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Ferroelectric perovskite-type films with robust in-plane polarization toward efficient room-temperature chemiresistive sensing

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Fundamental Research 2023年第3期3卷 362-368页

作者： shiguo han Guan-E Wang Gang Xu Junhua Luo Zhihua Sun State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesNo.155 Yangqiao West RoadFuzhou 350002China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China No.155 Yangqiao West RoadFuzhou 350002China University of Chinese Academy of Sciences Chinese Academy of SciencesNo.19A Yuquan RoadBeijing 100039China

Ferroelectric materials have become key components for versatile device applications,and their thin films are highly desirable for integrating the miniaturized *** substantial endeavors,it is still challenging to achieve effective chemiresistive sensing in the ferroelectric ***,for the first time,we have exploited ferroelectric thin films of 2D hybrid perovskite BA_(2)EA_(2)Pb_(3)I_(10)(1),to fabricate the high-performance chemiresistor gas *** spin-coated films of 1 exhibit high orientation and good crystallinity,thus preserving robust in-plane spontaneous polarization(P_(s)~2.0μC/cm^(2))and low electric ***,such ferroelectric filmbased sensors after electric poling enable the dramatic room-temperature sensing responses to NO_(2) gas,including high sensitivity(0.05 ppm^(-1)),extremely low detection limit(1 ppm)and fast responding rate(~6 s).Besides,the chemiresistive responses are remarkably enhanced by threefold(up to 320%)through electric *** is proposed that this behavior closely involves with strong in-plane ferroelectric polarization of 1 that generates a built-in electric field inhibiting the recombination of charge *** far as we know,this ferroelectric-based film chemiresisor is one of the best room-temperature sensors for NO_(2) gas among all the existing candidate *** findings highlight great potential of ferroelectrics toward effective chemiresistive performances,and also establish a bright direction to explore their future device applications.

关键词： Ferroelectric-based films Hybrid perovskite 2D quantum-well In-plane polarization Chemiresistive sensing

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Triethylammonium picrate： An above-room-temperature phase transition material to switch quadratic nonlinear optical properties

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Chinese Chemical Letters 2018年第2期29卷 285-288页

作者： Muhammad Adnan Asghar Jing Zhang shiguo han Zhihua Sun Chengmin Ji Aurang Zeb Junhua Luo State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou 350002 China University of the Chinese Academy of Sciences Beijing 100039 China

To switch quadratic nonlinear optical（NLO） effects has become an exciting branch of the NLO material science. However, solid-state molecular crystals showing tunable and switchable NLO behaviors remain scarce. Here, we report an organic picrate-based binary molecular crystal, triethylammonium picrate（TEAP）, which undergoes an above-room-temperature phase transition at T_c=319 K, being solidly confirmed by the thermal and dielectric measurements. A large thermal hysteresis of ~7 K discloses the first-order feature for its phase transition. More strikingly, the quadratic NLO effects of TEAP can be switched in the vicinity of Tc. That is, TEAP exhibits NLO-active response of ~1.5 times as large as that of KDP below T_c（i.e., NLO-on state）, while its NLO effects totally disappear above T_c（NLO-off state）. Structure analyses disclose that the order-disorder transformations of triethylammonium cations and picrate anions collectively contribute to its phase transition, as well as switchable NLO behaviors. This work opens up a new pathway to the designing and assembling of stimuli-responsive materials.

关键词： Phase transition Nonlinear optical properties Dielectric properties Order-disorder

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Unusual bendable soft molecule-based ferroelectric crystals enabling the flexible photo-pyroelectric detection

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InfoMat 2024年第10期6卷 44-52页

作者： Liwei Tang Xinxu Zhu Yu Ma Haojie Xu shiguo han Yi Liu Yaoyao Chen Daohua Wang Junhua Luo Zhihua Sun State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhouFujianthe People's Republic of China University of Chinese Academy of Sciences Chinese Academy of SciencesBeijingthe People's Republic of China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China FuzhouFujianthe People's Republic of China

Soft molecule-based ferroelectrics with unique structural flexibility hold apromise for versatile applications of non-volatile memory, imaging and photovoltaicdevices. Except for few polymers (e.g., polyvinylidene fluoride, PVDF),it is challenging to exploit soft ferroelectric crystals toward free-standing flexiblephotoactive devices. We here report a multiaxial soft molecule-based ferroelectric,(n-PA)_(2)PbCl_(4) (1, where n-PA^(+)is n-pentylammonium), of whichspontaneous polarization can be reversibly switched in both crystal and powderforms. Strikingly, single crystals of 1 have unusual structural flexibility andbendability, achieving the self-standing bending with a bending radius of0.22 mm. Besides, the pyroelectric activities are also preserved for these singlecrystals after several bending cycles. Further, the bendable crystal-basedphotodetector of 1 allows broadband photoactivities via the photo-pyroelectriceffect, covering a wide range from 405 to 940 nm spectral region, breakingthrough the limit of optical absorption bandgap. As the first study of bendablefree-standing photo-pyroelectric detectors in ferroelectric crystals, our worksheds light on the assembly of flexible smart photoelectric devices.

关键词： broadband photoresponse photo-pyroelectric effect self-standing bendable crystals soft molecular-based ferroelectric

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Ultrasensitive polarized-light photodetectors based on 2D hybrid perovskite ferroelectric crystals with a low detection limit

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Science Bulletin 2021年第2期66卷 158-163,M0004页

作者： Jiaqi Wang Yi Liu shiguo han Yu Ma Yaobin Li Zhiyun Xu Junhua Luo Maochun Hong Zhihua Sun College of Chemistry Fuzhou UniversityFuzhou 350116China State Key Laboratory of Structure Chemistry Fujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China

Polarized-light photodetectors are the indispensable elements for practical optical and optoelectronic device ***-dimensional(2D)hybrid perovskite ferroelectrics,in which the coupling of spontaneous polarization(P_(s))and light favors the dissociation of photo-induced carriers,have taken a booming position within this ***,polarized-light photodetectors with a low detectionlimit remain unexplored in this 2D ferroelectric *** this work,the high-quality individual crystals of a 2D perovskite ferroelectric,BA_(2)CsPb_(2)Br_(7)(1,where BA^(+)is n-butylammonium),were used to fabricate ultrasensitive polarized-light *** unique bilayered structural motif results in quite strong electric and optical anisotropy with a large absorption ratio of a_(c)/α_(a)≈3.2(λ=405 nm).Besides,the presence of ferroelectric Psalso endows high built-in electric field along the polar c-axis that favors photoelectric *** an extremely low detectable limit of 40 n W/cm^(2),the detector of 1 exhibits a notable dichroism ratio(I_(ph)^(c)/I_(ph)^(a)≈1.5),a large responsivity of~39.5 m A/W and a specific detectivity of~1.2×10^(12)***,crystal-based devices of 1 also exhibit a fast response speed(~300μs)and excellent anti-fatigue *** work highlights great potentials of hybrid perovskite ferroelectrics toward polarized-light photodetection.

关键词： Ferroelectric Hybrid perovskite Polarized-light detection Low detection limit

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Rational alloying of secondary and aromatic ammonium cations in a metal-halide perovskite toward crystal-array photodetection

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Science China Materials 2022年第1期65卷 179-185页

作者： Wuqian Guo Huaixi Chen Xitao Liu Yu Ma Jiaqi Wang Yi Liu shiguo han Haojie Xu Junhua Luo Zhihua Sun Fujian Institute of Research on the Structure of Matter Chinese Academy of SciencesFuzhou 350002China University of Chinese Academy of Sciences Chinese Academy of SciencesBeijing 100039China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou 350108China

Two-dimensional(2D)hybrid perovskites with the Ruddlesden-Popper lattice(A')_(2)(A)_(n-1)M_(n)X_(3n+1)are emerging as the promising optoelectronic candidates,both the inorganic and organic ingredients of which can be tailored to modulate the physical ***,there is a scarcity of 2D multilayered motifs with the A-site large-size cations occupying perovskite ***,by rational mixedcation alloying,we present a new 2D hybrid perovskite,(4-TFBMA)_(2)(DMA)Pb_(2)I_(7)(1),in which the secondary cation of CH_(3)NH_(2)CH_(3)^(+)(DMA)is located inside the perovskite cage while the aromatic 4-(trifluoromethyl)benzylammonium(4-TFBMA)cation acts as a spacer *** from the quantum structure of alternating organic spacers and inorganic networks,crystal-array detectors of 1 show fascinating in-plane photodetection responses of large detectivity(~2.95×10^(12)Jones)and responsivity(~1.97AW^(-1)),comparable to those of some inorganic 2D *** addition,a fast response rate(~264μs)and a low dark current are also realized,related to the high crystalline quality and suppression of the hopping barrier due to the insulating organic spacing *** result sheds light on the further exploration of new 2D hybrid perovskites toward high-performance photodetector applications.

关键词： two-dimensional hybrid perovskites photodetection array

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二维有机-无机杂化钙钛矿铁电材料的研究进展

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化学学报 2021年第1期79卷 23-35页

作者：徐豪杰韩世国孙志华罗军华中国科学院福建物质结构研究所福州350002 中国科学院大学北京101408

铁电性通常是指电介质材料的自发极化取向随着外加电场发生变化的性能.以自发极化为核心,铁电材料表现出优异的介电响应、热释电性、压电性、电光效应和非线性光学效应等,是一类具有广阔应用前景的功能材料.近年来,二维有机-无机杂化钙... 详细信息

铁电性通常是指电介质材料的自发极化取向随着外加电场发生变化的性能.以自发极化为核心,铁电材料表现出优异的介电响应、热释电性、压电性、电光效应和非线性光学效应等,是一类具有广阔应用前景的功能材料.近年来,二维有机-无机杂化钙钛矿化合物在铁电研究领域崭露头角,逐渐发展为铁电材料的重要组成部分.此类材料具有独特的结构兼容性与可调控性,能够实现多种功能的共存或耦合,是发展新型多功能材料的理想体系.本综述基于居里原理的对称性方法,以铁电材料的结构相变为基础,阐述了铁电体的晶体学对称性破缺现象.具体结合二维有机-无机杂化钙钛矿铁电体的典型实例,揭示材料铁电性能的结构来源及光电性能调控的潜在途径,最后对该铁电材料体系的发展趋势和应用前景提出了展望.

关键词：铁电体对称性破缺二维结构杂化钙钛矿光电性能

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机械零件制造成本估算方法研究

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山东机械 2004年第5期 17-19,31页

作者：韩式国济南电子机械工程学校济南250101

本文讨论了一种基于模糊贴近度的机械零件成本估算方法。与人工主观估算方法相比,该方法更为客观、真实的反映了成本的变化特性,为机械零件技术经济评价提供了可靠的科学的依据。

关键词：机械零件成本估算模糊贴近度可靠制造成本估算方法技术经济评价

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自由曲面数控加工表面形貌仿真

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工具技术 2007年第8期41卷 17-19页

作者：赵军方文勇韩式国山东大学

建立了整体式螺旋刃球头立铣刀和可转位式球头立铣刀的几何刃线模型。基于自由曲面方程,由矩阵运算得出刃线运动包络面,对球头铣刀加工的表面形貌进行了建模和仿真。结果表明:加工平面时,刀轴摆角的选择对表面形貌影响较大;而加工自由... 详细信息

建立了整体式螺旋刃球头立铣刀和可转位式球头立铣刀的几何刃线模型。基于自由曲面方程,由矩阵运算得出刃线运动包络面,对球头铣刀加工的表面形貌进行了建模和仿真。结果表明:加工平面时,刀轴摆角的选择对表面形貌影响较大;而加工自由曲面时,刀轴摆角的变化对表面形貌影响不大。

关键词：球头铣刀自由曲面表面形貌仿真

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大尺寸二维卤化物钙钛矿铁电晶体的生长及偏振光电探测性能研究

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化学学报 2022年第3期80卷 237-243页

作者：张芬李霄琪韩世国邬发发刘希涛孙志华罗军华福建师范大学化学与材料学院福州350007 中国科学院福建物质结构研究所福州350002

低维半导体材料,尤其是近些年快速发展的二维卤化物钙钛矿材料,因其固有的结构各向异性、独特的量子限域效应和优异的半导体特性,在偏振光电探测等领域展现出巨大的应用潜力.其中,铁电极化所产生的体光伏效应为实现高灵敏的偏振光电探... 详细信息

低维半导体材料,尤其是近些年快速发展的二维卤化物钙钛矿材料,因其固有的结构各向异性、独特的量子限域效应和优异的半导体特性,在偏振光电探测等领域展现出巨大的应用潜力.其中,铁电极化所产生的体光伏效应为实现高灵敏的偏振光电探测提供了一种简单有效的途径.然而二维卤化物钙钛矿铁电体的大尺寸晶体生长仍然是其在光电器件应用中所面临的一个科学难题.本工作中,利用溶液降温法生长出了厘米级尺寸的高质量二维卤化物钙钛矿(iPA)_(2)EA_(2)Pb_(3)I_(10)(iPA为异戊胺,EA为乙胺)铁电单晶,其最大晶体尺寸达15 mm×15 mm×3 mm.实验结果表明二维钙钛矿结构赋予(iPA)_(2)EA_(2)Pb_(3)I_(10)晶体强的光学各向异性、窄的光学带隙(1.80 eV)和极其优异的光电特性(光电响应开关比达到103).更重要的是,基于(iPA)_(2)EA_(2)Pb_(3)I_(10)铁电单晶组装的光电探测器在弱偏振光的照射下表现出极其优异的光电特性,包括大二色比(2.3)、高响应度(193 mA·W^(-1))和探测率(7.0×10^(11)Jones),超过大多数基于材料本征光学各向异性的光电探测器件.这项工作不仅为高度各向异性卤化物钙钛矿铁电体的晶体生长指明了方向,而且推动了铁电材料在高性能偏振光电探测器等方面的应用.

关键词：铁电体晶体生长杂化钙钛矿二维结构偏振光电探测

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基于模糊可变评价模型的地下水脆弱性研究

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水电能源科学 2010年第9期28卷 26-29页

作者：练建军许士国韩成伟大连理工大学建设工程学部水利工程学院辽宁大连116024

针对传统DRASTIC方法中将指标离散化、权重定额划分及人类活动影响的问题,以通辽市地下水脆弱性评价为背景,应用模糊可变评价模型从水量及人类活动复合作用角度评价了地下水脆弱性。实例表明,该模型信息处理综合性强,评价结果可信度高,... 详细信息

针对传统DRASTIC方法中将指标离散化、权重定额划分及人类活动影响的问题,以通辽市地下水脆弱性评价为背景,应用模糊可变评价模型从水量及人类活动复合作用角度评价了地下水脆弱性。实例表明,该模型信息处理综合性强,评价结果可信度高,可应用于地下水脆弱性的综合评价中。

关键词：模糊可变评价模型地下水脆弱性评价 Fuzzy Evaluation Model Based Groundwater Vulnerability 人类活动影响综合评价信息处理评价结果复合作用 DRASTIC 综合性通辽市离散化可信度指标问题水量

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