硅酸盐学报

掺铒锆钛酸铅镧反铁电薄膜的反常电控光致发光效应

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高畅 ¹ , 张天祐 ¹ , 吴世喆 ² , 裴家杰 ¹ , 徐泽东 ³ , 赵纯林 ¹ , 吴啸 ¹ , 林枞 ¹ , 高旻 ¹

硅酸盐学报 | 研究论文 2026,54(6): 1883-1891

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硅酸盐学报 |研究论文 2026 , 54 (6) : 1883 -1891

掺铒锆钛酸铅镧反铁电薄膜的反常电控光致发光效应

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高畅¹, 张天祐¹, 吴世喆², 裴家杰¹, 徐泽东³, 赵纯林¹, 吴啸¹, 林枞¹, 高旻¹

作者信息

^1．福州大学材料科学与工程学院，福州 350108

^2．天津工业大学材料科学与工程学院，天津 300387

^3．天津工业大学电子与信息工程学院，量子材料与器件研究院，天津 300387

通讯作者:

高旻（1990—），男，博士，副教授。

作者简介:

高畅（2001—），女，硕士研究生。

Anomalous Electric-Field-Modulation of Photoluminescence in Er³⁺-Doped Antiferroelectric Pb_0.98La_0.02Zr_0.95Ti_0.05O₃ Thin Films

Chang GAO¹, Tianyou ZHANG¹, Shize WU², Jiajie PEI¹, Zedong XU³, Chunlin ZHAO¹, Xiao WU¹, Cong LIN¹, Min GAO¹

Affiliations

^1.College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China

^2.School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China

^3.Institute of Quantum Materials and Devices, School of Electronics and Information Engineering, Tiangong University, Tianjin 300387, China

Corresponding Author:

{GAO} Min (1990-), male, Ph.D., Associate Professor. E-mail: gaom@fzu.edu.cn

GAO Chang (2001-), female, Master candidate. E-mail: 13181731076@163.com

出版时间: 2026-05-12 doi: 10.14062/j.issn.0454-5648.20250928

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摘要

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光致发光效应的电场调控可以用于光信息存储与通信等领域。如何在薄膜材料中实现光致发光强度的巨幅调控至关重要。以铒离子（Er³⁺）掺杂的锆钛酸铅镧（Pb_0.98La_0.02Zr_0.95Ti_0.05O₃，PLZT-Er）反铁电薄膜为对象，深入分析其电控光致发光效应。在外加电场为830 kV·cm^-1时，可逆光致发光强度调控幅度达-85%，远超PLZT-Er陶瓷材料（+30%）。完全相反的电控光致发光变化趋势表明了PLZT-Er薄膜与陶瓷材料在电场作用下存在结构演化差异。PLZT-Er薄膜在电场作用下反常的光致发光强度减弱现象揭示了薄膜中Er³⁺周围局部晶体场对称性在电场调制下增强，其原因可归结于基底钳位效应导致的反铁电正交相向铁电正交相的相变过程，以及电场强度不足时亚铁电相向反铁电相的不完全相变。

关键词

稀土掺杂 / 光致发光 / 电场调控 / 相变 / 薄膜

Abstract

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Introduction

The photoluminescence (PL) of rare-earth-doped materials is predominantly controlled by the local crystal field symmetry around rare-earth ions. Using electric fields (E) to modify the PL properties is particularly intriguing as it is compatible with modern electronics and is promising for advanced applications in optical information storage and communication. It is reported that the E-induced structural evolution in host ferroelectrics (FEs) can effectively manipulate the crystal field environment surrounding rare-earth ions, consequently enabling a dynamic modulation of PL intensity (i.e., the E-PL effect). However, the hysteresis behavior in FEs limits the PL modulation range. Antiferroelectrics (AFEs) show a reversible AFE-FE phase transform with zero remanent polarization, particularly promising for realizing reversible E-PL modulation with large tunability. In AFE thin films, the clamping effect from the substrate may exert a significant influence on the structural evolution during the E-induce phase transition. Therefore, compared with the ceramic forms, it is possible to analyze distinct E-PL behavior in rare-earth doped AFE thin films.

Methods

1% Er³⁺-dopedPb_0.98La_0.02Zr_0.95Ti_0.05O₃ (PLZT-Er) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a sol-gel/spin-coating method with lead acetate trlhydrate (PbC₄H₆O₄·3H₂O, 99.99%(379.33), Aladdin Co., China), lanthanum nitrate hexahydrate (LaN₃O₉·6H₂O, 99%(433.03), Aladdin Co., China), erbium trinitrate pentahydrate (Er(NO₃)₃·5H₂O, 99.9%(443.37), Aladdin Co., China), zirconium propoxide (C₁₂H₂₈O₄Zr, 70%(327.56), Aladdin Co., China), and titanium butoxide (C₁₆H₃₆O₄Ti, ≥99.0%(340.32), Aladdin Co., China) as the raw materials. The crystal structure was characterized by X-ray diffraction (XRD, Ultima III, Rigaku Co., Japan). The surface morphology was observed using atomic force microscopy (AFM, ICON, Bruker Co., Germany). The polarization (P-E) and current (I-E) loops were measured by a ferroelectric analyzer (AIX ACT, TF2000) at 1 kHz. The down-conversion photoluminescence (DCPL) emission spectra were measured by fluorescence spectroscopy (ULS2048x64TEC, Avantes Co., the Netherlands) under 405 nm and 532 nm laser excitation. For the E-PL tests, 20 nm-thick transparent indium tin oxide (ITO) top electrodes were deposited on the surfaces of PLZT-Er thin film by magnetron sputtering in argon atmosphere (2.0 Pa) at 320 wd3.

Results and discussion

The structural, PL, and E-PL properties of PLZT-Er AFE thin films are systematically investigated. The XRD patterns confirm a pure perovskite structure with a lattice shrinkage due to the substitution of Er³⁺ at A-sites, whereas the AFM analysis reveals a smooth surface with a roughness of approximately 3 nm. The double P-E loop and characteristic I-E peaks verify the AFE nature of PLZT-Er thin films, with reversible AFE→FE transitions at ±452 kV·cm^-1 and FE→AFE transitions at ±199 kV·cm^-1. Under 405 nm excitation, the PLZT-Er exhibits 487 nm (⁴F_7/2→⁴I_15/2) and 610 nm (⁴F_9/2→⁴I_15/2) emissions, whereas an excitation at 532 nm induces 560 nm (⁴S_3/2→⁴I_15/2), 660 nm (⁴F_9/2→⁴I_15/2), and 850 nm (⁴S_3/2→⁴I_13/2) emissions, all originating from efficient energy transfer and relaxation of Er³⁺ ions. The reults of E-PL tests demonstrate a remarkable reversible modulation. In 830 kV·cm^-1, the emission at 487 nm shows an 85.14% reduction, with stable switching over six cycles. This performance outperforms PLZT-Er ceramics (+30% modulation) and most reported FE/AFE materials, which is attributed to their higher breakdown strength. The opposite E-PL tuning compared to PLZT-Er ceramics is explained by increased local crystal field symmetry around Er³⁺ ions, arising from either substrate clamping-induced antiferroelectric orthorombic →ferroelectric orthorombic phase transition or incomplete ferrielectric→antiferroelectric transition in an insufficient electric field. These findings highlight the PLZT-Er thin films as promising candidates for optical information storage and communication devices.

Conclusions

Er³⁺-doped Pb_0.98La_0.02Zr_0.95Ti_0.05O₃ (PLZT-Er) thin films exhibited a reversible electric-field-modulated photoluminescence (E-PL) effect. Under 405 nm laser excitation, a PL reduction of -85% could be achieved in an applied electric field of 830 kV·cm^-1. This negative E-PL tuning trend was anomalously opposite to that in bulk PLZT-Er ceramics. Two potential mechanisms could be proposed to explain this anomalous phenomenon, i.e., either the antiferroelectric orthorombic (AFE_O) to ferroelectric orthorombic (FE_O) phase transition or the incomplete ferrielectric (FiE) to antiferroelectric (AFE) phase transition in PLZT-Er thin films could increase the local crystal field symmetry around Er³⁺ ions.

Key words

rare-earth doping / photoluminescence / electric-field-modulation / phase transition / thin films

引用本文

高畅, 张天祐, 吴世喆, 裴家杰, 徐泽东, 赵纯林, 吴啸, 林枞, 高旻. 掺铒锆钛酸铅镧反铁电薄膜的反常电控光致发光效应. 硅酸盐学报, 2026 , 54 (6) : 1883 -1891 . DOI: 10.14062/j.issn.0454-5648.20250928

Chang GAO, Tianyou ZHANG, Shize WU, Jiajie PEI, Zedong XU, Chunlin ZHAO, Xiao WU, Cong LIN, Min GAO. Anomalous Electric-Field-Modulation of Photoluminescence in Er³⁺-Doped Antiferroelectric Pb_0.98La_0.02Zr_0.95Ti_0.05O₃ Thin Films[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (6) : 1883 -1891 . DOI: 10.14062/j.issn.0454-5648.20250928

基金

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国家自然科学基金(52102126; 52072075; 12104093)
福建省自然科学基金(2022J01087; 2022J01552; 2025J01470)
天津市光电检测技术与系统重点实验室开放项目(2024LODTS101)

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2026年第54卷第6期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250928

接收时间：2025-12-24
首发时间：2026-10-22
出版时间：2026-05-12

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出版历史

收稿日期：2025-12-24
修回日期：2026-01-28

基金

国家自然科学基金(52102126; 52072075; 12104093)

福建省自然科学基金(2022J01087; 2022J01552; 2025J01470)

天津市光电检测技术与系统重点实验室开放项目(2024LODTS101)

作者信息

^1．福州大学材料科学与工程学院，福州 350108

^2．天津工业大学材料科学与工程学院，天津 300387

^3．天津工业大学电子与信息工程学院，量子材料与器件研究院，天津 300387

通讯作者:

高旻（1990—），男，博士，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250928

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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