硅酸盐学报

金属有机框架材料图案化技术研究进展

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许潇逸 , 吴月梅 , 黄宁

硅酸盐学报 | 综合评述 2026,54(7): 2325-2337

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硅酸盐学报 |综合评述 2026 , 54 (7) : 2325 -2337

金属有机框架材料图案化技术研究进展

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许潇逸, 吴月梅, 黄宁

作者信息

硅及先进半导体材料全国重点实验室，浙江大学高分子科学与工程学系，杭州 310027

通讯作者:

黄宁（1985—），男，博士，研究员。

作者简介:

许潇逸（1996—），男，博士。

Research Progress on Patterning Techniques for Metal-Organic Frameworks

Xiaoyi XU, Yuemei WU, Ning HUANG

Affiliations

State Key Laboratory of Silicon and Advanced Semiconductor Materials, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding Author:

{HUANG} Ning (1985-), male, Ph.D., Professor. E-mail: nhuang@zju.edu.cn

XU Xiaoyi (1996-), male, Ph.D. E-mail: xxyzsq@zju.edu.cn

出版时间: 2026-06-02 doi: 10.14062/j.issn.0454-5648.20260150

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金属有机框架（MOFs）是一类由金属离子与有机配体通过配位作用自组装形成的晶态多孔材料，具有结构可调、孔隙率高和功能多样等特点。然而，MOFs通常以粉末形态存在，难以直接应用于微纳器件中，因此发展能够实现高精度空间排布与图案化的技术，成为推动MOFs从材料基础研究迈向功能集成器件的关键。本文系统综述了MOFs图案化技术的研究进展，着重分析了从间接组装（如模板法、印刷技术）到直接图案化（如光刻、电子束、激光直写）的技术发展路径。文中详细介绍了紫外光、电子束、X射线及激光等直接图案化方法的工作原理，并与间接策略在分辨率、结构保持能力和工艺兼容性等方面进行了对比。最后，总结了该领域在提升分辨率、实现工艺标准化及异质材料集成等方面所面临的挑战，并对MOFs图案化技术与半导体工艺相结合的未来发展方向进行了展望，以期为MOFs微纳器件的制备与应用提供参考。

关键词

金属有机框架 / 图案化 / 光刻 / 微纳加工

Abstract

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Metal-organic frameworks (MOFs) are crystalline porous materials constructed from metal ions or metal clusters and organic linkers through coordination bonds. MOFs become one of the most actively studied functional porous materials due to their long-range structural order, high porosity, exceptionally large specific surface areas, and tunable pore environments. Researchers can design framework topologies in an atomic level and regulate channel dimensions, pore shapes, and surface chemistry in a nanoscale via selecting metal nodes with different coordination geometries and organic linkers with tailored sizes, conformations, and functional groups. These characteristics endow MOFs with a broad application potential in gas storage, molecular separation, heterogeneous catalysis, chemical sensing, optoelectronics, and emerging micro/nano devices. In particular, continuous progress on component design and post-synthetic modification make it possible to modulate the electrical, optical, and interfacial properties of MOFs systems, thereby creating opportunities for their integration into microelectronic, photonic, and sensing platforms.

Despite these advantages, the practical use of MOFs in integrated devices remains strongly limited by their common physical forms. Most of MOFs are still prepared and utilized as polycrystalline powders, bulk crystals, or randomly deposited particles, which are difficult to position precisely on substrates or to incorporate into device architectures with controlled dimensions. As modern microelectronics, integrated photonics, and high-density sensor technologies continue to evolve toward miniaturization, multifunctionality, and on-chip integration, it is important to convert the intrinsic physicochemical properties of MOFs into device-relevant thin films and micro-/nano-structures. In this context, patterning technology plays a central role. It provides an essential bridge between the unique properties of MOFs and the fabrication requirements of practical devices via enabling high-quality MOF films or well-defined micro/nanopatterns to be formed on silicon wafers, glass, metals, and flexible polymer substrates. The development of reliable and precise patterning strategies is thus a key prerequisite for the implementation of MOFs in integrated circuits, sensor arrays, optical components, and other miniaturized functional systems.

However, MOFs also present some distinctive challenges for micro-/nano-fabrication. Their frameworks are mainly stabilized by coordination bonds, which are generally weaker than the covalent or ionic bonds in conventional inorganic semiconductors. As a result, many MOFs possess a limited mechanical robustness and are sensitive to heat, moisture, irradiation, reactive chemicals, and aggressive processing environments. Furthermore, their interconnected nanoporous channels can be easily blocked or damaged during conventional lithographic and etching procedures. Standard microfabrication methods such as plasma etching, wet chemical corrosion, and resist-assisted processing often involve high-energy species or chemical agents that may degrade framework integrity, alter surface functionality, or collapse pore structures. In addition, the compatibility of many MOFs with established semiconductor processing conditions is also insufficient, especially with respect to thermal stability, solvent tolerance, and interface adhesion. These factors motivate the development of MOF-specific patterning methods that can deliver a high spatial precision, while preserving crystallinity, porosity, and functionality.

According to whether the intrinsic structure of the MOF is directly transformed during processing, the existing MOF patterning technologies can be broadly divided into indirect and direct strategies. Indirect patterning does not primarily rely on structural modification of preformed MOFs. Instead, it controls where MOFs nucleate, grow, or deposit through external spatial confinement, surface chemical guidance, or material transfer. Representative approaches include template-assisted growth, inkjet printing, microcontact printing, selective growth on chemically modified substrates, and other spatially guided assembly methods. These routes are attractive because they are relatively simple, often mild, and generally effective for preserving the original porous framework. They play an important role in the early development of patterned MOF films and arrays, especially on nontraditional substrates and in proof-of-concept sensing devices. Nevertheless, their pattern fidelity is often restricted by template dimensions, droplet spreading, solvent evaporation, or interfacial diffusion. As a consequence, it remains difficult for many indirect methods to achieve high-resolution submicron-sized features, excellent film uniformity over large areas, and precise three-dimensional integration. Direct patterning strategies emerge as a major focus of recent research. Unlike indirect routes, they directly process pre-deposited MOF films or their precursor-derived layers through localized irradiation or other targeted energy inputs. Ultraviolet light, electron beams, X-rays, and lasers are the most widely explored tools. Their underlying mechanisms can be generally categorized into two types. The first involves irradiation-induced chemical changes, such as ligand crosslinking, framework decomposition, bond cleavage, or surface functionalization, which create solubility or wettability contrast between exposed and unexposed regions and thus enable selective development. The second involves direct material removal or transformation through physical ablation, decomposition, densification, or phase change. Compared with conventional resist-based lithography, direct patterning often reduces the need for sacrificial organic photoresists and can minimize residue-induced pore blockage. The carefully-designed direct methods can achieve a higher resolution, while retaining a large fraction of the crystallinity, pore accessibility, and chemical functionality of MOFs. Recent studies demonstrate that X-ray and electron-beam lithography can produce features well below 50 nm, ultraviolet-based chemistry can offer an effective balance between resolution and scalable processing, and laser-induced methods can enable localized consolidation, shaping, and even three-dimensional structuring.

From a broader perspective, the evolution of MOF patterning reflects a transition from externally guided deposition toward irradiation-driven in-situ material transformation. This transition is essential for addressing several key demands simultaneously, including precise positioning, high-resolution micro-/nano-structuring, heterogeneous integration, and compatibility with existing device fabrication workflows. Also, patterning requirements for MOFs can be understood as progressive levels of spatial control, i.e., one-dimensional control over film thickness, two-dimensional control over in-plane location and geometry, and three-dimensional control over complex architectures and multilayer arrangements. Expanding from simple film formation to sophisticated three-dimensional pattern construction will be crucial for realizing advanced device concepts in optics, sensing, electronics, and biomedicine.

Summary and Prospects

Although substantial progress is achieved, several important challenges still limit a broader implementation of patterned MOFs. First, the existing methods are material-specific and depend on MOFs containing radiation-sensitive ligands or specially designed functional groups, which restricts universality across the large MOF family. Second, the mechanisms of structural evolution under irradiation or localized processing remain insufficiently understood, particularly regarding changes in crystallinity, pore structure, surface chemistry, and transport properties. Third, an inherent trade-off still exists between ultimate resolution and scalable, high-throughput manufacturing. Techniques with nano-sized precision are often slow and costly, whereas more scalable approaches usually sacrifice pattern fidelity. Future research should therefore focus on designing process-compatible and radiation-responsive MOFs, developing stable colloidal and thin-film platforms, clarifying structure-property relationships during patterning, and combining top-down lithography with bottom-up selective growth. Progress along these directions is expected to accelerate the transformation of MOFs from high-performance porous materials into programmable micro-/nano-building blocks for next-generation integrated devices.

Key words

metal-organic frameworks / patterning / lithography / micro-nano fabrication

引用本文

许潇逸, 吴月梅, 黄宁. 金属有机框架材料图案化技术研究进展. 硅酸盐学报, 2026 , 54 (7) : 2325 -2337 . DOI: 10.14062/j.issn.0454-5648.20260150

Xiaoyi XU, Yuemei WU, Ning HUANG. Research Progress on Patterning Techniques for Metal-Organic Frameworks[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (7) : 2325 -2337 . DOI: 10.14062/j.issn.0454-5648.20260150

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浙江省杰出青年科学基金(LR25B040001)

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2026年第54卷第7期

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doi: 10.14062/j.issn.0454-5648.20260150

接收时间：2026-03-13
首发时间：2026-10-22
出版时间：2026-06-02

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收稿日期：2026-03-13
修回日期：2026-04-02

基金

浙江省杰出青年科学基金(LR25B040001)

作者信息

硅及先进半导体材料全国重点实验室，浙江大学高分子科学与工程学系，杭州 310027

通讯作者:

黄宁（1985—），男，博士，研究员。

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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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