Nano-chemistry and scanning probe nanolithographies
TL;DR: This tutorial review presents the most promising probe-based nanolithographies that are based on the spatial confinement of a chemical reaction within a nanometer-size region of the sample surface.
Abstract: The development of nanometer-scale lithographies is the focus of an intense research activity because progress on nanotechnology depends on the capability to fabricate, position and interconnect nanometer-scale structures. The unique imaging and manipulation properties of atomic force microscopes have prompted the emergence of several scanning probe-based nanolithographies. In this tutorial review we present the most promising probe-based nanolithographies that are based on the spatial confinement of a chemical reaction within a nanometer-size region of the sample surface. The potential of local chemical nanolithography in nanometer-scale science and technology is illustrated by describing a range of applications such as the fabrication of conjugated molecular wires, optical microlenses, complex quantum devices or tailored chemical surfaces for controlling biorecognition processes.
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758 citations
TL;DR: The fundamentals of scanning probe lithography and its use in materials science and nanotechnology are reviewed, focusing on robust methods, such as those based on thermal effects, chemical reactions and voltage-induced processes, that demonstrate a potential for applications.
Abstract: The nanoscale control afforded by scanning probe microscopes has prompted the development of a wide variety of scanning-probe-based patterning methods. Some of these methods have demonstrated a high degree of robustness and patterning capabilities that are unmatched by other lithographic techniques. However, the limited throughput of scanning probe lithography has prevented its exploitation in technological applications. Here, we review the fundamentals of scanning probe lithography and its use in materials science and nanotechnology. We focus on robust methods, such as those based on thermal effects, chemical reactions and voltage-induced processes, that demonstrate a potential for applications.
531 citations
Soochow University (Suzhou)1, Stanford University2, Polytechnic University of Milan3, University of California, Santa Barbara4, University of California, Los Angeles5, University of Modena and Reggio Emilia6, University of Massachusetts Amherst7, Katholieke Universiteit Leuven8, Peking University9, University College London10, National Chiao Tung University11, University of Texas at Austin12, IBM13, University of Granada14, Autonomous University of Barcelona15, Singapore University of Technology and Design16, East China Normal University17, University of Michigan18, Liverpool John Moores University19, Tsinghua University20, Chinese Academy of Sciences21, Technische Universität München22, RWTH Aachen University23
TL;DR: This manuscript describes the most recommendable methodologies for the fabrication, characterization, and simulation of RS devices, as well as the proper methods to display the data obtained.
Abstract: Resistive switching (RS) is an interesting property shown by some materials systems that, especially during the last decade, has gained a lot of interest for the fabrication of electronic devices, with electronic nonvolatile memories being those that have received the most attention. The presence and quality of the RS phenomenon in a materials system can be studied using different prototype cells, performing different experiments, displaying different figures of merit, and developing different computational analyses. Therefore, the real usefulness and impact of the findings presented in each study for the RS technology will be also different. This manuscript describes the most recommendable methodologies for the fabrication, characterization, and simulation of RS devices, as well as the proper methods to display the data obtained. The idea is to help the scientific community to evaluate the real usefulness and impact of an RS study for the development of RS technology. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
441 citations
TL;DR: In this article, the authors summarize the recent progress in applications of piezoresponse force microscopy (PFM) for imaging, manipulation and spectroscopy of ferroelectric switching processes.
Abstract: Ferroelectrics and multiferroics have recently emerged as perspective materials for information technology and data storage applications. The combination of extremely narrow domain wall width and the capability to manipulate polarization by electric field opens the pathway toward ultrahigh (>10 TBit inch−2) storage densities and small (sub-10 nm) feature sizes. The coupling between polarization and chemical and transport properties enables applications in ferroelectric lithography and electroresistive devices. The progress in these applications, as well as fundamental studies of polarization dynamics and the role of defects and disorder on domain nucleation and wall motion, requires the capability to probe these effects on the nanometer scale. In this review, we summarize the recent progress in applications of piezoresponse force microscopy (PFM) for imaging, manipulation and spectroscopy of ferroelectric switching processes. We briefly introduce the principles and relevant instrumental aspects of PFM, with special emphasis on resolution and information limits. The local imaging studies of domain dynamics, including local switching and relaxation accessed through imaging experiments and spectroscopic studies of polarization switching, are discussed in detail. Finally, we review the recent progress on understanding and exploiting photochemical processes on ferroelectric surfaces, the role of surface adsorbates, and imaging and switching in liquids. Beyond classical applications, probing local bias-induced transition dynamics by PFM opens the pathway to studies of the influence of a single defect on electrochemical and solid state processes, thus providing model systems for batteries, fuel cells and supercapacitor applications.
405 citations
IBM1
TL;DR: A scanning probe lithography method based on the local desorption of a glassy organic resist by a heatable probe is presented and demonstrated at a half pitch down to 15 nanometers without proximity corrections and with throughputs approaching those of Gaussian electron beam lithography at similar resolution.
Abstract: For patterning organic resists, optical and electron beam lithography are the most established methods; however, at resolutions below 30 nanometers, inherent problems result from unwanted exposure of the resist in nearby areas. We present a scanning probe lithography method based on the local desorption of a glassy organic resist by a heatable probe. We demonstrate patterning at a half pitch down to 15 nanometers without proximity corrections and with throughputs approaching those of Gaussian electron beam lithography at similar resolution. These patterns can be transferred to other substrates, and material can be removed in successive steps in order to fabricate complex three-dimensional structures.
313 citations
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TL;DR: A direct-write "dip-pen" nanolithography (DPN) has been developed to deliver collections of molecules in a positive printing mode, making DPN a potentially useful tool for creating and functionalizing nanoscale devices.
Abstract: A direct-write “dip-pen” nanolithography (DPN) has been developed to deliver collections of molecules in a positive printing mode. An atomic force microscope (AFM) tip is used to write alkanethiols with 30-nanometer linewidth resolution on a gold thin film in a manner analogous to that of a dip pen. Molecules are delivered from the AFM tip to a solid substrate of interest via capillary transport, making DPN a potentially useful tool for creating and functionalizing nanoscale devices.
2,843 citations
TL;DR: The Dip-Pen Nanolithography (DPN) is a direct-write tool for generating surface-patterned chemical functionality on the sub-100 nm length-scale as discussed by the authors.
Abstract: The ability to tailor the chemical composition and structure of a surface on the 1-100 nm length scale is important to researchers studying topics ranging from electronic conduction, to catalysis, to biological recognition in nanoscale systems. Dip-pen nanolithography (DPN) is a new scanning-probe based direct-write tool for generating such surface-patterned chemical functionality on the sub-100 nm length-scale, and it is a technique that is accessible to any researcher who can use an atomic force microscope. This article introduces DPN and reviews the rapid growth of the field of DPN-related research over the past few years. Topics covered range from the development of new classes of DPN-compatible chemistry, to experimental and theoretical advances in the understanding of the processes controlling tip-substrate ink transport, to the implementation of micro-electro-mechanical system (MEMS) based strategies for parallel DPN applications.
911 citations
TL;DR: In this paper, the chemical modification of hydrogen-passivated n-Si surfaces by a scanning tunneling microscope (STM) operating in air is reported, and the modified surface regions have been characterized by STM spectroscopy, scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (TOF SIMS), and chemical etch/Nomarski microscopy.
Abstract: The chemical modification of hydrogen‐passivated n‐Si (111) surfaces by a scanning tunneling microscope (STM) operating in air is reported. The modified surface regions have been characterized by STM spectroscopy, scanning electron microscopy (SEM), time‐of‐flight secondary‐ion mass spectrometry (TOF SIMS), and chemical etch/Nomarski microscopy. Comparison of STM images with SEM, TOF SIMS, and optical information indicates that the STM contrast mechanism of these features arises entirely from electronic structure effects rather than from topographical differences between the modified and unmodified substrate. No surface modification was observed in a nitrogen ambient. Direct writing of features with 100 nm resolution was demonstrated. The permanence of these features was verified by SEM imaging after three months storage in air. The results suggest that field‐enhanced oxidation/diffusion occurs at the tip‐substrate interface in the presence of oxygen.
723 citations
TL;DR: An overview of various patterning methodologies can be found in this paper, which is organized into three major sections: generation of patterns, replication of patterns and three-dimensional patterning.
Abstract: This article provides an overview of various patterning methodologies, and it is organized into three major sections: generation of patterns, replication of patterns, and three-dimensional patterning. Generation of patterns from scratch is usually accomplished by serial techniques that are able to provide arbitrary features. The writing process can be carried out in many different ways. It can be achieved using a rigid stylus; or a focused beam of photons, electrons, and other energetic particles. It can also be accomplished using an electrical or magnetic field; or through localized add-on of materials such as a liquid-like ink from an external source. In addition, some ordered but relatively simple patterns can be formed by means of self-assembly. In replication of patterns, structural information from a mask, master, or stamp is transferred to multiple copies with the use of an appropriate material. The patterned features on a mask are mainly used to direct a flux of radiation or physical matter from a source onto a substrate, whereas a master/stamp serves as the original for replication based on embossing, molding, or printing. The last section of this article deals with three-dimensional patterning, where both vertical and lateral dimensions of a structure need to be precisely controlled to generate well-defined shapes and profiles. The article is illustrated with various examples derived from recent developments in this field.
632 citations
TL;DR: In this article, the authors examined the kinetics and mechanism of local oxidation of silicon and how factors such as the strength of the electric field, ambient humidity, and thickness of the oxide affect its rate and resolution.
Abstract: Atomic force microscope induced local oxidation of silicon is a process with a strong potential for use in proximal probe nanofabrication. Here we examine its kinetics and mechanism and how such factors as the strength of the electric field, ambient humidity, and thickness of the oxide affect its rate and resolution. Detection of electrochemical currents proves the anodization character of the process. Initial very fast oxidation rates are shown to slow down dramatically as a result of a self-limiting behavior resulting from the build up of stress and a reduction of the electric field strength. The lateral resolution is determined by the defocusing of the electric field in a condensed water film whose extent is a function of ambient humidity.
441 citations