Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.

Graphene-Based Materials: Synthesis, Characterization, Properties, and Applications

In the past few years, spiropyran has emerged as the molecule-of-choice for the construction of novel dynamic materials. This unique molecular switch undergoes structural isomerisation in response to a variety of orthogonal stimuli, e.g. light, temperature, metal ions, redox potential, and mechanical stress. Incorporation of this switch onto macromolecular supports or inorganic scaffolds allows for the creation of robust dynamic materials. This review discusses the synthesis, switching conditions, and use of dynamic materials in which spiropyran has been attached to the surfaces of polymers, biomacromolecules, inorganic nanoparticles, as well as solid surfaces. The resulting materials show fascinating properties whereby the state of the switch intimately affects a multitude of useful properties of the support. The utility of the spiropyran switch will undoubtedly endow these materials with far-reaching applications in the near future.

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Spiropyran-based dynamic materials

Graphene, as the fundamental 2D carbon structure with exceptionally high crystal and electronic quality, has emerged as a rapidly rising star in the field of material science. Its sudden discovery in 2004 led to an explosion of interest in the study of graphene with respect to its unique physical, chemical, and mechanical properties, opening up a new research area for materials science and condensed-matter physics, and aiming for wide-ranging and diversified technological applications. In this critical review, we will describe recent advances in the development of graphene-based materials from the standpoint of electrochemistry. To begin with, electron transfer properties of graphene will be discussed, involving its unusual electronic structure, extraordinary electronic properties and fascinating electron transport. The next major section deals with the exciting progress related to graphene-based materials in electrochemistry since 2004, including electrochemical sensing, electrochemiluminescence, electrocatalysis, electrochemical energy conversion and FET devices. Finally, prospects and further developments in this exciting field of graphene-based materials are also suggested (224 references).

Graphene-based materials in electrochemistry

2.3. Ionic Liquids (ILs) 5374 2.4. Complexation Reactions on Oxidized CNTs 5375 2.5. Halogenation 5376 2.6. Cycloaddition Reactions 5377 2.7. Radical Additions 5379 2.8. Nucleophilic Additions 5381 2.9. Electrophilic Additions 5381 2.10. Electrochemical Modifications 5381 2.11. Plasma-Activation 5381 2.12. Mechanochemical Functionalizations 5382 3. Noncovalent Interactions 5382 3.1. Polynuclear Aromatic Compounds 5382 3.2. Interactions with Other Substances 5384 3.3. Interactions with Biomolecules 5385 4. Endohedral Filling 5386 4.1. Encapsulation of Fullerenes 5386 4.2. Encapsulation of Organic Substances 5387 4.3. Encapsulation of Inorganic Substances 5387 5. Decoration of CNTs with Metal Nanoparticles 5388 5.1. Covalent Linkage 5388 5.2. Direct Formation on Defect Sites 5388 5.3. Electroless Deposition 5388 5.4. Electrodeposition 5389 5.5. Chemical Decoration 5390 5.6. Deposition of Nanoparticles onto CNTs 5391 5.7. π-π Stacking and Electrostatic Interactions 5391 6. Concluding Remarks 5392 7. Acknowledgments 5392 8. References 5392

Current progress on the chemical modification of carbon nanotubes.

Creating functional electrical circuits using individual or ensemble molecules, often termed as “molecular-scale electronics”, not only meets the increasing technical demands of the miniaturization of traditional Si-based electronic devices, but also provides an ideal window of exploring the intrinsic properties of materials at the molecular level. This Review covers the major advances with the most general applicability and emphasizes new insights into the development of efficient platform methodologies for building reliable molecular electronic devices with desired functionalities through the combination of programmed bottom-up self-assembly and sophisticated top-down device fabrication. First, we summarize a number of different approaches of forming molecular-scale junctions and discuss various experimental techniques for examining these nanoscale circuits in details. We then give a full introduction of characterization techniques and theoretical simulations for molecular electronics. Third, we highlig...

Molecular-Scale Electronics: From Concept to Function

This study reports a general methodology for making stable high-performance photosensitive field effect transistors (FET) from self-assembled columns of polycyclic aromatic hydrocarbons by using single-walled carbon nanotubes (SWNTs) as point contacts. In particular, the molecules used in this work are liquid crystalline materials of tetra(dodecyloxy)hexabenzocoronenes (HBCs) that are able to self-organize into columnar nanostructures with a diameter similar to that of SWNTs and then form nanoscale columnar transistors. To rule out potential artifacts, 2 different structural approaches were used to construct devices. One approach is to coat thin films of HBCs onto the devices with the SWNT–metal junctions protected by hydrogensilsesquioxane resin (HSQ), and the other is to place a droplet of HBC exactly on the nanogaps of SWNT electrodes. Both types of devices showed typical FET behaviors, indicating that SWNT–molecule–SWNT nanojunctions are responsible for the electrical characteristics of the devices. After thermally annealing the devices, HBC molecules assembled into columnar structures and formed more efficacious transistors with increased current modulation and higher gate efficiency. More interestingly, when the devices were exposed to visible light, photocurrents with an on/off ratio of >3 orders of magnitude were observed. This study demonstrates that stimuli-responsive nanoscale transistors have the potential applications in ultrasensitive devices for environmental sensing and solar energy harvesting.

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Photoresponsive nanoscale columnar transistors.

A facile method to make optoelectronic devices formed from organic thin-film transistors that are functionalized by photochromic spiropyran dyes in a nondestructive manner has been developed. When PDMS stamps are employed, alkane-containing spiropyran molecules can be coated simply onto the surface of organic thin films in a noninvasive manner. Upon UV irradiation, the molecules undergo isomerization from the neutral closed form to the charge-separated merocyanine form, producing the local electrostatic environment. This photoinduced electrostatic environment can function as a local negative gate voltage, thus increasing the electrical conductivity in p-type devices and decreasing the electrical conductivity in n-type devices. Further irradiation with visible light or keeping the devices in the dark can switch the device conductance back to their initial value. This method is reversible and reproducible on different devices with different thickness over a long period of time.

Conformation-Induced Electrostatic Gating of the Conduction of Spiropyran-Coated Organic Thin-Film Transistors

Dotting the i's: Stimuli-responsive optoelectronic devices are formed from the title transistors functionalized with photoactive quantum dots. The p-type semiconducting tubes show a fast current decrease under UV irradiation and reversibility when the UV irradiation is switched off. In contrast, ambipolar tubes show mirror-image photoswitching effects when negative and positive gate bias voltages are applied.

Mirror‐Image Photoswitching of Individual Single‐Walled Carbon Nanotube Transistors Coated with Titanium Dioxide

Bottom-contact monolayer thin-film transistors (MTFTs) were fabricated using copper phthalocyanine (CuPc) Langmuir–Blodgett monolayer as the active channel. The devices with tens of micrometers long channels showed typical p-type field-effect properties and obvious saturation regimes. Mobilities of these CuPc MTFTs were channel length dependent. The best performance obtained from the molecule-scaled CuPc MTFT with a channel length of 5 μm showed mobility even higher than that of the 50 nm thick vacuum-deposited films. These MTFTs may find potential applications in sensors and organic integrated circuits.

Langmuir–Blogett monolayer transistors of copper phthalocyanine

We present a universal lithographic methodology for creating single molecule devices based on single-walled carbon nanotubes as point contacts. These contacts are formed by electron beam lithography and precise oxygen plasma etching. Through robust amide linkages, functional molecular bridges with diamines are covalently wired into carboxylic acid-functionalized nanogaps to afford single molecule devices with desired functionalities.

/pdf/functional-single-molecule-devices-based-on-swnts-as-point-6k7bqhv5bh.pdf

Functional single-molecule devices based on SWNTs as point contacts

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