Nanopatterning of carbonaceous structures by field-induced carbon dioxide splitting with a force microscope

García, Ricardo García; Losilla, N. S.; Martínez, Javier López; Martínez, Ramsés V.; Palomares, F. J.; Huttel, Yves; Calvaresi, Matteo; Zerbetto, Francesco

doi:10.1063/1.3374885

Cited by 47 publications

(58 citation statements)

References 31 publications

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“…The potential of b-SPL goes beyond the field of nanolithography. The method has been applied to understand new processes to decompose very stable chemical species such as carbon dioxide 39 . These results expand and strengthen the applications of SPL and nanochemistry 45 .…”

Section: Bias-induced Splmentioning

confidence: 99%

Advanced scanning probe lithography

2014

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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 their exploitation in technological applications. Here, we review the fundamentals of scanning probe lithography and its use in materials science and nanotechnology. We focus on the methods and processes that offer genuinely lithography capabilities such as those based on thermal effects, chemical reactions and voltage-induced processes. Published in:Nature Nanotechnology 9, 577-587 (2014) Progress in nanotechnology depends on the capability to fabricate, position, and interconnect nanometre-scale structures. A variety of materials and systems such as nanoparticles, nanowires, two-dimensional materials like graphene and transition metal dichalcogenides, plasmonics materials, conjugated polymers and organic semiconductors are finding applications in nanoelectronics, nanophotonics, organic electronics and biomedical applications. The success of many of the above applications relies on the existence of suitable nanolithography approaches. However, patterning materials with nanoscale features aimed at improving integration and device performance poses several challenges. The limitations of conventional lithography techniques related to resolution, operational costs and lack of flexibility to pattern organic and novel materials have motivated the development of unconventional fabrication methods [1][2][3] .Since the first patterning experiments performed with a scanning probe microscope in the late 80s, scanning probe lithography (SPL) has emerged as an alternative lithography for academic research that combines nanoscale feature-size, relatively low technological requirements and the ability to handle soft matter from small organic molecules to proteins and polymers. Scanning probe lithography experiments have provided striking examples of its capabilities such as the ability to pattern 3D structures with nanoscale features 4 , the fabrication of the smallest field-effect transistor 5 or the patterning of proteins with 10 nm feature size 6 . Figure 1a shows a general scheme of SPL operation. There is a variety of approaches to modify a material in a probe-surface interface which have generated several SPL methods. Scanning probe lithographies can be either classified by emphasizing the distinction between the general nature of the process, chemical versus physical, or by considering if SPL implies the removal or addition of material. However, we consider it is more inclusive and systematic to classify the different SPL methods in terms of the driving mechanisms used in the patterning process, namely thermal, electrical, mechanical and diffusive methods (Fig. 1b). Challenges in nanoscale lithographyThe workhorse of large volume CMOS fabrication, o...

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Section: Bias-induced Splmentioning

confidence: 99%

Advanced scanning probe lithography

2014

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“…[ 12 ] The last includes probe-based oxidation and reduction lithographies. Although oxidative processes are known, and have been exploited extensively, [13][14][15] reductive processes under ambient conditions are less common.Here we show, in a facile single-step approach, reversible local reductive and oxidative patterning of thin fi lms of an electroactive organic material performed with a commercial conductive AFM (c-AFM) under ambient conditions. This constructive nanolithography [ 16 ] approach locally modifi es the top layer of the organic thin fi lm without inducing any of the topographic or structural changes typical of "destructive" small 2015, 11, No.…”

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Conductive‐AFM Patterning of Organic Semiconductors

Brown

Picco

Miles

et al. 2015

Small

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local-oxidation nanolithography techniques. [ 17,18 ] This constructive c-AFM redox-writing (cAROW) methodology shows potential for further exploration and development into a scalable, fast write-read technology. [ 19,20 ] The organic semiconductor used in this investigation is based on phenyl/amine-capped tetra(aniline), Ph/NH 2 -TANI , a short-chain, functional, and well-defi ned low molecular weight oligomeric analogue of the well-known conducting polymer, poly(aniline), PANI. Ph/NH 2 -TANI retains the desirable optoelectronic properties of PANI while circumventing the issues of poor solubility, processability, and polydispersity that have previously limited the applications of the polymer. [ 21 ] It is possible to fi ne-tune the optoelectronic properties of tetra(aniline) derivatives, and higher oligomers, simply through modifi cation of the central unit and variation of the end-group functionalization. [ 22 ] Similar to PANI, these oligomeric materials can be reversibly switched (doped) from their conductive emeraldine salt (ES) state to either the nonconductive fully reduced leucoemeraldine base (LEB) or emeraldine base (EB) states through redox, and acid-base chemistry, respectively. [ 23 ] An extensive range of possible inorganic and organic acid dopants exists, with the latter able to simultaneously act as dopants and plasticisers.In this work, N -(4-(((1E,4E)-4-((4-(phenylamino)-phenyl) imino)-cyclohexa-2,5-dien-1-ylidene)amino)phenyl)octanamide ( TANI-C 8 ) doped to the conductive ES state with the prototypical PANI dopant camphorsulfonic acid ( CSA ) was chosen, as this combination formed smooth, continuous thin fi lms on highly oriented pyrolytic graphite (HOPG). Unlike EB-state TANI -based materials, [ 24 ] fi lms prepared from ESstate TANI-C 8 (see the Experimental Section for details) The atomic force microscope (AFM) has developed into a mature and widespread topography characterisation tool since its inception in the 1980s. The high resolution and precision nature of this tool has also led to widespread use, under ambient conditions, for diverse applications. These applications include the direct observation of single-molecule events, [ 1,2 ] molecular force measurements, [ 3,4 ] the fabrication of nanostructures via a variety of nanoscale lithographies, [ 5,6 ] including electrochemical deprotection to yield responsive monolayers, [ 7,8 ] enzymatic oxidative poly merization to locally form conducting polymers, [ 9 ] formation of polymerized sulphur nanostructures, [ 10 ] and direct writing of metallic nanostructures. [ 11 ] These applications were recently classifi ed into mechanical, thermal, diffusive, and electrical processes according to the dominant tip-surface interaction involved. [ 12 ] The last includes probe-based oxidation and reduction lithographies. Although oxidative processes are known, and have been exploited extensively, [13][14][15] reductive processes under ambient conditions are less common.Here we show, in a facile single-step approach, reversible local reductive and oxida...

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“…However, nanoscale probing and manipulation of matter through electrical currents - a key step towards development of techniques for probing of local ionic transport behavior as well as local electrochemical reactions - remains a challenge. This progress is required for breakthroughs in applications ranging from energy storage2 and conversion to electrochemical actuation3 to nanofabrication456, and will potentially enable new and serendipitous areas of science and technology.…”

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Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Kumar

Arruda

Tselev

et al. 2013

Sci Rep

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Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

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Nanopatterning of carbonaceous structures by field-induced carbon dioxide splitting with a force microscope

Cited by 47 publications

References 31 publications

Advanced scanning probe lithography

Advanced scanning probe lithography

Conductive‐AFM Patterning of Organic Semiconductors

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

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