Article(id=1319954840202105356, tenantId=1146029695717560320, journalId=1278651732997652489, issueId=1319954807939515170, articleNumber=null, orderNo=null, doi=10.12086/oee.2026.260025, pmid=null, cstr=32245.14.oee.2026.260025, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1769097600000, receivedDateStr=2026-01-23, revisedDate=1775577600000, revisedDateStr=2026-04-08, acceptedDate=1776960000000, acceptedDateStr=2026-04-24, onlineDate=1792631357478, onlineDateStr=2026-10-22, pubDate=1784908800000, pubDateStr=2026-07-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792631357478, onlineIssueDateStr=2026-10-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792631357478, creator=13701087609, updateTime=1792631357478, updator=13701087609, issue=Issue{id=1319954807939515170, tenantId=1146029695717560320, journalId=1278651732997652489, year='2026', volume='53', issue='7', pageStart='250354', pageEnd='1', issueExtLink='null', onlineDate='null', pubDate='1784908800000', pubDateStr='2026-07-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=1, specialIssue=null, createTime=1792631349786, creator='13701087609', updateTime=1792720386185, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1320328253928222956, tenantId=1146029695717560320, journalId=1278651732997652489, issueId=1319954807939515170, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1320328253928222957, tenantId=1146029695717560320, journalId=1278651732997652489, issueId=1319954807939515170, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=260025, endPage=1, ext={EN=ArticleExt(id=1319954840424403469, articleId=1319954840202105356, tenantId=1146029695717560320, journalId=1278651732997652489, language=EN, title=Advances in artificial chiral micro/nanostructures and devices, columnId=1279512304261776153, journalTitle=Opto-Electronic Engineering, columnName=Review, runingTitle=null, highlight=null, articleAbstract=
Significance

Chirality, a fundamental geometric property ubiquitous in nature, confers upon matter the ability to interact asymmetrically with circularly polarized light, manifesting as unique optical responses such as circular dichroism (CD) and optical rotation. These properties render chiral structures highly promising for applications in biochemical sensing, optical field manipulation, quantum information, and enantiomer separation. However, conventional fabrication methods relying on mechanical engraving or chemical synthesis face inherent limitations including weak chiroptical responses, low design freedom for geometric configurations, and challenges in scalable production. Recent advancements in nanofabrication technologies, particularly electron beam lithography (EBL), focused ion beam (FIB), and direct laser writing (LDW), have provided revolutionary means for the precise and customized construction of artificial chiral micro/nanostructures. These techniques, characterized by high resolution, excellent programmability, and three-dimensional manufacturing capabilities, are powerfully driving the transition of chiral photonics from fundamental research to functional device applications.

Progress

This review systematically summarized fabrication strategies and recent research progress for chiral structures based on these mainstream nanofabrication technologies. For electron beam lithography, the research focus has shifted from mature two-dimensional planar chiral arrays (e.g., swastika-shaped structures) to more challenging quasi-three-dimensional architectures. Innovative processes such as multi-layer alignment, utilization of proximity effects, and exposure on non-planar substrates successfully realized complex chiral metasurfaces featuring multilayer stacking and suspended bridging, significantly enhancing optical chiral responses (e.g., CD values exceeding 20°). Focused ion beam technology, leveraging its integrated capabilities for milling, deposition, and imaging, demonstrated unique advantages in direct forming of 3D chiral structures. Fabrication of asymmetric aperture arrays via tilted scanning achieved tunable CD transmittance up to 78%. Combined with the "nano-kirigami" technique, FIB induced controllable buckling and twisting of 2D thin films, constructing dynamic 3D biomimetic cilium structures with strong chiroptical responses (g-factor reaching 0.8). Direct laser writing, especially based on two-photon polymerization, excelled in the freeform fabrication of complex 3D chiral architectures. This technique efficiently produced various 3D chiral models including helices, vortices, and petal-like structures. Integration with functional materials like semiconductor quantum dots and liquid crystal elastomers enabled the fusion of chirality with properties such as photoluminescence and stimulus-responsiveness, expanding functional dimensions. Recent breakthroughs, such as the "3D Pin" technique, further broadened material choices by enabling direct printing of chiral structures from high-purity inorganic semiconductors.

Conclusions and Prospects

These precisely tailored chiral structures demonstrated remarkable performance across several cutting-edge application domains. In sensing, chiral metasurfaces based on materials like magnesium hydride and silicon achieved high-sensitivity, real-time detection of parameters such as hydrogen concentration and pressure through changes in their chiroptical signals. For optical modulation, mechanisms like photoinduced carrier excitation enabled dynamic and reversible switching of chiroptical responses (e.g., the sign of CD), laying groundwork for reconfigurable photonic devices. In light absorption and particle separation, designed chiral metamaterials achieved efficient selective absorption of specific circularly polarized light and generated chirality-dependent optical gradient forces at the nanoscale, offering novel principle-based solutions for high-efficiency separation of chiral particles below 10 nm. It indicate that nanofabrication technologies have become the core driver for the design and manufacturing of artificial chiral structures. Future research in this field will concentrate on several directions: At the process level, continuous pursuit of higher resolution, efficiency, lower cost, and development of multi-material and heterogeneous integration strategies is essential. Regarding structural design, exploration of more complex multi-level chiral, dynamically reconfigurable, and intelligently responsive architectures is needed. For applications, promoting chiral micro/nanodevices towards broader interdisciplinary fields such as on-chip integrated systems, biocompatible sensing platforms, and quantum light source manipulation is crucial. With the deepening integration of nanofabrication technologies with materials science, photonics, and life sciences, high-performance, multifunctional, and integrated chiral micro/nanodevices will undoubtedly inject new vitality into the future development of information, energy, and health technologies.

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手性作为自然界普遍存在的一种基本特性,带来的独特光学响应 (如圆二色性、旋光性)使其在传感检测、光学调控、量子信息等领域具有不可替代的应用价值。微纳加工技术凭借高分辨率、可编程性强等优势,已成为微纳尺度手性结构加工的优质方案。本文探讨了电子束光刻、聚焦离子束及激光直写三种主流微纳加工技术的加工原理、工艺特点、创新路径及典型应用范式。同时,介绍了一些通过微纳加工制备的手性结构用于传感器、光学调控、圆偏振光吸收,手性粒子分离等的成果,并展望了该领域未来在工艺优化、功能集成及跨场景应用等方面的发展方向,为手性微纳器件的研发与产业化提供参考。

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作者贡献

白海霖:文献搜集与筛选、图表制作、论文初稿写作;陈智:指导论文选题、论文修改与定稿、基金项目;邱健备:指导论文选题、论文修改、基金项目。

白海霖 (2001-),男,硕士研究生,研究方向:基于飞秒激光微纳加工的圆偏振发光/激光器件。E-mail:

陈智 (1987-),男,特聘教授,博士生导师,研究方向:玻璃基光量子芯片底层架构的超快激光3D微纳制造。E-mail:

邱建备 (1970-),男,教授,博士生导师,研究方向:稀土或过渡金属离子掺杂的玻璃材料与光功能材料。E-mail:

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Reconfigurable origami chiral response for holographic imaging and information encryption[J]. Opto-Electron Sci, 2025, 4(4): 240026., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1319954846472589877, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, xref=null, ext=[AuthorCompanyExt(id=1319954846480978486, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, companyId=1319954846472589877, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=School of Materials Science and Engineering, Kunming University of Science and Technology, Yunnan Key Laboratory of New Materials Preparation and Processing, Kunming, Yunnan 650093, China), AuthorCompanyExt(id=1319954846489367095, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, companyId=1319954846472589877, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=昆明理工大学材料科学与工程学院,云南省新材料制备与加工重点实验室,云南 昆明 650093)])], figs=[ArticleFig(id=1319954849614123597, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.1, caption=Schematic diagram of circular dichroism (CD) spectroscopy[29], figureFileSmall=C0Vo9R2ZnWsealsn+fwwog==, figureFileBig=L5BP9931dz+WTtQZat0d3w==, tableContent=null), ArticleFig(id=1319954849693815374, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图1, caption=CD光谱仪原理图[29], figureFileSmall=C0Vo9R2ZnWsealsn+fwwog==, figureFileBig=L5BP9931dz+WTtQZat0d3w==, tableContent=null), ArticleFig(id=1319954849903530575, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.2, caption=Schematic diagram of a polarimeter[30], figureFileSmall=Qvw7Mh1pYbPpzRwxDOSsiw==, figureFileBig=yBZCjwffWN7/AKn3FGmBlA==, tableContent=null), ArticleFig(id=1319954849983222352, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图2, caption=旋光仪原理图[30], figureFileSmall=Qvw7Mh1pYbPpzRwxDOSsiw==, figureFileBig=yBZCjwffWN7/AKn3FGmBlA==, tableContent=null), ArticleFig(id=1319954850054525521, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.3, caption=Chiral structures fabricated by EBL. (a) Bilayered planar chiral metallic microstructure with interlayer coupling,when $ a=0 $, the two planes coincide and the chirality disappears [42]; (b) SEM image of a swastika-shaped chiral array[44]; (c) A bulk array whose chirality can be tuned by changing the structural angle. When the blocks are not rotated, or are rotated by a multiple of 90°, the structure does not exhibit chirality [49]; (d) A chiral structure with separated top surfaces and bridged bottom surfaces[54]; (e) Top and bottom views of SEM images for a fabricated right-handed (RH) metasurface [54]; (f) Various 3D structures fabricated by EBL on a non-planar substrate[55], figureFileSmall=1JsxEntVuivKbBFK1C2U8w==, figureFileBig=2mh34ZQDsgiu09HegDDXkQ==, tableContent=null), ArticleFig(id=1319954850142605906, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图3, caption=EBL加工的各类手性结构。 (a)具有感应跨层耦合的双层平面手性金属微结构,当a=0时,两层平面重合,手性消失[42]; (b)“卐”型手性阵列的SEM图像[44]; (c)通过改变结构角度来调整手性大小的块状阵列,当块不旋转或旋转90°的倍数时,结构不显示出手性[49]; (d)一种上表面分离,下表面桥接的手性结构,其结构尺寸与所用EBL加工时的功率有关,为完成背面的桥接需要探索合适的加工功率[54]; (e)制造的RH超表面的 SEM图像的顶视图和底视图[54]; (f)在不平整底座上用EBL加工出的各类三维结构[55], figureFileSmall=1JsxEntVuivKbBFK1C2U8w==, figureFileBig=2mh34ZQDsgiu09HegDDXkQ==, tableContent=null), ArticleFig(id=1319954850226491987, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.4, caption=Chiral structures fabricated by focused ion beam (FIB). (a) Schematic diagram of the transformation process from a ring aperture (RA) to a split-ring aperture (SRA) and then to a slanted split-ring aperture (SSRA). The SSRA structure is derived from the RA and exhibits mirror symmetry in all three orthogonal planes. By converting the ring aperture into an achiral SRA, further tilting in the x-z plane transforms the SRA into a chiral SSRA structure with a slanted opening [12]; (b) SEM image of the structure prepared by FIB before thermal oxidation[64]; (c) Cross-sectional STEM image of the as-prepared nanostructure before annealing; the orange arrow indicates the selective scanning direction, and points A and B mark locations of structural variation within the layer [64]; (d) Cross-sectional STEM image of the nanostructure after annealing at 1100°C; the orange arrow indicates the line-scan direction[64]. (e) Two schemes for 2D patterning on a silica substrate using EBL and FIB, respectively [39]; (f) Three-dimensional biomimetic nanocilia obtained after wet etching and subsequent low-dose FIB shaping [39], figureFileSmall=BB+KJ2/Rg05AlugaZBha+g==, figureFileBig=4hyyGOVYgbDBJmbNhtaB0g==, tableContent=null), ArticleFig(id=1319954850301989460, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图4, caption=FIB加工的各类的手性结构。 (a)从环形孔径 (RA)到裂环孔径 (SRA)再到倾斜裂环孔径 (SSRA)的转换过程示意图。SSRA结构是由RA演变而来的,在三个正交平面上都具有镜像对称性通过将环孔径转换为非手性的SRA,在x-z平面内的进一步倾斜使SRA变为具备手性的倾斜开口的SSRA结构[12]; (b)进行热氧化前,FIB制备的结构的SEM图[64]; (c)退火前制备的纳米结构STEM横截面图像,橙色箭头和A点和B点分别指示选择性扫描方向和层中结构变化的位置[64]; (d) 1100℃退火后制备的纳米结构STEM横截面图像,橙色箭头表示线扫描方向[64]; (e)分别使用EBL和FIB在二氧化硅基底上进行二维图案化的两种方案[39]; (f) 经过湿法蚀刻和随后的低剂量 FIB 变形后获得立体仿生纳米纤毛[39], figureFileSmall=BB+KJ2/Rg05AlugaZBha+g==, figureFileBig=4hyyGOVYgbDBJmbNhtaB0g==, tableContent=null), ArticleFig(id=1319954850373292629, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.5, caption=Chiral structures fabricated by direct laser writing (LDW). (a) Schematic of femtosecond laser printing for direct-writing fluorescent silver helical structures within an agarose matrix[80]; (b) A single twisted omega-shaped particle[81]; (c) A petal-like chiral structure composed of six micropillars[82]; (d) A petal-like chiral structure composed of twelve micropillars [82]; (e) Vortex-like chiral structures fabricated[83]; (f) Coffee-ring-like chiral structure generated by laser processing via chiral self-assembly[84], figureFileSmall=j4Xt8uSUT5riiTbzkRc+eQ==, figureFileBig=i5F6oCC+WIawO1nZAqk0yw==, tableContent=null), ArticleFig(id=1319954850452984406, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图5, caption=LDW加工的各类手性结构。 (a)飞秒激光打印在琼脂糖基质中直写荧光银螺旋结构的示意图[80]; (b)单个扭曲omega粒子[81]; (c)由六根微柱组成的花瓣状手性结构[82]; (d)由十二根微柱组成的花瓣状手性结构[82]; (e)漩涡状手性结构[83]; (f)通过手性自组装,用激光加工出的咖啡环状手性结构[84], figureFileSmall=j4Xt8uSUT5riiTbzkRc+eQ==, figureFileBig=i5F6oCC+WIawO1nZAqk0yw==, tableContent=null), ArticleFig(id=1319954850524287575, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.6, caption=Fabrication of diverse chiral structures in inorganic materials via direct laser writing (LDW). (a) Schematic illustrating the mechanism of LDW in semiconductors[86]; (b, c) Helical array and individual helical chiral structures fabricated using this mechanism[86]; (d) Schematic of the 3D Pin printing mechanism[87]; (e, f) Designed and 3D Pin-printed tapered helical chiral knots, The handedness of schematic e is RH [87], figureFileSmall=/1jz/ql8/5+I4rfMgVjf4A==, figureFileBig=smeCK9GYma+nyqDav6A3oQ==, tableContent=null), ArticleFig(id=1319954850620756568, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图6, caption=LDW用于无机材料制备各种手性结构。 (a)半导体用于LDW机制图解[86]; (b, c)该机制用于制备的螺旋阵列与单体螺旋手性结构[86]; (d) 3D Pin打印机制图解[87]; (e, f)设计并通过3D Pin打印出的锥形螺旋手性结构,示意图(e)的旋向为RH[87], figureFileSmall=/1jz/ql8/5+I4rfMgVjf4A==, figureFileBig=smeCK9GYma+nyqDav6A3oQ==, tableContent=null), ArticleFig(id=1319954850750779993, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.7, caption=Chiral micro/nanostructures for sensing applications. (a) SEM image of a planar hydrogen-absorbing structure with left-handed chirality [92]; (b) Working principle of hydrogen-modulated chiral optical response and simulated field distributions of the hybrid structure before and after hydrogen loading[92]; (c) Temporal evolution of the measured circular dichroism (CD) spectra for the left-handed sample after hydrogen loading. CD spectra were recorded continuously at 10-minute intervals. The CD response (red line) was quenched upon exposure to 0.25 vol% hydrogen for 100 minutes (blue line). The absorption peaks in the figure correspond to the dimensions of the structure, which determine the positions of the absorption peaks [92]; (d) SEM image of a planar helical metamaterial (exhibiting no intrinsic chirality in this state)[93]; (e) Displacement of the helical structure under applied pressure, which generates and progressively enhances chirality with increasing deformation[93]; (f) CD spectra of the helical structure at different levels of mechanical deformation[93], figureFileSmall=4LFFxoyBb1lQaBhvBCvPgg==, figureFileBig=yoGh/Sco80qBNL5LAKkSXQ==, tableContent=null), ArticleFig(id=1319954850864026202, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图7, caption=微纳加工的手性结构用于传感。 (a)左手手性的吸氢平面结构SEM图[92];(b)氢调节手性光学响应的工作原理与混合结构在氢加载前后的模拟场分布[92]; (c)氢负载后测量的左手样品CD光谱随时间的变化。CD光谱以10 min的间隔连续记录。 100分钟后,CD响应 (红线)被0.25% 氢气关闭 (蓝线),图中的吸收峰与结构的尺寸相匹配,结构的尺寸决定了吸收峰的位置[92]; (d)螺旋平面超材料的SEM图像 (此时无手性)[93]; (e)螺旋结构相对于施加压力的位移,此时会随着形变程度,手性逐渐增加[93]; (f)不同形变程度下该螺旋结构的CD性能[93], figureFileSmall=4LFFxoyBb1lQaBhvBCvPgg==, figureFileBig=yoGh/Sco80qBNL5LAKkSXQ==, tableContent=null), ArticleFig(id=1319954850943717979, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.8, caption=Chiral micro/nanostructures for optical modulation[96]. (a) SEM image of the chiral structure, where purple, blue, and yellow represent gold structures in different layers, and two silicon pads are marked in green. Scale bar: 10 µm; (b) Schematic diagram of the chirality-switching metamaterial structure; (c) A set of repeating units composed of four chiral resonators with four-fold rotational symmetry; (d) Circular dichroism (CD) spectra without (black) and with (red) optical excitation, showing a reversal of the chiroptical response under the two conditions, figureFileSmall=4j6NCVu1GF9r6aPWbHKmBg==, figureFileBig=jtL/fFK7seCK0ONvE3A6Cw==, tableContent=null), ArticleFig(id=1319954851031798364, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图8, caption=微纳加工的手性结构用于光学调控[96]。 (a)该手性结构的SEM图,紫色、蓝色和黄色代表不同层的金结构,两个硅垫标记为绿色。比例尺:10 µm; (b)该手性转换超材料的结构示意图; (c)由四个具有四重旋转对称性的手性谐振器组成的一组重复单元; (d)没有光激发 (黑色)和有光激发 (红色)的CD谱。两种环境下CD性能发生翻转, figureFileSmall=4j6NCVu1GF9r6aPWbHKmBg==, figureFileBig=jtL/fFK7seCK0ONvE3A6Cw==, tableContent=null), ArticleFig(id=1319954851115684445, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.9, caption=Chiral micro/nanostructures for circularly polarized light absorption. (a) Chiral structure designed on a silver substrate for absorbing circularly polarized light at specific wavelengths[98]; (b) Absorption spectra for left-circularly polarized (LCP) light at various incident angles (Φ = 0°) along the x-direction, ranging from 0.4° to 16.4° in 2° increments[98]; (c) Split-ring chiral structure capable of absorbing circularly polarized light at different wavelengths by adjusting its geometric parameters and gap size[99]; (d) Measured circular dichroism (CD) spectra for structures with different split-ring dimensions[99], figureFileSmall=1oP0EdcMA87B58KDEYJWyw==, figureFileBig=5DKf3F+vI1zmv3pO8W96pg==, tableContent=null), ArticleFig(id=1319954851186987614, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图9, caption=微纳加工的手性结构用于圆偏振光的吸收。 (a)银基板上设计的手性结构,用于吸收特定波长的圆偏振光[98]; (b) LCP光的吸收光谱在入射角沿 x 方向 (Φ = 0°)以2°间隔从0.4°到16.4°变化时的图像[98]; (c)开口环状的手性结构,通过改变尺寸参数和开口大小,能用于吸收不同波长的圆偏振光[99]; (d)不同开环大小的CD光谱测试[99], figureFileSmall=1oP0EdcMA87B58KDEYJWyw==, figureFileBig=5DKf3F+vI1zmv3pO8W96pg==, tableContent=null), ArticleFig(id=1319954852831154783, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Fig.10, caption=Chiral micro/nanostructures for separation of chiral particles. (a) Schematic diagram of a gold double-split-ring structure[104]; (b) Distribution of the force gradient experienced by chiral structures positioned within the gap of the split rings[104]; (c) Schematic diagram of a split-ring-disk coupled structure[105]; (d) SEM image of the split-ring-disk structure[105], figureFileSmall=FzGfqrIQ78QYI/tBfjMGHg==, figureFileBig=pk+/UVA2hgs07QcPOHvZ6w==, tableContent=null), ArticleFig(id=1319954852910846560, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=图10, caption=微纳加工的手性结构用于手性粒子的分离。 (a)金双裂环结构示意图[104]; (b)处于裂环之间不同手性结构所受到的力梯度分布图[104]; (c)裂环-圆盘结构示意图[105]; (d)裂环-圆盘结构SEM图[105], figureFileSmall=FzGfqrIQ78QYI/tBfjMGHg==, figureFileBig=pk+/UVA2hgs07QcPOHvZ6w==, tableContent=null), ArticleFig(id=1319954852990538337, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=EN, label=Tab.1, caption=

Key characteristics of EBL, FIB, and LDW

, figureFileSmall=null, figureFileBig=null, tableContent=
Comparison dimensionEBLFIBLDW
ResolutionExtremely high (< 2~10 nm)High (< 5~20+ nm)High (Sub-micron to hundreds of nm)
Fabrication dimensionality2D3D3D
Material versatilityIndirect (Requires resist)Extremely broadRequires material response
Throughput/speedExtremely lowMediumRelatively high
Overall costVery highHighRelatively low
), ArticleFig(id=1319954853099590242, tenantId=1146029695717560320, journalId=1278651732997652489, articleId=1319954840202105356, language=CN, label=表1, caption=

三种加工方式的参数对比

, figureFileSmall=null, figureFileBig=null, tableContent=
Comparison dimensionEBLFIBLDW
ResolutionExtremely high (< 2~10 nm)High (< 5~20+ nm)High (Sub-micron to hundreds of nm)
Fabrication dimensionality2D3D3D
Material versatilityIndirect (Requires resist)Extremely broadRequires material response
Throughput/speedExtremely lowMediumRelatively high
Overall costVery highHighRelatively low
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人工手性微纳结构及器件研究进展
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白海霖 , 陈智*, * , 邱建备*, *
作者信息
  • 昆明理工大学材料科学与工程学院,云南省新材料制备与加工重点实验室,云南 昆明 650093
通讯作者:
作者简介:

作者贡献

白海霖:文献搜集与筛选、图表制作、论文初稿写作;陈智:指导论文选题、论文修改与定稿、基金项目;邱健备:指导论文选题、论文修改、基金项目。

白海霖 (2001-),男,硕士研究生,研究方向:基于飞秒激光微纳加工的圆偏振发光/激光器件。E-mail:

陈智 (1987-),男,特聘教授,博士生导师,研究方向:玻璃基光量子芯片底层架构的超快激光3D微纳制造。E-mail:

邱建备 (1970-),男,教授,博士生导师,研究方向:稀土或过渡金属离子掺杂的玻璃材料与光功能材料。E-mail:

Advances in artificial chiral micro/nanostructures and devices
Hailin Bai , Zhi Chen , Jianbei Qiu
Affiliations
  • School of Materials Science and Engineering, Kunming University of Science and Technology, Yunnan Key Laboratory of New Materials Preparation and Processing, Kunming, Yunnan 650093, China
  • Corresponding Author:
出版时间: 2026-07-25 doi: 10.12086/oee.2026.260025
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手性作为自然界普遍存在的一种基本特性,带来的独特光学响应 (如圆二色性、旋光性)使其在传感检测、光学调控、量子信息等领域具有不可替代的应用价值。微纳加工技术凭借高分辨率、可编程性强等优势,已成为微纳尺度手性结构加工的优质方案。本文探讨了电子束光刻、聚焦离子束及激光直写三种主流微纳加工技术的加工原理、工艺特点、创新路径及典型应用范式。同时,介绍了一些通过微纳加工制备的手性结构用于传感器、光学调控、圆偏振光吸收,手性粒子分离等的成果,并展望了该领域未来在工艺优化、功能集成及跨场景应用等方面的发展方向,为手性微纳器件的研发与产业化提供参考。

手性结构  /  微纳加工  /  手性光子器件
Significance

Chirality, a fundamental geometric property ubiquitous in nature, confers upon matter the ability to interact asymmetrically with circularly polarized light, manifesting as unique optical responses such as circular dichroism (CD) and optical rotation. These properties render chiral structures highly promising for applications in biochemical sensing, optical field manipulation, quantum information, and enantiomer separation. However, conventional fabrication methods relying on mechanical engraving or chemical synthesis face inherent limitations including weak chiroptical responses, low design freedom for geometric configurations, and challenges in scalable production. Recent advancements in nanofabrication technologies, particularly electron beam lithography (EBL), focused ion beam (FIB), and direct laser writing (LDW), have provided revolutionary means for the precise and customized construction of artificial chiral micro/nanostructures. These techniques, characterized by high resolution, excellent programmability, and three-dimensional manufacturing capabilities, are powerfully driving the transition of chiral photonics from fundamental research to functional device applications.

Progress

This review systematically summarized fabrication strategies and recent research progress for chiral structures based on these mainstream nanofabrication technologies. For electron beam lithography, the research focus has shifted from mature two-dimensional planar chiral arrays (e.g., swastika-shaped structures) to more challenging quasi-three-dimensional architectures. Innovative processes such as multi-layer alignment, utilization of proximity effects, and exposure on non-planar substrates successfully realized complex chiral metasurfaces featuring multilayer stacking and suspended bridging, significantly enhancing optical chiral responses (e.g., CD values exceeding 20°). Focused ion beam technology, leveraging its integrated capabilities for milling, deposition, and imaging, demonstrated unique advantages in direct forming of 3D chiral structures. Fabrication of asymmetric aperture arrays via tilted scanning achieved tunable CD transmittance up to 78%. Combined with the "nano-kirigami" technique, FIB induced controllable buckling and twisting of 2D thin films, constructing dynamic 3D biomimetic cilium structures with strong chiroptical responses (g-factor reaching 0.8). Direct laser writing, especially based on two-photon polymerization, excelled in the freeform fabrication of complex 3D chiral architectures. This technique efficiently produced various 3D chiral models including helices, vortices, and petal-like structures. Integration with functional materials like semiconductor quantum dots and liquid crystal elastomers enabled the fusion of chirality with properties such as photoluminescence and stimulus-responsiveness, expanding functional dimensions. Recent breakthroughs, such as the "3D Pin" technique, further broadened material choices by enabling direct printing of chiral structures from high-purity inorganic semiconductors.

Conclusions and Prospects

These precisely tailored chiral structures demonstrated remarkable performance across several cutting-edge application domains. In sensing, chiral metasurfaces based on materials like magnesium hydride and silicon achieved high-sensitivity, real-time detection of parameters such as hydrogen concentration and pressure through changes in their chiroptical signals. For optical modulation, mechanisms like photoinduced carrier excitation enabled dynamic and reversible switching of chiroptical responses (e.g., the sign of CD), laying groundwork for reconfigurable photonic devices. In light absorption and particle separation, designed chiral metamaterials achieved efficient selective absorption of specific circularly polarized light and generated chirality-dependent optical gradient forces at the nanoscale, offering novel principle-based solutions for high-efficiency separation of chiral particles below 10 nm. It indicate that nanofabrication technologies have become the core driver for the design and manufacturing of artificial chiral structures. Future research in this field will concentrate on several directions: At the process level, continuous pursuit of higher resolution, efficiency, lower cost, and development of multi-material and heterogeneous integration strategies is essential. Regarding structural design, exploration of more complex multi-level chiral, dynamically reconfigurable, and intelligently responsive architectures is needed. For applications, promoting chiral micro/nanodevices towards broader interdisciplinary fields such as on-chip integrated systems, biocompatible sensing platforms, and quantum light source manipulation is crucial. With the deepening integration of nanofabrication technologies with materials science, photonics, and life sciences, high-performance, multifunctional, and integrated chiral micro/nanodevices will undoubtedly inject new vitality into the future development of information, energy, and health technologies.

chiral structures  /  micro/nanofabrication  /  chiral photonic devices
白海霖, 陈智, 邱建备. 人工手性微纳结构及器件研究进展. 光电工程, 2026 , 53 (7) : 260025 -1 . DOI: 10.12086/oee.2026.260025
Hailin Bai, Zhi Chen, Jianbei Qiu. Advances in artificial chiral micro/nanostructures and devices[J]. Opto-Electronic Engineering, 2026 , 53 (7) : 260025 -1 . DOI: 10.12086/oee.2026.260025
手性 (Chirality)在自然界中普遍存在。可以用一个常见的例子来理解它:就像我们的左手和右手,看起来几乎一样,但无论怎样旋转或移动,左手都无法与右手完全重合。这种“无法重合”的性质,就是手性[1]。
在物质结构层面上,手性来自物体的对称性残缺。在分子层面上,手性通常来源于分子中存在的“手性中心” (chiral center),即一个连接了四种不同原子的原子 (通常为碳原子)。手性物体与其对映体虽然在大多数物理性质 (如熔点、沸点)及化学性质 (非手性环境中)上具有相似的性能[2],但它们会在手性环境 (如生物体内或光学活性实验中)下表现出某些显著差异。例如,20世纪60年代曾用作镇静剂的非处方药物,沙利度胺 (Thalidomide),其手性对映异构体却会导致胎儿严重畸形[3]。
而在光学研究中,因手性结构存在对称性残缺,这使得它们对左旋圆偏振光 (left-handed circular polarized light, LCP)和右旋圆偏振光 (right-handed circular polarized light, RCP)表现出不同的响应[4-5]。当一束线偏振光穿过手性介质时,由于手性结构对LCP和RCP的折射率不同,原本由等幅LCP与RCP分量合成的线偏振光的振动方向就会发生偏转,这种性质称作旋光性 (optical rotation, OR)[6],其至今依旧是探测手性分子存在的重要手段之一。手性介质除了对圆偏振光的折射率不同外,对左旋和右旋圆偏振光的吸收程度常常也不一样,这种现象称为圆二色性 (circular dichroism, CD)。简单来说,一种手性结构可能更容易吸收某一种旋转方向的圆偏振光。透射的光中,两种旋光的强度就有了差异,合成的光不再是标准的圆偏振光,而变成了椭圆偏振光。CD光谱仪利用CD这一特性可测试结构的手性。CD谱图已成为解析蛋白质、DNA等生物大分子二级结构,以及鉴别有机手性化合物构型的重要工具[7]。利用这些独特的光学性质,手性材料可用于污染物检测[8-9]、药物筛选[10-11]、制成光学器件[12-13]、量子信息处理[14-15]、非线性光学的研究[16-17]、光学加密[18-19]、光学电池[20]等领域。
在传统光学系统中,手性结构主要通过高精度机械雕刻手段或化学合成制备而成[21-24]。然而随着微纳加工的发展,对于纳米尺寸结构的生产与加工有了新的思路[25-27]。常见的微纳加工有将预先设计的图形转移涂覆至基底表面的光刻胶上,通过刻蚀或沉积工艺实现结构成型;或用粒子束对材料进行精密加工。具备高度灵活、可编程性强、分辨率高等特点,适用于科研探索、原型开发与高端器件制造[28]。根据曝光光源、图形转移方式与分辨率等核心参数的不同,微纳加工技术可划分为多种具有显著差异的技术路线。其中具有代表性的包括:利用高能电子束进行直写的电子束光刻 (electron beam lithography, EBL)、通过高度聚焦离子束进行精密加工的聚焦离子束 (focused ion beam, FIB),以及基于激光扫描曝光的激光直写技术 (laser direct writing, LDW)等。这些技术在特征尺寸、工艺成本、生产通量及适用材料体系等方面各具优势,因而在研发与生产的不同场景中形成明确的技术分工与互补。
本文首先介绍几种在常规材料表征之外,手性结构所需要的常见表征参数。然后围绕常见的微纳加工技术,既介绍利用各类技术优点所诞生的成功范式,也展示在技术缺陷上攻克难题的创新路径。最后举例说明一些通过微纳加工制备的手性结构在实际运用方面的成果,旨在展示微纳加工手性结构的内在潜力,相信这个领域在不久的将来会有更多进展。
CD的测量主要依赖专业光谱仪器,其核心原理在于精确探测样品对左右旋圆偏振光的选择性吸收差异。测量时,平面偏振光首先经过高速旋转的光弹调制器 (photo elastic modulator),被周期性调制成交替的左旋与右旋圆偏振光。该偏振光通过待测样品后,透射光强由光电倍增管接收并解调,经信号处理获得两者吸收强度差,最终输出以波长-吸光度差 (通常以毫度为单位)为表征的光谱曲线。该过程的基本原理示意如图1所示[29]。
通过仪器得到左旋圆偏振光的吸光度AL与右旋圆偏振光的吸光度AR,即可得到待测手性结构对左、右圆偏振光的吸光度差值∆A,单位常为毫度,计算式如式(1)所示。
$ \Delta\mathit{A}=\mathit{A}_{\mathrm{L}}-\mathit{A}_{\mathrm{R}}\; . $
CD光谱不仅可直接表征手性结构的光学响应强度,更是评判其功能性能、几何保真度与应用潜力的核心指标。基于微纳加工制备的微纳结构,其手性响应源于精确设计的非对称几何形貌在宏观尺度上诱发的空间对称性破缺,而非常规手性分子自身的化学组成或浓度效应。因此,CD光谱能够直接反映微纳加工工艺对手性结构的实现精度,并为手性功能的有效传递提供关键验证依据。
旋光度的测定常借助旋光仪完成,其核心原理建立在对手性化合物旋转平面偏振光能力的定量分析之上,如图2所示[30]。实验中,由单色光源产生的光,经起偏器形成线性偏振光。该偏振光穿过待测样品时,其偏振面因手性结构的相互作用而发生偏转,偏转角度随后通过检偏器进行精密测量。最终,仪器直接给出以度 (°)为单位的观测值,即旋光度 (α)。这一方法为手性结构的表征提供了一种经典且可量化的光学分析手段[31-32]。
不对称因子 (g-factor)是用于量化手性结构对左旋与右旋圆偏振光响应差异的重要参数,广泛应用于圆偏振发光、CD谱图及手性光学材料研究中。其测试方法一般基于两类技术,一类是基于吸收的手性表征 (如上文的CD光谱),测得gabs值[33];更常见的则是结合荧光光谱系统进行圆偏振发光(circularly polarized luminescence,CPL)测试,获得总发射光谱,得到glum值,计算方法如式(2)所示。
$ {g}_{{\mathrm{lum}}}=\frac{2({I}_{{\mathrm{L}}}-{I}_{{\mathrm{R}}})}{{I}_{{\mathrm{L}}}+{I}_{{\mathrm{R}}}} \;,$
其中:IL与IR分别表示样品LCP发光强度与RCP发光强度[34]。
不对称因子不仅是衡量结构手性光学响应的关键性能指标,同时也为面向功能导向的逆向设计提供了重要反馈依据。基于微纳加工工艺的结构优化,可通过系统调节几何参数 (如螺旋角、晶格排列周期、层间扭转角度等)以及引入剪纸构型或多级形变等复杂构型,来主动调控其共振模式的空间分布与对称性破缺的宏观表现,从而在宽谱范围内实现对不对称因子的精确调谐与优化[35]。
源于各工艺在加工机制、分辨率、三维加工能力,以及材料兼容等特性上的差异,在测试过程以及对表征结果的偏重上有所区别。此节将简述本文介绍的三种工艺的特点,据此解释表征方面存在的分歧,而关于三种工艺特点的详细介绍将在后续章节逐一展开。
EBL通过聚焦电子束在光刻胶上逐点绘制图案,将数字设计转化为物理实体,制备的结构通常具有高几何精度和良好的重复性。因此,研究者不仅需要定性地观察到CD信号的存在,更需在定量层面实现理论模型与实验测量的高度吻合。这包括精确匹配模型与实际样品在CD光谱中特征峰的峰位、吸收峰的整体轮廓形状,以及关键的性能指标——不对称因子。EBL因其优越的加工精度,常用于制备小尺寸的圆偏振光学元件,而在旋光性的测试上,光通过仅仅十几纳米乃至几纳米的手性结构,只有极小的光程用于偏振光的旋转,这让旋光仪的测试结果具有过大的误差。因此CD信号和不对称因子常是EBL制备手性结构的核心表征指标,而旋光性的测试常用于EBL加工较大的结构。
FIB利用高能离子束通过溅射精确去除材料,具有一定的3D加工能力。然而,FIB加工过程中会引入离子损伤、非晶化及镓污染,导致介电环境扰动和本征光学损耗,这常常让模拟测试表征与实际结构的表征结果相去甚远。因此,FIB制备过程可以通过尝试不同加工功率,以及后处理对结构进行抛光用于改善实际的结构性能。而在测试过程中,也可引入同质的非手性对照结构,识别并扣除伪CD信号来减少与手性无关的吸收。如上文所述,FIB虽然能进行CD光谱、不对称因子,以及旋光性的测试,但在此之前应先聚焦于结构的后处理、测试方法的改进,才能提供更精确、有效的表征数据。
LDW则是一种支持三维、多材料手性结构的直写技术。它利用双光子吸收 (two-photon absorption,TPA)效应,在激光束的焦点处实现材料的局部激发和聚合。LDW制备的手性结构通常具有比上述两类加工方式更大的几何手性和低对称性,这带来了更强的旋光性和可观测的不对称因子。但CD信号可能受双光子吸收各向异性及聚合梯度的影响,因而需要与旋光性联合表征,以区分结构手性与材料手性对光学响应的贡献。因此在LDW中,旋光性、CD和g-factor均具有互补的表征需求。
EBL凭借其纳米级的分辨能力,已成为前沿半导体器件、精密光子学结构、等离激元元件及生物传感芯片等领域的核心微纳制造技术。该技术的工作原理是基于聚焦电子束在覆有光刻胶的基底表面进行直写式图案化,无需物理掩模即可实现复杂图形的灵活构建。目前,EBL已能稳定实现5~10 nm量级的特征尺寸加工,其分辨率显著突破了传统光学光刻的衍射极限,为纳米尺度功能结构的制备提供了关键工艺支撑[36]。
EBL的典型加工流程主要包括预处理、曝光与显影三个核心步骤。首先,将聚甲基丙烯酸甲酯 (poly(methyl methacrylate),PMMA)或α-氯代丙烯酸甲酯与α-甲基苯乙烯的共聚物‌ (ZEP)等正性或负性电子束光刻胶通过旋涂方式均匀涂覆于硅片、玻璃等衬底表面,形成特定厚度的感光层。随后,在真空腔室内,计算机控制的偏转系统精确引导聚焦电子束,使其按照预设图案对光刻胶层进行扫描曝光,引发曝光区域内光刻胶分子链发生交联或降解等化学变化。此后,通过将样品置于相应有机溶剂 (如甲基异丁基酮与异丙醇的混合液)中进行显影,溶解去除可溶部分,从而在衬底上得到所需微纳结构[37]。值得注意的是,该流程获得的往往为光刻胶图形;为将其转化为功能性器件,常需后续结合干法刻蚀 (如反应离子刻蚀)[38]、湿法刻蚀[39]等工艺,将图形进一步转移至目标功能材料层。
近年来,对EBL的改进集中于提升加工的效率和分辨率、抑制邻近效应 (proximity effect),以及克服绝缘衬底上的电荷累积问题。除此之外,传统EBL系统基于平面基底扫描曝光,这种单向投影式的写入模式本质上限制了其在三维空间中的自由成型能力。再者由于邻近效应,电子在材料内部发生散射,使电子束能量扩散至非目标区域,难以构建具有悬臂、空腔或者多面连接的立体构型,严重降低了EBL对三维结构的加工精度[40],而累积电荷造成的图象畸变、多层对准误差同样对EBL的三维加工造成很大阻碍。
当前,对手性元件的加工,EBL加工二维结构已趋于成熟。而EBL虽然无法真正意义上进行三维加工,但当下也报道了很多制备出准三维结构的手段。近年来的研究也主要着眼于通过解决上述缺陷,实现分辨率与效率更高的EBL对准三维结构的加工方法。
因真实的材料具有一定的厚度,二维手性结构与几何上二维与三维的概念有所区别。定义上,二维手性产生的主要因素与三维手性类似,均在于破坏结构的镜面对称性和反转对称性,但在二维手性中,不对称性则体现在二维平面上,通过平面内的拓扑不对称性构建手性环境[41]。
在21世纪初,就有关于EBL制造二维手性结构的研究,Potts的团队开展了一系列相关工作。2001年该团队发表了对双层平面手性金属微结构元件(图3(a))的研究发现,通过调整两个耦合的亚波长介电材料金属条的各项尺寸参数以及耦合时的角度,能让结构的旋光性发生改变[42]。在2004年发表的文章中讨论了从纯粹的几何角度如何测量结构的二维手性,并用于测量设计的卍字形图案[43]。随后,在2007年通过EBL加工出该卐字图案构成的平面手性阵列(图3(b)),实现了亚20 nm分辨率的加工,该研究还通过在光刻胶表面涂抹一层导电聚合物,有助于消散电荷,一定程度上解决了电荷累积问题[44]。
上述涉及的仅通过调整图形耦合角度,就能让结构产生不同强度的手性响应,在设计手性结构时也是一种常见思路,而相关原理则涉及到绝对手性 (absolute chirality)与相对手性 (relative chirality)这两个概念。
绝对手性根植于经典几何对称性破缺,是指一个物体或系统固有的、无法通过任何平移或旋转操作与其镜像完全重合的拓扑属性。该性质不随观测参考系变化,而是由其内部结构的本征对称性缺失所决定。这一经典概念可追溯至开尔文的定义,即若一个结构不具备对称面、对称中心或旋转反射轴等对称元素,则其具有绝对手性[45]。典型的例子如生命体系中的L-氨基酸与D-氨基酸、手性药物中的 (R)-乳酸与 (S)-乳酸等,它们的手性构型是独立存在的物理事实,可通过X射线单晶衍射结合反常散射效应等实验手段直接测定[46]。
与之不同,相对手性并非独立的本体属性,而是一种在特定参照框架下才显现出的关系性特征。它描述的是两个非对映异构体相对于某一共同基准所表现出的方向差异,而其各自本身未必具备绝对手性。理论研究表明,在二维平方可积波函数体系中,手性可被表述为一个连续变量,从而超越传统的“手性/非手性”二元划分。在此理论框架下,相对手性体现为波函数相位分布的空间畸变程度,其数值可在0至1之间连续变化,形成从“近手性”至“强手性”的渐变谱[47-48]。这意味着在某些物理与数学语境中,手性可被视为一种可量化、具连续谱系的强度参量,而不仅限于离散的类别属性。譬如,2023年Gryb等[49]通过EBL将原本不具有“绝对手性”的块状超原子排列在超表面上,并旋转一定角度(图3(c))所示。该亚波长结构对800 nm波长的光产生旋光性,且随着角度的变化,结构整体的手性强弱存在连续性变化。在旋转至0°、45°、−45°时变为非手性,而在22.5°左右时表现出最强的手性响应。这个例子表明一些结构的手性并不是一个离散的量,而是能够随着结构或环境的变化而产生连续变化的量,这便是相对手性。
由于EBL能制备的三维结构类型十分有限,且设计自由度较低,此处以“准三维结构”来进行称呼,这种准三维结构主要可分为三类。一类是利用EBL对二维结构的加工优势,通过多次曝光、对准,将不同层的图案叠加,构建出堆叠式结构[50-52]。第二类则是通过一次扫描能同时打印多层结构,例如Leong等[53]在2015年利用单步EBL在氮化硅薄膜两面同时对准加工出L形和圆盘型结构,检测出手性。第三类还可以在不平整表面进行加工,从而跳脱二维加工的束缚。这些制备出准三维结构的方法将在下文中分别介绍。
前文已提到过EBL加工过程中存在的邻近效应会影响加工精度,这是EBL制造三维结构的主要障碍之一,通过在结构设计中融入该效应,巧妙利用其产生的影响也是设计手性结构的一类思路。2022年,Cen等[54]用EBL设计并制备出一种双层超表面(如图3(d))。该结构中间是一层氮化硅片,每个单元上表面是两个分离的纳米块,下表面两个纳米块之间则相互连接。通过制备一组上下表面同为分离纳米块的对照样品,可以论证出下表面的桥接结构是破坏结构对称性,产生手性的根本来源。这也正是该结构利用邻近效应的精妙之处,即利用EBL加工过程中,电子束在光刻胶、氮化硅等介质中传播时发生散射,会导致实际影响范围逐渐大于电子束原本的尺寸。在通过氮化硅衬底后,下表面电子束加工范围大于上表面,通过实验设计控制尺寸,即可利用邻近效应达成顶部分离而底部连结的手性结构。该结构在波长为1200 nm左右的近红外区存在CD响应,右旋(right-handed, RH)结构CD达22.1°,左旋(left-handed, LH)则为−20.7°。
为解决EBL加工三维结构的问题,也可以从加工基底入手。传统EBL如前文所言,基于平面基底扫描曝光。但随着近年来技术发展,有许多方法解决在非平面扫描时的失真问题[56-57],进行高精度电子束控制。另一方面,关于非平面的电荷积累问题也存在方法进行有效规避[58-59]。Chen等[55]用EBL结合ICP蚀刻,先制备出球冠状硅基板底座,再于该不平整底座上进行EBL曝光,最后能制备出单螺旋、双螺旋、四重旋转对称图形等三维结构(如图3(f)),图中组成结构的纳米线宽度约为120 nm。通过对结构参数的改变,能调控超表面的CD响应。文中以四重旋转对称图形为例,纳米线宽度的减少使CD谱图的峰值降低,而增加纳米线的长度或增加结构的高度,会使CD峰值红移。
FIB在微纳加工领域也是一项关键工具,比起EBL的平面扫描,使用FIB制备手性结构在设计上的灵活性更强。FIB在制造上同样具有无需掩膜、高分辨率等特点,同时它还能倾斜扫描和多模式集成 (铣削、沉积、成像),根据选择的模式既能增材制造,亦能减材制造,为直接构建纳米级手性结构提供了有效方法。常见的FIB加工步骤分为四步[60-62]:首先需要制样与装载,样品的制作除去清理污染物等常规步骤外,对于非导电材料常需溅射一层薄金或碳层,防止电荷积累导致后续成像失真。其次,需进行目标区域精确定位与成像。FIB多采用双束配置,在确认目标区域时使用扫描电镜进行观察与标记,随后切换至FIB模式,用低功率进行进一步试探表面信息,确认加工起点。第三步需要确认加工路径与参数。根据需要的目标结构,选择进行铣削、诱导沉积或者是截面分析,由此设计各类加工参数 (加速电压、离子束电流、扫描速度等)。涉及沉积时还需要引入前驱体气体(如W(CO)6用于钨沉积)。最后则是实际加工阶段,用离子束轰击样品完成铣削,在轰击过程用扫描电镜观察可实现截面分析,离子束作用于前驱体气体可进行沉积。
虽然FIB加工灵活,功能多样,但也不乏局限性。第一,加工速度慢是FIB技术的瓶颈之一,FIB逐点扫描加工的方式让其难以实现大面积快速图案化,即使使用较高束流,完成微米级别的加工也需要耗时数小时[63]。其次,离子束引起的材料损伤会降低加工出的材料性能,如加工光学器件可能会导致使用时光学损耗大于预期[64]。再者,FIB存在再沉积效应,在铣削过程中被离子束溅射出的材料颗粒可能重新沉积在待加工区域,形成非预期附着,使结构失真[65-66]。最后,FIB也存在与EBL一样的邻近效应,限制了FIB的最小分辨率[67]。
利用FIB能够倾斜扫描样品的特性,Chen等[12]设计了一种倾斜裂环孔径阵列(图4(a)),在近红外区表现出超过78%的CD透射率。该结构的基本设计原理是通过保持一定入射角倾斜纳米孔,并使其一侧开裂为结构引入对称性缺陷,从而产生手性。该手性超材料可以通过一步倾斜聚焦离子束制备,步骤较少,并且可通过改变孔径的倾斜角度、面内旋转角度改变其手性性能,具有简便性、可控性与可调节性。
而关于上一小节提到的FIB加工过程中可能产生材料损伤以及再沉积效应,Rogov等[64]的工作对此做出了讨论,该团队用镓离子束进行铣削流程,通过热氧化改进了FIB加工后的材料性能。在铣削过程中,镓离子束加工和溅射原子的再沉积引入的杂质可能改变制备的纳米结构,增加吸收损耗,制备的手性结构平面图如图4(b)所示。执行铣削后,取材料某一区域用高分辨扫描电镜进行观察(图4(c)),受损硅层 (d-Si)上注入了镓,以及非晶硅夹杂物 (c-Si)。该结构此时测试的光传输率低于20%。为了在 FIB 铣削工艺后去除杂质,进行了热氧化处理并退火。处理后拍摄的高分辨扫描电镜图像 (图4(d))表明受损的硅层被氧化硅取代,且结构形状未发生明显的改变。该清洁程序可将传输强度提高70%,清洁后测试得该结构在575 nm的可见光波长范围内存在手性响应,旋光性20°,CD值达−0.3。
纳米剪纸 (Nano-kirigami)技术是一种新兴的仿生微纳结构加工策略,其灵感汲取自中国的传统剪纸与折纸艺术[68]。该技术借鉴“剪纸”的理念,常利用FIB作为“纳米剪刀”,通过对二维平面材料进行精确的图案化“切割”和局部应力诱导的“折叠”,实现复杂三维微纳结构的可控构筑。其核心加工机理在于利用FIB等纳米加工工具在金属薄膜、硅或氮化硅等柔性薄膜的特定区域引入可控的应力场,从而编程式地驱动材料发生屈曲、卷曲等形变,最终形成螺旋、悬臂、拱形等多种动态可调的立体构型[69-71]。而诱导材料发生形变的方式,大体分为两种,一种是为离子注入产生晶体缺陷导致结构发生形变,即当高能离子束轰击材料表面时,部分离子会注入材料内部,导致晶格损伤、空位或非晶化区域的形成。这些注入的离子和产生的缺陷会引起材料局部膨胀或收缩,从而在材料内部产生内应力,譬如Ga+离子束已被观察到能在Si3N4、SiO2、晶体硅、多晶硅、Al和Au等材料中通过造成晶体缺陷来引入纳米级的局部拉伸应力[72]。另一种则是利用FIB刻蚀导致厚度不对称,从而引发结构形变。当离子束仅对薄膜的一侧进行辐照时,会导致该侧材料的损失,造成厚度的不对称性,当结构释放这些不平衡应力时,就会发生弯曲或卷曲,例如通过对Au/SiO2/Si叠层薄膜进行聚焦离子束选择性辐照,可在Au层表面引入非对称的应力梯度,从而诱导其自发向上弯曲,精确形成特定倾角的悬臂梁阵列或三维环状结构[69]。而在手性结构加工中,Liu等[39]受启发于自然界中动物体上的纤毛在受到外部应力时会发生移位、扭曲的特性,利用纳米剪纸技术来制备具有扭曲纤毛配置和手性特征的纳米级纤毛超表面。该纤毛二维结构(图4(e))可通过EBL或者FIB进行加工,通过湿法刻蚀修整后,即可利用微量FIB变形为三维扭曲状纤毛结构,变形后的纤毛结构如图4(f)所示。通过CD表征,二维纤毛几乎不存在CD响应,而变为三维结构后该结构具有0.8的尖锐CD峰值。
基于双光子聚合 (Two-photon polymerization, TPP)原理的双标水法(doubly labeled water, DLW)技术凭借其突破衍射极限的空间分辨率和高自由度的三维加工能力,逐渐成为构建任意手性微纳结构的理想平台。该技术利用飞秒激光脉冲诱导光刻胶在焦点内发生非线性双光子吸收,发生局部聚合反应,从而实现亚波长尺度下,体素级的精确控制。加工分辨率发展至今,甚至能做到低至5 nm[73],主流的LDW则大部分在30~80 nm。
此外,LDW技术的一个重要发展方向在于超越单一材料体系,通过多材料集成策略实现功能维度的显著拓展。例如,将半导体量子点与光刻胶体系相结合,可在三维手性结构中原位引入光致发光特性,从而构建出具有强圆偏振发光的手性纳米天线或高灵敏度单分子探测平台[74]。若与液晶弹性体等智能响应材料结合,则可进一步赋予手性结构外部场 (如温度、光场)响应的能力,实现形貌与光学性质可动态调控的智能手性器件[75]。此外,通过对打印参数 (包括激光功率、扫描速度、曝光时间及后处理条件等)的调整与优化可以精细调控发生双光子聚合后,聚合物网络的交联密度或残余应力分布等参数,进而影响最终结构的机械稳定性与形变等性能[76]。
EBL和FIB相比,LDW具有许多自身的优势。首先,LDW拥有更为自由的三维加工能力,不需要支撑材料[77]。其次,在加工环境上EBL与FIB依赖高真空环境,以避免电子或离子束与空气分子发生散射,这既增加了系统复杂性和运行成本,还限制了可处理的材料类型 (如含挥发性成分的生物材料),相比之下,LDW可在常压、室温环境下对光刻胶直接加工,适合集成于生物洁净室或与其他湿化学工艺联用[78]。
最后,在加工速度与可并行化潜力方面,LDW展现出更显著的发展前景。传统的EBL受限于其扫描方式的串行特性,在大面积、高分辨率图形化方面通常耗时冗长;FIB技术因涉及物理刻蚀,加工效率更为受限。虽然单束LDW同样面临串行写入的速度瓶颈,但该技术可利用空间光调制器或多焦点分束技术,实现多光束并行曝光,从而有效提升大面积制造的吞吐量[79]。
然而,在其他关键性能指标上,EBL与FIB技术仍具备不可替代的优势。例如,EBL的加工极限分辨率可达5 nm以下,显著优于当前LDW系统的30~80 nm量级,因此在对特征尺寸要求极高的纳米光子器件和量子结构制备中具有不可替代的价值。FIB则同时集成了高精度纳米加工与实时的扫描电子成像能力,可在同一加工区域内实现微区刻蚀、材料沉积和形貌观测,使其在原型快速迭代、器件局部修正,以及微观时效分析等领域具有独特的应用优势。此外,从材料适用性角度看,FIB能够直接加工金属、陶瓷与半导体等多种无机材料;而LDW主要作用于有机光刻胶体系,所成结构通常需要经过灰化、电镀或干法刻蚀等后续工艺步骤,才能转换为金属或其他功能性材料体系。
螺旋作为自然界中十分常见的结构,也是手性结构的代表,具有明显的CD光谱信号与旋光性,通过控制螺旋的各项参数 (螺距、旋向、高度、半径等)能对结构的手性性能进行调控。因此,利用LDW三维加工的优势,对螺旋结构的加工与性能研究在手性光学领域具有广阔前景[8]。Wen等[80]利用多光子吸收特性,在532 nm波长的飞秒激光照射下使琼脂糖水凝胶中的银纳米颗粒与银纳米簇发生光还原,如图5(a)所示。琼脂糖为光还原反应提供了均一场地,并且虽然前文提到LDW加工不需要支撑材料,但设计结构时也需考虑常规物理因素 (如重力、加工过程中一些冲击力等)导致发生塌陷,琼脂糖能作为支撑螺旋结构不发生坍塌的介质。团队还通过调整螺旋匝数,当匝数从2增加到4后,结构的g值也从0.5增大到0.58。
当然,LDW的三维加工能力不必拘泥于某一种结构,其加工自由度能够支持加工各类天马行空的手性结构。Yin等[81]用LDW技术制备出三维扭曲的omega结构((图5(b)),再通过化学镀银进行加工。Hu等[82]利用飞秒激光打印微柱结构,再通过毛细现象诱导自组装成花瓣状手性结构(图5(c)、5(d))。Luo等[83]则设计了一种漩涡状结构(图5(e)),并讨论了制造的结构尺寸对激光功率和单次曝光时间的依赖性。Wang等[84]则通过手性自组装,利用流体效应制备出咖啡环状手性结构。
LDW主要依赖光刻胶通过双光子聚合进行3D打印,且根据光刻胶的种类,该过程通常属于光引发的自由基聚合或阳离子开环聚合。下文以主要成分为丙烯酸酯单体与硫杂蒽酮类引发剂的光刻胶为例简述该过程 (该种类的光刻胶反应机理为自由基聚合),具体在激光下经过下述三个过程完成打印[85]。
第一步,在特定波长的激光下 (波长的选取由所用引发剂决定),处于基态的光引发剂 (photoinitiator,PI)同时吸收两个光子,生成带有电荷的初级自由基 (式(3)中用R·表示)。
$ \mathrm{PI}+2h\nu \xrightarrow{{\quad}}\mathrm{R}\cdot \;.$
第二步,生成的自由基通过作用于丙烯酸酯单体的碳碳双键,形成单体自由基,通过单体自由基与单体加成,生成新的自由基,由此完成链增长过程。
$ \mathrm{R}\cdot +\mathrm{CH}_2\mathrm{}\xlongequal{\;\;\;\;}\mathrm{CH}-\mathrm{COOR'}\xrightarrow{{\quad}} \mathrm{R}-\mathrm{CH}_2\mathrm{}-\mathrm{C}\cdot \mathrm{H}-\mathrm{COOR'} \;.$
第三步,最终不同聚合物长链上的官能团相互产生连接,发生交联,制备出不溶的三维固体结构。
通过上述步骤制备出的手性结构主要成分为有机物,后续可以通过电镀等手段向结构中引入无机材料。但这种方法加工出的无机结构纯度较低,性能也可能达不到预期需要。
为了解决这一问题,Liu等[86]在2022年,利用光激发诱导半导体量子点表面改性,从而在原料之间生成化学键联结,使半导体量子点能直接用于LDW加工。反应原理如图6(a)所示 (举例使用的为3-硫基丙酸 (MPA)封端的CdSe/ZnS核壳量子点),半导体量子点在激光激发下产生电子空穴对,通过捕获这种高能载流子,就能改变材料局部的电子态从而调整颗粒间产生化学键的反应性能。利用这种特性,能制造以半导体材料为主要成分的微纳结构,如图6(b)所示,即为使用该方法制备的半导体基的手性结构。2023年该课题组又设计了一种利用胶体量子点 (quantum dots, QDs)的3D打印方式,命名为3D Pin,将能用于LDW的无机材料拓宽到更广的范围。该方法与常规的聚合物单体与光引发剂构成的光刻胶相比,利用的是无机纳米晶体表面的有机配体 (制备中不可或缺的结构,能增加无机纳米材料的溶解度)与少量双叠氮化物 (光引发剂),由飞秒激光激活产生氮宾自由基 (初级自由基),从而引导无机纳米材料表面的有机配体发生聚合反应 (链增长过程)。由图6(c)可以看出,作为聚合位点的无机纳米粒子的有机配体,在氮宾自由基的作用下发生反应进行连接,带动无机纳米粒子一并发生连接,从而直写出无机材料含量更高的结构,其中有机物的质量分数低于10%。通过该策略,该课题组尝试了许多不同结构来检测分辨率,此方法也能用于加工手性结构。如图6(d)所示,设计了一种半径随螺纹变化的锥形螺旋,其电镜图如6(e)展示,测试得不对称因子达0.24。通过此方法能加工出高无机材料纯度的结构,在氧化物、半导体、金属材料等都得到了成功运用[87]。
上文对EBL、FIB和LDW各自的技术路线与核心原理进行了阐述。在此基础上,下文将聚焦于这三种工艺,从分辨率、加工维度、材料选择、加工效率、总体成本五个维度,对它们的差异进行系统性的对比分析,如表1所示。
分辨率上,EBL利用电子极短的德布罗意波长,理论上可达原子级,是三者中精度最高的技术。FIB虽然成像分辨率可达5 nm以下,但加工精度受离子束溅射过程影响,通常为十几到几十纳米。LDW利用双光子聚合技术可突破光学衍射极限,实现百纳米级精度。
加工维度上,EBL主要用于平面图形曝光。虽可通过堆叠2D结构或在不平整表面上加工出3D结构,但不擅长加工复杂的3D结构。FIB通过逐层扫描溅射,可以加工真正的3D结构,如微柱、悬臂梁、空腔等,但自由度不及LDW。而LDW是制造复杂三维微纳结构的理想工具,具备极高的设计自由度。
材料选择上,EBL加工的材料取决于沉积的材料或刻蚀底座,需在样品上涂覆光刻胶,曝光显影后通过沉积或刻蚀,将图形转移至底层材料。FIB对材料无选择性通过物理溅射,几乎可加工任何固体材料,如金属、陶瓷、半导体等。LDW加工的材料需能与激光发生相互作用,可加工光刻胶、聚合物,也能通过光热/光化学效应直接合成或还原材料。
加工效率上,EBL的加工效率极低,只能通过串行点对点扫描方式,速度量级为cm2/h。FIB的加工效率中等,材料去除速率通常为μm3/s 量级。LDW的加工速率较高,串行的线扫描速度可达m/s量级,面速度约mm2/min,并且能进行多束并行扫描,可进一步提升吞吐量。
总体成本上,EBL设备本身极为昂贵,且需高真空系统,运行和维护成本高,但因无需掩模,适合小批量研发。FIB设备成本同样高昂,与EBL相当或略低,但功能多样 (成像+加工),是很多分析实验室的核心工具。LDW设备成本显著低于EBL和FIB。可在大气或惰气环境下工作,运行和维护成本也低得多,性价比突出。
综上,三者虽然都可用于微纳加工,但加工参数存在明显差异,这为三种技术带来不同的使用环境。EBL常用于掩模版制造、纳米器件研发等二维结构的制备。FIB多用在TEM等样品制备,芯片电路修复、编辑等需要减材制造的场景。LDW则用于微光学元件 (如微透镜阵列)、传感器、3D光子晶体等在结构上更加复杂的三维结构加工。
深入探索这些机制差异,近年来许多研究也展现出三种技术在微纳加工方面的协同潜力,精确把握工艺特点对于设计高效、高精度的混合制造流程至关重要。2024年,Madigawa等[88]利用EBL在大面积上定义高精度的基准图形或电极阵列,然后使用FIB对特定区域进行局域化的纳米级修正、切割或TEM样品制备,这种组合充分发挥了EBL的高通量 (相较于FIB)和FIB的超高局域操控能力。而在2021年,Rajabasadi等[89]则结合LDW的三维加工能力以及EBL的高精度分辨率,先用LDW快速构建复杂的三维微支架或微流控通道,再在支架的特定位置利用EBL精确镀覆高分辨率的金属电极或超导量子电路。由此可见,三种技术因其物理原理不同,在加工能力上形成了明确的分工和互补,而制备过程中也不必拘泥于单一方式:EBL能对目标结构进行精确加工;FIB能利用实时成像能力对材料进行定点加工;而LDW能对复杂结构进行快速成型。
近年来,微纳加工技术制备的手性结构在传感领域展现出重要的应用潜力。此类方法的核心优势在于,能够以高精度、可重复且适于大规模集成的方式,精确构建具有预设几何构型的微纳尺度手性体系。相比天然分子,这类人工设计结构通常表现出更强烈的CD响应,并在外部环境 (如折射率、分子吸附、应力等)变化时产生更显著的信号偏移,从而为实现高灵敏、可集成的传感功能奠定了坚实的物理基础[54,90-91]。
Duan等[92]报道了一种用EBL加工的类似卐字形的平面手性结构,扫描电镜结果如图7(a)所示。利用Mg易吸氢,设计Mg纳米粒子为结构主体,Au纳米粒子辅助增强手性响应,在氢气浓度较高的环境下,Mg逐渐变化为MgH2,导致结构的手性性能发生明显变化(基本原理如图7(b))。如图7(c)所示,测试了在0.25%(体积分数,余同)的氢气环境下每隔10 min样品的CD性能,可见原本结构表征出明显的CD响应 (红线),在100 min后变得趋于平缓 (蓝线),以此为原理制备成检测环境中氢气浓度的传感器。Duan等测试了在体积分数为0.25%~3%氢气环境下,制备的氢气传感器相关性能。在氢气含量为0.3%环境下,在出现CD性能变化前需要大约120 s的积累时间,而在氢气含量达3%则可完成瞬时响应;同时也对该结构的循环稳定性做了一定的测试与优化,通过将同一样品分别在0.25%、0.5%与2.0%浓度梯度下进行120 min的吸氢测试,样品中的Mg粒子出现一定程度的开裂,这来源于样品吸氢后的体积膨胀与氧还原后的收缩。通过在Mg表面镀一层5 nm厚度的Ti层来释放Mg体积变化产生的应力,能对这一状况做出一定程度的改善。然而传统氢气传感器的测试下限通常能达到10 ppm (1 ppm=10-6),远低于测试范围的0.25% (2500 ppm),且循环寿命也能达到1×104次以上,只有在响应时间上,该结构接近传统氢气传感器。但不可否认,该设计为微纳加工手性结构的应用提供了一种有趣的思路。
类似的,Kan等[93]通过光刻与蚀刻制备了一种二维螺旋超材料,其扫描电镜结果如图7(d)所示。当该结构受到压力时,螺旋线会发生形变,化为三维螺旋并产生手性响应 (原理图如图7(e))。利用该特性,当环境气压增大时会导致该结构产生形变,结构的CD响应也会随着形变量增大而逐步增强,如图7(f)所示,从而可以用作气压测试设备中的传感器。关于该结构对气压的测量范围则与结构尺寸有关,结构愈大,尺寸在气压下的形变量愈大,测量范围愈广,而结构的CD性能则限制了尺寸的上限,只有当光的波长与尺寸匹配时才会产生CD信号,因为这类限制,该结构无法做到传统气压检测器的检测范围 (10−5~103 Pa覆盖6个数量级),尚需未来进一步改良。
在材料识别中,检测材料的CD性能是一种重要的表征手段,这意味着分子的手性通常是接近一个固定值,在外加条件刺激下改变的幅度并不大[94-95],因此利用材料本征性质来制备可调控手性光学元件存在一定设计难度。而微纳加工的手性结构则不必拘泥于此,常规思路上可通过改变温度、电磁场或改变形状来调控结构的手性,制备出的手性光学调控元件拥有更强的光学响应与可调控性。
7.1节中所介绍的两种结构同样可以用于光学调控,除此之外,Zhang等[96]通过LDW技术与干法蚀刻制备了一种通过额外光场来进行光学调控的手性结构,其扫描电镜表征如图8(a),结构示意如图8(b)所示,由4个旋转不同的角度的结构单体构成一组重复单元 (图8(c))。在强光照射下,光子能量大于硅的带隙,光载流子的激发将合并的硅垫从绝缘状态转变为高导电状态,硅垫中产生光载流子,导致结构的手性发生转变。实验测试见图8(d),可以观察到在光激发下结构的CD光谱信号发生翻转。在这项工作中,通过将微纳加工的人工手性结构与光活性介质相结合,达成了在不改变手性结构的情况下进行手性切换。让人工手性结构能达到与有机分子类似的响应环境而实时改变手性的效果。
在成像、检测、显示、通信系统、传感器设备、生物检测、太阳能收集、光催化、隐形等领域,材料的吸光性有着广泛应用。CD作为手性结构的特征之一,除去作为手性性能的评判外,其本身的物理含义即是表达结构对圆偏振光的原则性吸收能力,而通过微纳加工制备的手性结构能够在可见至近红外波段实现强烈的CD性能。并且,通过对微纳结构的几何参数调控,能够改变其吸收波长的峰位与手性光学响应强度[97],这些特点为这些结构用在光的吸收上提供了坚实的理论基础。
Li等[98]设计了一种由两对正交放置的硅棒组成的结构,由此结构组成的全电介质超表面,如图9(a)所示。该结构通过对几何结构参数与光的入射参数来达到对圆偏振光的选择性以及高效的吸收性,在图9(a)中,当增大x方向的硅条宽度W1其吸收峰位将红移,增大硅条厚底H也同样能使吸收峰位红移。而通过改变光的入射角,能够调节其对光的吸收率和选择性吸收的光波长,如图9(b)所示 (该入射角参数测试,使用的样品尺寸参数为H=360 nm,W1=260 nm,W2=148 nm,L1=L2=330 nm,a=800 nm),当入射角增大时,其吸收峰位也会发生红移,且峰值也会发生变化,测试在1591 nm附近出现近似于1的吸收峰。这种随着入射角的改变,吸收峰位发生变化的现象来源于斜入射打破了入射角为0°时的对称条件。Shen等[99]报道了一种由两个开口的金环组成的手性结构 (如图9(c)),可以通过改变结构的几何参数和环开口之间的旋转角度来调节吸收峰和手性,如图9(d),对圆偏振光的吸收范围在900~1050 nm与1200~1600 nm,两种开环方向的吸收峰值分别在1000 nm与1400 nm左右,吸收率能达到96%~98%。通过对图9(d)的观察,可以很直观的看出结构图9(c)中旋转角α与β对结构性能的影响,展现出微纳加工手性结构的可调性与设计的自由度。
许多药物都具有手性,而其不同的对映异构体可能产生截然不同的治疗效果,甚至于其中某些异构体存在致命的毒性[100]。因此,开发高效的对映异构体分离和识别技术对于药物开发和生命科学研究至关重要。在分子尺度上,手性分子具有相同的物理和化学性质,但在与手性环境相互作用时会表现出不同的行为,这使得手性分离成为获取纯对映异构体的有效方法,尤其在制药、农业、食品等行业中具有重要意义[101]。
近年来,随着微纳加工技术的发展,手性微纳结构因其独特的手性光学效应和在手性物质相互作用中的选择性,为实现高效手性分离提供了新途径[102],这些人工手性结构的光学手性响应可以比天然手性材料高出数个数量级[103]。
Cao等[104]在2017年设计了一种通过EBL制备的金双裂环纳米结构(如图10(a)),在圆偏振光入射时可以激发多极法诺(Fano)共振,使裂环间隙处产生手性梯度力,将间隙上方不同手性纳米颗粒分离,图10(b)展示了不同手性在该区域所受力的梯度分布[104]。次年,该课题组[105]对之前的设计做出改进,制备了一种用EBL制备的圆盘-双列环结构(如图10 (c, d)),通过破坏结构对称性,激发偶极-八极Fano共振模式。增强结构的手性性能,其裂环和圆盘之间可以产生较强的手性梯度力,分离的粒子尺寸下限能达到10 nm。同时,该结构在100 mW的低光功率下运行,既避免了高功率对分子的破坏,又降低了运行能耗。在与传统的化学/色谱手性分离方法对比上,该方法无需手性拆分剂,且过程中仅涉及光学作用,避免了分离过程中化学试剂对分子结构的破坏,为手性粒子分离提供了一种低损耗、低能耗的优质方案。
手性微纳结构的功能特性高度依赖于其精确的几何构型与可控的对称破缺设计,而现代微纳加工技术的持续进步为这一目标的实现提供了关键的技术支撑。本文系统梳理了EBL、FIB及LDW三种主流微纳加工技术的工艺原理、近年来的重要突破及其在手性结构制备中的典型应用案例,阐明了微纳加工技术在该领域所展现的灵活性与优越性:从EBL实现的高精度二维手性阵列,到FIB基于纳米剪纸技术构建的三维扭曲构型,再到LDW在多材料集成与复杂三维手性器件制备中的广泛应用,微纳加工正不断推动加工分辨率、结构维度与材料兼容性等方面的边界。
在应用层面,本文综述了基于微纳加工制备的手性结构在传感检测、手性光场调控、可调谐圆偏振响应,以及手性粒子分离等领域的突出表现。该类结构所具备的高灵敏度、动态可调谐特性,以及规模化集成潜力,为突破传统手性材料在性能与制备工艺方面的局限提供了有效途径。未来,进一步优化加工效率、扩展结构自由度并降低工艺成本,将是该领域发展的重点方向。
尽管本文介绍了三种加工方式的诸多成就,但上述技术固有的物理限制也在所举例子中有所体现,对实际应用带来了不小的阻碍,未来的研究工作也应聚焦于克服这些短板。对此,受本文第6节启发,可以使用协同加工的方式进行改进。
譬如针对EBL串行直写导致效率低下,可以考虑从直写加工转向模具化加工。通过在加工中引入纳米压印技术 (nanoimprint lithography, NIL),将高精度的EBL用于制备“母版”,再利用纳米压印进行快速、低成本的复制,这除了能改善加工速度带来的不便,也能规避在批量生产中反复应对电荷累计的困扰。而对于FIB在加工速度与材料损伤相互制约的情况,也可以通过混合加工策略来做出改进。为了避免大功率带来的Ga+污染,可以将FIB从高能铣削的用法转变为低功率辅助加工,且在使用后引入抛光等步骤来去除FIB加工产生的重离子损伤层。最后,关于LDW在材料维度上的局限性,可以与原子层沉积 (atomic layer deposition, ALD)等技术协同加工,先利用LDW打印出高精度的聚合物模板或支架,再通过ALD沉积高介电常数的材料或金属,最后通过灰化去除聚合物成分,从而实现高精度无机三维结构的制备,打破LDW在无机材料加工上的壁垒。
随着微纳加工技术与材料科学、量子光学及模拟计算等学科的交叉融合[106-108],手性微纳器件正逐步向小型化、集成化与智能化方向演进。可以预见,在持续的研究探索与技术迭代推动下,微纳加工将进一步拓展手性结构的性能边界与应用场景,为光子学、传感技术及相关交叉领域的发展注入持续创新动力。而未来的微纳加工也不会是单一技术的独角戏,通过多种技术带来的多元融合模式,有望在加工精度、材料普适性、生产效率与生产成本之间找到新的平衡点。

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2026年第53卷第7期
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doi: 10.12086/oee.2026.260025
  • 接收时间:2026-01-23
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  • 出版时间:2026-07-25
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