Table of contents

A useful synergy is being established between terahertz research and nanotechnology. High power sources [1–3] and detectors [4] in what was once considered the terahertz 'frequency gap' [5] in the electromagnetic spectrum have stimulated research with huge potential benefits in a range of industries including food, medicine and security, as well as fundamental physics and astrophysics. This special section, with guest editors Masayoshi Tonouchi and John Reno, gives a glimpse of the new horizons nanotechnology is broaching in terahertz research.

While the wavelengths relevant to the terahertz domain range from hundreds of micrometres to millimetres, structures at the nanoscale reveal interesting low energy dynamics in this region. As a result terahertz spectroscopy techniques are becoming increasingly important in nanomaterial characterization, as demonstrated in this special section by colleagues at the University of Oxford in the UK and the Australian National University. They use terahertz spectroscopy to identify the best nanostructure parameters for specific applications [6]. The low energy dynamics in nanostructures also makes them valuable tools for terahertz detection [7]. In addition the much sought after terahertz detection over broadband frequency ranges has been demonstrated, providing versatility that has been greatly in demand, particularly in spectroscopy applications [8, 9]. Also in this special section, researchers in Germany and China tackle some of the coupling issues in terahertz time domain spectroscopy with an emitter specifically well suited for systems operated with an amplified fibre [3].

'In medical imaging, the advantage of THz radiation is safety, because its energy is much lower than the ionization energy of biological molecules, in contrast to hazardous x-ray radiation,' explains Joo-Hiuk Son from the University of Seoul in Korea in his review [10]. As he also points out, the rotational and vibrational energies of water molecules are within the THz spectral region providing an additional benefit. His review describes the principle, characteristics, and applications of terahertz molecular imaging, where the use of nanoparticle probes allows dramatically enhanced sensitivity.

Jiaguang Han and Weili Zhang and colleagues in China, Saudi Arabia, Japan and the US report exciting developments for optoelectronics [11]. They describe work on plasmon-induced transparency (PIT), an analogue of electromagnetically induced transparency (EIT) where interference leads to a sharp transparency window that may be useful for nonlinear and slow-light devices, optical switching, pulse delay, and storage for optical information processing. While PIT has advantages over the cumbersome experimental systems required for EIT, it has so far been constrained to very narrow band operation. Now Zhang and colleagues present the simulation, implementation, and measurement of a broadband PIT metamaterial functioning across a frequency range greater than 0.40 THz in the terahertz regime.

'We can foresee a historic breakthrough for science and technology through terahertz research,' concluded Masayoshi Tonouchi in his review over five years ago as momentum in the field was mounting [12]. He added, 'It is also noteworthy that THz research is built on many areas of science and the coordination of a range of disciplines is giving birth to a new science.' With the inherently multidisciplinary nature of nanotechnology research it is not so strange to see the marriage of the two fields form such a fruitful partnership, as this special section highlights.

References

[1] Williams B S, Kumar S, Hu Q and Reno J L 2006 High-power terahertz quantum-cascade lasers Electron. Lett.42 89–91

[2] Köhler R et al 2002 Terahertz semiconductor-heterostructure laser Nature417 156–9

[3] Mittendorff M, Xu M, Dietz R J B, K¨unzel H, Sartorius B, Schneider H, Helm M and Winnerl S 2013 Large area photoconductive THz emitter for 1.55 μm excitation based on an InGaAs heterostructure Nanotechnology24 214007

[4] Chen H-T, Padilla W J, Zide J M O, Gossard A C, Taylor A J and Averitt R D 2006 Active terahertz metamaterial devices Nature444 597–600

[5] Hans H 1991 Microwave technology in the terahertz region Brand Conf. Proc.—European Microwave Conf. vol 1, pp 16–35

[6]Joyce H J, Docherty C J, Gao Q, Tan H H, Jagadish C, Lloyd-Hughes J, Herz L M and Johnston M B 2013 Electronic properties of GaAs, InAs and InP nanowires studied by terahertz spectroscopy Nanotechnology24 214006

[7] Knap W, Rumyantsev S, Vitiello M S, Coquillat D, Blin S, Dyakonova N, Shur M, Teppe F, Tredicucci A and Nagatsuma T 2013 Nanometer size field effect transistors for terahertz detectors Nanotechnology24 214002

[8] Kawano Y 2013 Wide-band frequency-tunable terahertz and infrared detection with graphene Nanotechnology24 214004

[9]Romeo L, Coquillat D, Pea M, Ercolani D, Beltram F, Sorba L, Knap W, Tredicucci A and Vitiello M S 2013 Nanowire-based field effect transistors for terahertz detection and imaging systems Nanotechnology24 214005

[10] Son J-H 2013 Principle and applications of terahertz molecular imaging Nanotechnology24 214001

[11] Zhu Z, Yang X, Gu J, Jiang J, Yue W, Tian Z, Tonouchi M, Han J and Zhang W 2013 Broadband plasmon induced transparency in terahertz metamaterials Nanotechnology24 214003

[12] Tonouchi M 2007 Cutting-edge terahertz technology Nature Photon.1 97–105

The principle, characteristics and applications of molecular imaging with terahertz electromagnetic waves are reviewed herein. The terahertz molecular imaging (TMI) technique uses nanoparticle probes to achieve dramatically enhanced sensitivity compared with that of conventional terahertz imaging. Surface plasmons, induced around the nanoparticles, raise the temperature of water in biological cells, and the temperature-dependent changes in the optical properties of water, which are large in the terahertz range, are measured differentially by terahertz waves. TMI has been applied to cancer diagnosis and nanoparticle drug delivery imaging. The technique is also compared with magnetic resonance imaging by using a dual-modality nanoparticle probe.

Nanometer size field effect transistors can operate as efficient resonant or broadband terahertz detectors, mixers, phase shifters and frequency multipliers at frequencies far beyond their fundamental cut-off frequency. This work is an overview of some recent results concerning the application of nanometer scale field effect transistors for the detection of terahertz radiation.

Plasmon induced transparency (PIT) could be realized in metamaterials via interference between different resonance modes. Within the sharp transparency window, the high dispersion of the medium may lead to remarkable slow light phenomena and an enhanced nonlinear effect. However, the transparency mode is normally localized in a narrow frequency band, which thus restricts many of its applications. Here we present the simulation, implementation, and measurement of a broadband PIT metamaterial functioning in the terahertz regime. By integrating four U-shape resonators around a central bar resonator, a broad transparency window across a frequency range greater than 0.40 THz is obtained, with a central resonance frequency located at 1.01 THz. Such PIT metamaterials are promising candidates for designing slow light devices, highly sensitive sensors, and nonlinear elements operating over a broad frequency range.

We report a graphene-based frequency-selective terahertz (THz) and infrared (IR) detector. The experimental results have demonstrated that the graphene transistor under a magnetic field is capable of detecting THz and IR waves in a very wide band of frequencies (0.76–33 THz) and that the detection frequency is tuned by changing the magnetic field. We have further imaged electric potential distribution in the graphene detector and have observed local step structure associated with impurities. The THz and IR photoconductivity properties of graphene are likely to be sensitive to such potential steps.

The development of self-assembled nanostructure technologies has recently opened the way towards a wide class of semiconductor integrated devices, with progressively optimized performances and the potential for a widespread range of electronic and photonic applications. Here we report on the development of field effect transistors (FETs) based on semiconductor nanowires (NWs) as highly-sensitive room-temperature plasma-wave broadband terahertz (THz) detectors. The electromagnetic radiation at 0.3 THz is funneled onto a broadband bow-tie antenna, whose lobes are connected to the source and gate FET electrodes. The oscillating electric field experienced by the channel electrons, combined with the charge density modulation by the gate electrode, results in a source–drain signal rectification, which can be read as a DC signal output. We investigated the influence of Se-doping concentration of InAs NWs on the detection performances, reaching responsivity values higher than 100 V W⁻¹, with noise-equivalent-power of ∼10⁻⁹ W Hz^−1/2. Transmission imaging experiments at 0.3 THz show the good reliability and sensitivity of the devices in a real practical application.

We have performed a comparative study of ultrafast charge carrier dynamics in a range of III–V nanowires using optical pump–terahertz probe spectroscopy. This versatile technique allows measurement of important parameters for device applications, including carrier lifetimes, surface recombination velocities, carrier mobilities and donor doping levels. GaAs, InAs and InP nanowires of varying diameters were measured. For all samples, the electronic response was dominated by a pronounced surface plasmon mode. Of the three nanowire materials, InAs nanowires exhibited the highest electron mobilities of 6000 cm² V⁻¹ s⁻¹, which highlights their potential for high mobility applications, such as field effect transistors. InP nanowires exhibited the longest carrier lifetimes and the lowest surface recombination velocity of 170 cm s⁻¹. This very low surface recombination velocity makes InP nanowires suitable for applications where carrier lifetime is crucial, such as in photovoltaics. In contrast, the carrier lifetimes in GaAs nanowires were extremely short, of the order of picoseconds, due to the high surface recombination velocity, which was measured as 5.4 × 10⁵  cm s⁻¹. These findings will assist in the choice of nanowires for different applications, and identify the challenges in producing nanowires suitable for future electronic and optoelectronic devices.

We present scalable large area terahertz (THz) emitters based on a nanoscale multilayer InGaAs/InAlAs heterostructure and a microstructured electrode pattern. The emitters are designed for pump lasers working at the telecommunication wavelength of 1.55 μm. Electric THz fields of more than 2.5 V cm⁻¹ are reached with moderate pump powers of 80 mW, the corresponding spectrum extends up to 3 THz. The saturation characteristics have been investigated for different pump laser spot sizes. For small pump powers of less than 50 mW the emitted THz field is nearly independent of the spot size, for higher pump powers and small spot sizes a clear saturation of the generated THz pulse can be observed. Hence the use of scalable emitters is especially promising for high power fibre laser systems. The spectral content of the generated radiation is nearly independent of the parameters spot size, pump power, and bias voltage, which allows for stable operation in spectroscopic applications.

In this study, an enzymatic glucose biosensor based on a three-dimensional gold nanodendrite (GND) modified screen-printed electrode was developed. The GNDs were electrochemically synthesized on the working electrode component of a commercially available screen-printed electrode using a solution acquired by dissolving bulk gold in aqua regia as the precursor. The 3D GND electrode greatly enhanced the effective sensing area of the biosensor, which improved the sensitivity of glucose detection. Actual glucose detections demonstrated that the fabricated devices could perform at a sensitivity of 46.76 μA mM⁻¹ cm⁻² with a linear detection range from 28 μM–8.4 mM and detection limit of 7 μM. A fast response time (∼3 s) was also observed. Moreover, only a 20 μl glucose oxidase is required for detection owing to the incorporation of the commercially available screen-printed electrode.

Currently, gold nanorods can be synthesized in a wide range of sizes. However, for the intended biological applications gold nanorods with approximate dimensions 50 nm × 15 nm are used. We investigate by computer simulation the effect of particle dimensions on the optical and thermal properties in the context of the specific applications of photoacoustic imaging. In addition we discuss the influence of particle size in overcoming the following biophysical barriers when administrated in vivo: extravasation, avoidance of uptake by organs of the reticuloendothelial system, penetration through the interstitium, binding capability and uptake by the target cells. Although more complex biological influences can be introduced in future analysis, the present work illustrates that larger gold nanorods, designated by us as 'nanobig rods', may perform better at meeting the requirements for successful in vivo applications compared to their smaller counterparts, which are conventionally used.

Theoretical calculations based on density functional theory were performed to provide better understanding of the size dependent electronic properties of InP quantum dots (QDs). Using a hybrid functional approach, we suggest a reliable analytical equation to describe the change of energy band gap as a function of size. Synthesizing colloidal InP QDs with 2–4 nm diameter and measuring their optical properties was also carried out. It was found that the theoretical band gaps showed a linear dependence on the inverse size of QDs and gave energy band gaps almost identical to the experimental values.

We report the fabrication of quantum wells in ZnO nanowires (NWs) by a crystal phase engineering approach. Basal plane stacking faults (BSFs) in the wurtzite structure can be considered as a minimal segment of zinc blende. Due to the existing band offsets at the wurtzite (WZ)/zinc blende (ZB) material interface, incorporation of a high density of BSFs into ZnO NWs results in type II band alignment. Thus, the BSF structure acts as a quantum well for electrons and a potential barrier for holes in the valence band. We have studied the photoluminescence properties of ZnO NWs containing high concentrations of BSFs in comparison to high-quality ZnO NWs of pure wurtzite structure. It is revealed that BSFs form quantum wells in WZ ZnO nanowires, providing an additional luminescence peak at 3.329 eV at 4 K. The luminescence mechanism is explained as an indirect exciton transition due to the recombination of electrons in the QW conduction band with holes localized near the BSF. The binding energy of electrons is found to be around 100 meV, while the excitons are localized with the binding energy of holes of ∼5 meV, due to the coupling of BSFs, which form QW-like structures.

The relationship between the profile of the structures obtained by multiphoton polymerization and the optical parameters of nanofabrication systems has been studied theoretically for a multipulse scheme. We find that the profile of sub-wavelength structures is greatly affected by the evanescent waves affect. Not only is the photocured polymer voxel affected by the beam profile, but the beam propagation behavior is influenced by the photocured polymer voxel. This gives us a new view of matter–light interactions in multipulse polymerization process, which is useful to the accurate control of the nanofabrication profile and the selection of new nanofabrication materials.

The process of templating a manganese nanocluster with the 12 × 12 moiré and other two slightly distorted graphene/Ru(0001) moirés was investigated by scanning tunneling microscopy (STM). At the initial stage of nucleation, different adsorption modes for Mn monomer, dimer and trimer guided by various moiré periodicities were observed. Upon Mn coverage increasing, STM measurements revealed that Mn clusters exhibit a detectable preference for adsorption sites on all the three different moirés. The most favorable adsorption sites for Mn clusters are the fcc regions, where ordering of Mn clusters was observable, and the lateral size of the clusters are tunable with coverage. A density functional theory calculation also showed that magnetism appears with a magnetic moment of 3.79μ_B for Mn monomer on MLG/Ru(0001).

In the present investigation, we report on the thermoelectric properties of PbSe_0.5Te_0.5: x (PbI₂) from room temperature to 625 K. High-resolution transmission electron micrographs of the samples reveal endotaxial nanostructures embedded in a PbSe_0.5Te_0.5 matrix. The combined effect of mass fluctuation and nanostructures reduces the thermal conductivity to a great extent compared to PbTe and PbSe, without affecting the carrier mobility. As a result, a thermoelectric figure of merit with a value of 1.5 is achieved at 625 K. This value is significantly higher than that of the available state-of-the-art n-type materials.

Transparent flexible electrodes made of metallic nanowires, and in particular silver nanowires (AgNWs), appear as an extremely promising alternative to transparent conductive oxides for future optoelectronic devices. Though significant progresses have been made the last few years, there is still some room for improvement regarding the synthesis of high quality silver nanowire solutions and fabrication process of high performance electrodes. We show that the commonly used purification process can be greatly simplified through decantation. Using this process it is possible to fabricate flexible electrodes by spray coating with sheet resistance lower than 25 Ω sq⁻¹ at 90% transparency in the visible spectrum. These electrodes were used to fabricate an operative transparent flexible touch screen. To our knowledge this is the first reported AgNW based touch sensor relying on capacitive technology.

Copolymerization of styrene (St) and 1-vinyl-3-ethylimidazolium bromide (VEIB), novel poly(St-co-VEIB) microspheres were generated. Owing to the presence of imidazolium groups, such microspheres having an average diameter of 125 nm, behave electropositively when dispersed in aqueous solution. Furthermore, due to the presence of imidazolium groups, having a capacity of ion-exchange and weak reducibility on the surface of the PS microspheres, [Fe(CN)₆]³⁻ was absorbed on the surface of poly(St-co-VEIB) microspheres, and simultaneously, Fe³⁺ was reduced to Fe²⁺. Thus, in situ growth of Prussian blue (PB) nanoparticles could occur on the surface of poly(St-co-VEIB) microspheres without the addition of any other reducing agent. This methodology, utilizing the ion-exchange and weak reducibility properties of the imidazolium groups on the surface of micro-/nanostructures is a novel general method for assembling hierarchical nanostructured materials. Finally, the electrochemical property of the strawberry-like PS/PB composite microspheres was also investigated by applying a glassy carbon electrode. A good repeatability of the cyclic voltammetry responses, having a good linearity and sensitivity, for the electrocatalytic reduction of H₂O₂ was obtained.

Anodic porous alumina, which exhibits a characteristic nanohoneycomb structure, has been used in a wide range of nanotechnology applications. The conventional fabrication method of mild anodization (MA) requires a prolonged anodization time which is impractical for batch processing, and self-ordered porous structures can only be formed within narrow processing windows so that the dimensions of the resultant structures are extremely limited. The alternative hard anodization (HA) may easily result in macroscopic defects on the alumina surface. In this work, by systematically varying the anodization conditions including the substrate grain orientation, electrolyte concentration, temperature, voltage, and time, a new oxalic acid based anodization method, called high acid concentration and high temperature anodization (HHA), is found, which can result in far better self-ordering of the porous structures at rates 7–26 times faster than MA, under a continuous voltage range of 30–60 V on (001) oriented Al grains. Unlike HA, no macroscopic defects appear under the optimum self-ordered conditions of HHA at 40 V, even for pore channels grown up to high aspect ratios of more than 3000. Compared to MA and HA, HHA provides more choices of self-ordered nano-porous structures with fast and mechanically stable formation features for practical applications.

The growth of Te nanotubes by the direct vapor phase process is dominated by the vapor–solid mechanism, where the intrinsic anisotropic crystal structure of tellurium and axial dislocations contained in the Te nanostructures should play crucial roles. During the growth process, Te nanoparticles will nucleate on the growth substrate in the initial stage, and then grow into nanoflakes and two-faced nanoscreens lying horizontally on the substrate until they fully cover the substrate. Some of the nanoscreens with certain horizontal angles with respect to the substrate surface will protrude out of the growth substrate and become preferential absorption sites for the incoming Te atoms. The two-faced nanoscreens then gradually develop into three-faced nanoscreens, four-faced nanogrooves, and finally perfect hexagonal nanotubes due to the lateral diffusion of Te atoms. Upon exposure to CO and NO₂ at room temperature, Te nanotube sensors showed the same direction of resistance change, adequate sensitivities, and fast response and recovery times, making them promising candidates for use in air-quality single sensors.

Copper metal nanoparticles were used as a reducing agent to reduce graphene oxide (GO). The reaction was complete in about 10 min and did not involve the use of any toxic reagents or acids that are typically used in the reduction of GO by Zn and Fe powders. The high reduction activity of the Cu nanoparticles, compared to Cu powder, may be the result of the formation of Cu₂O nanoparticles. The effect of the mass ratio of the metal to GO for this reduction was also investigated. The reduction of the GO was verified by ultraviolet–visible absorption spectroscopy, x-ray diffraction, thermogravimetric analysis, Raman spectroscopy, x-ray photoelectron spectroscopy and transmission electron microscopy. After reduction, Cu₂O supported on reduced GO was formed and showed superior catalytic ability for the degradation of a model dye pollutant, methylene blue.

We use a dynamic scanning electron microscope (DySEM) to analyze the movement of oscillating micromechanical structures. A dynamic secondary electron (SE) signal is recorded and correlated to the oscillatory excitation of scanning force microscope (SFM) cantilever by means of lock-in amplifiers. We show, how the relative phase of the oscillations modulate the resulting real part and phase pictures of the DySEM mapping. This can be used to obtain information about the underlying oscillatory dynamics. We apply the theory to the case of a cantilever in oscillation, driven at different flexural and torsional resonance modes. This is an extension of a recent work (Schröter et al 2012 Nanotechnology23 435501), where we reported on a general methodology to distinguish nonlinear features caused by the imaging process from those caused by cantilever motion.

Surface potential distribution, V_CPD, and evolution of atmospheric adsorbates on few and multiple layers (FLG and MLG) of graphene grown on SiC($0 0 0\bar {1}$) substrate have been investigated by electrostatic and Kelvin force microscopy techniques at T = 20–120 ° C. The change of the surface potential distribution, ΔV_CPD, between FLG and MLG is shown to be temperature dependent. The enhanced ΔV_CPD value at 120 ° C is associated with desorption of adsorbates at high temperatures and the corresponding change of the carrier balance. The nature of the adsorbates and their evolution with temperature are considered to be related to the process of adsorption and desorption of the atmospheric water on MLG domains. We demonstrate that both the nano- and microscale wettability of the material are strongly dependent on the number of graphene layers.

Bismuth telluride (Bi₂Te₃) nanorods and polyaniline (PANI) nanoparticles have been synthesized by employing solvothermal and chemical oxidative processes, respectively. Nanocomposites, comprising structurally ordered PANI preferentially grown along the surface of a Bi₂Te₃ nanorods template, are synthesized using in situ polymerization. X-ray powder diffraction, UV–vis and Raman spectral analysis confirm the highly ordered chain structure of PANI on Bi₂Te₃ nanorods, leading to a higher extent of doping, higher chain mobility and enhancement of the thermoelectric performance. Above 380 K, the PANI–Bi₂Te₃ nanocomposite with a core–shell/cable-like structure exhibits a higher thermoelectric power factor than either pure PANI or Bi₂Te₃. At room temperature the thermal conductivity of the composite is lower than that of its pure constituents, due to selective phonon scattering by the nanointerfaces designed in the PANI–Bi₂Te₃ nanocable structures. The figure of merit of the nanocomposite at room temperature is comparable to the values reported in the literature for bulk polymer-based composite thermoelectric materials.