021, 239:118347.
[33] SHAO Y Q, CHEN Y Z, MA Z Z, et al. Growth and spectroscopic properties investigation of Er-doped BGSO single crystal:A potential gain medium for eye-safe laser[J]. Ceram Int, 2023, 49(11):17534–17541.
[34] ZHOU L, HUANG F, REN G, et al. Efficient Er3+:4I11/2→4I13/2radiative transition regulated by optimizing the sensitization mechanism[J]. Spectrochim Acta A Mol Biomol Spectrosc, 2020, 228:117853.
[35] TAN X J, XU S L, LIU F H, et al. Highly efficient up-conversion green emission in Ho/Yb Co-doped yttria-stabilized zirconia single crystals[J]. J Lumin, 2019, 209:95–101.
[36] GOPI S, REMYA MOHAN P, SREEJA E, et al. Optical characteristics of Dy3+ions in alkali fluoroborate glasses for WLEDs[J]. J Electron Mater, 2019, 48(7):4300–4309.
[37]陈炳炎,刘粤惠,陈东丹,等. Te O2–ZnO–Na2O–K2O玻璃中Er3+离子掺杂浓度对其发光及荧光寿命的影响[J].物理学报, 2005, 54(7):3418–3423.CHEN Bingyan, LIU Yuehui, CHEN Dongdan, et al. Acta Phys Sin,2005, 54(7):3418–3423.
[38] SOKóLSKA I, HEUMANN E, KüCK S, et al. Laser oscillation of Er3+:YVO4 and Er3+, Yb3+:YVO4 crystals in the spectral range around1.6μm[J]. Appl Phys B, 2000, 71(6):893–896.
[39] LISIECKI R, RYBA-ROMANOWSKI W, CAVALLI E, et al. Optical spectroscopy of Er3+-doped LaVO4 crystal[J]. J Lumin, 2010, 130(1):131–136.
[40] SOYEZ G, EASTMAN J A, THOMPSON L J, et al.Grain-size-dependent thermal conductivity of nanocrystalline yttria-stabilized zirconia films grown by metal–organic chemical vapor deposition[J]. Appl Phys Lett, 2000, 77(8):1155–1157.
基本信息:
DOI：10.14062/j.issn.0454-5648.20250442
中图分类号:O782;O734
引用信息:
[1]陈宇轩,蒋新,申慧,等.直径6英寸YSZ:Er晶体生长与光谱[J].硅酸盐学报,2025,53(12):3476-3483.DOI:10.14062/j.issn.0454-5648.20250442.
基金信息:
国家自然科学基金(51572175)