Scanning Tunneling Luminescence Research Articles

Nanoscale Mapping of Sub‐Gap Electroluminescence from Step‐Bunched, Oxidized 4H‐SiC Surfaces

Scanning tunneling luminescence microscopy (STLM) along with scanning tunneling spectroscopy (STS) is applied to a step-bunched, oxidized 4H-SiC surface prepared on the silicon face of a commercial, n-type SiC wafer using a silicon melt process. The step-bunched surface consists of atomically smooth terraces parallel to the [0001] crystal planes, and rougher risers consisting of nanoscale steps formed by the termination of these planes. The rather striking topography of this surface is well resolved with large tip biases of the order of -8 V and set currents of magnitude less than 1 nA. Hysteresis in the STS spectra is preferentially observed on the risers suggesting that they contain a higher density of surface charge traps than the terraces where hysteresis is more frequently absent. Similarly, at 50 K intense sub-gap light emission centered around 2.4 eV is observed mainly on the risers albeit only with larger tunneling currents of magnitude equal to or greater than 10 nA. These results demonstrate that STLM holds great promise for the observation of impurities and defects responsible for sub-gap light emission with spatial resolutions approaching the length scale of the defects themselves.

Investigation of ultrafast excited-state dynamics at the nanoscale with terahertz field-induced electron tunneling and photon emission

The combination of terahertz (THz) pulses with scanning tunneling microscopy (STM) enables us to investigate ultrafast dynamics at material surfaces with high spatial (nanoscale) and temporal (femtosecond) resolution. In this Perspective, we review the basic principles of THz-STM, outline the related literature, and discuss its future outlook capable of advancing nanoscience, especially by introducing further combination of THz-STM with scanning tunneling luminescence spectroscopy, which can extract more fruitful information about nanoscale materials via obtaining luminescence spectra compared to just observing the net tunneling current induced by THz pulses in THz-STM. By shining THz pulses onto an STM tip, we can observe plasmon luminescence locally confined between the tip and the surface, whose spectrum changes with tip conditions. The combined approach is a stepping stone toward investigating the ultrafast excited-state dynamics of nanoscale materials with high spatiotemporal resolution.

Probing Local Emission Properties in InGaN/GaN Quantum Wells by Scanning Tunneling Luminescence Microscopy

Scanning tunneling electroluminescence (STL) microscopy is performed on a 3 nm‐thick InGaN/GaN quantum well (QW) with [In] = 0.23 such that the main light emission occurs in the green. The technique is used to map the radiative recombination properties at a scale of a few nanometers and correlate the local electroluminescence map with the surface topography simultaneously imaged by scanning tunneling microscopy. While the expected green emission is observed all over the sample, measurements performed on a 500 nm × 500 nm area around a 150 nm‐large and 2.5 nm‐deep hexagonal defect reveal intense emission peaks at higher energies close to the defect edges, features which are not visible in the macrophotoluminescence spectrum of the sample. Via a fitting of the local tunneling electroluminescence spectra, quantitative information on the fluctuations of the intensity, peak energy, width, and phonon replica intensity of the different spectral contributions is obtained, which provides information on carrier localization in the QW. This procedure also indicates that the carrier diffusion length on the probed area of the QW is shorter than 50 nm.

Nanoscale Mapping of Sub‐Gap Electroluminescence from Step‐Bunched, Oxidized 4H‐SiC Surfaces

Scanning tunneling luminescence microscopy (STLM) and scanning tunneling spectroscopy (STS) are used to study step‐bunched, oxidized 4H‐SiC surfaces prepared using a silicon melt process. The step‐bunched surface consists of atomically smooth terraces parallel to [0001] crystal planes, and rougher risers containing nanoscale steps formed by the termination of these planes. The striking topography of this surface is well resolved with large tip biases around −8 V and set currents less than 1 nA. Hysteresis in the STS spectra is preferentially observed on risers, suggesting that they contain a higher density of surface charge traps than the terraces where hysteresis is more frequently absent. Similarly, intense sub‐gap light emission centered around 2.4 eV is observed mainly on the risers albeit only with larger tunneling currents equal to or greater than 10 nA. The surface‐oxide‐related origin of this emission is reinforced by comparing tunneling electroluminescence spectra on the 4H‐ and 6H‐polytypes, and by the observation of a drastic reduction in emitted intensity after removal of the oxide in buffered HF. These results demonstrate the capability of STLM for the observation of surface impurities and defects responsible for sub‐gap light emission with spatial resolutions approaching the length scale of the defects themselves.

(Invited) Development of THz-Field-Driven Scanning Tunneling Luminescence Spectroscopy for Future Investigation of Exciton Dynamics

Exciton dynamics is responsible for the photophysical and photochemical functions, such as energy harvesting, light emission, and photosynthesis. In particular, energy conversions, transfers, and dissipations at interfaces and nanostructures govern the dynamics of excitons. Nevertheless, the spatial resolutions of conventional optical methods are limited to several hundred nanometers due to the diffraction limit of light. Luminescence measurements combined with scanning tunneling microscopy (STM) enable to investigate optical properties with sub-nanometer spatial resolution in various systems such as metals[1], semiconductors[2], 2D materials[3], and molecules[4-5]. In this method, the scanning tunneling luminescence (STL) spectroscopy, photons induced by the tunneling current of STM are detected. Since the tunneling current can be controlled with atomic spatial resolution, it is possible to investigate optical phenomena in localized regions. While STL spectroscopy is a powerful tool for investigating exciton dynamics with atomic-scale spatial resolution, the time resolution of STL spectroscopy is limited because it uses “steady-state” tunneling current for the excitation. Therefore, this method cannot be applicable to track the ultrafast exciton dynamics in real-time.For overcoming the limitation of time resolution of STM, a single-cycle terahertz (THz) electric field has recently been installed to drive tunneling electrons[6-9]. By coupling the THz pulse to an atomically sharp metal tip of STM, the electric field is confined to the tip, and it enables to manipulate the tunneling electrons with extremely high spatiotemporal resolution. This method, THz-STM, has been utilized to track the ultrafast carrier dynamics[6-8] and motion of a molecule[9] with sub-picosecond time resolution. In this work, we combined a photon detection system with THz-STM to establish THz-STL spectroscopy (Fig. 1a). We measured visible photon emission from the radiative decay of a localized plasmon as the first demonstration of THz-STL spectroscopy[10]. We anticipate that the THz-STL spectroscopy will open new avenues for “real-time” and “real-space” investigations of exciton dynamics in near future.In this work, we generated single-cycle THz pulses via optical rectification of laser pulses from a Yb fiber laser in a LiNbO3 prism using a tilted-pulse-front configuration (Fig. 1b). The generated THz pulses were guided into a low-temperature STM and focused to the STM junction (Fig. 1a). Figure 1c shows a current trace on Ag(111) surface, where the current induced by the THz pulses was measured as 2.65 pA. Based on the simulation of electron tunneling probability, the maximum magnitude of the voltage applied by the THz pulse was estimated to be ~6.5 V. Figure 1d shows STL spectra when the THz pulse was either introduced to the STM (red) or blocked (grey). Whereas no peak is seen in the grey spectrum, a broad peak ranging from 1.3 eV to 2.3 eV appears in the red spectrum, which is originated from the radiative decay of a plasmon localized in the gap.In this presentation, we would like to discuss the detailed mechanism of plasmon excitation by THz-field-driven electrons as well as the challenges of applying THz-STL to the real-time investigation of exciton dynamics in a molecule.[1] R. Berndt et al., Phys. Rev. Lett. 67, 3796 (1991). [2] J. K. Gimzewski et al., Z. Phys. B Condensed Matter 72, 497 (1988). [3] Schuler et al., Sci. Adv. 6, eabb5988 (2020). [4] H. Imada et al., Nature 538, 364 (2016). [5] K. Kimura et al., Nature 570, 210 (2019). [6] T. L. Cocker et al., Nat. Photon. 7, 620 (2013). [7] K. Yoshioka et al., Nat. Photon. 10, 762 (2016). [8] V. Jelic et al., Nature Physics 13, 591 (2017). [9] D. Peller et al., Nature 585, 58 (2020). [10] K. Kimura et al., ACS photon. 8, 982 (2021). Figure 1

Atomic-Scale Photon Mapping Revealing Spin-Current Relaxation.

A nanoscopic understanding of spin-current dynamics is crucial for controlling the spin transport in materials. However, gaining access to spin-current dynamics at an atomic scale is challenging. Therefore, we developed spin-polarized scanning tunneling luminescence spectroscopy (SP STLS) to visualize the spin relaxation strength depending on spin injection positions. Atomically resolved SP STLS mapping of gallium arsenide demonstrated a stronger spin relaxation in gallium atomic rows. Hence, SP STLS paves the way for visualizing spin current with single-atom precision.

Circular Dichroism of Emergent Chiral Stacking Orders in Quasi-One-Dimensional Charge Density Waves.

Chirality-driven optical properties in charge density waves are of fundamental and practical importance. Here, we investigate the interaction between circularly polarized light and emergent chiral stacking orders in quasi-one-dimensional (quasi-1D) charge-density waves (CDWs) with density-functional theory calculations. In our specific system, self-assembled In nanowires on a Si(111) surface, spontaneous mirror symmetry breaking leads to four symmetrically distinct degenerate quasi-1D CDW structures, which exhibit geometrical chirality. Such geometrical chirality may naturally induce optically active phenomena even when the quasi-1D CDW structures are stacked perpendicular to the CDW chain direction. Indeed, we find that left- and right-chiral stacking orders show distinct circular dichroism responses while a nonchiral stacking order has no circular dichroism. Such optical responses are attributed to the existence of glide mirror symmetry of the CDW stacking orders. Our findings suggest that the CDW chiral stacking orders can lead to diverse active optical phenomena such as chirality-dependent circular dichroism, which can be observed in scanning tunneling luminescence measurements with circularly polarized light.

Investigation of selective triplet exciton formation by scanning tunneling luminescence

Investigation of selective triplet exciton formation by scanning tunneling luminescence

Influence of the Tip Shape on Scanning Tunneling Luminescence Spectra: Implications for Nanomaterial Characterization

Scanning tunneling luminescence (STL) provides a unique opportunity to determine the optical properties of nanostructures beyond the diffraction limit. However, the relationship between the STL spe...

Tunable Plasmonic Quantum Light Source with Silver Nanoclusters on a Silver Surface

Scanning tunneling luminescence (STL) can be used to investigate the optical properties of nanostructures with high spatial resolution beyond the diffraction limit of light. To get appropriate STL spectra, one needs to modify the tip repeatedly. However, such irreversible tip modification often leads to very unstable tips. Here, by using a scanning tunneling microscope (STM) tip, we demonstrate that STL spectra are tunable via silver nanocluster arrays fabricated directly on a silver surface. The silver nanoclusters are created by transferring silver atoms from the silver tip to the silver surface under STM. We found that the STL spectra were enhanced (suppressed) at higher (lower) energy on the clusters and that they showed opposite behaviors between the nanoclusters. Without relying on the irreversible tip shape modification, our findings indicate that we can tune the STL spectra simply by moving the STM tip over the nanoclusters. Our method can be used to provide a tunable light source for systematic nano-optical experiments and for nanoscale optical devices.

Near-Field Manipulation in a Scanning Tunneling Microscope Junction with Plasmonic Fabry-Pérot Tips.

Near-field manipulation in plasmonic nanocavities can provide various applications in nanoscale science and technology. In particular, a gap plasmon in a scanning tunneling microscope (STM) junction is of key interest to nanoscale imaging and spectroscopy. Here we show that spectral features of a plasmonic STM junction can be manipulated by nanofabrication of Au tips using focused ion beam. An exemplary Fabry–Pérot type resonator of surface plasmons is demonstrated by producing the tip with a single groove on its shaft. Scanning tunneling luminescence spectra of the Fabry–Pérot tips exhibit spectral modulation resulting from interference between localized and propagating surface plasmon modes. In addition, the quality factor of the plasmonic Fabry–Pérot interference can be improved by optimizing the overall tip shape. Our approach paves the way for near-field imaging and spectroscopy with a high degree of accuracy.

Evidence of nanoscale Anderson localization induced by intrinsic compositional disorder in InGaN/GaN quantum wells by scanning tunneling luminescence spectroscopy

We present direct experimental evidences of Anderson localization induced by the intrinsic alloy compositional disorder of InGaN/GaN quantum wells. Our approach relies on the measurement of the luminescence spectrum under local injection of electrons from a scanning tunneling microscope tip into a near-surface single quantum well. Fluctuations in the emission line shape are observed on a few-nanometer scale. Narrow emission peaks characteristic of single localized states are resolved. Calculations in the framework of the localization landscape theory provide the effective confining potential map stemming from composition fluctuations. This theory explains well the observed nanometer scale carrier localization and the energies of these Anderson-type localized states. The energy spreading of the emission from localized states is consistent with the usually observed very broad photo- or electro-luminescence spectra of InGaN/GaN quantum well structures.

走査トンネル顕微鏡発光分光法による分子間エネルギー移動の実空間計測

走査トンネル顕微鏡発光分光法による分子間エネルギー移動の実空間計測

High-resolution microscopy of plasmon field distributions by scanning tunneling luminescence and photoemission electron microscopies

Abstract The exploitation of plasmon resonances to promote the interaction between conjugated molecules and optical fields motivates intensive research. The objectives are to understand the mechanisms of plasmon-mediated interactions, and to realize molecularly- or atomically-precise metal nanostructures, combining field enhancements and optical antenna effects. In this review paper, we present examples of plasmonic-field mappings based on scanning tunneling microscope (STM)-induced light emission or multiphoton photoemission (PEEM), two techniques among those which offer todayʼs best spatial resolutions for plasmon microscopy. An unfamiliar property of the junction of an STM is its ability to behave as a highly localized source of light. It can be exploited to probe optoelectronic properties, in particular plasmonic fields, with ultimate subnanometer spatial resolution, an advantage balanced by a sometimes delicate deconvolution of local-probe influence. Alternatively, local-probe disadvantages can be overcome by imaging the photoemitted electrons, using well-established electron optics. This allows obtaining two-dimensional intensity maps reflecting the unperturbed distribution of the optical near field. This approach provides full field spectroscopic images with a routine spatial resolution of the order of 20 nm (down to 5 nm with recent aberration corrected instruments).

Scanning Tunneling Luminescence of Individual CdSe Nanowires

The local luminescence properties of individual CdSe nanowires composed of segments of zinc blende and wurtzite crystal structures are investigated by low-temperature scanning tunneling luminescence spectroscopy. Light emission from the wires is achieved by the direct injection of holes and electrons, without the need for coupling to tip-induced plasmons in the underlying metal substrate. The photon energy is found to increase with decreasing wire diameter due to exciton confinement. The bulk bandgap extrapolated from the energy versus diameter dependence is consistent with photon emission from the zinc blende-type CdSe sections.

Simple and efficient scanning tunneling luminescence detection at low-temperature

We have designed and built an optical system to collect light that is generated in the tunneling region of a low-temperature scanning tunneling microscope. The optical system consists of an in situ lens placed approximately 1.5 cm from the tunneling region and an ex situ optical lens system to analyze the emitted light, for instance, by directing the light into a spectrometer. As a demonstration, we measured tip induced photoluminescence spectra of a gold surface. Furthermore, we demonstrate that we can simultaneously record scanning tunneling microscope induced luminescence and topography of the surface both with atomic resolution.

Recent Advances in the STM-based Luminescence Microscopy of Cu(In,Ga)Se2 thin films

AbstractWe report on recent advances in the development of a luminescence spectroscopy based on scanning tunneling microscopy (STM) and its application to fundamental aspects of Cu(In,Ga)Se2 (CIGS) thin films. Relevant to our discussion is the specifics of the surface electronics. The CIGS shows pronounced stoichiometric deviations at the surface and, consequently, distinct surface electronics that has been shown to be critical in achieving high efficiency. Cathodoluminescence (CL), a luminescence spectrum imaging mode in scanning electron microscopy (SEM), provides a direct correlation between the microstructure of the CIGS and its electronic properties. As such, cathodoluminescence can resolve the emission spectrum between grain boundaries and grain interiors or be used to investigate the influence of local orientation and stoichiometry on the electronic properties of the CIGS at the microscale. Cathodoluminescence is not a surface microscopy, however, and resolving the electronic structure of the CIGS surface remains elusive to all luminescence microscopies. With this motivation, we have developed a luminescence microscopy based on STM, in which tunneling electrons are responsible for the excitation of luminescence (scanning tunneling luminescence or STL). The hot-tunneling-electron excitation is confined to the surface and, consequently, the tunneling luminescence spectrum reveals the electronic states near the surface. The STM is integrated inside the SEM and, therefore, both CL and STL can be measured over the same location and compared. Using this setup, the transition from the grain interior to the surface can be investigated. We have improved the collection of our optics to a level in which tunneling luminescence spectrum imaging can be performed. Here we present a detailed account on our investigation of the surface electronics in CIGS deposited in the regime of selenium deficiency as defined by <Se>/(<Cu> + <In> + < Ga >) = 1.

Photon emission in CuInSe2 thin films observed by scanning tunneling microscopy

We report on the observation of photon emission from CuInSe2 (CIS) thin films by scanning tunneling microscopy (STM), which results from the radiative recombination induced by tunneling electrons. Scanning tunneling luminescence (STL) spectroscopy suggests that photons are emitted near the surface of CIS. STL is excited by recombination of tunneling electrons with available holes in CIS or electron-hole recombination by impact ionization—unipolar and bipolar excitation, respectively. Which process becomes predominant depends on the voltage applied to the STM tip. Under unipolar excitation, the photon intensity decreases on grain boundaries when compared to grain interiors. Under bipolar excitation, on the other hand, no differences are observed in photon intensity. A reduction of the density of holes in grain boundaries, relative to grain interiors, can explain the observed behavior.

Scanning Tunneling Luminescence of Semiconductors

ABSTRACTWe review scanning tunneling luminescence (STL) – a photon emission spectroscopy based on scanning tunneling microscopy (STM) – and report on its application to photovoltaics. As part of this exploratory research, we have investigated CuInSe2 thin films, solar cells based on quantum dots, and dilute nitride compounds. STL is very attractive because it is capable of nanometer resolution, which is being demanded by the spectacular advancement of nanoscience and nanotechnology. In addition, STM offers both unipolar and bipolar excitation of the luminescence and, consequently, the transport and recombination of electrons and holes can be investigated independently.

Optical and Electronic Spectroscopy of Artificial Atoms and Molecules

A combination of scanning tunneling luminescence (STL) and current-voltage scanning tunneling spectroscopy (STS) has been employed to image the charge density of the confined electronic states and to spatially resolve the extent of the orbitals of InGaAs quantum dots produced by epitaxial Stranski–Krastanow growth. The selective investigation of isolated dots and coupled dots (dot-to-dot distance of the order of few nm) clearly reveals the formation of atomic-like and molecular-like states. The tunneling current images have been compared with calculated tunneling current profiles and the observed tunneling current contrast has been associated with the localized quantum dot states.