硅酸盐学报

Pb(Zr_xTi₁-x)O₃铁电基自驱动紫外光电探测器的制备与性能

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王梓赫 , 黄敏捷 , 张清风

硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026,54(4): 1202-1209

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硅酸盐学报 | 第15届无机非金属材料专题研讨会专题(一)——研究论文 2026, 54(4): 1202-1209

Pb(Zr_xTi₁-x)O₃铁电基自驱动紫外光电探测器的制备与性能

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王梓赫, 黄敏捷, 张清风

作者信息

湖北大学材料科学与工程学院，武汉 430062

王梓赫（2002—），男，硕士研究生。

WANG Zihe (2002-), male, Master candidate. E-mail: 627527318@qq.com

通讯作者:

张清风（1983—），男，教授。

Preparation and Properties of Self-driven Ultraviolet Photodetectors Based on Pb(Zr_xTi₁-x)O₃ Ferroelectric Materials

Zihe WANG, Minjie HUANG, Qingfeng ZHANG

Affiliations

Hubei Key Laboratory of Micro-Nanoelectronic Materials and Devices, School of Materials Science and Engineering, Hubei University, Wuhan 430062, China

出版时间: 2026-03-09 doi: 10.14062/j.issn.0454-5648.20250810

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摘要

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传统自供电紫外光探测器通常基于p-n结或肖特基结界面效应设计，然而由于光生电子和空穴无法有效分离，其响应度和探测率往往较低。与半导体材料不同，铁电材料通常拥有起源于自身大剩余极化强度且能贯穿整体的高退极化电场，因此可实现光生电子与空穴有效分离。基于此，本工作通过溶胶-凝胶工艺精准调控锆钛比例，制备出了不同锆钛比的Pb（Zr_xTi_1-_x）O₃（PZT）铁电薄膜和光电性能优异的Au/PZT/FTO自驱动紫外光电探测器，并系统研究了组分对薄膜晶体结构、表面形貌、铁电性能及器件光电响应特性的影响规律。微结构测试表明：不同锆钛比的PZT薄膜均拥有优良的结晶质量和纯的钙钛矿相结构，且薄膜表面平整致密。铁电性能测试揭示：所有组分的PZT薄膜均展现出了良好的铁电性（退极化电场）且最大剩余极化强度高达32.1 μC/cm²。光电测试结果发现：当锆钛比为0.52∶0.48时，器件的光电性能最为优异，在320 nm紫外光间歇照射下表现出稳定且可重复的光电流响应，且在-2 V电压极化下，器件的响应度和探测率均显著提升。

关键词

锆钛酸铅 / 铁电薄膜 / 溶胶-凝胶 / 自驱动紫外光电探测器

Abstract

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Introduction

With the advancement of the era, the demand for ultraviolet photodetectors in environmental monitoring and communication security continues to grow, leading to increasingly stringent performance requirements. In this case, self-driven ultraviolet photodetectors emerge to meet the needs of energy conservation and device miniaturization. However, conventional self-driven ultraviolet photodetectors still face some challenges such as low efficiency in photo-generated carrier separation, poor photoresponse performance, and limited response speed. Ferroelectric thin films with a high remnant polarization can form a depolarization field that penetrates the entire bulk material, enabling an effective separation of internally generated photo-generated electrons and holes. This provides a promising solution to the aforementioned issues. Pb(Zr_xTi1-x)O₃(PZT) is a typical ABO₃-type perovskite ferroelectric material. This material is widely used in ferroelectric memories, micro-electromechanical systems, and photodetectors due to its excellent ferroelectric, piezoelectric, and photoelectric properties. Extensive studies show that the composition significantly affects the crystal phase structure and ferroelectric properties of PZT thin films. However, its impact on the photoelectric performance requires a further systematic investigation. This work was to analyze the photoelectric characteristics of PZT thin films with different Zr/Ti ratios, in order to elucidate the influence of compositional modulation on the photoelectric effect.

Methods

Pb(Zr_xTi₁-x)O₃ ferroelectric thin films with different Zr/Ti ratios were prepared by a sol-gel method. The selected precursors and solvents were high-purity lead acetate [Pb(CH₃COO)₂·3H₂O], zirconium n-propoxide (C₁₂H₂₈O₄Zr), and titanium isopropoxide (C₁₂H₂₈O₄Ti) as sources for lead, zirconium, and titanium, respectively, glacial acetic acid as a chelating agent, and n-propanol as a stabilizer. Semitransparent gold electrodes were deposited on the surface of the thin films by a model VZZ-300 high-vacuum thermal evaporation system (VANNO Co., China) to fabricate self-driven ultraviolet photodetectors with an Au/PZT/FTO vertical structure. The crystal structure of the films was characterized by a model D8 Advance X-ray diffractometer (XRD, Bruker Co., USA). The surface roughness of the films was determined by an atomic force microscope (AFM, Bruker Dimension Edge Co., USA). The optical properties of the films were analyzed by a model UV-3600 Plus ultraviolet-visible-near-infrared spectrophotometer (UV-Vis-NIR, Shimadzu, Japan). The ferroelectric properties were measured by a model Precision LC II ferroelectric test system (Radiant Co., USA). The current-time (I-t) curves were obtained by a model Keithley 2400 source meter, with a 150 W ultraviolet-enhanced xenon lamp as a light source.

Results and discussion

The XRD patterns indicate that the three prepared PZT thin films with different Zr/Ti ratios all exhibit a typical perovskite structure, and no diffraction peaks from impurity phases appear aside from those originating from the FTO substrate. As the Zr content increases, the surface morphology of the films transitions from elongated needle-like structures to island-like structures, and finally to wavy undulations. The lowest root mean square (RMS) roughness of 2.62 nm is obtained at a Zr/Ti ratio of 0.52:0.48. The remnant polarization first increases from 27.9 μC/cm² (Zr/Ti=0.49/0.51) to a maximum of 33.2 μC/cm² (Zr/Ti=0.52/0.48), and then decreases to 31.1 μC/cm² (Zr/Ti=0.55/0.45) as the Zr content increases. A higher remnant polarization is beneficial to forming a stronger built-in electric field, thereby improving the separation efficiency of photogenerated carriers. The PZT films with different Zr/Ti ratios are all wide-bandgap semiconductors (>3.6 eV). As the Zr content increases, the bandgap widens from 3.60 eV to 3.68 eV, showing a blue-shift trend. When a negative poling voltage is applied, the depolarization field inside the PZT aligns with the built-in field induced by the interfacial Schottky barrier, synergistically enhancing the driving force for carrier separation and leading to a significant increase in photocurrent. For the sample with a Zr/Ti ratio of 0.52:0.48 at a poling voltage of -2 V, the responsivity and detectivity reach 3.2 mA/W and 0.33×10¹¹ Jones, respectively. Even under a weak illumination of as low as 0.17929 mW/cm², the device still generates a photocurrent of 1.02 nA, demonstrating the excellent detection sensitivity.

Conclusions

Pb(Zr_xTi₁-x)O₃ ferroelectric thin films with different zirconium-to-titanium ratios (i.e., Zr/Ti=0.49:0.51, 0.52:0.48, 0.55:0.45) were fabricated by a sol-gel method, and self-driven ultraviolet photodetectors with an Au/PZT/FTO structure were constructed. The structural characterization revealed that all PZT thin films exhibited a pure perovskite phase with a good crystalline quality. The AFM analysis indicated that the film surfaces were smooth, dense, and displayed a uniform grain distribution. The ferroelectric property measurements further confirmed that all films with different Zr/Ti ratios showed characteristic ferroelectric hysteresis loops and possessed a high remnant polarization, having a maximum value of 33.2 μC/cm² at Zr/Ti=0.52:0.48. The results of photoelectric tests demonstrated that the device based on this optimal composition exhibited stable and reproducible photocurrent responses. At a poling voltage of -2 V, its responsivity and detectivity were significantly enhanced. In summary, the rational adjustment of the Zr/Ti ratio could effectively optimize both the ferroelectric properties of PZT thin films and the photoelectric characteristics of the corresponding devices. This work could innovatively utilize the inherent bulk depolarization field of PZT ferroelectrics as a driving force to achieve an efficient separation of photogenerated electron-hole pairs. Moreover, it could provide a systematic optimization strategy from the perspectives of compositional design and polarization modulation, offering an effective material- and physics-based solution to overcome the key bottlenecks of low responsivity and detectivity in self-driven ultraviolet photodetectors.

Key words

lead zirconate titanate / ferroelectric films / sol-gel / self-driven ultraviolet photodetectors

引用本文

王梓赫, 黄敏捷, 张清风. Pb(Zr_xTi₁-x)O₃铁电基自驱动紫外光电探测器的制备与性能. 硅酸盐学报, 2026 , 54 (4) : 1202 -1209 . DOI: 10.14062/j.issn.0454-5648.20250810

Zihe WANG, Minjie HUANG, Qingfeng ZHANG. Preparation and Properties of Self-driven Ultraviolet Photodetectors Based on Pb(Zr_xTi₁-x)O₃ Ferroelectric Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (4) : 1202 -1209 . DOI: 10.14062/j.issn.0454-5648.20250810

基金

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国家自然基金(52572127; 52172113)
湖北省科技创新基地（平台）项目(2025CSA140)

参考文献

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2026年第54卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250810

接收时间：2025-11-07
首发时间：2026-05-20
出版时间：2026-03-09

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收稿日期：2025-11-07
修回日期：2025-12-15

基金

国家自然基金(52572127; 52172113)

湖北省科技创新基地（平台）项目(2025CSA140)

作者信息

湖北大学材料科学与工程学院，武汉 430062

通讯作者:

张清风（1983—），男，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250810

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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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