Tip-induced nano-engineering of strain, bandgap, and exciton dynamics in 2D semiconductors
Yeonjeong Koo, Yongchul Kim, Soo Ho Choi, Hyeongwoo Lee, Jinseong Choi, Dong Yun Lee, Mingu Kang, Hyun Seok Lee, Ki Kang Kim, Geunsik Lee, Kyoung-Duck Park
The tunability of the bandgap, absorption and emission energies, photoluminescence (PL) quantum yield, exciton transport, and energy transfer in transition metal dichalcogenide (TMD) monolayers provides a new class of functions for a wide range of ultrathin photonic devices. Recent strain-engineering approaches have enabled us to tune some of these properties, yet dynamic control at the nanoscale with real-time and -space characterizations remains a challenge. Here, we demonstrate a dynamic nano-mechanical strain-engineering of naturally-formed wrinkles in a WSe2 monolayer, with real-time investigation of nano-spectroscopic properties using hyperspectral adaptive tip-enhanced PL (a-TEPL) spectroscopy. First, we characterize nanoscale wrinkles through hyperspectral a-TEPL nano-imaging with <15 nm spatial resolution which reveals the modified nano-excitonic properties by the induced tensile strain at the wrinkle apex, e.g., an increase in the quantum yield due to the exciton funneling, decrease in PL energy up to ~10 meV, and a symmetry change in the TEPL spectra caused by the reconfigured electronic bandstructure. We then dynamically engineer the local strain by pressing and releasing the wrinkle apex through an atomic force tip control. This nano-mechanical strain-engineering allows us to tune the exciton dynamics and emission properties at the nanoscale in a reversible fashion. In addition, we demonstrate a systematic switching and modulation platform of the wrinkle emission, which provides a new strategy for robust, tunable, and ultracompact nano-optical sources in atomically thin semiconductors.
Doping of semiconductors is essential in modern electronic and photonic devices. While doping is well understood in bulk semiconductors, the advent of carbon nanotubes and nanowires for nanoelectronic and nanophotonic applications raises some key questions about the role and impact of doping at low dimensionality. Here we show that for semiconducting carbon nanotubes, bandgaps and exciton binding energies can be dramatically reduced upon experimentally relevant doping, and can be tuned gradually over a broad range of energies in contrast to higher dimensional systems. The later feature is made…
The two-dimensional (2D) C3N has emerged as a material with promising applications in high performance device owing to its intrinsic bandgap and tunable electronic properties. Although there are several reports about the bandgap tuning of C3N via stacking or forming nanoribbon, bandgap modulation of bilayer C3N nanoribbons (C3NNRs) with various edge structures is still far from well understood. Here, based on extensive first-principles calculations, we demonstrated the effective bandgap engineering of C3N by cutting it into hydrogen passivated C3NNRs and stacking them into bilayer heterostruct…
A new analytical expression for the size-dependent bandgap of colloidal semiconductor nanocrystals is proposed within the framework of the finite-depth square-well effective mass approximation in order to provide a quantitative description of the quantum confinement effect. This allows one to convert optical spectroscopic data (photoluminescence spectrum and absorbance edge) into accurate estimates for the particle size distributions of colloidal systems even if the traditional effective mass model is expected to fail, which occurs typically for very small particles belonging to the so-called …
We study quasi-ballistic heat transfer through air between a hot nanometer-scale tip and a sample. The hot tip/surface configuration is widely used to perform nonintrusive confined heating. Using a Monte-Carlo simulation, we find that the thermal conductance reaches 0.8 MW.m-2K-1 on the surface under the tip and show the shape of the heat flux density distribution (nanometer-scale thermal spot). These results show that a surface can be efficiently heated locally without contact. The temporal resolution of the heat transfer is a few tens of picoseconds.
The newly synthesized ultrathin carbon nanothreads have drawn great attention from the carbon community. Here, based on first-principles calculations, we investigate the electronic properties of carbon nanothreads under the influence of two important factors: the Stone-Wales (SW) type defect and the lattice strain. The SW defect is intrinsic to the polymer-I structure of the nanothreads and is a building block for the general hybrid structures. We find that the bandgap of the nanothreads can be tuned by the concentration of SW defects in a wide range of $3.92 \sim 4.82$ eV, interpolating betwe…
We show that the band structure of a carbon nanotube (NT) can be dramatically altered by mechanical strain. We employ an atomic force microscope tip to simultaneously vary the NT strain and to electrostatically gate the tube. We show that strain can open a bandgap in a metallic NT and modify the bandgap in a semiconducting NT. Theoretical work predicts that bandgap changes can range between +100meV and -100meV per 1% stretch, depending on NT chirality, and our measurements are consistent with this predicted range.
We report a novel atom extraction mechanism from the native substrate by means of a scanning tunneling microscope tip-crash on a Ag(111) surface at 5 K. Individual atoms are scattered on the surface when a silver coated tip is dipped into the substrate at low tunneling biases. Quantitative analyses reveal that the mechanical energy supplied by the tip-crash dominates the atom extraction process. Application of this procedure is demonstrated by constructing quantum structures using the extracted atoms on an atom-by-atom basis.
Using focused-electron-beam-induced deposition, Cobalt magnetic nanospheres with diameter ranging between 100 nm and 300 nm are grown at the tip of ultra-soft cantilevers. By monitoring the mechanical resonance frequency of the cantilever as a function of the applied magnetic field, the hysteresis curve of these individual nanospheres are measured. This enables to evaluate their saturation magnetization, found to be around 430 emu/cm^3 independently of the size of the particle, and to infer that the magnetic vortex state is the equilibrium configuration of these nanospheres at remanence.
Search for low-dimensional materials with unique electronic properties is important for the development of electronic devices in nano scale. Through systematic first-principles calculations, we found that the band gaps of the two-dimensional honeycomb monolayers and one-dimensional single-walled nanotubes of IIB-VI semiconductors (ZnO, CdO, ZnS and CdS) are nearly chirality-independent and weakly diameter-dependent. Based on analysis of the electronic structures, it was found that the conduction band minimum is contributed by the spherically symmetric $s$ orbitals of cations and the valence ba…
It has been shown in recent experiments that electronic transport through a gold monatomic nanowire is dissipative above a threshold voltage due to excitation of phonons via the electron-phonon interaction. We address that data by computing, via density functional theory, the zone boundary longitudinal phonon frequency of a perfect monatomic nanowire during its mechanical elongation. The theoretical frequency that we find for an ideally strained nanowire is not compatible with experiment if a uniformly distributed stretch is assumed. With the help of a semi-empirical Au-Au potential, we model …
Here, we demonstrate an approach that provides a precise control of the dimension of InAs from one-dimensional nanowires to wafer-scale free-standing two-dimensional nanosheets, which have a high degree of crystallinity and outstanding electrical and optical properties, using molecular-beam epitaxy by controlling catalyst alloy segregation. In our approach, two-dimensional InAs nanosheets can be obtained directly from one-dimensional InAs nanowires by silver-indium alloy segregation, which is much easier than all previously reported method, such as traditional buffering technique and select ar…
Irradiation of a sharp tungsten tip by a femtosecond laser and exposed to a strong DC electric field led to gradual and reproducible surface modifications. By a combination of field emission microscopy and scanning electron microscopy, we observed asymmetric surface faceting with sub-ten nanometer high steps. The presence of well pronounced faceted features mainly on the laser-exposed side implies that the surface modification was driven by a laser-induced transient temperature rise -- on a scale of a couple of picoseconds -- in the tungsten tip apex. Moreover, we identified the formation of a…
One of severe limits of graphene nanoribbons (GNRs) in future applications is that zigzag GNRs (ZGNRs) are gapless, so cannot be used in field effect transistors (FETs). In this paper, using tight-binding approach and first principles method, we derived and proved a general edge (boundary) condition for the opening of a significant bandgap in ZGNRs with defective edge structures. The proposed semiconducting GNRs have some interesting properties including the one that they can be embedded and integrated in a large piece of graphene without the need of completely cutting them out. We also demons…
We report nanoscale bandgap engineering via a local strain across the inhomogeneous ferroelectric interface, which is controlled by the visible-light-excited probe voltage. Switchable photovolatic effects and the spectral response of the photocurrent were explore to illustrate the reversible bandgap variation (~0.3eV). This local-strain-engineered bandgap has been further revealed by in situ probe-voltage-assisted valence electron energy-loss spectroscopy (EELS). Phase-field simulations and first-principle calculations were also employed for illustration of the large local strain and the bandg…
The electronic band structure of complex nanostructured semiconductors has a considerable effect on the final electronic and optical properties of the material and, ultimately, on the functionality of the devices incorporating them. Valence electron energy-loss spectroscopy (VEELS) in the transmission electron microscope (TEM) provides the possibility of measuring this property of semiconductors with high spatial resolution. However, it still represents a challenge for narrow-bandgap semiconductors, since an electron beam with low energy spread is required. Here we demonstrate that by means of…
Nanoscale semiconductor materials have been extensively investigated as the channel materials of transistors for energy-efficient low-power logic switches to enable scaling to smaller dimensions. On the opposite end of transistor applications is power electronics for which transistors capable of switching very high voltages are necessary. Miniaturization of energy-efficient power switches can enable the integration with various electronic systems and lead to substantial boosts in energy efficiency. Nanotechnology is yet to have an impact in this arena. In this work, it is demonstrated that nan…
Graphene nanoribbons are the counterpart of carbon nanotubes in graphene-based nanoelectronics. We investigate the electronic properties of chemically modified ribbons by means of density functional theory. We observe that chemical modifications of zigzag ribbons can break the spin degeneracy. This promotes the onset of a semiconducting-metal transition, or of an half-semiconducting state, with the two spin channels having a different bandgap, or of a spin-polarized half-semiconducting state -where the spins in the valence and conduction bands are oppositely polarized. Edge functionalization o…
Excitons, Coulomb-bound electron and hole pairs, are elementary photo-excitations in semiconductors, that can couple directly to light through radiative relaxation. In contrast to these bright excitons, dark excitons X$\rm{_D}$ with anti-parallel electron spin polarization exist, with generally forbidden radiative emission. Because of their associated long lifetimes, these dark excitons are appealing candidates for quantum computing and opto-electronic devices. However, optical read-out and control of X$\rm{_D}$ states have remained a major challenge due to their decoupling from light. Here, w…
We present a method to realize active optical tips for use in near-field optics that can operate at room temperature. A metal-coated optical tip is covered with a thin polymer layer stained with CdSe nanocrystals or nanorods at low density. The time analysis of the emission rate and emission spectra of the active tips reveal that a very small number of particles - possibly down to only one - can be made active at the tip apex. This opens the way to near-field optics with a single inorganic nanoparticle as a light source.
Optical field localization at plasmonic tip-sample nanojunctions has enabled high spatial resolution chemical analysis through tip-enhanced linear optical spectroscopies, including Raman scattering and photoluminescence. Here, we illustrate that nonlinear optical processes, including parametric four-wave mixing (4WM), second harmonic/sum-frequency generation (SHG and SFG), and two-photon photoluminescence (TPPL), can be enhanced at plasmonic junctions and spatio-spectrally resolved simultaneously with few-nm spatial resolution under ambient conditions. More importantly, through a detailed anal…
We use conducting-tip atomic force microscopy (AFM) to measure local electronic properties of single wall carbon nanotube (SWNT) circuits on insulating substrates. When a voltage is applied to the tip and AFM feedback is used to position the tip, images formed from the tip-sample tunnel current have single tube resolution (near 1 nm diameter), more than an order of magnitude better than simultaneously acquired topographic AFM images. By finding points where the tip-sample current is zero, it is possible to measure the electrochemical potential within the circuit, again with nanometer resolutio…
All-dielectric nanoantennas have recently opened exciting opportunities for functional nanophotonics, owing to their strong optical resonances along with low material loss in the near-infrared range. Pushing these concepts to the visible range is hindered by a larger absorption coefficient of Si and other high-index semiconductors, thus encouraging the search for alternative dielectrics for nanophotonics. In this paper, we employ bandgap engineering to synthesize hydrogenated amorphous Si nanoparticles (a-Si:H NPs) offering ideal features for functional nanophotonics. We observe significant ma…
Steep-slope $β$-Ga$_2$O$_3$ nano-membrane negative capacitance field-effect transistors (NC-FETs) are demonstrated with ferroelectric hafnium zirconium oxide in gate dielectric stack. Subthreshold slope less than 60 mV/dec at room temperature is obtained for both forward and reverse gate voltage sweeps with a minimum value of 34.3 mV/dec at reverse gate voltage sweep and 53.1 mV/dec at forward gate voltage sweep at $V_{DS}$=0.5 V. Enhancement-mode operation with threshold voltage ~0.4 V is achieved by tuning the thickness of $β$-Ga$_2$O$_3$ membrane. Low hysteresis of less than 0.1 V is obtain…
A thin, narrow-bandgap semiconductor Bi$_2$O$_2$Te nanosheet is obtained via mechanical exfoliation and a Hall-bar device is fabricated from it on a heavily doped Si/SiO$_2$ substrate and studied at low temperatures. Gate transfer characteristic measurements show that the transport carriers in the nanosheet are of $n$-type. The carrier density, mobility, and mean free path in the nanosheet are determined by measurements of the Hall resistance and the longitudinal resistance of the Hall-bar device and it is found that the electron transport in the nanosheet is in a quasi-two-dimensional (2D), s…
We investigate the motion of a nano tippe top, which is formed from a C60 fullerene, and which is assumed to be spinning on either a graphene sheet or the interior of a single-walled carbon nanotube. We assume no specific geometric configuration for the top, however for example, the nano tippe top might be formed by joining a fullerene C60 with a small segment of a smaller radius carbon nanotube. We assume that it is spinning on a graphene sheet or a carbon nanotube surface only as a means of positioning and isolating the device, and the only effect of the graphene or the carbon nanotube surfa…
Graphene nanoribbon (GNR) field-effect transistors (FETs) with widths down to 12 nm have been fabricated by electron beam lithography using a wafer-scale chemical vapor deposition (CVD) process to form the graphene. The GNR FETs show drain-current modulation of approximately 10 at 300 K, increasing to nearly 106 at 4 K. The strong temperature dependence of the minimum current indicates the opening of a bandgap for CVD-grown GNR-FETs. The extracted bandgap is estimated to be around 0.1 eV by differential conductance methods. This work highlights the development of CVD-grown large-area graphene …
Tip-enhanced nano-spectroscopy and -imaging, such as tip-enhanced photoluminescence (TEPL), tip-enhanced Raman spectroscopy (TERS), and others, have become indispensable from materials science to single molecule studies. However, the techniques suffer from inconsistent performance due to lack of nanoscale control of tip apex structure, which often leads to irreproducible spectral, spatial, and polarization resolved imaging. Instead of refining tip-fabrication to resolve this problem, we pursue the inverse approach of optimizing the nano-optical vector-field at the tip apex via adaptive optics.…
We use an Atomic Force Microscope (AFM) tip to locally probe the electronic properties of semiconducting carbon nanotube transistors. A gold-coated AFM tip serves as a voltage or current probe in three-probe measurement setup. Using the tip as a movable current probe, we investigate the scaling of the device properties with channel length. Using the tip as a voltage probe, we study the properties of the contacts. We find that Au makes an excellent contact in the p-region, with no Schottky barrier. In the n-region large contact resistances were found which dominate the transport properties.
We study the effect of torsional deformations on the electronic properties of single-walled transition metal dichalcogenide (TMD) nanotubes. In particular, considering forty-five select armchair and zigzag TMD nanotubes, we perform symmetry-adapted Kohn-Sham density functional theory calculations to determine the variation in bandgap and effective mass of charge carriers with twist. We find that metallic nanotubes remain so even after deformation, whereas semiconducting nanotubes experience a decrease in bandgap with twist -- originally direct bandgaps become indirect -- resulting in semicondu…
The electronic band structure of armchair carbon nanotubes may be considerably modified by potentials with angular dependence. Different angular modes V_q ~ cos(q*theta) have been studied within a tight-binding scheme. Using symmetry arguments, we demonstrate a bandgap opening in these metallic nanotubes when certain selection rules are satisfied for both potential and nanotube structure. We estimate the bandgap opening as a function of both the external potential strength and the nanotube radius and suggest an effective mechanism of metal-semiconductor transition by combination of different f…
Many classes of two-dimensional (2D) materials have emerged as potential platforms for novel electronic and optical devices. However, the physical properties are strongly influenced by nanoscale heterogeneities in the form of edges, grain boundaries, and nucleation sites. Using combined tip-enhanced Raman scattering (TERS) and photoluminescence (TEPL) nano-spectroscopy and -imaging, we study the associated effects on the excitonic properties in monolayer WSe2 grown by physical vapor deposition (PVD). With <15 nm spatial resolution we resolve nonlocal nanoscale correlations of PL spectral inten…
