Hybrid silicon/molecular FETs: a study of the interaction of redox-active molecules with silicon MOSFETs

Redox-active molecular monolayers were incorporated in silicon MOSFETs to obtain hybrid silicon/molecular FETs. Cyclic voltammetry and FET characterization techniques were used to study the properties of these hybrid devices. The redox-active molecules have tunable charge states, which are quantized at room temperature and can be accessed at relatively low voltages. The discrete molecular states were manifested in the drain current and threshold voltage characteristics of the device, confirming the presence of distinct energy levels within the molecules at room temperature. This study demonstrates the modulation of Si-MOSFETs' drain currents via redox-active molecular monolayers. The single-electron functionality provided by the redox-active molecules is ultimately scalable to molecular dimensions, and this approach can be extended to nanoscale field-effect devices including those based on carbon nanotubes. The molecular states coupled with CMOS devices can be utilized for low-voltage, multiple-state memory and logic applications and can extend the impact of silicon-based technologies.     

Advances in Molecular Electronics: A Brief Review

The field of molecular electronics, also known as moletronics, deals with the assembly of molecular electronic components using molecules as the building blocks. It is an interdisciplinary field that includes physics, chemistry, materials science, and engineering. Moletronics mainly deals with the reduction of size of silicon components. Novel research has been performed in developing electrical-equivalent molecular components. Moletronics has established its influence in electronic and photonic applications, such as conducting polymers, photochromics, organic superconductors, electrochromics, and many more. Since there is a need to reduce the size of the silicon chip, attaining such technology at the molecular level is essential. Although the experimental verification and modeling of molecular devices present a daunting task, vital breakthroughs have been achieved in this field. This article combines an overview of various molecular components, such as molecular transistors, diodes, capacitors, wires, and insulators, with a discussion of the potential applications of different molecules suitable for such components. We emphasize future developments and provide a brief review of different achievements that have been made regarding graphene-based molecular devices.     

Assessing charge carrier trapping in silicon nanowires using picosecond conductivity measurements

Free-standing semiconductor nanowires on bulk substrates are increasingly being explored as building blocks for novel optoelectronic devices such as tandem solar cells. Although carrier transport properties, such as mobility and trap densities, are essential for such applications, it has remained challenging to quantify these properties. Here, we report on a method that permits the direct, contact-free quantification of nanowire carrier diffusivity and trap densities in thin (～25 nm wide) silicon nanowires-without any additional processing steps such as transfer of wires onto a substrate. The approach relies on the very different terahertz (THz) conductivity response of photoinjected carriers within the silicon nanowires from those in the silicon substrate. This allows quantifying both the picosecond dynamics and the efficiency of charge carrier transport from the silicon nanowires into the silicon substrate. Varying the excitation density allows for quantification of nanowire trap densities: for sufficiently low excitation fluences the diffusion process stalls because the majority of charge carriers become trapped at nanowire surface defects. Using a model that includes these effects, we determine both the diffusion constant and the nanowire trap density. The trap density is found to be orders of magnitude larger than the charge carrier density that would be generated by AM1.5 sunlight.     

Nanowires for integrated multicolor nanophotonics

Nanoscale light-emitting diodes (nanoLEDs) with colors spanning from the ultraviolet to near-infrared region of the electromagnetic spectrum were prepared using a solution-based approach in which emissive electron-doped semiconductor nanowires were assembled with nonemissive hole-doped silicon nanowires in a crossed nanowire architecture. Single- and multicolor nanoLED devices and arrays were made with colors specified in a predictable way by the bandgaps of the III-V and II-VI nanowire building blocks. The approach was extended to combine nanoscale electronic and photonic devices into integrated structures, where a nanoscale transistor was used to switch the nanoLED on and off. In addition, this approach was generalized to hybrid devices consisting of nanowire emitters assembled on lithographically patterned planar silicon structures, which could provide a route for integrating photonic devices with conventional silicon microelectronics. Lastly, nanoLEDs were used to optically excite emissive molecules and nanoclusters, and hence could enable a range of integrated sensor/detection "chips" with multiplexed analysis capabilities.     

Linker-free directed assembly of high-performance integrated devices based on nanotubes and nanowires

Advanced electronic devices based on carbon nanotubes (NTs) and various types of nanowires (NWs) could have a role in next-generation semiconductor architectures. However, the lack of a general fabrication method has held back the development of these devices for practical applications. Here we report an assembly strategy for devices based on NTs and NWs. Inert surface molecular patterns were used to direct the adsorption and alignment of NTs and NWs on bare surfaces to form device structures without the use of linker molecules. Substrate bias further enhanced the amount of NT and NW adsorption. Significantly, as all the processing steps can be performed with conventional microfabrication facilities, our method is readily accessible to the present semiconductor industry. We use this method to demonstrate large-scale assembly of NT- and NW-based integrated devices and their applications. We also provide extensive analysis regarding the reliability of the method.     

Molecular nanostructures with strong dipole moments on the Si(111) 5 × 2-Au surface

Switchable organic molecules adsorbed on a silicon surface combine the flexibility and the low cost of molecular electronic devices with the sophistication of modern silicon technology. The first step towards creating such hybrid devices is the formation of regular, ordered patterns of molecules on a silicon surface. A stepped Si surface passivated by a sub-monolayer of gold is found to provide a useful substrate for forming ordered molecular patterns. Molecules with strong dipole moments, such as fluorophenols, form a one-dimensional molecular array on such a substrate by adsorbing on top of the step edges. Local barrier height measurement by scanning tunneling spectroscopy demonstrates the possibilities to detect the direction of the dipole moment of an individual molecule. Polarization-dependent x-ray absorption spectroscopy reveals an oriented adsorption in both the azimuthal and polar directions.     

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron–Phonon Coupling

Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH₃NH₃PbI₃) following photoexcitation, enabling an ultrafast probe of charge separation, hot‐carrier transport, and carrier–lattice coupling under 1‐sun‐equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band‐edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot‐carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz‐frequency lattice distortions, associated with reorganizations of the lead‐iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far‐above‐gap photoexcitation. This study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.     

Charge transport physics of conjugated polymer field-effect transistors

Field‐effect transistors based on conjugated polymers are being developed for large‐area electronic applications on flexible substrates, but they also provide a very useful tool to probe the charge transport physics of these complex materials. In this review we discuss recent progress in polymer semiconductor materials, which have brought the performance and mobility of polymer devices to levels comparable to that of small‐molecule organic semiconductors. These new materials have also enabled deeper insight into the charge transport physics of high‐mobility polymer semiconductors gained from experiments with high charge carrier concentration and better molecular‐scale understanding of the electronic structure at the semiconductor/dielectric interface.     

非晶硅薄膜晶化方法

多晶硅薄膜由于具有较高的载流子迁移率和良好的光电性能,广泛应用于集成电路及光电器件中,尤其在太阳电池领域引起了广泛关注。多晶材料晶界处会发生载流子的复合,降低载流子寿命。结晶度与晶粒尺寸是多晶硅薄膜取得良好性能的关键因素,直接制备的多晶硅薄膜一般晶粒尺寸较小、晶界较多,所以常采用非晶硅晶化法制备出晶粒尺寸较大的多晶硅薄膜。介绍了几种常见的非晶硅薄膜晶化方法,总结了各种晶化方法的机理和制备的薄膜的物理性质。     

Manipulation with molecules

Photonic molecules are mesoscopic hierarchical structures, constructed from ‘monomer’ units with typical dimensions of 1–5 μm, which function as coupled optical resonators. These structures are so named because they confine electromagnetic fields in modes that are closely analogous to bonding and antibonding electronic molecular orbitals in real molecules. Recent experimental advances have shown that photonic molecules can be fabricated in a variety of ways with different functionality. We review here recent work in this newly developing interdisciplinary field that blends chemistry, materials science, and optical physics. Finally, we speculate on possible applications and future research directions.For many years now, researchers in materials and photonics have been keenly interested in the design and fabrication of structures that confine and manipulate electromagnetic fields on length scales comparable to optical wavelengths. The ultimate goal is an all-optical information processing and computation platform using photons in ways analogous to electrons in silicon devices on similar length scales. Specific focus areas such as wafer-scale integration, parallel processing, and frequency management (e.g. add-drop filters), on micron or sub-micron length scales are active areas of photonics research. While a great deal of progress has been made in the burgeoning field of microphotonics, we are still a long way off from realizing important goals such as the optical transistor and all-optical integrated circuits¹.     

A New Ba0.6Sr0.4TiO3–Silicon Hybrid Metamaterial Device in Terahertz Regime

Metamaterials, offering unprecedented functionalities to manipulate electromagnetic waves, have become a research hotspot in recent years. Through the incorporation of active media, the exotic electromagnetic behavior of metamaterials can be dramatically empowered by dynamic control. Many ferroelectric materials such as BaSrTiO₃ (abbreviated as BST), exhibiting strong response to external electric field, hold great promise in both microwave and terahertz tunable devices. A new active Ba_0.6Sr_0.4TiO₃–silicon hybrid metamaterial device, namely, a SRR (square split‐ring resonator)–BaSrTiO₃ thin film‐silicon three‐layer structure is fabricated and intensively studied. The active Ba_0.6Sr_0.4TiO₃ thin film hybrid metamaterial, with nanoscale thickness, delivers a transmission contrast up to ≈79% due to electrically enabled carrier transport between the ferroelectric thin film and silicon substrate. This work has significantly increased the low modulation rate of ferroelectric based devices in terahertz range, a major problem in this field remaining unresolved for many years. The proposed BST metamaterial is promising in developing high‐performance real world photonic devices for terahertz technology.     

Field-effect electroluminescence in silicon nanocrystals

There is currently worldwide interest in developing silicon-based active optical components in order to leverage the infrastructure of silicon microelectronics technology for the fabrication of optoelectronic devices. Light emission in bulk silicon-based devices is constrained in wavelength to infrared emission, and in efficiency by the indirect bandgap of silicon. One promising strategy for overcoming these challenges is to make use of quantum-confined excitonic emission in silicon nanocrystals. A critical challenge for silicon nanocrystal devices based on nanocrystals embedded in silicon dioxide has been the development of a method for efficient electrical carrier injection. We report here a scheme for electrically pumping dense silicon nanocrystal arrays by a field-effect electroluminescence mechanism. In this excitation process, electrons and holes are both injected from the same semiconductor channel across a tunnelling barrier in a sequential programming process, in contrast to simultaneous carrier injection in conventional pn-junction light-emitting-diode structures. Light emission is strongly correlated with the injection of a second carrier into a nanocrystal that has been previously programmed with a charge of the opposite sign.     

Properties of functionalized redox-active monolayers on thin silicon dioxide-a study of the dependence of retention time on oxide thickness

Self-assembled monolayers of redox-active molecules were formed on varying thickness of silicon dioxide (SiO/sub 2/). Cyclic voltammetry (CyV) and impedance spectroscopy (capacitance-voltage and conductance-voltage) techniques were used to characterize these structures. The charge retention properties of these molecule-oxide-silicon capacitor structures were studied by applying oxidizing voltages in two successive CyV scans without applying a reducing voltage in between the two scans. A variation of this technique, wherein a reducing voltage is applied in the second scan, was also employed. The wait time between the two scans was varied from 0 to 300 s. The number of molecules oxidized (or reduced) in the second scan increased (or decreased) with increasing wait time, which is attributed to increasing charge leakage with increasing time. The retention properties of these structures were studied and correlated to increasing oxide thickness. It was observed that the retention times increased with increasing oxide thickness if the voltage applied during the wait time was in between the oxidation and reduction peak voltages. The molecular scalability and ability to tune the retention times by varying the oxide thickness make these Si/molecular hybrid devices attractive candidates for next-generation memory applications.     

Single-molecule devices: materials,structures and characteristics

This review article provides a brief survey of materials, structures and current state-of-the-art techniques used to measure the charge conduction characteristics of single molecules. Single molecules have been found to exhibit several unique functionalities including rectification, negative differential resistance and electrical bistable switching, all of which are necessary building blocks for the development and configuration of molecular devices into circuits. Conjugated organic molecules have received considerable interest for their low fabrication cost, three dimensional stacking and mechanical flexibility. Furthermore, the ability of molecules to self-assemble into well-defined structures is imperative for the fabrication of molecule based circuits. The theoretical formalisms are presented for studying single-molecule Coulomb blockade effects, ballistic transport in a molecular chain and electromagnetic coupling between a surface-plasmon field and a single molecule. Moreover, the experimental current–voltage results are discussed using basic principles of carrier transport mechanisms.     

Spatiotemporally Controllable Peptide‐Based Nanoassembly in Single Living Cells for a Biological Self‐Portrait

Simultaneous precise localization and activity evaluation of a biomolecule in a single living cell is through an enzyme‐specific signal‐amplification process, which involves the localized, site‐specific self‐assembly, and activation of a presignaling molecule. The inactive presignaling tetraphenylethylene (TPE)‐peptide derivative, TPE‐YpYY, is nondetectable and highly biocompatible and these small molecules rapidly diffuse into living cells. Upon safely arriving at an active site, and accessing the catalytic pocket of an enzyme, TPE‐YpYY immediately and quantitatively accumulates in situ in response to enzymatic activity, forms an enzyme anchor TPE‐YYY nanoassembly, displays aggregation‐induced emission behavior, and finally lights up the active enzyme, indicating its activity, and allowing its status in living cells to be tracked. This simple and direct self‐portrait method can be used to monitor dynamic self‐assembly processes in individual living cells and may provide new insights that reveal undiscovered biological processes and that aid in developing biomedical hybrid devices. In the future, this strategy of molecular design can be further expanded to the noninvasive investigation of other bioactive molecules, thus facilitating quantitative imaging.     

High-performance lithium battery anodes using silicon nanowires

There is great interest in developing rechargeable lithium batteries with higher energy capacity and longer cycle life for applications in portable electronic devices, electric vehicles and implantable medical devices. Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g(-1); ref. 2). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials, silicon anodes have limited applications because silicon's volume changes by 400% upon insertion and extraction of lithium which results in pulverization and capacity fading. Here, we show that silicon nanowire battery electrodes circumvent these issues as they can accommodate large strain without pulverization, provide good electronic contact and conduction, and display short lithium insertion distances. We achieved the theoretical charge capacity for silicon anodes and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.     

Fabrication of Reproducible,Integration‐Compatible Hybrid Molecular/Si Electronics

Reproducible molecular junctions can be integrated within standard CMOS technology. Metal–molecule–semiconductor junctions are fabricated by direct Si–C binding of hexadecane or methyl‐styrene onto oxide‐free H‐Si(111) surfaces, with the lateral size of the junctions defined by an etched SiO₂ well and with evaporated Pb as the top contact. The current density, J, is highly reproducible with a standard deviation in log(J) of 0.2 over a junction diameter change from 3 to 100 μm. Reproducibility over such a large range indicates that transport is truly across the molecules and does not result from artifacts like edge effects or defects in the molecular monolayer. Device fabrication is tested for two n‐Si doping levels. With highly doped Si, transport is dominated by tunneling and reveals sharp conductance onsets at room temperature. Using the temperature dependence of current across medium‐doped n‐Si, the molecular tunneling barrier can be separated from the Si‐Schottky one, which is a 0.47 eV, in agreement with the molecular‐modified surface dipole and quite different from the bare Si–H junction. This indicates that Pb evaporation does not cause significant chemical changes to the molecules. The ability to manufacture reliable devices constitutes important progress toward possible future hybrid Si‐based molecular electronics.     

Single molecule electronic devices

Single molecule electronic devices in which individual molecules are utilized as active electronic components constitute a promising approach for the ultimate miniaturization and integration of electronic devices in nanotechnology through the bottom-up strategy. Thus, the ability to understand, control, and exploit charge transport at the level of single molecules has become a long-standing desire of scientists and engineers from different disciplines for various potential device applications. Indeed, a study on charge transport through single molecules attached to metallic electrodes is a very challenging task, but rapid advances have been made in recent years. This review article focuses on experimental aspects of electronic devices made with single molecules, with a primary focus on the characterization and manipulation of charge transport in this regime.     

Single‐Molecule Devices: Single Molecule Electronic Devices (Adv. Mater. 14/2011)

Single molecule electronic devices in which individual molecules are utilized as active electronic components constitute a promising approach for the ultimate miniaturization and integration of electronic devices in nanotechnology through the bottom‐up strategy. Thus, the ability to understand, control, and exploit charge transport at the level of single molecules has become a long‐standing desire of scientists and engineers from different disciplines for various potential device applications. Indeed, a study on charge transport through single molecules attached to metallic electrodes is a very challenging task, but rapid advances have been made in recent years. This review article focuses on experimental aspects of electronic devices made with single molecules, with a primary focus on the characterization and manipulation of charge transport in this regime.     

Electronic Coolers Based on Superconducting Tunnel Junctions: Fundamentals and Applications

Thermo-electric transport at the nano-scale is a rapidly developing topic, in particular in superconductor-based hybrid devices. In this review paper, we first discuss the fundamental principles of electronic cooling in mesoscopic superconducting hybrid structures, the related limitations and applications. We review recent work performed in Grenoble on the effects of Andreev reflection, photonic heat transport, phonon cooling, as well as on an innovative fabrication technique for powerful coolers.