Probing excitonic states in suspended two-dimensional semiconductors by photocurrent spectroscopy.

The optical response of semiconducting monolayer transition-metal dichalcogenides (TMDCs) is dominated by strongly bound excitons that are stable even at room temperature. However, substrate-related effects such as screening and disorder in currently available specimens mask many anticipated physical phenomena and limit device applications of TMDCs. Here, we demonstrate that that these undesirable effects are strongly suppressed in suspended devices. Extremely robust (photogain > 1,000) and fast (response time < 1 ms) photoresponse allow us to study, for the first time, the formation, binding energies, and dissociation mechanisms of excitons in TMDCs through photocurrent spectroscopy. By analyzing the spectral positions of peaks in the photocurrent and by comparing them with first-principles calculations, we obtain binding energies, band gaps and spin-orbit splitting in monolayer TMDCs. For monolayer MoS2, in particular, we obtain an extremely large binding energy for band-edge excitons, E bind ≥ 570 meV. Along with band-edge excitons, we observe excitons associated with a van Hove singularity of rather unique nature. The analysis of the source-drain voltage dependence of photocurrent spectra reveals exciton dissociation and photoconversion mechanisms in TMDCs.

Giant enhancement of hydrogen transport in rutile TiO2 at low temperatures.

Measurements of the O-H and O-D vibrational lifetimes show that the room-temperature hydrogen diffusion rate in rutile TiO2 can be enhanced by 9 orders of magnitude when stimulated by resonant infrared light. We find that the local oscillatory motion of the proton quickly couples to a wag-mode-assisted classical transfer process along the c channel with a jump rate of greater than 1 THz and a barrier height of 0.2 eV. This increase in proton transport rate at moderate temperatures provides new insight into hydrogen transport in solids, which could play a role in applications ranging from fuel cells to hydrogen production.

Proton tunneling: a decay channel of the O-H stretch mode in KTaO3.

The vibrational lifetimes of the O-H and O-D stretch modes in the perovskite oxide KTaO3 are measured by pump-probe infrared spectroscopy. Both stretch modes are exceptionally long lived and exhibit a large "reverse" isotope effect, due to a phonon-assisted proton-tunneling process, which involves the O-Ta-O bending motion. The excited-state tunneling rate is found to be 7 orders of magnitude larger than from the ground state in the proton conducting oxide, BaCeO3 [Phys. Rev. B 60, R3713 (1999)].

Low-frequency electromagnetic field effects on functional groups in human skin keratinocytes cells revealed by IR-SNOM.

Human HaCaT cells, exposed for 24 h to a 1 mT (rms) 50 Hz sinusoidal magnetic field in a temperature-regulated solenoid, suffer detectable changes in their biochemical properties and shapes. By using infrared wavelength-selective scanning near-field optical microscopy, we observed changes in the distribution of the inner chemical functional groups and in the cell morphology with a resolution of 80-100 nm.

Infrared scanning near-field optical microscopy investigates order and clusters in model membranes.

Due to its surface sensitivity and high spatial resolution, scanning near-field optical microscopy (SNOM) has a significant potential to study the lateral organization of membrane domains and clusters. Compared to other techniques, infrared near-field microscopy in the spectroscopic mode has the advantage to be sensitive to specific chemical bonds. In fact, spectroscopic SNOM in the infrared spectral range (IR-SNOM) reveals the chemical content of the sample with a lateral resolution around 100 nm (Cricenti et al., 1998a, 1998b, 2003). Model lipid membranes were studied by IR-SNOM at several wavelengths. Topographical micrographs reveal the presence of islands at the surface and the optical images indicate the formation of locally ordered multiple bilayers - both critically important features for biotechnology and medical applications.

Desorption of H from Si(111) by resonant excitation of the Si-H vibrational stretch mode.

Past efforts to achieve selective bond scission by vibrational excitation have been thwarted by energy thermalization. Here we report resonant photodesorption of hydrogen from a Si(111) surface using tunable infrared radiation. The wavelength dependence of the desorption yield peaks at 0.26 electron volt: the energy of the Si-H vibrational stretch mode. The desorption yield is quadratic in the infrared intensity. A strong H/D isotope effect rules out thermal desorption mechanisms, and electronic effects are not applicable in this low-energy regime. A molecular mechanism accounting for the desorption event remains elusive.

Vibrational lifetimes and frequency-gap law of hydrogen bending modes in semiconductors.

Vibrational lifetimes of hydrogen and deuterium related bending modes in semiconductors are measured by transient bleaching spectroscopy and high-resolution infrared absorption spectroscopy. We find that the vibrational lifetimes follow a universal frequency-gap law; i.e., the decay time increases exponentially with increasing decay order, with values ranging from 1 ps for a one-phonon process to 265 ps for a four-phonon process. The temperature dependence of the lifetime shows that the bending mode decays by lowest-order multiphonon process. Our results provide new insights into vibrational decay and the giant isotope effect of hydrogen in semiconductor systems.

Vibrational lifetimes and isotope effects of interstitial oxygen in silicon and germanium.

Decay dynamics of local vibrational modes provides unique information about energy relaxation processes to solid-state phonon bath. In this Letter the lifetimes of the asymmetric stretch mode of interstitial 16O and 17O isotopes in Si are measured at 10 K directly by time-resolved, transient bleaching spectroscopy to be 11.5 and 4.5 ps, respectively. A calculation of the three-phonon density of states shows that the 17O mode lies in the highest phonon density resulting in the shortest lifetime. The lifetime of the 16O mode in Ge is measured to be 125 ps, i.e., approximately 10 times longer than in Si. The interaction between the local modes and the lattice vibrations is discussed according to the activity of phonon combinations.

Structure-dependent vibrational lifetimes of hydrogen in silicon.

The lifetimes of the Si-H vibrational stretch modes of the H(*)(2) ( 2062 cm(-1)) and HV.VH((110)) ( 2072.5 cm(-1)) defects in crystalline Si are measured directly by transient bleaching spectroscopy from 10 K to room temperature. The interstitial-type defect H(*)(2) has a lifetime of 4.2 ps at 10 K, whereas the lifetime of the vacancy-type complex HV.VH((110)) is 2 orders of magnitude longer, 295 ps. The temperature dependence of the lifetime of H(*)(2) is governed by TA phonons, while HV.VH((110)) is governed by LA phonons. This behavior is attributed to the distinctly different local structure of these defects and the accompanying local vibrational modes.

Lifetimes of hydrogen and deuterium related vibrational modes in silicon.

Lifetimes of hydrogen and deuterium related stretch modes in Si are measured by high-resolution infrared absorption spectroscopy and transient bleaching spectroscopy. The lifetimes are found to be extremely dependent on the defect structure, ranging from 2 to 295 ps. Against conventional wisdom, we find that lifetimes of Si-D modes typically are longer than for the corresponding Si-H modes. The potential implications of the results on the physics of electronic device degradation are discussed.

Spectroscopic scanning near-field optical microscopy with a free electron laser: CH2 bond imaging in diamond films.

Hydrogen chemistry in thin films and biological systems is one of the most difficult experimental problems in today's science and technology. We successfully tested a novel solution, based on the spectroscopic version of scanning near-field optical microscopy (SNOM). The tunable infrared radiation of the Vanderbilt free electron laser enabled us to reveal clearly hydrogen-decorated grain boundaries on nominally hydrogen-free diamond films. The images were obtained by SNOM detection of reflected 3.5 microm photons, corresponding to the C-H stretch absorption, and reached a lateral resolution of 0.2 microm, well below the lambda/2 (lambda = wavelength) limit of classical microscopy.

Local vibrational modes of isolated hydrogen in germanium.

Two distinct isolated hydrogen defects are observed in crystalline Ge by in situ infrared absorption spectroscopy. Implantation of protons into Ge at cryogenic temperatures gives rise to two intense absorption lines at 745 and 1794 cm(-1). The lines originate from distinct defects, each of which contains one H atom located on a <111> axis. The 1794-cm(-1) line is assigned to bond center H in the positive charge state, whereas the 745-cm(-1) line is ascribed to negatively charged H located on a <111> axis close to the tetrahedral site.

Laser ablation as a function of the primary absorber in dentin.

BACKGROUND AND OBJECTIVE: Infrared transmission spectra of dentin reveal a broad absorption band between 6.0 and 7.0 microns composed of absorption peaks of water, collagen and carbonated hydroxyapatite. The nearly constant absorption and the existence of absorption peaks of different tissue components were used to investigate ablation as a function of the primary absorber. STUDY DESIGN/MATERIALS AND METHODS: Laser ablation of dentin as a function of fluence was studied in the wavelength range between 6.0 and 7.5 microns using the Vanderbilt Free-Electron Laser (FEL). Depth and volume of the ablation crater were determined with a silicon replica method and subsequent confocal laser topometry. SEM investigations were performed on the irradiated surfaces. For the description of the experimental data an ablation model is developed. RESULTS: At all applied wavelengths we found a linear increase of ablation depth as a function of fluence above a threshold fluence. The lower absorption of dentin at 7.5 microns compared to the absorption at 6.0, 6.5 and 7.0 microns results in a greater ablation threshold. At 6.0, 6.5 and 7.0 microns wavelengths the ablation thresholds are comparable. The experimental data are in good agreement with an ablation model using a mean absorption coefficient of the target material. No thermal cracking is observed after ablation in dentin. The post ablative surface structure at 6.0 and 7.0 microns looks similar whereas at 7.5 microns the surface reveals a greater roughness. CONCLUSION: The ablation efficiency and threshold depend on the mean absorption but do not depend upon the chemical identity of the primary absorber in dentin. Calculations show that heat conduction during the laser pulse leads to a thermal equalization between the heated microstructures and surrounding tissue resulting in an ablation with little dependence on the primary absorber.

Near-monochromatic X-ray beams produced by the free electron laser and Compton backscatter.

The intense photon output of a free electron laser may be made to collide with its own high energy electron beam to create nearly monochromatic x-rays using Compton backscatter techniques. These x-rays can be used for imaging and non-imaging diagnostic and therapeutic experiments. The initial configuration of the Vanderbilt Medical Free Electron Laser (Sierra Laser Systems, Sunnyvale, CA) produces intense x-rays up to 17.9 keV, although higher energies are easily attainable through the use of frequency doubling methods, alteration of the energy of the electron beam and coupling to conventional laser inputs.