Publication database
Non-Poissonian photon statistics from macroscopic photon cutting materials
In optical materials energy is usually extracted only from the lowest excited state, resulting in fundamental energy-efficiency limits such as the Shockley–Queisser limit for single-junction solar cells. Photon-cutting materials provide a way around such limits by absorbing high-energy photons and ‘cutting’ them into multiple low-energy excitations that can subsequently be extracted. The occurrence of photon cutting or quantum cutting has been demonstrated in a variety of materials, including semiconductor quantum dots, lanthanides and organic dyes. Here we show that photon cutting results in bunched photon emission on the timescale of the excited-state lifetime, even when observing a macroscopic number of optical centres. Our theoretical derivation matches well with experimental data on NaLaF4:Pr3+, a material that can cut deep-ultraviolet photons into two visible photons. This signature of photon cutting can be used to identify and characterize new photon-cutting materials unambiguously.
Photodissociation spectroscopy of protonated leucine enkephalin
Protonated leucine enkephalin (YGGFL) was studied by ultraviolet photodissociation (UVPD) from 225 to 300 nm utilizing an optical parametric oscillator tunable wavelength laser system (OPO). Fragments were identified by absolute mass measurement in a 9.4 T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Bond cleavage was preferred in the vicinity of the two aromatic residues, resulting in high ion abundances for a4, a1, b3, y2 and y1 fragments. a, b and y ions dominated the mass spectrum, and full sequence coverage was achieved for those types. Photodissociation was most effective at the short wavelength end of the studied range, which is assigned to the onset of the La π–π* transition of the tyrosine chromophore, but worked well also at the Lb π–π* chromophore absorption maxima in the 35 000–39 000 cm−1 region. Several side-chain and internal fragments were observed. H atom loss is observed only above 41 000 cm−1, consistent with the requirement of a curve crossing to a repulsive 1πσ* state. It is suggested that the photochemically generated mobile H atom plays a role in further backbone cleavages, similar to the mechanism for electron capture dissociation. The b4 fragment is most intense at the Lb chromophore absorptions, undergoing additional fragmentation at higher photon energies. The high resolution of the FT-ICR MS revealed that out of all x and z-type fragments only x3 and x4 were formed, with low intensity. Other previously reported x- and z-fragments were re-assigned to internal fragments, based on exact mass measurement.
Sibling rivalry: intrinsic luminescence from two xanthene dye monoanions, resorufin and fluorescein, provides evidence for excited-state proton transfer in the latter
While the emission spectrum of fluorescein monoanions isolated in vacuo displays a broad and featureless band, that of resorufin, also belonging to the xanthene family, has a sharp band maximum, clear vibronic structure, and experiences a small Stokes shift. Excited-state proton transfer in fluorescein can account for the differences.
A cylindrical quadrupole ion trap in combination with an electrospray ion source for gas-phase luminescence and absorption spectroscopy
A relatively simple setup for collection and detection of light emitted from isolated photo-excited molecular ions has been constructed. It benefits from a high collection efficiency of photons, which is accomplished by using a cylindrical ion trap where one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The geometry permits nearly 10% of the emitted light to be collected and, after transmission losses, approximately 5% to be delivered to the entrance of a grating spectrometer equipped with a detector array. The high collection efficiency enables the use of pulsed tunable lasers with low repetition rates (e.g., 20 Hz) instead of continuous wave (cw) lasers or very high repetition rate (e.g., MHz) lasers that are typically used as light sources for gas-phase fluorescence experiments on molecular ions. A hole has been drilled in the cylinder electrode so that a light pulse can interact with the ion cloud in the center of the trap. Simulations indicate that these modifications to the trap do not significantly affect the storage capability and the overall shape of the ion cloud. The overlap between the ion cloud and the laser light is basically 100%, and experimentally >50% of negatively charged chromophore ions are routinely photodepleted. The performance of the setup is illustrated based on fluorescence spectra of several laser dyes, and the quality of these spectra is comparable to those reported by other groups. Finally, by replacing the optical system with a channeltron detector, we demonstrate that the setup can also be used for gas-phase action spectroscopy where either depletion or fragmentation is monitored to provide an indirect measurement on the absorption spectrum of the ion.
Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend
Organic nanomaterials are attracting a great deal of interest for use in flexible electronic applications such as logic circuits, displays and solar cells. These technologies have already demonstrated good performances, but flexible organic memories are yet to deliver on all their promise in terms of volatility, operational voltage, write/erase speed, as well as the number of distinct attainable levels. Here, we report a multilevel non-volatile flexible optical memory thin-film transistor based on a blend of a reference polymer semiconductor, namely poly(3-hexylthiophene), and a photochromic diarylethene, switched with ultraviolet and green light irradiation. A three-terminal device featuring over 256 (8 bit storage) distinct current levels was fabricated, the memory states of which could be switched with 3 ns laser pulses. We also report robustness over 70 write–erase cycles and non-volatility exceeding 500 days. The device was implemented on a flexible polyethylene terephthalate substrate, validating the concept for integration into wearable electronics and smart nanodevices.
Investigation into the advantages of pure perovskite film without PbI₂ for high performance solar cell
In CH3NH3PbI3-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI2 impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI2. This was mainly due to the inferior morphology of pure perovskite film without PbI2, inevitably produced when the remaining PbI2 forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI2 impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI2, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI2. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI2 impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured.
Magneto-elasto-electroporation (MEEP): In-vitro visualization and numerical characteristics
A magnetically controlled elastically driven electroporation phenomenon, or magneto-elasto-electroporation (MEEP), is discovered while studying the interactions between core-shell magnetoelectric nanoparticles (CSMEN) and biological cells in the presence of an a.c. magnetic field. In this paper we report the effect of MEEP observed via a series of in-vitro experiments using core (CoFe2O4)-shell (BaTiO3) structured magnetoelectric nanoparticles and human epithelial cells (HEP2). The cell electroporation phenomenon and its correlation with the magnetic field modulated CSMEN are described in detail. The potential application of CSMEN in electroporation is confirmed by analyzing crystallographic phases, multiferroic properties of the fabricated CSMEN, influences of d.c. and a.c. magnetic fields on the CSMEN and cytotoxicity tests. The mathematical formalism to quantitatively describe the phenomena is also reported. The reported findings provide insights into the underlying MEEP mechanism and demonstrate the utility of CSMEN as an electric pulse-generating nano-probe in electroporation experiments with a potential application toward accurate and efficient targeted cell permeation.
Nile blue shows its true colors in gas-phase absorption and luminescence ion spectroscopy
Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm−1) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone.
Optoacoustic effect is responsible for laser-induced cochlear responses
Optical stimulation of the cochlea with laser light has been suggested as an alternative to conventional treatment of sensorineural hearing loss with cochlear implants. The underlying mechanisms are controversially discussed: The stimulation can either be based on a direct excitation of neurons, or it is a result of an optoacoustic pressure wave acting on the basilar membrane. Animal studies comparing the intra-cochlear optical stimulation of hearing and deafened guinea pigs have indicated that the stimulation requires intact hair cells. Therefore, optoacoustic stimulation seems to be the underlying mechanism. The present study investigates optoacoustic characteristics using pulsed laser stimulation for in vivo experiments on hearing guinea pigs and pressure measurements in water. As a result, in vivo as well as pressure measurements showed corresponding signal shapes. The amplitude of the signal for both measurements depended on the absorption coefficient and on the maximum of the first time-derivative of laser pulse power (velocity of heat deposition). In conclusion, the pressure measurements directly demonstrated that laser light generates acoustic waves, with amplitudes suitable for stimulating the (partially) intact cochlea. These findings corroborate optoacoustic as the basic mechanism of optical intra-cochlear stimulation.
Recent Advances in Laser Utilization in the Chemical Modification of Graphene Oxide and Its Applications
A dramatic rise in research interest in laser-induced graphene oxide (GO) reduction and modification requires an overview of the most recent works on this subject. Typical methods for the recognition and confirmation of modified graphene and its derivatives, such as Raman, Fourier-transform infra-red (FTIR), X-ray photoelectron (XP), and ultraviolet-visible (UV–vis) spectroscopies, are introduced briefly in this review. A major part of the survey is devoted to the main modification ways and the laser parameters used in the literature. A discussion of possible reduction and modification mechanisms is also presented. Recent applications, especially in the biomedical field such as cell therapy treatment, as well as significant results of GO modification, are discussed in detail. Finally, perspectives for the application of laser-induced GO modifications in passive THz photonics and biomedicine are briefly addressed.