通过电化学图像化的半导体电子和功能特性的产生和调谐。

IF 14.7 Q1 CHEMISTRY, MULTIDISCIPLINARY
Accounts of materials research Pub Date : 2025-08-01 eCollection Date: 2025-09-26 DOI:10.1021/accountsmr.5c00104
Denis Gentili, Edoardo Chini, Massimiliano Cavallini
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引用次数: 0

摘要

这篇文章介绍了表面电化学纳米图作为一种强大的和未被充分开发的策略,用于工程电化学活性材料的电子和功能特性。通过在微纳米尺度上对电子状态进行精确、局部的操作,这项技术为解锁和控制材料的固有特性提供了一条独特的途径。这些能力开辟了材料科学的新领域,其影响范围从催化到先进多功能设备的制造。传统的光刻技术,如光刻、电子束光刻和纳米压印,主要关注表面形貌的塑造。相比之下,电化学纳米图引入了一种完全不同的方法:它修饰材料本身。通过改变氧化态,产生或修复缺陷,以及调整表面化学,这种方法可以直接控制材料的性质。因此,它极大地扩展了应用范围,使开发具有定制电子和功能特征的材料成为可能。本帐户特别侧重于印章辅助电化学光刻(ECL),一种多功能和可扩展的技术。我们首先概述ECL的基本原理,包括驱动它的电化学过程,即氧化、还原和缺陷生成。接下来,我们追溯其历史发展,并强调其相对于传统纳米制造方法的优势,特别是在简单性、成本效益和与广泛材料的兼容性方面。通过精心挑选的案例研究,我们展示了ECL如何用于(i)生成和调整电子特性,(ii)赋予各种功能行为,以及(iii)实现空间控制缺陷工程,特别是在半导体中。至关重要的是,制造大面积样品的能力使我们能够利用以前通过扫描探针技术在电化学纳米光刻中无法实现的尺寸依赖特性,例如催化和纳米团簇的原位制造。这些发现极大地扩展了ECL的科学和技术潜力,为创新和应用开辟了新的途径。之所以选择这些案例,是因为它们与材料科学和新兴技术当前面临的挑战有关。值得注意的应用包括电阻开关器件的原位愈合,无关键元素催化剂的开发以及器件内活性元件的直接制造。其中许多研究在发表时都是开创性的,直到最近才获得广泛的认可,因为人们对可持续、低成本和可扩展的纳米制造技术的兴趣日益浓厚。我们强调ECL在实现可再生电阻开关、功能纳米颗粒的空间选择性纳米嵌入和创建功能表面图案方面的独特能力。这些特点使ECL成为弥合基础研究和实际设备集成之间差距的有前途的工具。此外,该方法与环境条件的兼容性及其大面积加工的潜力使其对工业应用特别有吸引力。在最后一节,我们讨论了ECL的前沿和前景。我们提出了提高分辨率、可重复性和与现有制造平台集成的策略。我们还概述了未来的发展方向,包括混合模式方法的发展。展望未来,我们预计ECL将在下一代材料和设备的开发中发挥核心作用,特别是在精确控制局部特性对性能和功能都至关重要的领域。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Generation and Tuning of Semiconductor Electronic and Functional Properties through Electrochemical Patterning.

This Account presents surface electrochemical nanopatterning as a powerful and underexplored strategy for engineering the electronic and functional properties of electrochemically active materials. By enabling precise, localized manipulation of electronic states at the micro- and nanoscale, this technique offers a unique pathway to unlock and control intrinsic material properties. These capabilities open new frontiers in materials science, with implications ranging from catalysis to the fabrication of advanced, multifunctional devices. Traditional lithographic techniques, such as photolithography, electron beam lithography, and nanoimprinting, mainly focus on shaping surface topography. In contrast, electrochemical nanopatterning introduces a fundamentally different approach: it modifies the material itself. By changing oxidation states, creating or healing defects, and tuning surface chemistry, this method allows for direct control of material properties. Consequently, it greatly expands the range of applications, enabling the development of materials with customized electronic and functional features. This Account focuses specifically on stamp-assisted electrochemical lithography (ECL), a versatile and scalable technique. We start by outlining the fundamental principles of ECL, including the electrochemical processes that drive it, namely oxidation, reduction, and defect generation. Next, we trace its historical development and highlight its advantages over traditional nanofabrication methods, particularly in terms of simplicity, cost-effectiveness, and compatibility with a wide range of materials. Through a curated selection of case studies, we demonstrate how ECL can be used to (i) generate and tune electronic properties, (ii) impart various functional behaviors, and (iii) achieve spatially controlled defect engineering, especially in semiconductors. Crucially, the ability to fabricate large-area samples has allowed us to harness size-dependent properties that were previously inaccessible in electrochemical nanolithography performed via scanning probe techniques, such e catalysis and the in situ fabrication of nanoclusters. These findings dramatically expand the scientific and technological potential of ECL, opening new avenues for innovation and application. The example cases were selected for their relevance to current challenges in materials science and emerging technologies. Notable applications include in situ healing in resistive switching devices, the development of critical-element-free catalysts, and the direct fabrication of active components within devices. Many of these studies were pioneering at the time of publication and have only recently gained broader recognition due to the growing interest in sustainable, low-cost, and scalable nanofabrication techniques. We emphasize ECL's unique capabilities in enabling regenerable resistive switching, spatially selective nanoembedding of functional nanoparticles, and creating functional surface patterns. These features position ECL as a promising tool for bridging the gap between fundamental research and practical device integration. Moreover, the method's compatibility with ambient conditions and its potential for large-area processing make it particularly attractive for industrial applications. In the final section, we discuss the frontier and the perspectives of ECL. We propose strategies to enhance resolution, reproducibility, and integration with existing manufacturing platforms. We also outline future directions, including the development of hybrid patterning approaches. Looking ahead, we envision ECL playing a central role in the development of next-generation materials and devices, particularly in fields where precise control over local properties is essential for both performance and functionality.

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